International Conference (Bio)Degradable Polymers from ... · International Conference (Bio)Degradable Polymers from Renewable Resources Vienna, November 18 – 21, 2007 ... degradable

International Conference

(Bio)Degradable Polymersfrom Renewable Resources

Vienna, November 18 – 21, 2007

ABSTRACTS

Polish Academy of SciencesScientific Centre in Vienna

The Conference is held under auspices of the

European Polymer Federation

Sponsors

Polish Academy of SciencesPolska Akademia Nauk

Ministry of Science and Higher Education, PolandMinisterstwo Nauki i Szkolnictwa Wyzszego

Federal Ministry of Transport, Innovation and Technology, AustriaBundesministerium für Verkehr, Innovation und Technologie

ACS PUBLICATIONSHIGH QUALITY. HIGH IMPACT.

CONTENTS

Conference Committees and Organizers . . . . . . . . . . . . . . . . . . . . . . . . . 5

Conference Programme . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Conference Venues. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8

Overview of Abstracts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

Abstracts of Invited Lectures. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .13

Abstracts of Poster Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

List of Participants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111

SCIENTIFIC COMMITTEE

Ann-Christine Albertsson (Sweden) – co-ChairGerhart Braunegg (Austria) – co-Chair

Francesco Ciardelli (Italy)Danuta Ciechanska (Poland)

Andrzej Dworak (Poland)Zbigniew Florjanczyk (Poland)

Shiro Kobayashi (Japan)Izabella Krucinska (Poland)

Andrej Krzan (Slovenia)Christopher K. Ober (USA)Gabriel Rokicki (Poland)

Tadeusz Spychaj (Poland)Robert F. Stepto (UK)Piotr Tomasik (Poland)

Jean-Pierre Vairon (France)Danuta Zuchowska (Poland)

Chairman of the Conference

Stanislaw Penczek

Chairman of the Organizing Committee

Stanislaw Slomkowski

Conference Secretary

Andrzej Nadolny

CO-ORGANIZERS OF THE CONFERENCE

Polish Academy of Sciences, Scientific Centre in Vienna, Austria

International Network (Bio)degradable Polymers from Renewable Resources

Centre of Molecular and Macromolecular Studies,Polish Academy of Sciences, Lodz, Poland

Institute of Biotechnology and Biochemical Engineering,Graz University of Technology, Graz, Austria

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CONFERENCE PROGRAMME

TIME VENUE

Sunday, November 18 Scientific Centre

17:00 – 21:00 Registration and Welcome Party

Monday, November 19 Studio 44

8:00 – 9:15 Registration

9:15 – 9:25 Opening: Stanislaw Penczek and Stanislaw Slomkowski

Chair: Maria Nowakowska9:25 – 10:00 I-01 Ramani Narayan: BioPlastics and Biodegradable Plastics – Role

in sustainability, Reducing Carbon Footprint and EnvironmentalResponsibility

10:00 – 10:20 Coffee break

Chair: Zbigniew Florjanczyk10:20 – 10:55 I-02 Ann-Christine Albertsson: (Bio)Degradable Polymers from

Renewable Resources

10:55 – 11:30 I-03 Andrzej Duda: Controlled Polymerization of Cyclic Esters


Chair: Mariastella Scandola11:50 – 12:25 I-04 Philippe Dubois: Polylactide-based Materials: from Micro- to

Nanocompositions

12:25 – 13:00 I-05 Andrzej Galeski: Physical Modification of Polylactide

13:00 – 14:30 Buffet lunch

Chair: Andrzej Dworak14:30 – 15:05 I-06 Richard A. Gross: New Biocatalytic Routes to Monomers,

Macromers and Polymers

15:05 – 15:40 I-07 Francesco Ciardelli: Modification of Biorelated Macromoleculesthrough Grafting of Short and Long Side Chains

15:40 – 16:15 I-08 Yves Gnanou: Dextran Based Block Copolymers: Synthesis andSelf Assembly in Solution

16:30 – 18:30 Poster session, Wine and cheeseAuthors-in-attendance time:16:30 – 17:30 odd numbers, 17:30 – 18:30 even numbers

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TIME VENUE

Tuesday, November 20 Studio 44

Chair: Danuta Ciechanska9:00 – 9:35 I-09 Piet J. Lemstra: Petro vs. Bio-based Plastics

9:35 – 10:10 I-10 Jan Feijen: Injectable Biodegradable Hydrogels for ProteinDelivery


Chair: Izabella Krucinska10:40 – 11:15 I-11 Martin Moeller: Polyether - Polyester Conjugates for

Biodegradable Hydrophilic Microgels and Hyperbranched Polymers

11:15 – 11:50 I-12 Emo Chiellini: Hydro- and Oxo-Biodegradable Polymers fromFossil Feedstock vs. Their Counterparts from Renewable Resources

11:50 – 12:25 I-13 Gerhart Braunegg: Polyhydroxyalkanoates (PHAs):Biodegradable Polyesters from Agricultural Waste and SurplusMaterials

Renaissance Penta Vienna Hotel

19:00 – 23:00 Conference Dinner

Wednesday, November 21 Scientific Centre

Chair: Andrej Krzan9:00 – 9:35 I-14 Marek M. Kowalczuk: (Bio)degradation of Polymeric Materials

Containing PHA and their Synthetic Analogues

9:35 – 10:10 I-15 Andreas Greiner: Novel Biodegradable Polymers and Scaffoldsfor Tissue Engineering


Chair: Gerhart Braunegg10:40 – 11:15 I-16 Maria Nowakowska: Novel Photosensitizers Based on

Polysaccharides

11:15 – 11:50 I-17 Piotr Tomasik: The Polarized Light-Induced EnzymaticFormation and Degradation of Biopolymers

11:50 – 12:00 Closing remarks

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CONFERENCE VENUES

Scientific Centre of the Polish Academy of Sciences in ViennaBoerhaavegasse 25, A-1030 Wien

and

Studio 44, Austrian LotteriesRennweg 44, A-1038 Wien

1

2

50m

ARTIS Hotel

71

Aspangstr.

Schützeng.

S7

Rennweg

Bo

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aave

g.

Kle

istg

.

Sta

nis

lau

sg.

Esla

rng.

Aspangstr.

Kleistgasse

1 – Scientific Centre 2 – Studio 44entrance: Kleistgasse

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OVERVIEW OF ABSTRACTS

Invited LecturesI-01 R. Narayan: BioPlastics and Biodegradable Plastics – Role in sustainability, Reducing Carbon

Footprint and Environmental Responsibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

I-02 A.-C. Albertsson: (Bio)Degradable Polymers from Renewable Resources . . . . . . . . . . . . . . . . . . . . . . 15

I-03 A. Duda: Controlled Polymerization of Cyclic Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

I-04 M. Murariu, A. Da Silva Ferreira, M. Pluta, M. Alexandre, L. Bonnaud, and P. Dubois:Polylactide-based Materials: from Macro- to Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

I-05 A. Galeski, E. Piorkowska, and M. Pluta: Physical Modification of Polylactide . . . . . . . . . . . . . . . . . . . 18

I-06 R. A. Gross: New Biocatalytic Routes to Monomers, Macromers and Polymers . . . . . . . . . . . . . . . . . . 20

I-07 F. Ciardelli, S. Bronco, M. Bertoldo, F. Signori, M. B. Coltelli, and G. Zampano: Modification ofBiorelated Macromolecules through Grafting of Short and Long Side Chains . . . . . . . . . . . . . . . . . . . . 21

I-08 C. Houga, J.-F. Lemeins, R. Borsali, D. Taton, and Y. Gnanou: Dextran-Based BlockCopolymers: Synthesis and Self-Assembly in Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

I-09 P. J. Lemstra: Petro vs. Bio-based Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24I-10 C. Hiemstra, R. Jin, W. Zhou, L. J. van der Aa, P. J. Dijkstra, Z. Zhong, and J. Feijen: Injectable

Biodegradable Hydrogels for Protein Delivery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

I-11 H. Keul, M. Hans, M. Erberich, J. Meyer, and M. Moeller: Polyether- Polyester Conjugates forBiodegradable Hydrophilic Microgels and Hyperbranched Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

I-12 E. Chiellini: Hydro- & Oxo-Biodegradable Polymers from Fossil Feedstock vs their Counterpartsfrom Renewable Resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

I-13 G. Braunegg, A. Atlic, M. Koller, and C. Kutschera: Polyhydroxyalkanoates (PHAs):Biodegradable Polyesters from Agricultural Waste and Surplus Material . . . . . . . . . . . . . . . . . . . . . . . . 28

I-14 M. M. Kowalczuk: (Bio)degradation of Polymeric Materials Containing PHA and their SyntheticAnalogues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29

I-15 Y. Chen, R. Dersch, M. Gensheimer, U. Bourdiot, S. Agarwal, J. H. Wendorff, and A. Greiner:Novel Biodegradable Polymers and Scaffolds for Tissue Engineering . . . . . . . . . . . . . . . . . . . . . . . . . . 30

I-16 M. Nowakowska, K. Szczubiałka, S. Zapotoczny, and Ł. Moczek: Novel Photosensitizers Basedon Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

I-17 A. Molenda-Konieczny, M. Fiedorowicz, and P. Tomasik: The Polarized Light-induced EnzymaticFormation and Degradation of Biopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Poster Contributions

P-01 A. Piegat and M. El Fray: Biodegradation of Polyester Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . 34

P-02 P. Rychter, G. Adamus, and M. M. Kowalczuk: ESI-MS Studies of Slow-release Conjugate of2,4-D with a-PHB for Agricultural Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

P-03 P. Wozniak, S. Sosnowski, and S. Slomkowski: Polymer-inorganic Hybrid Materials for TissueEngineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

P-04 E. Vidovic, D. Klee, and H. Höcker: Biodegradable Hydrogels Based on Poly(vinyl alcohol)-graft-[poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

P-05 J. B. Chardhuri, M. G. Davidson, M. J. Ellis, M. D. Jones, and X. Wu: Fabrication ofHoneycomb-Structured Polylactide and Poly(lactide-co-glycolide) Films and their Use forOsteoblast-Like Cell Culture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

P-06 H. Nilsson, A. Olsson, M. Lindström, and T. Iversen: Bark Suberin as a Renewable Source ofLong-chain ω-Hydroxyalkanoic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

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P-07 A. Tiwari and A. P. Mishra: Studied on Electrical Conducting Biopolymer-poly(thiazole)Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

P-08 A. Zemaitatitis, R. Klimaviciute, and R. Kavaliauskaite: Antibacterial Activity of CationicStarch-iodine Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

P-09 A. Tiwari, S. P. Singh, S. S. Bawa, and B. D. Malhotra: Chitosan-co-polyaniline/WO3.nH2ONanocomposites: Green Polymer Composite for Sensor Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 42

P-10 K. Wilpiszewska, S. Spychaj, and T. Spychaj: Chemical Modification of Starch withHexamethylene Diisocyanate Amide Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

P-11 K. Wilpiszewska and T. Spychaj: Starch Plasticisation via Twin-screw Extrusion . . . . . . . . . . . . . . . . . 44

P-12 C. Duncianu and C. Vasile: Study of Interpolymeric Complexes Based on Polymers fromRenewable Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

P-13 A. Pandey and B. Garnaik: Homopolymerization and Copolymerization of L, L-Lactide inPresence of Novel Zinc Proline Organocmetallic Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

P-14 F. Faÿ, I. Linossier, and K. Vallée-Réhel: Poly(lactic acid) Microcapsules Containing BioactiveMolecules: Study of Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

P-15 W. Sikorska, P. Dacko, M. Sobota, J. Rydz, M. Musioł, and M. M. Kowalczuk: Degradation Studyof Polymers from Renewable Resources and their Blends in Industrial Composting Pile . . . . . . . . . . . 48

P-16 D. Macocinschi, D. Filip, and S. Vlad: Polyurethanes from Renewable Resources as Candidatesfor Friendly Environment New Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

P-17 P. Dacko, M. Sobota, H. Janeczek, J. Dzwonkowski, J. Gołebiewski, and M. M. Kowalczuk:Viscoelastic and Thermal Proprieties of the Biodegradable Polymer Materials ContainingPolylactide, Aliphatic-Aromatic Polyester and Synthetic Poly[(R,S)-3-hydroxybutyrate] Receivedvia Injection Moulding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

P-18 V. Sedlarik, N. Saha, J. Bobalova, and P. Saha: Biodegradation of Blown Films Based onPolylactide Acid in Natural Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51

P-19 M. Bertoldo, F. Cognigni, F. Signori, S. Bronco, and F. Ciardelli: Molecular Modification ofGelatine by Reaction with Isocyanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

P-20 M.-B. Coltelli, F. Signori, C. Toncelli, C. E. Rondán, S. Bronco, and F. Ciardelli: Biodegradableand Compostable PLA-based Formulations to Replace Plastic Disposable Commodities . . . . . . . . . . 53

P-21 C. Peptu, V. Harabagiu, B. C. Simionescu, G. Adamus, and M. M. Kowalczuk: MassSpectrometry Studies of Cyclic Esters Ring Opening Oligomerization in the Presence ofDisperse Red 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

P-22 D. Ciolacu and F. Ciolacu: Supramolecular Structure – a Key Parameter for CelluloseBiodegradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

P-23 M. Kawalec, G. Adamus, H. Janeczek, P. Kurcok, M. M. Kowalczuk, and M. Scandola: Kineticsof Poly(3-hydroxybutyrate) Degradation Induced by Carboxylates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

P-24 R. P. Dumitriu and C. Vasile: Novel Biodegradable Matrices for Drug Delivery . . . . . . . . . . . . . . . . . . . 57

P-25 M. Michalak, M. Kawalec, C. Peptu, P. Kurcok, and M. M. Kowalczuk: Divergent Synthesis ofβ-Cyclodextrin-Cored Star -Poly([R,S]-3-hydroxybutyrate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

P-26 J.-R. Sarasua, E. Zuza, A. López-Arraiza, N. Imaz, and E. Meaurio: Crystallinity and CrystallineConfinement of the Amorphous Phase in Polylactides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59

P-27 D. Filip, A. I. Cosutchi, C. Hulubei, and S. Ioan: Liquid Crystal Template Applied forPolyimide-Cellulose Derivative Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

P-28 I. Spiridon, M. Ichim, and N. Anghel: Biomass Compounds with Pharmacological Applications . . . . . 61

P-29 M. Socka, M. Florczak, and A. Duda: Homo- and Copolymerization of Cyclic Aliphatic Esterswith Suppression of Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62

P-30 C.-I. Liu and C.-Y. Huang: Acid Modification and Application of Biodegradable Polymer-Starch . . . . . 63

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P-31 H.-K. Lao, E. Renard, V. Langlois, X. Pennanec, M. Cuart, K. Vallee-Rehel, and I. Linossier:Characterization of the Radical Polymeric Grafting of Hydroxylethyl Methacrylate ontoPoly(3-hydroxybutyrate-co-3-hydroxyvalerate) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

P-32 J. Jaworska, Y. Hu, J. Wei, J. Kasperczyk, P. Dobrzynski, and S. Li: Degradation Process ofBioresorbable PGLC Terpolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

P-33 G. Bogoeva-Gaceva, M. Avella, V. Srebrenkoska, A. Grozdanov, A. Buzarovska, M. E. Errico,and G. Gentile: Sustainable Green Polymer Composites Based on PLA . . . . . . . . . . . . . . . . . . . . . . . . 66

P-34 A. Błasinska and J. Drobnik: Accelerated Wound Repair by Di-O-butyrylchitin, the Polymer forNew Non-Woven Dressing Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

P-35 A. Šišková, W. Sikorska, M. Musioł, M. M. Kowalczuk, and W. J. Kowalski: Characterization ofBiodegradable Copolyesters Containing Aliphatic and Aromatic Repeating Units by Means ofElectrospray Ionization-mass Spectrometry after a Partial Depolymerization . . . . . . . . . . . . . . . . . . . . 68

P-36 M. Scandola, E. Zini, and M. L. Focarete: Commercial Biodegradable Polymers Reinforced withFlax Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

P-37 K. Gebarowska, J. Kasperczyk, P. Dobrzynski, M. Scandola, and E. Zini: Investigation of NovelShape-Memory Polymers’ Chain Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70

P-38 M. Scandola, C. Gualandi, M. L. Focarete, P. Dobrzynski, M. Kawalec, and P. Wilczek:Bioresorbable Electrospun Non-woven Scaffolds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71

P-39 J. M. Cardamone: Keratin Coating for Wool Fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72

P-40 K. S. Mikkonen, M. P. Yadav, S. Willför, K. B. Hicks, and M. Tenkanen: Films from SpruceGalactoglucomannan Blended with Poly (Vinyl Alcohol), Corn Arabinoxylan and KonjacGlucomannan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73

P-41 B. Zywicka, E. Zaczynska, A. Czarny, S. Pielka, J. Karas, and M. Szymonowicz: Activation ofTranscription Nuclear Factor NF-κB and Induction of Inflammatory Cytokines in ImmuneResponse on Resorbable Biomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

P-42 M. Szymonowicz, B. Zywicka, S. Pielka, L. Solski, D. Haznar, and J. Pluta: Influence of theGelatin-Alginate Matrixes with Calcium Lactate for the Blood Parameters Soft and TissueReaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75

P-43 M. Szymonowicz, A. Marcinkowska, B. Zywicka, S. Pielka, A. Gamian, D. Haznar, and J. Pluta:Cellular Response after Stimulation of the Gelatin-Alginate Matrixes . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

P-44 R. Makuška and R. Kulbokaitë: Synthesis and Properties of Chitosan – Poly(ethylene glycol)Comb Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77

P-45 M. Koller, P. Hesse, A. Atlic, C. Hermann-Krauss, C. Kutschera, and G. Braunegg:Polyhydroxyalkanoate (PHA) Biosynthesis from Whey Lactose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78

P-46 U. Janèiauskaite and R. Makuška: Synthesis and Study of Chitosan – Oligosaccharide GraftCopolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

P-47 M. Koller, P. Hesse, A. Atlic, C. Hermann-Krauss, C. Kutschera, and G. Braunegg: Selection ofCarbon Feed Stocks for Cost-Efficient Polyhydroxyalkanoate (PHA) Production . . . . . . . . . . . . . . . . . . 80

P-48 W.-L. Lu, C.-I. Liu, and C.-Y. Huang: Properties and Degradation of PVA/Starch Blends with aPVA-g-MA Compatibilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81

P-49 L. Santonja-Blasco, J. D. Badia, R. Moriana, and A. Ribes-Greus: Thermal and MechanicalBehaviour of a Commercial Poly(lactid acid) Submitted to Soil Burial Test . . . . . . . . . . . . . . . . . . . . . . 82

P-50 J. D. Badia, R. Moriana, L. Santonja-Blasco, and A. Ribes-Greus: A ThermogravimetricApproach to Study the Influence of a Biodegradation in Soil Test to a Poly(lactic acid) . . . . . . . . . . . . . 83

P-51 R. Moriana, L. Santonja-Blasco, J. D. Badia, and A. Ribes-Greus: Comparative Study about theBiodegradability and the Mechanical Performance of Different Biocomposites Based onThermoplastic Starch Reinforced with Cotton Fibre . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

11

P-52 S.-Y. Yang, C.-Y. Huang, and J.-Y. Wu: Improving the Processing Ability and MechanicalStrength of Starch/PVA Blends through Plasma and Acid Modification . . . . . . . . . . . . . . . . . . . . . . . . . 85

P-53 S.-Y. Yang, C.-Y. Huang, and J.-Y. Wu: Biodegradation of Starch and PVA/Starch BlendEnhanced by Rhizopus Arrhizus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

P-54 M. Kowalczyk and E. Piorkowska: Biodegradable Blends of Polylactide and Natural Rubber . . . . . . . 87P-55 G. Adamus and M. M. Kowalczuk: Synthetic Analogues of PHA Anionic Ring-opening

Polymerization of β-alkoxy Substituted β-lactones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88P-56 D. Ciechanska, J. Wietecha, J. Kazimierczak, D. Wawro, and E. Grzesiak: Biopolymer-based

Fluorescent Sensors for Quality Control of Food Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89P-57 S. Povolo and S. Casella: Polyhydroxyalkanoates Production by Isolates from a Polluted

Salt-lagoon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90P-58 M. Sobota, H. Janeczek, P. Dacko, and M. M. Kowalczuk: Thermal Properties for Blend of

Poly[(L)-lactide] and Highmolecular Weight Atactic Poly[(R,S)-3-hydroxybutyrate] . . . . . . . . . . . . . . . . 91

P-59 I. Poljanšek, B. Brulc, M. Gricar, E. Žagar, A. Kržan, and M. Žigon: Synthesis of Poly(asparticacid)-b-Polylactide Block Copolymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92

P-60 K. Krasowska, M. Rutkowska, and M. M. Kowalczuk: Compostability of Aliphatic-aromaticCopolyester and their Blends under Natural Weather Depending Conditions . . . . . . . . . . . . . . . . . . . . 93

P-61 A. Konieczna-Molenda, M. Molenda, M. Fiedorowicz, and P. Tomasik: Illumination of Cellulosewith Linearly Polarized Visible Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

P-62 W. Tomaszewski, A. Duda, M. Szadkowski, J. Libiszowski, and D. Ciechanska: Poly(l-lactide)Nano- and Micro-fibers by Electrospinning: Influence of Poly(l-lactide) Molecular Weight . . . . . . . . . . 95

P-63 G. C. Chitanu, I. Popescu, A. G. Anghelescu-Dogaru, and I. Dumistracel: BiomedicalApplications of Maleic Anhydride Copolymers and Their Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . 96

P-64 D. M. Suflet, G. C. Chitanu, and V. Trandafir: Complexation of Phosphorylated Cellulose withCollagen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

P-65 I. M. Pelin, G. C. Chitanu, V. Trandafir, and Z. Vuluga: Effect of Collagen on Sparingly SolubleInorganic Salts Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

P-66 I. Popescu, M. I. Popa, and G. C. Chitanu: Supramolecular Systems from Natural Polymers andMaleic Polyelectrolytes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

P-67 M. Gadzinowski, B. Miksa, and S. Slomkowski: Polylactide-polyglycidol Block Copolymer as aNew Nanoparticles Forming Material . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .100

P-68 M. Pluta and A. Galeski: Structure Evolution in Amorphous Poly(L/DL-lactide) upon Plain StrainCompression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .101

P-69 M. Pluta, M. Murariu, A. Da Silva Ferreira, M. Alexandre, A. Galeski, and P. Dubois: Structureand Physical Properties of PLA/Calcium Sulfate Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .102

P-70 M. Kozlowski, A. Iwanczuk, A. Kozlowska, and S. Frackowiak: Materials of Functional PropertiesBased on Biodegradable Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .103

P-71 D. Babic, Z. Kacarevic-Popovic, G. Mikova, and I. Chodak: Influence of Gamma-radiation onPCL/PHB Blends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104

P-72 S. Agarwal and L. Ren: Synthesis and Properties Evaluation of a New Class of DegradablePolymers: Poly(vinyl-co-ester)s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .105

P-73 A. Gregorova and R. Wimmer: Dynamic-Mechanical and Thermal Properties of BiodegradableComposites from Polylactic Acid (PLA) Reinforced with Wood Fibres . . . . . . . . . . . . . . . . . . . . . . . . .106

P-74 T. Eren and B. Taslica: New Derivatives of Methyl Oleate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .107

12

ABSTRACTSOF INVITEDLECTURES

13

I-01 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007

BioPlastics and Biodegradable Plastics -- Role in sustainability,

Reducing Carbon Footprint and Environmental Responsibility

Ramani Narayan

Department of Chemical Engineering & Materials Science,

Michigan State University, East Lansing MI 48824

BioPlastics offers the intrinsic value proposition for managing our carbon in a sustainable

manner and provide a carbon neutral footprint in complete harmony with the natural

biological carbon cycle. Biodegradable plastics offers the potential to manage single use,

short-life, disposable packaging and consumer goods in a environmentally responsible

manner. Plastics recycling and waste to energy operations also offer environmentally

responsible approaches to managing plastic waste.

Many questions arise:

What is a biobased plastic? Why and how are they sustainable and environmentally

responsible? How does one identify and measure biobased content? How does one document

and quantify the positive environmental attributes of biobased plastics?

What about biodegradable plastics? Is degrading the plastic the goal? Or is it more important

to ensure that these degraded fragments are completely consumed/assimilated by the

microorganisms within a reasonable and short time in the specified disposal environment?

Composting is one such environment under which biodegradability occurs. In the composting

environment, the nature of the environment, the degree of microbial utilization

(biodegradation), and the time frame within which it occurs are specified in an ASTM

standard. What are the environmental consequences and risks associated with degradable or

partially biodegradable plastics without ensuing complete biodegradability? What is the

relationship between biobased and biodegradable, biobased but not biodegradable? How does

one document the reduced carbon footprint (LCA) and obtain carbon credits.

The answers to these fundamental questions provide the basis and scientific rationale for

designing and engineering biobased, and biodegradable plastics, and lay the foundation for

standards and regulations world-wide. Life Cycle Assessment (LCAs) of these

renewable/biobased materials often show reduced environmental impact and energy use when

compared to petroleum-based materials, which we will review, and learn. We will look at

successful technology exemplars that showcase the above “bio” model.

Keywords: bioplastics; biodegradable plastics; carbon footprint

____________________________________

[1] Narayan, Ramani, Biobased and Biodegradable Materials, Rationale, Drivers, & Technology Exemplars,

ACS (An American Chemical Society Publication) Symposium Ser 939, Ch 18, pg 282, 2006

14

(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 I-02

(Bio)Degradable Polymers from Renewable Resources

Ann-Christine Albertsson

Fibre and Polymer Technology, School of Chemical Science and Engineering,

Royal Institute of Technology, SE-100 44 Stockholm, Sweden

During the last years, the interest in renewable and biodegradable materials has

increased tremendously in the global community. The global market for renewable and

biodegradable materials is anticipated to increase immensely in the near future following the

raising societal awareness of the climate situation and the expected results of a continued

consumer mentality. Still, the use of renewable and biodegradable materials has not been

realized to any significant extent and few really renewable materials are available on the

market.

Increasing the fundamental knowledge of the degradation and environmental

interactions of materials based on renewable and biodegradable polymers are the keys to

fulfilling the increasing demand of new materials. There is also a need for new materials and

more discriminating tools to predict the safety and degradation performance of the new

materials throughout the life cycle of the material and products. Indicator products and

chromatographic fingerprinting are thus powerful tools for the degradation state prediction [1-

3]. The material should have right mechanical properties and, if degradable, a suitable

degradation time for the given application and it should totally degrade to non-toxic water

soluble degradation products. The environment where the material is going to be used has a

large influence on the degradation and release rate. Materials of the future need to be

developed and made to function in all aspects of its existence, including production, use and

waste management.

Forestry and agricultural biomass holds huge potential as a renewable source of

reactants and materials, being cheap and abundant. Hemicelluloses present such a material

group, available for the production of functional materials, mainly hydrogels [4] and barrier

films [5-6]. PLA is another interesting candidate and one of the very few polymeric materials

today that are available from renewable resources, e.g. by fermentation of agricultural waste.

Keywords: degradable; bioresorbable polymers; renewable, green materials

____________________________________

[1] M. Hakkarainen; A.-C. Albertsson Adv. Polym. Sci., 169, 177 (2004).

[2] M. Hakkarainen; A. Höglund; K. Odelius; A.-C. Albertsson J. Am. Chem. Soc., 129, 6308 (2007).

[3] L. Burman; A.-C . Albertsson; M. Hakkarainen Adv. Polym. Sci.(2007)

http://dx.doi.org/10.1007/12_2007_114.

[4] M.S. Lindblad; E. Ranucci; A.-C. Albertsson Macromol. Rapid Comm., 22 (12), 962 (2001).

[5] J. Hartman, A.-C. Albertsson, J. Sjoberg Biomacromolecules, 7(6), 1983 (2006).

[6] J. Hartman, A.-C. Albertsson, M.S. Lindblad, J. Sjöberg, J.Appl. Polym. Sci., 100(4), 2985-2991 (2006).

15


Controlled Polymerization of Cyclic Esters

Andrzej Duda

Centre of Molecular and Macromolecular Studies Polish Academy of Sciences,

Sienkiewicza 112, Lodz, Poland

Ring-Opening Polymerization (ROP) of cyclic esters will be discussed, stressing that

independently on the initiator/catalyst used, i.e.: covalent metal alkoxide [1], carboxylate [2,

3], or acetyloacetonate [3], polymerization proceeds on the alkoxide species. Preparative

applications of the most often used catalysts: aluminum tris-isopropoxide and tin(II) bis-

octoate will be presented in more detail, on the example of synthesis of linear and star-like

poly(ε-caprolactone)s and polylactides [1-5] as well as poly[(R)-lactide]/poly[(S)-lactide]

stereocomplexes [6, 7].

It will be also shown that initiation with aluminum alkoxides that bear bulky, bidendate

phenolate-type ligands at the metal atom, results in an efficient suppression of both intra- and

intermolecular transesterification [6, 8, 9]. The latter finding enabled preparation of the (S,S)-

LA and ε-caprolactone (CL) di- and triblock copolymers via the poly(CL) (PCL) block

growth initiation with the living poly[(S,S)-LA] (PLA*) [9]. In the previous attempts to

prepare block copolymers this way only random copolyesters were obtained because the

PLA* + CL cross-propagation rate was lower than that of the PLA-CL* + PLA

transesterification.

Finally, it will be revealed that inversion of the initiator configuration may lead to a

substantial change of the reactivity ratios [10]. It is a well-known fact that CL

homopolymerization rate constant (kCC) exceeds considerably that of (S,S)-LA

homopolymerization (kLL). For example, in polymerizations initiated with (S)-(+)-2,2’-[1,1’-

binaphtyl-2,2’-diylbis-(nitrylomethylidyno)]-diphenolate aluminum isopropoxide (SBO2Al-

OiPr): kCC/kLL ≈ 60 (THF, 80 °C). However, the LA comonomer is consumed first from the

CL/(S,S)-LA mixture. The corresponding reactivity ratios are equal to: rL = 322 and rC = 19.

The observed phenomena can be explained assuming that the cross-propagation rate constant

kLC is relatively low. Change of the initiator configuration, from S to R, results in consumption

of both comonomers with a comparable rate (rL = 1.5 i rC = 1.9).

Keywords: aliphatic polyesters; lactide; ε-caprolactone; living polymerization; star-shaped polymers;

stereocomplexes; block copolymers; reactivity ratios; transesterification

____________________________________

[1] A. Kowalski, J. Libiszowski, A. Duda, S. Penczek, Macromolecules 33, 1964 (2000).

[2] A. Kowalski, J. Libiszowski, T. Biela, M. Cypryk, A. Duda, S. Penczek, Macromolecules 38, 8170 (2005).

[3] A. Kowalski, J. Libiszowski, K. Majerska, A. Duda, S. Penczek, Polymer 48, 3952 (2007).

[4] T. Biela, A. Duda, H. Pasch, K. Rode, J. Polym. Sci., Part A: Polym. Chem., 43, 6116 (2005).

[5] T. Biela, I. Polanczyk, J. Polym. Sci., Part A: Polym. Chem., 44, 4214 (2006).

[6] A. Duda, K. Majerska, J. Am. Chem. Soc. 126, 1026 (2004).

[7] T. Biela, A. Duda, S. Penczek, Macromolecules 39, 3710 (2006).

[8] J. Mosnacek, A. Duda, J. Libiszowski, S. Penczek, Macromolecules 38, 2027 (2005).

[9] M. Florczak, J. Libiszowski, J. Mosnacek, A. Duda, S. Penczek, Macromol. Rapid Commun. 28, 1385,

(2007).

[10] M. Florczak, A. Duda, in preparation.

16


Polylactide-based Materials: from Macro- to Nanocomposites

M. Murariu1, A. Da Silva Ferreira

1, M. Pluta², M. Alexandre

1,

L. Bonnaud1, and Ph. Dubois

1

1Laboratory of Polymeric and Composite Materials, Materia Nova Research Center &

University of Mons-Hainaut, Place du Parc 20, 7000- Mons, Belgium 2Department of Polymer Physics, Centre of Molecular and Macromolecular Studies, Polish

Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland

The market for biodegradable polymers is growing every year and important demands can be expected for those applications where biodegradability offers clear advantage for customers and environment. In this context, polylactide (PLA) is undoubtedly one of the most promising candidates; it is not only biodegradable but also produced from renewable resources (sugar beets, corn starch, etc.). Because PLA has been recently considered as alternative in replacing petrochemical polymers, there is a strong demand to enlarge the range of PLA properties.

For further applications, the profile of PLA properties and its price can be changed by combining this matrix with different dispersed phases: fillers or reinforcements, (nano)additives, other polymers. Therefore, several types of mineral (nano)fillers (e.g., clays, calcium phosphate, hydroxyapatite, etc.) can be incorporated into PLA in order to obtain (nano)composite materials. For some applications where the property of transparency is not strictly needed, the use of PLA with mineral (micro)fillers can be an interesting solution to reduce the global cost and to improve some specific properties such as rigidity, heat deflection temperature, processability, isotropic shrinkage, etc.

In this objective, two products with the same source as origin, i.e., issued from the production and use of lactic acid, PLA and one main byproduct - calcium sulphate, have been first mixed by melt-compounding to prepare new polymer composites. The calcium sulphate microfiller was previously dried during one hour at 500 °C, to isolate the anhydrite II form (AII), which was specifically used for any further melt-compounding processes. Various

amounts of AII (10 to 50 wt%) were mixed together with PLA pellets at 190 °C. Interestingly, remarkable AII filler dispersion could be achieved even at high filler loadings resulting in a very good stiffness vs. toughness compromise. Other properties like durability, thermal stability and gas barrier properties have been evaluated as well and proved efficient with respect to the starting unfilled PLA.

The thermo-mechanical performances of these novel PLA/gypsum compositions have been further tuned up via the addition of plasticizers, toughening polymeric agents and nanofillers like organo-clays. Indeed, the field of polymer nanocomposites based on clays, such as montmorillonite, has given rise to a steadily increasing interest from scientists and industrials, as the nanoscale distribution of such high aspect ratio fillers brings up some large improvements to the polymer matrix in terms of mechanical, fire retardant, rheological, gas barrier and optical properties, especially at low clay content (as tiny as 1 wt%). As a result, novel ternary formulation, i.e, PLA filled with both AII and selected organo-clays, have been produced by melt blending yielding unequal thermo-mechanical properties, e.g., significantly improved flame retardancy behavior.

Keywords: biodegradable; polyesters; nanocomposites; organoclays; blends.

____________________________________

M. Murariu, A. Da Silva Ferreira, Ph. Degée, M. Alexandre, Ph. Dubois, Polymer, 48, 2613 (2007)

M. Pluta, M. Murariu, A. Da Silva Ferreira, M. Alexandre, A. Galeski, Ph. Dubois, J. Polym. Sci. B: Polym.

Phys., 45, 2770-2780 (2007)

G. Gorrasi, V. Vittoria, M. Murariu, A. Da Silva Ferreira, M. Alexandre, Ph. Dubois, Biomacromolecules, in

press (2007)

17


Physical Modification of Polylactide

A.Galeski, E.Piorkowska, and M.Pluta

Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,

90-363 Lodz, Poland

Light weight and durability, valuable feature of plastics, become serious flaws when they turn

to waste: post-consumer polymer packaging degrade slowly and they occupy large space in

plastics waste disposal. One of the solutions are biodegradable polymers that are transformed

quickly by enzymes into water and carbon dioxide. Most interesting is polylactide (PLA) that

can be produced from renewable resources: agricultural products and side products of food

production. Potential applications of PLA are: foil packaging, foil fibers, injection

mouldings and extruded profiles.

Due to a broad range of applications PLA must be subjected to serious modifications in order

to accomplish the best performance. Chemical modification is achieved by introducing a

fraction of lactide of opposite chirality or by copolymerization with selected biodegradable

co-monomers. Simpler and easier way is by physical modification. In our research we

explored various means of physical modifications: by thermal treatment, plastification, filling

with natural fibrous fillers and particulate mineral fillers, compounding with various organo-

modified nanoclays and by molecular orientation resulting from cavity-free plastic

deformation [1-10]. The driving force of the investigation was an expected improvement of

mechanical and physical properties of PLA and PLA based systems.

Plastic deformation in cavity-free manner (channel die) of amorphous copolymer P(L/DL)LA,

70/30 (i.e. unable to crystallize thermally), was studied at the temperature from 60 to 90 oC.

Evolution of structure and modification of mechanical properties were investigated as a

function of compression ratio. Transformation of amorphous P(L/DL)LA to crystalline texture

oriented in the direction of plastic flow without a trace of lamellar structure was clearly

detected. Formed crystalites (α crystallographic form) were small up to 9 nm in the transverse

direction to the flow, while the crystallinity was not exceeding 9% at highest compression

ratios. Significant increase of Tg and few fold increase of tensile strength of 120 MPa as

compared to 33 MPa for unoriented PLA.

Improvement of deformability of PLA both amorphous and crystalline was achieved by

elaborating of a new plasticizer – poly(propylene glycol) (PPG). PPG is soluble in PLA and is

not exuded by a crystallizing front of spherulites and remains dissolved in the amorphous

phase of PLA. Improvement of deformability depends on the amount of plasticizer and is very

effective for amorphous PLA. However, in the case of crystalline PLA PPG is concentrated in

the amorphous phase between crystalline lamellae and plasticizes PLA very efficiently: by a

decrease of yield stress, an increase of strain at fracture up to 100%, and an increase of tensile

impact strength from 36 to 60 kJ/m2 for 10wt.% of plasticizer. Improvement of mechanical

properties of crystalline PLA by plastification demonstrated the use of crystalline PLA at

temperature higher than its Tg, up to the melting point of crystals (+160-170oC), i.e. cups for

hot drinks, plates for hot food, micro-oven heating etc.

Filling PLA with natural fibrous fillers such as hemp fibers, grinded cacao shells, grinded

apple pomace, oat chaff and other leads to the increase of tensile modulus. Plasticizing such

systems with PPG or poly(ethylene glycol) allows the recovery of drawability.

Studies of nanocomposites of PLA with organo-modified nanoclay showed that the dispersion

of nanoclay depends on the nature of organo-modification and it is best with Cloisite 30B.

Exfoliation of nanoclay can be increased by increasing the mixing time with fixed other

compounding parameters. It indicates that the main mechanism of exfoliation is stripping clay

18


platelets one by one. Nanocomposites were characterized by thermal, rheological, structural

and mechanical studies. It was found that the molar mass of PLA decreases during mixing,

nevertheless the main parameter influencing the performance of PLA nanocomposites is their

phase structure. The best exfoliated PLA nanocomposite showed the best barrier properties

for gas diffusion. The barrier properties of PLA nanocomposites are especially important

because of possible application of PLA for food and drink packaging. The presented results

illustrate a broad range of physical modifications including plastification, molecular

orientation, filling with fibrous and particulate natural fillers as well as nanofillers. The role of

those factors is extending beyond to interaction during mechanical loading to modification of

supermolecular structure and all physical properties of PLA based systems.

____________________________________

[1] Z.Kulinski, E.Piorkowska, Polymer, 46, 10290- 10300 (2005).

[2] A.Gałęski, E.Piórkowska, M.Pluta, Z.Kuliński, R.Masirek, Polimery, 50, 562-569

(2005).

[3] Z.Kulinski, E.Piorkowska, K.Gadzinowska, M.Stasiak, Biomacromolecules, 7, 2128-

2135 (2006).

[4] E.Piorkowska, Z.Kulinski, A.Galeski, R.Masirek, Polymer, 47, 7178-7188 (2006).

[5] R.Masirek, E.Piorkowska, A.Galeski, M.Mucha, J.Appl.Polym.Sci. 105, 282–290

(2007).

[6] R.Masirek, Z.Kulinski, D.Chionna, E.Piorkowska, M.Pracella, J.Appl.Polym.Sci. 105,

255–268 (2007).

[7] M.Kozlowski, R.Masirek, E.Piorkowska and M.Gazicki-Lipman, Appl.Polym.Sci. 105,

269–277 (2007).

[8] E.Lezak, Z.Kulinski, R.Masirek, E.Piorkowska, M.Pracella, K.Gadzinowska,

Composites Polym.Sci,. in print.

[9] E.Piórkowska, A.Gałęski, Z.Kuliński, Polish patent application URP, 2006, Nr.

P376080, Worls patent application.

[10] M.Pluta, A.Galeski, Biomacromolecules, 8, 9-16 (2007).

[11] M.Pluta, J Polym Sci Part B:Polym Phys, 44, 392 (2006).

[12] M. Pluta, M. Murariu, A. S. Ferreira, M. Alexandre, A.Galeski and Ph. Dubois,

J.Polym.Sci. Phys Ed. in print (2007).

[13] M. Pluta, J.K. Jeszka, G. Boiteux, Europ.Polym.J. 43, 2819-2835 (2007).

[14] Pluta M, Paul MA, Alexandre M, Dubois P, J.Polym.Sci. Part B-Polym.Phys., 44 (2):

299-311, (2006).

[15] Pluta M, Polymer , 45 (24): 8239-8251, (2004).

[16] Pluta M., Paul MA, Alexandre M, Dubois P, J.Polym.Sci. Part B-Polym.Phys., 44 (2):

312-325, (2006).

[17] Galeski A, Piorkowska E, Pluta M, Kulinski Z, Masirek R, Polimery, 50 (7-8): 562-569

(2005).

[18] Pluta M, Galeski A, J.Appl.Polym.Sci., 86 (6): 1386-1395, (2002).

[19] Pluta M, Galeski A, Alexandre M, Paul MA, Dubois P, J.Appl.Polym.Sci., 86 (6): 1497-

1506, (2002).

19


New Biocatalytic Routes to Monomers, Macromers and Polymers

Richard A. Gross

NSF I/UCRC for Biocatalysis and Bioprocessing of Macromolecules, Department of

Chemical and Biological Sciences; Polytechnic University, Six Metrotech Center,

Brooklyn, NY 11201

New and versatile biocatalytic methods were developed that offer mild and efficient options

for macromer and polymer synthesis. Lipase B from Candida antartica (CALB), physically

immobilized on hydrophobic macroporous resins, is a remarkable catalyst for both ring-

opening and step-condensation reactions. CALB catalysis enabled the synthesis of aliphatic

polyolpolyesters and polycarbonates by using a wide range of building blocks including sugar

alcohols such as glycerol and sorbitol. Lipase regioselectivity enables direct

copolymerizations of polyols with diols and diacids to give non-crosslinked high molecular

weight materials with controlled branching. The mild reaction conditions (50 to 90 oC)

allowed incorporation of chemically and/or thermally sensitive co-monomers such as

silicones. For example, poly(ester-amides) were prepared containing silicone chain segments

and carbohydrates were directly linked to silicones (“sweet silicones”), the latter giving

materials with interesting surfactant properties.

Enzymatic routes to new monomers and their polymerization will also be discussed. For

example, fatty acids were transformed by an engineered Candida tropicalis strain to their

corresponding α,ω-dicarboxylic acids, α-carboxyl-ω-hydroxyl fatty acids, or a mixture of

these products. Enzyme-catalyzed copolymerizations of these fatty acid derived monomers

resulted in new functional copolyesters. Also, sophorolipids were prepared by microbial

fermentation of Candida bombicola were converted by metathesis polymerization to

functional biomaterials.

Cutinases from different micro-organisms have been evaluated for polymer synthesis and

modification reactions. It was discovered that cutinases also possess impressive catalytic

activity for lactone ring-opening and diacid/diol polycondensation reactions. In addition to

polymer synthesis, cutinases have been revealed that have interesting activities for polymer

modification and hydrolysis. As examples, the results of cutinase-catalyzed hydrolysis of PET

and de-acetylation of poly(vinyl acetate) will be presented.

Keywords: Enzyme-catalysis, lipase, cutinase, polyesters, polycarbonates, immobilization

____________________________________

Hunsen, M.; Azim, A.; Mang, H.; Wallner, S. R.; Ronkvist, A.; Xie, W.; Gross, R. A.

A Cutinase with Polyester Synthesis Activity. Macromolecules; 2007; 40(2); 148-150 (2007).

Gao, W.; Hagver, R.; Shah, V.; Xie, W.; Gross, R. A.; Ilker, M. F.; Bell, C.; Burke, K. A.; Coughlin,

E. B. Glycolipid Polymer Synthesized from Natural Lactonic Sophorolipids by Ring-Opening

Metathesis Polymerization. Macromolecules;40(2); 145-147 (2007).

Hu, J; Gao, W.; Kulshrestha, A.; Gross, R.A. "Sweet polyesters": Lipase-catalyzed condensation -

Polymerizations of alditols, Macromolecules 39 (20): 6789-6792 (2006).

Kulshrestha, A. S.; Gao, W.; Gross, R.A. “Glycerol Copolyesters: Control of Branching and

Molecular Weight Using a Lipase Catalyst”, Macromolecules, (2005); 38(8); 3193-3204.

Sahoo, B.; Brandstadt, K. F.; Lane, T. H.; Gross, R. A. “Sweet Silicones": Biocatalytic Reactions to

Form Organosilicon Carbohydrate Macromers Org. Lett.; 7(18); 3857-3860 (2005).

Mei, Y.; Miller, L.; Gao, W.; Gross, R. A.; Imaging the Distribution and Secondary Structure of

Immobilized Enzymes Using Infrared Microspectroscopy Biomacromolecules; 4(1); 70-74 (2003).

20


Modification of Biorelated Macromolecules through

Grafting of Short and Long Side Chains

Francesco Ciardelli1,2, Simona Bronco

1, Monica Bertoldo

1, Francesca Signori

2,

Maria Beatrice Coltelli3 , and Giovanni Zampano

2

1PolyLab-CNR, Pisa, Italy

2Dipartimento di Chimica e Chimica Industriale, Università di Pisa,

via Risorgimento 35, 56126, Pisa

3C.I.P.,Mestre,Venezia Italy

Macromolecules of natural origin are either characterized by a hyprophobicity and low

content of polar reactive groups ( as polyesters ) or by a high number of functional hydrogen

bonding side chains . In order to improve the possible use of this materials as bioplastics , the

chemical modification of the side chains and/or the combination with other macromolecules

are highly necessary. Following our previous and current work in the functionalization [1] and

blending [2] of polyolefins we are now attempting similar routes for proteins, polysaccharides

and polylactic acid to improve their suitability in the development of innovative multiphase

materials combining renewability and biodegradability with advanced thermomechanical and

functional properties.

As far a proteins are concerned we combined an experimental approach [3] with a molecular

dynamic modelling [4] to study the modification of molecular and supramolecular structure of

Collagen and Gelatine. In the experimental approach gelatine was successfully modified

according to different routes namely crosslinking with 1,6-diisocyanatohexane (HDI) [5], side

chain binding of hydrophobic florescent groups with 1-naphtylisocyanate (NpI) and grafting

of isocyanate terminated polypropylenglycole monobutyl ether chains (PPG). The modified

gelatine derivatives showed that the modification procedures all based on the reaction of

isocyanate with reactive side chains provides materials with a large variety of water swelling

and solubility properties.

The controlled modification of cellulose fibres by grafting with a synthetic polymer was also

investigated. The first step was the controlled esterification of cellulose fibre surface with α-

bromoisobutyrylbromide (BIBB), an ATRP initiator. Ethyl acrylate (EA) was grafted-

polymerised from functionalised cellulose under ATRP conditions with or without the

presence of a sacrifical free radical initiator (ethyl α-bromoisobutyrate). The adopted

polymerisation methods allowed to control grafting degree, grafted polymer chain length and,

in perspective, grafted polymer structure, namely random and block copolymers.

Finally in case of polylactic acid the number of reactive groups in the original homopolymer

was increased by transesterification with citric acid.

____________________________________

[1] S. Coiai, E. Passaglia, M. Aglietto, F. Ciardelli, Macromolecules, 37, 8414 (2004).

[2] M.-B. Coltelli, M. Angiuli, E. Passaglia, V. Castelvetro, F. Ciardelli, Macromolecules,

39, 2153 (2006).

[3] M. Bertoldo, C. Cappelli, S. Catanorchi, V. Liuzzo, S. Bronco, Macromolecules, 38, 1385

(2005).

[4] (a). Bronco, S.; Cappelli, C ,Monti, S. J. Phys. Chem. B , 108, 10101(2004).;

(b) Monti,S., Bronco, S.; Cappelli, C J. Phys. Chem. B ,109,11389(2005).

[5] M. Bertoldo, S.Bronco, T. Gragnoli, F. Ciardelli, Macromolecular Bioscience, 7, 328-338

(2007).

21


Dextran-Based Block Copolymers: Synthesis and Self-Assembly in Solution

Clément Houga, Jean-François Lemeins, Redouane Borsali,

Daniel Taton, and Yves Gnanou

Université BORDEAUX I-ENSCPB-CNRS, Laboratoire de Chimie des Polymères

Organiques, 16 Avenue Pey Berland, 33607 PESSAC cedex, France

Naturally occurring polysaccharides such as cellulose, dextran, etc… are an abundant source of

raw materials that attract an increasing interest due to their biodegradability and renewable

character. A convenient and classical means to tailor the physicochemical properties of these

natural macromolecules is to modify their backbone by graft copolymerisation. A number of

applications have thus been developed from such graft copolymers but seldom as nanodevices

or nanosystems.

An attractive route to obtain nanostructures with well-defined morphologies is to let block

copolymers to self-assemble in a selective solvent, but the synthesis of polysaccharide-based

block copolymers has so far presented challenging difficulties. In this work, we describe the

first synthesis of dextran-b-polystyrene diblock copolymers from a dextran-based ATRP

macroinitiator and the preliminary results of the self-assembly of such diblocks in water.

Dextran is a highly water-soluble polysaccharide composed of α-D-glucopyranosyl units

mainly linked by (1→6) bonds and exhibiting a low degree of branching. The first step in our

synthetic endeavor was to introduce an appropriate ATRP site at the anomeric extremity of a

commercial dextran of Mn= 6600 g.mol-1. This terminal anomeric aldehyde was subjected to

reductive amination, using a specifically designed coupling agent fitted with ω-amino and α-

tertiary bromide groups. Before growing the polystyrene (PS) block by ATRP from the tertiary

bromide-ended dextran, the OH groups of the latter were silylated to make it soluble in regular

organic solvents.

Next, styrene was polymerized from the corresponding silylated dextran-based ATRP

macroinitiator. ATRP experiments were carried out in toluene using CuBr/PMDETA as

catalyst. Five diblock copolymers whose DPn of the PS block ranged from 5 to 775 were

synthesized from the same dextran-based precursor and characterized by SEC using THF as

eluent. Finally, these (silylated dextran)-b-PS block copolymers were readily desilylated under

acidic conditions (Scheme 1), affording the targeted amphiphilic dextran-b-PS block

copolymers.

OMe3SiO

Me3SiO

Me3SiO

Me3SiO O

OMe3SiO

Me3SiO

Me3SiOO

OHO

HO

HO

HOO

OHO

HO

HO O

OHHO

HO

HONH

HN

O

Br

OSiMe3Me3SiO

Me3SiO

Me3SiONH

HN

Br

O

n

i) Toluene PMDETA CuBr Styrene

ii) HCl

n

Next, the self-assembling properties in water of these diblock copolymers were investigated.

Block copolymers with the smallest content in PS could be directly dissolved in water at ~90°C.

The nanoparticules thus formed adopted a micelle-like spherical shape with a diameter of 56

22


nm, as determined by dynamic light scattering (DLS) and 50 nm from atomic force microscopy

(AFM). Samples with larger contents in PS could not be directly transferred in water; they were

first dissolved in a DMSO/THF mixture before slowly substituting water for the organic phase,

the latter being totally removed by dialysis. For instance, a sample with a 87% content in PS

exhibited a vesicular morphology as seen by Transmission Electron Microscopy (TEM). DLS

and static light scattering measurements on the same sample afforded a ratio of 1 for Rg/RH,

thus confirming the formation of a vesicle.

The self-assembly in water of other diblock copolymers led to a variety of stable morphologies

(vesicles ovoides, etc.) whose size strongly depended on the overall composition.

23


Petro vs. Bio-based Plastics

P. J. Lemstra

Eindhoven University of Technology/Dept SKT,

Eindhoven, The Netherlands

Currently, approximately 200 million tonnes of plastics are produced annually, viz. 30

kg/capita in the world. In view of the unbalanced distribution regarding the consumption of

plastics, appr. 150 kg/capita in the Western world and Japan, and less than an average of 10

kg/capita in Asia, expectations are running high regarding the future growth of plastics. Some

EU studies predict the plastic consumption to grow even by a factor of 10 in the year 2100,

viz. 2000 million tonnes/annum!

Plastics are based on oil and currently appr. 5% of the world oil production is used to make

plastics. If the consumption of plastics increases in this Century as forecasted by several

studies then we might need up to 50% of the current oil production to produce plastics. In

view of oil depletion towards the end of this Century, this growth can not be realized based on

oil.

Bio-based plastics are promoted as an alternative to replace petro-based plastics and many

marketing studies predict that bioplastics will grow with at least 20% per annum. The

European Bioplastics society (www.european-bioplastics.org), however, predict a much faster

growth, close to 900.000 tonnes/annum by 2010, of which 800.000 tonnes based on

bioplastics based on renewable sources (Thermoplastic Starch/TPS, PLA and PHB).

At this point in time, however, one has to conclude that the expectations regarding the growth

of bio-based plastics as alternatives for petro-based plastics is below any forecast. The main

problem with bio-based polymers is their poor processability, notably of biopolymers which

have grown intra-cellular and possess a very high molar mass (to reduce the osmotic pressure)

such as PHB and starch, and/or they lack the physical/mechanical properties of synthetic

counterparts, viz. PLA vs. PET.

Bio-based plastics might have a growth potential if proper legislation is implemented and but

alternative sources to make plastics are also coming up soon, e.g. ethylene derived from bio-

ethanol (Braskem) and feedstock (monomers) from gas (Sasol, BP, Shell).

In this lecture, some fact and figures will be presented aiming to forecast the (near) future.

Keywords: petro-based plastics; bio-based polymers; forecast

24


Injectable Biodegradable Hydrogels for Protein Delivery

C. Hiemstra, R. Jin, W. Zhou, L. J. van der Aa, P. J. Dijkstra, Z. Zhong, and J. Feijen

University of Twente, Faculty of Science and Technology, Institute for BioMedical

Technology (BMTi), Department of Polymer Chemistry and Biomaterials (PBM), P.O.Box 217, 7500 AE Enschede, The Netherlands

Injectable biodegradable hydrogels that are formed in situ from aqueous polymer solutions

under physiological conditions are of particular interest for tissue engineering and protein

delivery applications. In situ formed hydrogels provide many advantages. For instance, they

allow easy homogenous encapsulation of cells and/or proteins, preparation of complex

shapes, as well as minimally invasive implantation. However, current injectable hydrogels

often require photo-irradiation, auxiliary crosslinking agents, and/or organic solvents, which

may damage the cells or proteins of interest. In the past few years, we have developed several

novel types of rapidly in situ forming biodegradable hydrogels.

Stereocomplexed hydrogels. Based on stereocomplex formation between enantiomeric PLLA

and PDLA blocks, in situ forming hydrogels have been prepared from eight-arm

poly(ethylene glycol)-poly(L-lactide) (PEG-PLLA) and poly(ethylene glycol)-poly(D-lactide)

(PEG-PDLA) star block copolymers, wherein the gelation time (from instantaneous to 1 h)

and storage modulus (up to 14 kPa in PBS at 37 °C) were shown to depend on PLA block

length and polymer concentration [1, 2]. These stereocomplexed hydrogels have been used for

in vitro and in vivo protein release [3, 4].

Michael addition hydrogels. Highly elastic hydrogels were rapidly formed in situ under

physiological conditions by Michael type addition upon mixing aqueous solutions of dextran-

vinyl sulfone (dex-VS) and multi-functional PEG-SH at a concentration of 10 to 20 w/v% [5].

These dextran hydrogels have a low initial swelling and are degradable under physiological

conditions with degradation time varying from 3 to 21 days depending on the DS,

concentration, dextran molecular weight and PEG-SH functionality. Dextran hydrogels with

slower degradation (degradation time ranging from 3 to over 21 weeks) could be obtained

from thiol functionalized dextran (dex-SH) and PEG tetra-acrylate [6].

Enzymatic hydrogels. Dextran-tyramine (Dex-TA) conjugates have been designed to prepare

hydrogels via enzymatic oxidative crosslinking [7]. Interestingly, hydrogels were rapidly

formed under physiological conditions from Dex-TA at or above a concentration of 2.5 wt%

in the presence of H2O2 and horseradish peroxidase (HRP). The swelling/degradation studies

showed that under physiological conditions, Dex-TA hydrogels are rather stable with less

than 25% loss of gel weight in 5 months. Hydrogels with faster degradation could be achieved

by linking tyramine to dextran via an ester group.

Keywords: hydrogels, biodegradable, drug delivery systems

____________________________________

[1] C. Hiemstra et al., Macromol. Symp., 224, 119 (2005).

[2] C. Hiemstra et al., J. Biomacromolecules 7, 2790 (2006).

[3] C. Hiemstra et al., J. Control. Release, 116, e19 (2006).

[4] C. Hiemstra et al., J. Control. Release, 119, 320 (2007).

[5] C. Hiemstra et al., Macromolecules, 40, 1165 (2007).

[6] C. Hiemstra et al., J. Biomacromolecules, 8, 1548 (2007).

[7] R. Jin et al., J. Biomaterials, 28, 2791 (2007).

25


Polyether- Polyester Conjugates for Biodegradable Hydrophilic Microgels

and Hyperbranched Polymers

Helmut Keul, Marc Hans, Michael Erberich, Jörg Meyer, and Martin Moeller

Institute of Technical and Macromolecular Chemistry, RWTH Aachen, and DWI an der

RWTH Aachen e.V., Pauwelsstr. 8, D-52056 Aachen, Germany

Anionic polymerization of protected glycidols with mono- and multifunctional initiators

results in polymers with linear, graft, or star-shaped architectures. Removal of the protection

groups leads to polyglycidols which are used as multifunctional macroinitiators for the ring

opening polymerization of ε-caprolactone. Core-shell polymers with a hydrophilic polyether

core and a hydrophobic polyester shell are obtained. These amphiphilic core shell polymers

are able to encapsulate guest molecules or catalytically active hydrophilic species. In this

respect, polyether-polyester conjugates are attractive materials for drug delivery systems,

because of the biodegradability of the polyester arm building blocks and the biocompatibility

of the polyether core. Regarding biomedical applications increasing interest has been devoted

to enzyme catalyzed polymerization of lactones. In this respect, a comparison between

chemical and enzymatic catalysis using multifunctional macroinitiators for the ring opening

polymerization of ε-caprolactone was performed.[1]

Polyglycidols with two orthogonal protective groups were obtained via anionic ring-

opening copolymerization of allyl glycidyl ether (AGE), tert.butyl glycidyl ether (tBuGE),

and ethoxyethyl glycidyl ether (EEGE). Poly(AGE-co-tBuGE), poly(AGE-co-EEGE), and

poly(EEGE-co-tBuGE) were obtained with controlled degree of polymerization, narrow

molecular weight distribution and a predetermined ratio of repeating units. The following

conversions were achieved by selective removal of only one protection group: using aqueous

hydrochloric acid, poly(AGE-co-EEGE) was converted to poly(AGE-co-GE); using

trifluoroacetic acid, poly(AGE-co-tBuGE) was converted to poly(AGE-co-glycidyl

trifluoroacetate); and by using Pd/C and p-toluene sulfonic acid poly(AGE-co-tBuGE) was

converted to poly(GE-co-tBuGE). A selective removal of only one protection group from

poly(EEGE-co-tBuGE) was not possible.[2]

Free hydroxymethyl groups of the polymers were partially converted in a polymer

analogous reaction to give multifunctional polyglycidols or by using bifunctional reagents to

result in amphiphilic microgels.

P(tBuGE)-co-P(AGE): R1 = -C(CH3)3; R2 = -CH2-CH=CH2

P(tBuGE)-co-P(EEGE): R1 = -C(CH3)3; R2 = -CH(CH3)-O-CH2CH3

P(AGE)-co-P(EEGE): R1 = -CH2-CH=CH2; R2 = -CH(CH3)-O-CH2CH3

OO

R2O

OR1

m+n

OO

HO

OR1

m+n

selective deprotection

Keywords: biodegradable polymers; chemical and enzymatic ring-opening polymerization, grafting from

____________________________________

[1] M. Hans, P. Gasteier, H. Keul, M. Moeller, Macromolecules 39, 3184 (2006).

[2] M. Erberich, H. Keul, M. Moeller, Macromolecules 40, 3070 (2007).

26


Hydro- & Oxo-Biodegradable Polymers from Fossil Feedstock

vs their Counterparts from Renewable Resources

Emo Chiellini

INSTM Unit - Department of Chemistry and Industrial Chemistry,

University of Pisa, via Risorgimento 35, 56126 Pisa, Italy

BIOlab, via Vecchia Livornese 1291, 56122 Loc. S. Piero a Grado (Pi)

Synthetic and semisynthetic polymeric materials were originally developed for their durability

and resistance to all forms of degradation as promoted by physical, chemical and biological

means or combinations therefrom. Special performances are achieved in relevant items

produced under conditions guaranteeing for the maintenance of molecular weight and

functionality of the raw polymeric materials both during processing and under service

conditions. The polymeric materials had been and are currently widely accepted because of their

ease of processability and amenability to provide a large variety of cost effective items that

helped enhance the comfort and quality of life both in modern industrial society and in

developing countries. However all those good features, that make the polymeric materials so

convenient and useful to the human life and societal needs, have contributed to create a serious

plastic waste burden sometime exageratedly amplified by mass media and public opinionists.

On the other hand future expectations for polymeric materials demand in the next two decades

are in favour of two to three fold increase in production as a consequence of the increase of the

plastic consumption in developing countries and countries in transition.

The design, production and consumption of polymeric materials for commodity and specialty

plastic items have certainly to face all the constraints and regulations already in place or to be

issued in the near future, dealing with the management of primary and post-consume plastic

waste. In this respect the formulation of environmentally sound degradable polymeric materials

and relevant plastic items will constitute a key option among those available for the

management of primary and post-consume plastic waste. The technologies based on the

recovery of free energy content through recycling, including also the energy recovery by

incineration will be flanked by the increasing option of environmentally degradable polymeric

materials and plastics. These should be entitled to replace the conventional commodity plastics

in those segments in which recycling is difficult and labour-intensive with hence an heavy

penalisation on the cost-performance of the “recycled’ items. Moreover one has to take into

account the downgrading of the original material properties occurring both during the service

life of the items as well as during their reprocessing stages once they enter the post-consume

rank.

The strategies that are nowadays receiving a considerable deal of attention both at fundamental

and applied level imply design of new biobased polymeric materials, introduction of hybrid

polymeric formulations and revisiting and reengineering well-consolidated polymeric materials

of synthetic and natural origin.

In this connection the present contribution is aimed at providing an outline of the polymeric

materials consisting of macromolecules characterized by a full carbon as well as an

heteronuclear backbone. Whilst the latter are included into the class of hydro-biodegradable

systems, the former in order to be converted to oxo-biodegradable systems need to be eventually

reengineered to polymer grades susceptible to controlled and modulated environmental

oxidation followed by fragmentation and then ultimately by biodegradation to carbon dioxide,

water and cell biomass under aerobic conditions.

Case studies specifically focused on polyvinyl alcohol (as a water soluble thermoplastic) and

oxo-biodegradable polyethylene (as a water-insoluble thermoplastic) will be presented in

comparison to hydro-biodegradable counterparts.

27


Polyhydroxyalkanoates (PHAs): Biodegradable Polyesters

from Agricultural Waste and Surplus Material

G. Braunegg, A. Atlic, M. Koller, and C. Kutschera

Graz University of Technology, Institute of Biotechnology and Biochemical Engineering,

8010Graz, Petersgasse 12, Austria

Polyhydroxyalkanoates (PHAs) are biodegradable polyesters that are stored intracellular in

granules when growth of the producing bacteria is limited by essential nutritional compounds

like the nitrogen or phosphate source of the growth and production medium [1]. Under such

conditions the PHA content in the cells can increase to more than 80% of the cell dry weight

formed, and the quality of the polyesters stored can be influenced by feeding precursors for

synthesis of copolyesters or terpolyesters. A drawback for this development is the fact that in

most cases production costs for PHAs are still higher than costs for conventional resins.

Biotechnological polymer production occurs in aerobic processes, therefore only about 50%

of the main carbon sources, and even a lower percentage of the precursors used for production

of co-polyesters end up in the products wanted. To overcome this problem, cheap carbon and

nitrogen sources for microbial growth and PHA synthesis are needed to lower the production

costs. Such sources are available as agricultural waste and surplus materials, for example

lactose in cheese-whey or glycerol liquid phase (GLP) from the biodiesel production process

to be used as a cheap carbon source (Fig. 1), or meat and bone meal (MBM) to be used as

nitrogen source after hydrolysis [2]. Based on these renewable resources new technologies for

polymer production can be developed, integrating the principles of “Cleaner Production” and

“Life Cycle Analysis” into the strategies for process design [3].

a

0

5

10

15

20

25

0 24 48 72 96 120 144 168

Time [h]

Glycerol [g/L]

0

5

10

15

20

25

Protein, PHA [g/L]

b

0

2

4

6

8

10

12

14

16

0 24 48 72 96 120 144 168

Time [h]

PHA, 3-PHB [g/L]

0

0,2

0,4

0,6

0,8

1

1,2

1,4

1,6

1,8

2

3-PHV [g/L]

Figure 1: Production of poly-(3HB-co-3HV) from glycerol liquid phase (GLP) with

Haloferax mediterranei. (a) Patterns of glycerol, protein and PHA; (b) polyester formation

during the process

Keywords: polyhydroxyalkanoates; sustainable production; waste materials

____________________________________

[1] G. Braunegg, G. Lefebvre, K.F. Genser, J. Biotechnol. 65, 127 (1998).

[2] M. Koller, G. Braunegg, R. Bona, C. Herrmann, P. Horvat, J. Martinz, J. Neto, L. Pereira, M. Kroutil, P.

Varila, Biomacromolecules 6, 561 (2005).

[3] G. Braunegg, R. Bona, M. Koller, Polymer-Plastics Technology and Engineering 43, 1779 (2004).

28


(Bio)degradation of Polymeric Materials Containing PHA

and their Synthetic Analogues

Marek M. Kowalczuk

Polish Academy of Sciences, Centre of Polymer and Carbon Materials,

34 M. Curie-Skłodowska St, 41-800 Zabrze, Poland

Anionic ring opening polymerization (ROP) of β-butyrolactone (the monomer which

could be obtained using synthetic gas derived from coal or waste biomass gasification) has

been reported over twenty years ago.[1] The polymer chain growth proceeds regio-selectively

and stereo-selectively entirely via carboxylate anions. Propagation on carboxylate active

centers (much less sensitive to impurities than any other anionic species) enables scaling up

the anionic ROP process of β-butyrolactone to atactic poly[(R,S)-3-hydroxybutyrate]

(a-PHB), a synthetic amorphous analog of n-PHB.

Synthetic a-PHB undergoes heterogeneous enzymatic attack (by PHB depolymerse) in

the presence of second crystalline polymer which can be in form of component of binary

blend or block in a-PHB containing block copolymer. Moreover, the heterogeneous enzymatic

hydrolysis of a-PHB occurred both when the crystalline component was itself susceptible to

enzymatic attack as well as when it was non-biodegradable by the PHB depolymerase

employed. The enzymatic degradation of a-PHB can be induced also by its blending with

amorphous polymers with high glass transition temperature, e.g. atactic poly(L,D-lactic acid).

The plain a-PHB could be degraded to the mixture of monomer, dimer and trimer in the

presence of PHA depolymerases purified from Paucimonas lemoignei (PhaZ7) as well as

Acidovorax Sp. TP4 (PhaZaci).[2, 3]

Review of innovative results concerned with (bio)degradation of atactic PHB will be

presented. Novel results concerned with evaluation of the environmental degradation of

polyester blends containing a-PHB will be discussed.[4] Moreover, the ability to control

thermal degradation and stability of a-PHB as well as of its blends via concentration of the

carboxylate polymer end groups will be demonstrated.[5]

Acknowledgement. This research was supported by Eureka E! 3420 project and by Marie Curie Transfer of

Knowledge Fellowships of the European Community’s Sixth Framework Programme under the contract number

MTKD-CT-2004-509232.

Keywords: biodegradable polymers; atactic poly(3-hydroxybutyrate)

____________________________________

[1] Jedliński, Z.; Kurcok, P.; Kowalczuk, M.; Kasperczyk, J. Makromol. Chem. 1986, 187, 1651-1656;

[2] Handrick, R.; Reinhardt, S.; Focarete, M.L.; Scandola, M.; Adamus, G.; Kowalczuk, M.; Jendrossek, D.

J. Biol. Chem. 2001, 276, 36215-36224.

[3] Wang, Y.; Inagawa, Y.; Osanai, Y.; Kasuya, K.; Saito, T.; Matsumura, S.; Doi, Y.; Inoue, Y.

Biomacromolecules 2002, 3, 894-898.

[4] Rychter, P.; Biczak, R.; Herman, B.; Smylla, A.; Kurcok, P.; Adamus, G.; Kowalczuk, M.


[5] Kawalec, M.; Adamus, G.; Kurcok, P.; Kowalczuk, M.; Foltran, I.; Focarete, M. L.; Scandola, M.


29


Novel Biodegradable Polymers and Scaffolds for Tissue Engineering

Y. Chen, R. Dersch, M. Gensheimer,

U. Bourdiot, S. Agarwal, J.H.Wendorff, and A. Greiner

Philipps-University Marburg, Department of Chemistry and Scientific Center

for Materials Science, Hans-Meerwein-Str., D-35032 Marburg, Germany

Biodegradable polymers are important for subcutane medical applications such as drug

delivery, implants, suture materials, and tissue engineering. For bone tissue engineering new

biodegradable polymers with excellent mechanical properties may be required as well as

special scaffold design.

Here we will present new synthetic routes to new biodegradable polyesters and their

invitro degradation behaviour [1-7]. Speciality scaffold design based on electrospun

polylactide nanofibers [8] will be reported as well as their compatibility to mesenchym stem

cells for applications in tissue engineering [9]. Bacteria containing electrospun nanofibers will

be reported as a potentially new biohybrid material for applications in tissue engineering [10].

Acknowledgements

The authors are indebted to Deutsche Forschungsgemeinschaft for financial support.

Keywords: tissue engineering; bioresorbable polymers; biocompatibility, nanofibers, electrospinning

____________________________________

[1] G. Haderlein, H. Petersen, C. Schmidt, J. H. Wendorff, A. Schaper, D. B. Jones, J. Visjager, P. Smith, A.

Greiner; Macromol. Chem. Phys. 200, 2080 (1999)

[2] Y. Chen, R. Wombacher, J. H. Wendorff, J. Visjager, P. Smith, A. Greiner; Chem. Mater. 15, 694 (2003)

[3] Y. Chen, R. Wombacher, J. H. Wendorff, J. Visjager, P. Smith, A. Greiner; Biomacromolecules 4, 974

(2003)

[4] Y. Chen, Ralf Wombacher, J. H. Wendorff, A. Greiner; Polymer 44, 5513-5520 (2003)

[5] Y. Chen, Ralf Wombacher, J. H. Wendorff, A. Greiner; Chem Mater. 15, 694(2003).

[6] L. Ren, S. Agarwal, Macromol. Chem. Phys., 2007, 208, 245.

[7] S. Agarwal, Polymer J., 2006, 39, 163.

[8] Greiner, J. H. Wendorff, Angew. Chem., Int. Ed. 46, 5670 (2007).

[9] U. Boudriot, R. Dersch, A. Greiner, J. H. Wendorff, Artificial Organs 30, 785 (2006).

[10] M. Gensheimer, M. Becker, Astrid Brandis-Heep, J. H. Wendorff, R. K. Thauer, A. Greiner, Adv. Mat.19,

2480 (2007).

30


Novel Photosensitizers Based on Polysaccharides

Maria Nowakowska, Krzysztof Szczubiałka,

Szczepan Zapotoczny, and Łukasz Moczek

Faculty of Chemistry, Jagiellonian University, 30-060 Kraków, Ingardena 3, Poland

There is a growing interest in the development of novel polymeric photosensitizers.

Because of the environmental concerns the possibility of using the systems based on natural

polymers is considered. We have chosen polysaccharides as the most abundant natural

polymers in biosphere. They have a lot of advantages; they are cheap, can be easily modified

and are biodegradable. Polysaccharides such as cellulose, dextran, starch and chitosan were

modified by covalent attachment of required chromophores: naphthalene, anthracene, Rose

Bengal, porphyrin and chlorophyll [1-7] The lecture describes the synthesis, characterization,

photophysical/photochemical properties of these photosensitizers as well as their potential

applications. All the photosensitizers are soluble in water. Due to the presence of

hydrophobic substituents, the modified polysaccharide chains adopted a pseudomicellar

conformation in the aqueous solutions allowing an efficient solubilization of hydrophobic

compounds sparingly soluble in water. The obtained photosensitizers absorb light from the

near UV-visible spectral region, including solar light. Photophysical studies demonstrated

that the attachment of the chromophores to the polymeric chain does not influence

considerably their properties. The aggregation of chromophores is limited while the

efficiency of the energy migration is high and the energy transfer to the suitable acceptors is

efficient. It was found that these photosensitizers can induce various photochemical

reactions. The mechanisms of these processes are dependent on the type of chromophore

present in the system and the type of reactant. Two main mechanisms of the primary

photochemical process were identified and utilized in our studies: the photoinduced electron

transfer from the electronically excited chromophores of the photosensitizer to the reactant

(molecule of organic compound and/or oxygen) and energy transfer to the molecule of

reactant (molecule of organic compound and/or oxygen). These processes result in the

formation of very reactive species such as radical-ions, hydroxyl radicals or singlet oxygen

which induce secondary photochemical reactions. It was demonstrated that the

photosensitizers based on polysaccharides can induce the oxidation of pollutants and toxins

present in water such as polynuclear aromatics, chlorinated organic compounds, cyanides, or

pesticides. Finally, the fate of the photosensitizers after their prolonged irradiation in aqueous

solution was studied. It was found that they undergo slow photo-assisted degradation.

Keywords: photosensitizers, polysaccharides, pollutants

____________________________________

[1] M. Nowakowska, M. Sterzel, K. Szczubiałka, J. E. Guillet, Macromol.Rapid Commun., 23, 972 (2002).

[2] M. Nowakowska, S. Zapotoczny, M. Sterzel, E. Kot, Biomacromolecules 5, 1009 (2004).

[3] M. Nowakowska, M. Sterzel, S. Zapotoczny, Photochem.Photobiol. 81, 1227 (2005).

[4] M. Nowakowska, M. Sterzel, S. Zapotoczny, E. Kot, Appl.Catal. B: Environ. 57, 1 (2005).

[5] M. Nowakowska, M. Sterzel, K. Szczubiałka, J.Polym.Environ. 14, 59 (2006).

[6] Ł. Moczek, M. Nowakowska, Biomacromolecules 8, 433 (2007).

[7] M. Nowakowska, Ł. Moczek, unpublished results.

31


The Polarized Light-induced Enzymatic Formation

and Degradation of Biopolymers

Anna Molenda-Konieczny, Maciej Fiedorowicz, and Piotr Tomasik

Departament of Chemistry, Agricultural University,

Balicka Street, 122, 30-149 Cracow, Poland

It has been reported [1] that moonlight stimulated decomposition of polysaccharides in

plants. That phenomenon was interpreted [2] in terms of the activation of hydrolases with

polarized light of the moon. Subsequent studies [3-7] showed that white, linearly polarized

light decomposes starch, provided starch is crystalline. Definitely, no enzymes were involved

in that process. Initially, side branches of amylopectin undergo scission followed by

repolymerization of resulting short chains into linear amylose-like polysaccharide. Studies

with polarized color light [8] showed that red light stimulated depolymerization whereas

green light stimulated repolymerization.

Independently, focus on effect of the polarized light upon enzymatic reactions of

polysaccharides resulted in interesting discoveries. Thus, white, linearly polarized light

activated α-amylolysis of starch [9], hydrolysis of xylane with xylanase [10], hydrolysis of

chitin with chitinase and chitosan with chitosanase [11], hydrolysis of cellulose with cellulase

[12], and interestingly influenced production of cyclodextrins with cyclodextrin

glycosyltransferase [13]. Effect of duration of illumination of cyclodextrin glucosyltransferase

with polarized light had certain effect upon the yield and isomer ration of three isomeric

cyclodextrins.

Application of the polarized light required 1-2 hour illumination of the enzymes in a

small reaction vessel followed by admixture of so activated enzymes to a bioreactor. Further

reaction did not require any illumination. These studies are under development.

Keywords: chitin; chitosan; cyclodextrins, starch;

____________________________________

[1] E.S. Semmens, Nature 159, 613 (1947).

[2] A.E. Navez, B.B. Rubenstein, J. Biol. Chem. 80, 503 (1928).

[3] M. Fiedorowicz, P. Tomasik, C.Y. Lii, Carbohydr. Polym. 45, 75 (2001).

[4] M. Fiedorowicz, C.Y. Lii, P. Tomasik, Carbohydr Polym. 50, 57 (2002).

[5] M. Fiedorowicz, K. Rębilas, Carbohydr. Polym. 50, 315 (2002).

[6] M. Fiedorowicz, G. Khachatryan, J. Sci. Food Agric. 84, 36 (2004).

[7] M. Fiedorowicz, G. Khachatryan, V.P. Yuryev, L.A. Wasserman, From starch containing sources to

isolation of starches and their applications, Eds: V.P. Yurev, H. Ruck, P. Tomasik, Nova Science

Publishers, New York, 2004, ISBN:1-59454-014-4.

[8] H. Staroszczyk, M. Fiedorowicz, P. Janas, P. Tomasik, Polimery 52 (11-12), 63 (2007).

[9] M. Fiedorowicz, G. Khachatryan, J. Agric. Food. Chem. 51, 7815 (2003).

[10] [M. Fiedorowicz, A. Konieczna-Molenda, V.M.F. Lai, P. Tomasik, in preparation.

[11] [M. Fiedorowicz, A. Konieczna-Molenda, W. Zhong, P. Tomasik, Carbohydr. Res. submitted.

[12] [A. Konieczna-Molenda, Macromol. Symp..accepted.

[13] [M. Fiedorowicz, A.Konieczna-Molenda, G. Khachatryan, P. Tomasik Polish Patent, Appl. P-379950

(2006).

32

ABSTRACTSOF POSTER

CONTRIBUTIONS

33

P-01 (Bio)Degradable Polymers from Renewable Resources, Vienna 2007

Biodegradation of Polyester Nanocomposites

Agnieszka Piegat and Miroslawa El Fray

Szczecin University of Technology, Polymer Institute, Division of Biomaterials and

Microbiological Technologies, ul. Pulaskiego 10, 70-322 Szczecin

Poly(ethylene terephthalate) (PET) is a thermoplastic polyester widely used in fibres and

packing industry. PET is known as a material resistant to hydrolysis, therefore several

modifications have been made with the aim to render PET biodegradation. One of

commercially produced aliphatic-aromatic copolyester of PET is Biomax® [1]. This material

is fully biodegradable under composting conditions, because of the copolymerization of PET

with poly(lactic acid) (PLA), a common polymer from renewable resources. Other modifiers

of such origin are poly(glycolic acid) (PGA), poly(3-hydroxybutyrate) (PHB) [2],

polysaccharides like starch or cellulose [3]. Another group of biodegradable monomers from

renewable resources are dimer fatty acids, e.g. dilinoleic acid (DLA), obtained by

dimerization of unsaturated fatty acids derived from vegetable oils. This group of monomers

is widely used as modifier for polyurethanes, adhesives but also for thermoplastic elastomers

(TPE), where they form the soft phase. Their chemical and physical properties can be tuned

by the soft/hard segments ratio. For PET/DLA copolymers, higher susceptibility to

degradation was observed for copolymers with higher amount of DLA soft segments [5].

In this work, we report on PET modification with DLA and TiO2 nanoparticles. Such

physical modification with nanoparticles enhances not only mechanical properties, but also

controls the degradation profile [6]. The addition of ceramic components is already know as

an effective modification with the aim to obtain more controlled degradation conditions of

polymer/ceramic composites. Such solution was already applied for biodegradable poly(L,L-

lactide-co-glycolide) (PLGA), where addition of tricalcium phosphate reduced acidity of

degradation products and changed hydrophilicity of the material, what had strong influence

on the porosity of obtained scaffolds [7]. PET/DLA copolymers containing TiO2

nanoparticles (0.2 and 0.4 wt%) were degraded in PBS for 6 months. TiO2 nanoparticles

incorporated into copolymer matrix demonstrated a strong influence on such properties as:

absorption, crystallinity and molecular weight of composites. The decrease in Mn after 6

months was 68.8% for the neat PET/DLA copolymer, whereas only 41% for the same

copolymer containing 0.2 wt% TiO2 and 55% for this one containing 0.4 wt% TiO2. Changes

of thermal properties for PET/DLA were mainly observed in the hard segments region,

showing decrease of melting temperature from 130.6 to 102.4˚C. The melting temperature of

nanocomposites decreased by 6˚C and 18.4˚C for 0.2 and 0.4 wt% TiO2 nanoparicles,

respectively. Also the absorption level was highest for copolymer without TiO2 nanoparticles.

These results confirm that both DLA and TiO2 nanoparticles are effective modifiers of PET

enabling preparation of materials with controlled mechanical properties and degradation time.

Acknowledgements: This work was partially financed from research project 3T08E03628.

Keywords: biodegradation, polymer/ceramic nanocomposites, PET modification

____________________________________

[1] V. Nagarajan, M. Singh, H. Kane, M. Khalili, M. Bramucci, J Polym Environ 281, 14 (2007)

[2] D. Kint, S. Munoz-Guerra, Polym Int, 1999, 48, 346

[3] B.G. Girija, R.R.N. Sailaja, Giridhar Madras, Polym Degr Stability 147, 90 (2005)

[4] M. El Fray, Nanostructured Elastomeric Biomaterials for Soft Tissue Reconstruction, Publishing House of

the Warsaw University of Technology, Warszawa 2003, 1-144

[5] A. Piegat, M. El Fray, Polimery, in press

[6] M. El Fray, A.R. Boccaccini. Materials Letters, 2300, 59 (2005)

[7] F. Yang, W. Cui, Z. Xiong, L. Liu, J. Bei, S. Wang, Polym Degr Stability 3065, 91 (2006)

34

(Bio)Degradable Polymers from Renewable Resources, Vienna 2007 P-02

ESI-MS Studies of Slow-release Conjugate of 2,4-D with a-PHB

for Agricultural Applications

P. Rychter1, G. Adamus

2, and M. M. Kowalczuk

1,2

1 Institute of Chemistry and Environmental Protection, Jan Dlugosz University of

Czestochowa, 13/15 Armii Krajowej Av., 42–200 Czestochowa, Poland 2 Polish Academy of Sciences, Centre of Polymer and Carbon Materials

34 M. Sklodowskiej-Curie, 41-819 Zabrze, Poland

Depending on the natural conditions, only about 10% of the applied agrochemicals

reach their objectives. This process leads to undesirable side-effects causing increase of the

active agent concentration levels in surrounding environment. From the point of view of

public health, application of hazardous pesticides in agriculture should be limited.

Biodegradable polymers to be used as a matrix for agrochemicals may constitute one of the

possible way to solve this problem. The advantages of control release of agricultural chemical

systems are prolongation of action of such agrochemicals (by providing continuous, low

amounts of biocides maintaining appropriate dosage for the desired period of time), decrease

of cost and pollution [1,2].

In this communication the results concerned with synthesis of conjugate of selected

herbicide i.e. 2,4-dichlorophenoxyacetic acid (2,4-D) covalently bounded with atactic

oligo[(R,S)-3-hydroxybutyrate] will be demonstrated. Herbicide 2,4-D belongs to the

phenoxyacetic acids group of pesticides and is one of the most common and widely used for

control of broad leafed weeds and grasses in plantation crops such as sugar cane, oil palm

and weeds along highways. As previously reported, poly([R,S]-3-hydroxybutyrate) as well as

its degradation products are non-toxic for natural environment [3]. Moreover, [R,S]-3-

hydroxybutyric acid oligomers are biocompatible and can be potentially applied to

formulation of chemical conjugates for delivery of active agent, improving its taken up by

cells in vitro [4]. The ring opening anionic polymerization of [R,S]-β-butyrolactone initiated

with activated 2,4-dichlorophenoxyacetic acid salts as well as [R,S]-β-butyrolactone

oligomerization induced by 2,4-D have been selected as methods of synthesis of 2,4-D oligo-

3-hydroksybutyrate conjugates. Evaluation of the subtle structure of the conjugates obtained,

based on sequencing of individual macromolecular ions with the aid of ion-trap multistage

mass spectrometry (ESI-MSn), will be presented.

Keywords: slow-release formulations; biodegradable polymers; biocides

____________________________________

[1] J. Zhao, R.M. Wilkins, J. Agric. Food Chem. 53, 4076 (2005)

[2] M.G. Mogul, H. Akin, N. Hasirci, D.J. Trantolo, J.D. Gresser, D.L. Wise, Resources, Conservation and

Recycling 16, 289 (1996)

[3] P. Rychter, R. Biczak, B. Herman, A. Smylla, P. Kurcok, G. Adamus, M. Kowalczuk, Biomacromolecules 7,

3125 (2006)

[4] V. Piddubnyak, P. Kurcok, A. Matuszowicz, M. Glowala M., A. Fiszer-Kieszkowska, Z. Jedliński, M. Juzwa,

Z. Krawczyk, Biomaterials 25, 5271 (2004)

35


Polymer-inorganic Hybrid Materials for Tissue Engineering

Pawel Wozniak, Stanislaw Sosnowski, and Stanislaw Slomkowski

Centre of Molecular and Macromolecular Studies, Polish Academy of Science,

Sienkiewicza 112, 90-363 Lodz, Poland

There is a great interest in manufacturing objects with surface properties adaptable to

environment (e.g. exposing hydrophilic or hydrophobic surface elements to hydrophilic or

hydrophobic exterior). Such properties are very desirable in fabrication of scaffolds for tissue

engineering. Since we are interested in scaffolds for hard tissue building cells our efforts were

concentrated on modification of silica and glass (nanosilica and model glass plates) in a way

allowing changes of their interfacial hydrophilic/hydrophobic properties in contact with

hydrophilic or hydrophobic liquids. The mentioned above nanosilica has been used as a filler

increasing mechanical strength of polymer scaffolds made from polylactide and poly(lactide-

co-glycolide).

Modification of silica and of glass plates was did consist of grafting 3-glycidoxypropyl

trimethoxysilane (GPS) onto silica (reaction with hydroxyl groups on silica surface). In this

way epoxide groups were introduced. The next step included grafting of biocompatibile

polymers. Living poly(ethylene oxide) was grafted onto silica in reaction with epoxide

groups. Active centers created in this way initiated polymerization of lactide. In result

hydrophilic poly(ethylene oxide) and hydrophobic poly(L-cactide) chains were tethered to the

surface. Depending on hydrophilicity of the liquid being in contact with modified silica the

hydrophilic or hydrophobic chains were in expanded conformation. The resulting materials

were characterized by photoelectron spectroscopy, wetting angle measurements and (in case

of nanosilica) by 13

C CP MAS NMR. Mechanical properties of poly(L-lactide) and

poly(lactide-co-glycolide) with modified silica fillers were investigated.

Schematic illustration of modification of silica surface.

Keywords: silica; (3-glycidoxypropyl)trimethoxysilane; surface modification; poly(ethylene oxide); poly(L-

lactide)

Financial support of BIOMAT project and Ministry of Science and Higher Education is acknowledged.

36


Biodegradable Hydrogels Based on Poly(vinyl alcohol)-graft-

[poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)]

Elvira Vidović1, Doris Klee

2, and Hartwig Höcker

2

1Faculty of Chemical Engineering and Technology, University of Zagreb,

10000 Zagreb, Croatia 2Department of Textile and Macromolecular Chemistry, RWTH Aachen,

52056 Aachen, Germany

In this work a synthetic procedure is described towards a class of poly(vinyl alcohol)-graft-

[poly(D,L-lactide)/poly(D,L-lactide-co-glycolide)] copolymers which are sensitive to hydro-

lysis and therefore can be used for the development of controllably biodegradable hydrogels.

Poly(D,L-lactide) and poly(D,L-lactide-co-glycolide) with various composition were obtained

by reacting 2-hydroxyethyl methacrylate with D,L-lactide or glycolide dimers, followed by

the transformation of the terminal hydroxyl group into carboxylate with the assistance of

succinic anhydride. Coupling of those polyesters (PES) onto poly(vinyl alcohol) (PVA) was

performed via the carboxylate group in dimethyl sulfoxide using N,N-carbonyldiimidazole.

The graft copolymers were crosslinked via the methacrylate groups using a free radical

initiator [1,2].

crosslinking site

PVA backbone

R = H or CH3

PES graft chain

AIBN

50oC

n

O O

O O

R

R

O

O O

O

O

OH

O

p

z

q-z

O

CCH3

O

The resulting copolymers, in the course

of synthesis, were characterized with

respect to their molar composition by

means of 1H NMR spectra. Furthermore,

polymer networks were detected and

studied qualitatively by means of IR

spectroscopy. The influence of the glyco-

lide content in the polyester grafts and of

the number of ester units in the grafts on

thermal behavior and swellability were

studied, as well as surface properties of

hydrogels. Differential scanning calori-

metry showed a single glass transition

temperature that occurs in the range

between 51 °C and 69 °C indicating the

absence of phase separation.

Thermogravimetry analysis of the networks showed the main loss in weight in the

temperature range between 290 °C and 370 °C. The high swellability in water is characteristic

of all hydrogels. Hydrophilicity, an important property of hydrogels relevant to their

biomedical applications, was identified by the captive-bubble contact angle method.

Hydrogels display the values of contact angle between 37 and 45 ° which are significantly

higher in comparison with the polylactide sample (57°).

Keywords: biodegradable hydrogels; poly(vinyl alcohol); poly(D,L-lactide); poly(D,L-lactide-co-glycolide);

swellability; thermal properties; contact angle

____________________________________

[1] C.R. Nuttelman, S.M. Henry, K.S. Anseth, Biomaterials 23, 3617 (2002).

[2] E. Vidovic, Dissertation, RWTH-Aachen, Germany (2006).

37


Fabrication of Honeycomb-Structured Polylactide and Poly(lactide-co-

glycolide) Films and their Use for Osteoblast-Like Cell Culture

Julian B. Chardhuri1, Matthew G. Davidson

2, Marianne J. Ellis

1,

Matthew D. Jones2, and Xujun Wu

1, 2

1Centre for Regenerative Medicine, Department of Chemical Engineering,

University of Bath, Claverton Down, Bath, UK, BA2 7AY 2Department of Chemistry, University of Bath, Claverton Down, Bath, UK, BA2 7AY

Biodegradable polymers have been widely applied in tissue engineering and drug delivery

systems [1,2]. Recently, honeycomb-structured thin films have been reported to be good

candicates as scaffolds for cell culture [3]. In the present study, polylactide (PLA) and

poly(lactide-co-glycolide) [PLGA] were used to prepare honeycomb-structured thin films by

using a water droplet templating method. The influence factors on pattern formation, such as

solvents, humidity and ethanol sterilization were investigated. To study cell attachment and

proliferation on honeycomb-structured films, MG63 osteoblastic-like cell lines were cultured.

Cellular responses on PLA and PLGA with various compositions are discussed.

Keywords: honeycomb-structured film; Water droplet template; Polylactide; Poly(lactide-co-glycolide); Tissue

engineering

____________________________________

[1] Langer, R. and Vacanti, J. P. Science, 1993. 260 (5110): p. 920-926.

[2] Srivastava, R. K., Albertsson, A.-C. Biomacromolecules, 2006, 7, p. 2531-2538.

[3] Fukuhira, Y., Kitazon, E., Hayashi, T., Kaneko, H., Tanaka, M., Shimomura, M., Sumi, Y., Biomaterials,

2006. 27 (9): p. 1797-1802.

38


Bark Suberin as a Renewable Source of Long-chain

ω-Hydroxyalkanoic Acids

Helena Nilsson, Ann Olsson, Mikael Lindström, and Tommy Iversen

STFI-Packforsk AB, Box 5604, SE-114 86 Stockholm, Sweden

Production of paper pulp and timber results in by-product streams of which some have

potential commodity values. One example is bark, a low value by-product today mainly used

for energy production. The outer bark of birch species in northern Europe contain about 30%

of the natural aliphatic polyester suberin [1]. cis-9,10-Epoxy-18-hydroxyoctadecanoic acid

(1) is the principal monomer comprising about 100 g/kg dry outer bark in Betula verrucosa.

This epoxy acid, together with straight-chain even numbered C16 – C24 ω-hydroxy fatty acids,

can be isolated in high yield from alkali hydrolyzed birch outer bark, by extraction followed

by selective precipitation by acidification.

Lipase catalyzed polymerizations may sometimes allow straightforward synthesis strategies

for polyesters from sensitive monomers that do not survive more conventional polymerization

catalysts and this has, for example, been used for the preparation of polyesters from epoxy

containing monomers.

In this study we report polycondensations of cis-9,10-epoxy-18-hydroxyoctadecanoic (1)

acid isolated from birch outer bark using immobilized Candida antarctica lipase B

(Novozyme 435) as catalyst. The polycondensation performed in both toluene and bulk gave

the polyester (2) with fairly high molecular weights. For example, a Mw of 15 000 was

obtained after 3 hours reaction time (Mw/Mn 2.2) by bulk polymerization in an open vial

without any drying agent present.

O

(CH2)8 (CH2)7HO CO

O

(CH2)8 (CH2)7(O CO)n

O

(CH2)8 (CH2)7O COOH

O

(CH2)8 (CH2)7HO COOH 1

2

39


Studied on Electrical Conducting Biopolymer-poly(thiazole) Copolymers

Ashutosh Tiwari1 and A. P. Mishra

2

1National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi – 110 012, India

2Department of Science and Technology, Technology Bhawan,

New Maharauli Road, New Delhi –110 016, India

Water-soluble, biodegradable and electrical conducting copolymer of arabinogalactan-

poly(thiazole) was synthesized by adopting oxidative-radical polymerization method. UV-vis

and FTIR spectra were used to characterize the resulting copolymer. Electrical conductivity

and biodegradable behavior of copolymer was studied and optimized the composition to get

appropriate material for technological applications as varying concentration of thiazole

(THA), pH of the material and temperature. The electrical conductivity of the copolymer was

physically regulated via varying pH and temperature and could have interesting features on

these effects, as are semiconductors. Therefore materials have potential application for the

biosensor especially for the specific detection of microorganisms and hazardous gases.

Moreover, conducting biopolymer-based materials could be usefully exploited as

multifunctional electronic materials for technological applications. The materials might be of

great importance in the fabricating various sensor devices for in vivo and in vitro applications.

Keywords: arabinogalactan-polythiazole copolymer; electrical conductivity; biodegradability

Fig. Co-polymerization of biopolymers with synthetic polymer

40


Antibacterial Activity of Cationic Starch-iodine Derivatives

Algirdas Zemaitatitis, Rima Klimaviciute, and Rasa Kavaliauskaite

Kaunas University of Technology, Radvilenu 19, Kaunas LT-50524, Lithuania

Different compounds, such as phenol, halogen or derivatives of aldehydes, as well as

quaternary ammonium salts exhibit bactericidal properties and are used as disinfectants. It is

known, that cationic polymers with quaternary ammonium groups have higher antimicrobial

activity than corresponding low molecular weight compounds. Starch is a valuable material

for the production of cationic polysaccharides because of its high chemical activity and

peculiarities of structure. For this reason considerable efforts are now being made in the

research and development of modified polysaccharides as the basic material for new

applications.

The aim of this study was to synthesize cationic (CS) or cross-linked cationic (CCS) starch

chlorides and their iodine derivatives and to examine their antimicrobial activity.

CS or CCS with preserved micro granules, the degree of substitution from 0.2 to 0.6 and the

reaction efficiency from 82% to 93% might be obtained during catalytically etherification of

starch or cross-linked starch with a 2,3-epoxypropyltrimethylammonium chloride. In the ion

exchange reaction with inorganic iodide in water, CS or CCS chloride (CSCl or CCSCl) was

converted to CS or CCS iodide (CSI or CCSI). The chemical analysis confirmed that iodide

substituted for at least 95% of chloride counter ions.

In aqueous solutions having KI, cationic starches rapidly bind iodine and form polymer–

iodine complexes. Investigations of iodine binding by different cationic starches at

equilibrium showed that starches with quaternary ammonium groups were able to bind about

300 wt % of iodine from I2-KI solution and form complexes CSI·Im or CCSI·Im, where m ≤ 4.

Maximum two molecules of iodine could be incorporated, i.e., polymeric complexes of

pentaiodide could be formed. The stability of cationic starch–iodine complexes depended on

the quantity of involved iodine. Cationic starch triiodides (CSI·I2 or CCSI·I2) were the most

stable complexes.

The antibacterial activity of different starch derivatives against Enterococcus faecalis,

Bacillus subtilis, Pseudomonas aeruginosa, Salmonella typhimurium, Staphylococcus aureus,

Escherichia coli, Lysteria monocytogenes was studied by measuring the inhibition zone

diameter (agar diffusion plate test). It was found, that the diameter of inhibition zone

depended on both the counter ion of CS or CCS and examined microorganisms. In general,

cationic starches were bacteriostatic rather than bactericidal. The studied cationic starches can

be arranged in the following order according to their increasing antibacterial activity: CCSI <

CCSCl ≤ CSCl. However, cationic starch–iodine complexes were the most effective and

showed an excellent prolonged antibacterial activity. CCSI·I2 obtained from CCS with DS>0.2

were bactericides and 0,1 mg/mL of them killed 100% of E. Coli. The higher activity of

cationic starch–iodine complexes has been interpreted in terms of their stability in water at the

presence of iodine acceptors.

Keywords: highly cationic starch; cationic starch-iodine complexes; antibacterial activity

41


Chitosan-co-polyaniline/WO3.nH2O Nanocomposites:

Green Polymer Composite for Sensor Applications

Ashutosh Tiwari, S. P. Singh, S. S. Bawa, and B. D. Malhotra

National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi – 110 012, India

A monodispersed WO3.nH2O nanoparticles embedded chitosan-co-polyaniline have been prepared by one pot chemical precursor method. UV-visible, FTIR XRD and SEM analytical

tools were used to confirm the formation of nanocomposite. The composition of

WO3.nH2O precursor to chitosan-co-polyaniline was tailored in order to develop materials of controlled electrical conductivity. The electrical conductivity of the chitosan-co-

polyaniline/WO3.nH2O was stimulated with the exposure of HCl and NH3. Under

controlled conditions, hybrid material showed electrical conductivity in the range of 6.82

X 10-4 Scm

-1 at room temperature. The intercalations of cationic biopolymer based

electrically conducting copolymer apart with layered nanostructured inorganic solids

provide multifunctional nature, which have combined significant special features towards thermal-mechanical stability, biocompatibility, solubility, porosity and redox surface property.

Layered conducting biopolymer based host could be interesting regarded as an alternative

to obtain eco-friendly interlayer transition metal oxide bio-nanocomposites for

technological applications.

Figure: Layered structure of Chitosan-co-polyaniline/WO3.nH2O nanocomposite

Keywords: chitosan-co-polyaniline, WO3.nH2O nanocomposites, electrical conductivity, green

polymer composite, sensor applications

Chitosan-co-polyaniline WO3.nH2O Chitosan-co-polyaniline/WO3.nH2OChitosan-co-polyaniline WO3.nH2O Chitosan-co-polyaniline/WO3.nH2O

42


Chemical Modification of Starch with Hexamethylene

Diisocyanate Amide Derivatives

Katarzyna Wilpiszewska, Stanislawa Spychaj, and Tadeusz Spychaj

Polymer Institute, Szczecin University of Technology,

ul. Pulaskiego 10, 70-322 Szczecin, Poland

The growing interest in materials from renewable resources is observed [1]. Starch is a

biodegradable and easily available biopolymer. In Europe 45% of its total production is used

for nonfood applications (mostly paper industry) [2]. However, starch plastics are not widely

used because of some drawbacks, like: brittleness or sensitivity to water [3]. Chemical

modification of starch could, at least partially, prevent mentioned problems. Recently paper

describing synthesis of urethane and urea derivatives of hexamethylene diisocyanate (HMDI)

and their usage for starch chemical modification has been published [4].

Preparing starch plastics is in fact achieving a compromise between a few contradictory

features, such as: degree of substitution, level of hydrophobisation, susceptibility to

biodegradation, and melt flow features.

In this contribution chemical modification of potato starch with amide derivatives of

HMDI in a two-step process has been presented. At the first stage starch modifiers, i.e.

isocyanate amide derivatives were synthesised in the equimolar reaction between HMDI and

monocarboxylic acids, containing 2 to 18 carbon atoms in alkyl chain. HMDI was used as it is

relatively environmentally friendly [5]. FTIR spectra of the obtained HMDI derivatives

revealed the presence of bands for NCO, in the range of ~2300 cm-1 and amide groups at ca.

1700 cm-1.

At the second step the starch was modified with the synthesised HMDI derivatives, in

N-methylpyrrolidone (NMP) slurry. Some properties of the obtained starch polymers were

investigated and compared, i.e. efficiency of substitution, IR spectra, hydrophobic/hydrophilic

features, rheometric characteristics in temperature range up to 200°C, as well as moldability

(hot press melt flow).

Physicochemical properties of starch products depend greatly on degree of substitution

and alkyl chain length attached. The influence of the alkyl chain length attached to

polysaccharide as well as degree of substitution on some physicochemical and thermal

properties were evaluated. The hydrophilic/hydrophobic properties of the modified starches

evaluated by the measurement of their swelling indices in water were compared.

Keywords: thermoplastic starch; chemical modification of starch; urethane-amide starch derivatives

____________________________________

[1] Fakirov, S. & Bhattachatyya, S., Ed. Handbook of engineering biopolymers: homopolymers, blends, and

composites. Munich, Hanser Verlag (2007).

[2] A.D. Sorokin, S.L. Kachkarova-Sorokina, C. Donze, C. Pinel, P. Gallezot. Topics Cat. 27, 67 (2004).

[3] G. Engelmann, E. Bonatz, I. Bechthold, G. Rafler. Starch, 53, 560 (2001).

[4] K. Wilpiszewska, T. Spychaj. Carboh. Polym. doi:10.1016/j.carbopol.2007.04.023 (2007).

[5] T. Ohkita, S. Lee. J. Adh. Sci. Technol. 18, 905 (2004).

43


Starch Plasticisation via Twin-screw Extrusion

Katarzyna Wilpiszewska and Tadeusz Spychaj

Polymer Institute, Szczecin University of Technology,

ul. Pulaskiego 10, 70-322 Szczecin, Poland

The growing interest in materials from renewable resources is observed. Starch is

potentially useful material for technical uses because of its biodegradability, availability and

relatively low cost. In Europe 45% of total starch production is used for nonfood applications

(mostly for paper industry) [1]. Granular starch cannot be processed with conventional

technologies because its melting point (Tm = 220-240°C) and Tg are higher than its

degradation temperature (ca. 220°C) – it degrades before melting [2]. The addition of

plasticiser (commonly used glycerol) decreases Tg of starch, preventing its decomposition [3].

Moreover, the kind of plasticiser influences the mechanical and thermal properties of starch

material [4]. Extrusion is the most widespread method for producing thermoplastic starch.

In this contribution the preliminary results of starch twin-screw extrusion with

ε-caprolactam in the presence of glycerol with water admixture has been presented. Some

microorganisms could utilise ε-caprolactam as the sole source of carbon, nitrogen and energy

[5]. The extruded mixture contained: 9 – 17 wt. % ε-caprolactam, 11- 47 wt. % glycerol (with

water admixture) and 40-70 wt. % starch. The main processing parameters, i.e. temperature

regime, rotational speed as well as die pressure were changed. Their effect on extrusion

operating as well as extruded product is discussed.

Some properties of obtained starch products were investigated and compared, i.e.

hydrophobic/hydrophilic features and elongation at break. Water uptake of extruded starch

materials depends greatly on polysaccharide content and rises with its increase.

For comparison starch extruding with glycerol itself has been also performed. The

influence of starch/plasticizers content in the system on the water uptake and mechanical

properties was evaluated. Comparison of plasticised starch extrudates containing 70 wt. % of

starch and 30 wt. % of plasticiser(s) shows that material with ca. 18 wt. % ε-caprolactam and

11 wt. % glycerol + 1 wt. % water swells in water up to 270 % whereas starch plasticised with

30 wt. % glycerol (no water addition) up to 140 %. The probable reason for this finding is

both the presence of additional water as well as amide bond in the lactam ring.

Keywords: thermoplastic starch; starch extrusion; starch plasticisation

____________________________________

[1] A.D. Sorokin, S.L. Kachkarova-Sorokina, C. Donze, C. Pinel, P. Gallezot. Topics Cat. 27, 67 (2004).

[2] T. Czigany, G. Romhany, J.G. Kovacs. Chapter 3 in: Fakirov, S. & Bhattachatyya, S., Ed. Handbook of

engineering biopolymers: homopolymers, blends, and composites. Munich, Hanser Verlag, pp. 81-108 (2007).

[3] S.H.D. Hulleman, F.H.P. Janssen, H.Feil. Polymer, 39, 2043 (1998).

[4] K. Wilpiszewska, T. Spychaj. Polimery, 51, 325 (2006).

[5] C.C. Wang, C.M. Lee. J. Hazard. Mat. 145, 136 (2007).

44


Study of Interpolymeric Complexes Based on Polymers

from Renewable Sources

Catalina Duncianu and Cornelia Vasile

„Petru Poni” Institute of Macromolecular Chemistry,

41 A, Gr.Ghica Voda Alley, 700487, Iasi, Romania

The hydrogen-bonded interpolymeric complexes (IPC) have attracted great interest

due to their unique physical and chemical properties in comparison with pure components and

their wide applications in pharmaceutics as drug delivery carriers.

Intermacromolecular interactions via hydrogen bonds between a natural, renewable,

non-toxic polymer e.g. alginic acid (AgA) and syntethic polymers e.g. polyethyleneglycol

(PEG), poly (N-isopropyl acrylamide) (PNIPAM), polyacrylamide (PAM) in diluted and

semi-diluted solutions were investigated by means of viscometry, potentiometry and

conductometry. Thermodynamic functions have been evaluated. It has been established that

the alginic acid at a pH = 4 forms interpolymeric complexes with all three synthetic polymers

but their strengths vary with chemical structure and temperature.

Keywords: interpolymeric complexes, alginic acid, polyethyleneglycol, poly (N-isopropyl acrylamide),

polyacrylamide,

45


Homopolymerization and Copolymerization of L, L-Lactide

in Presence of Novel Zinc Proline Organocmetallic Catalyst

A. Pandey and B. Garnaik

Polymer Science and Engineering Division, National Chemical Laboratory,

Pune 411008, India

Poly (L, L-lactide) (PLA) and its copolymers from renewable resources have been studied

extensively because of their vast potential applications in many fields. Ring-opening

polymerization (ROP) of L, L-lactide to form poly (L, L-lactide) s by single-site metal

alkoxide precursors has attracted considerable recent attention since the properties of PLA are

determined by molecular weight, molecular weight distribution, and most importantly by its

microstructure analysis. Many metal complexes such as Al, Li, Mg, Fe, Sn, and Zn etc. have

been used as initiators/catalysts for ring opening polymerization (ROP) of cyclic esters [1-2].

However, in many cases, backbiting reaction/transesterification take place as side reactions,

resulting in the formation of macrocycles with a wide range of molecular weight distribution.

Using a bulky legands (both isomers of L- and D-proline ) coordinatively attached with

active metal center (zinc) and provided an asteric barrier for prevention of undesired side

reactions and minimized the undesired backbiting/transesterification reactions. The

homopolymerization of (L, L-lactide) and copolymerization by using PEG as macroinitiator

were conducted in presence of zinc proline catalyst. The kinetic and thermodynamic

parameters of ROP of L, L-lactide using zinc proline were studied. Polylactides were

characterized by various techniques such as GPC, DSC, FT IR, NMR, XRD and MALDI ToF

etc. The configurational sequence determination of PLA polymers were carried out by 13C

NMR quantitative analysis and compared by 13 CP/MAS NMR. The results of ROP of L, L-

lactide using zinc proline ( L- and D-proline) will be highlighted .

Figure 1. 13C NMR (500 MHz) of polylactide(CDCl3)

Keywords : renewable resources; zinc proline; polylactide; configurational sequence

____________________________________

[1] K. S. Fun, B. Teo, S.G. Teoh, K. Chinnakali, Acta Crystallog. C51, 244 (1995).

[2] Bradley M. Chamberlain, Ming. Cheng, David. R. Moore, Tina. M. Ovitt, B. Emil Lobkovsky, Geoffrey

W. Coate, J.C.A.S. 123, 3229 (2001).

46


Poly(lactic acid) Microcapsules Containing Bioactive Molecules:

Study of Activity

F. Faÿ, I. Linossier, and K. Vallée-Réhel

Laboratoire de Biotechnologie et Chimie Marines EA 3884, Université de Bretagne-Sud,

BP92116, 56321 Lorient cedex, France

In order to prevent the development of marine biofilm on immersed surfaces, it is required to

conceive preventing systems. Actually, this is realized by the blending of

poly(methylmethacrylate-co-butylmethacrylate) resins (PMMA-PBMA) with two types of

biocides : an organic biocide used in agriculture (herbicides, pesticides) and a mineral biocide

such as cuprous oxide. However, due to severe environmental degradations, the use of toxic

molecules and non degradable polymers is questioned. These concerns have created a

considerable interest to produce a new generation of protective systems based on

biodegradable polymers [1,2] and non toxics molecules. Two essential properties have been

clearly identified as discriminating factors of antifouling efficiency: erosion which is

controlled by biodegradable polymer such as polyester or poly(ester-anhydride) and presence

of biocides at the coating surface during immersion [3].

In this work, two active molecules were studied. The first is a bactericide molecule, called

chlorhexidine. Chlorhexidine is a bisdiguanide antiseptic widely used in dentistry as an anti-

plaque agent and has demonstrated good antibacterial activity against a wide range of

bacteria. The second is a quorum sensing autoinducer for the bacterial cell-to-cell

communication (furanone). However, previous works are shown that hydrosoluble molecules

were too rapidly released. These characteristics implicate their microencapsulation.

In a first part, this study presents i) the encapsulation of a commercial furanone (tetronic acid)

and chlorhexidine by using biodegradable polymer (PLA), prepared by the water-in-oil-in-

water solvent evaporation method ; ii) their characterization for their size, morphology and

encapsulation efficiency : imaging of the particles was performed by scanning electron (SEM)

and confocal laser microscopies (CLSM) ; iii) their incorporation in paint formulation.

The second part reports the influence of encapsulation : i) on biocide release determined by

EDX analysis and UV-spectrometry ; ii) on the growth, adhesion and viability of several

marine bacteria.

Keywords : PLA, encapsulation, antifouling

____________________________________

[1] F.Faÿ, I. Linossier, V. Langlois, E. Renard, K. Vallée-Réhel, Biomacromolecules. 7, 857 (2006).

[2] F. Faÿ, I. Linossier, V. Langlois, K. Vallée-Rehel, Biomacromolecules. 8, 1751 (2007).

[3] M. Thouvenin, J.J. Peron, C. Charreteur, Ph. Guerin, J.Y. Langlois, K. Vallee-Rehel, Prog. Org. Coat., 44, 75 (2002).

47


Degradation Study of Polymers from Renewable

Resources and their Blends in Industrial Composting Pile

W. Sikorska, P. Dacko, M. Sobota, J. Rydz, M. Musioł, and M. M. Kowalczuk

Centre of Polymer and Carbon Materials,

M.C.-Skłodowskiej 34, 41-819 Zabrze, Poland

New trends in solid waste management and rapid changes in public legislation made scientist

in increase activities on the design of new generation of biodegradable polymers as important

biomaterials for environmental, biomedical and pharmaceutical applications [1, 2]. For the

last few years, intensive research and development of new materials for packaging has been

also observed [3]. The most commercially available plastics are non-degradable and their

recycling is not feasible economically in many cases due to the deterioration of mechanical

properties and excessive cost. Selective use of biodegradable packaging materials in certain

applications may provide a solution to the above-mentioned environmental problems.

Polyesters, produced from renewable resources and susceptible to hydrolysis under the

industrial composting conditions offer ecological advantages as compared to thermoplastics

polymers and elastomers produced from fossil carbon sources [4]. Additionally, traditional

packing waste needs to have the PE it is coated with removed in the repulping process during

the recycling in paper-mill.

In the paper the results of degradation behavior of polymer blends of a-PHB,

poly[(D,L)-lactide] and additionally BTA in natural environment such as industrial

composting pile, consisting of leaves - 40%, branches - 30% and grass - 30%, have been

presented. The macroscopic observations of surface changes, the weight loss, changes of

molecular weight, polydispersity and composition of the tested materials were monitored

during experiments performed. The obtained results revealed that the investigated blends was

degradable in the industrial compost pile and in this environment the hydrolytic degradation

was occurred. Moreover the biodegradable polyesters systems are promised materials, which

can be use as paper coatings for multilayer packaging materials.

This research has been supported by a Marie Curie Transfer of Knowledge Fellowship of the

European Community’s Sixth Framework Programme under the contract number

MTKD-CT-2004-509232. The financial support of Polish Ministry of Science and Higher

Education: R&D project no. R05 055 02 is also acknowledged.

Keywords: renewable resources; biodegradable polymers; industrial composting pile

____________________________________

[1] Biodegradable Plastics: North America, Europe, Asia, Market-Technology Report PO119, New York, 2001.

[2] B. Kessler and B. Witholt, Macromol. Symp. 130, 245 (1998).

[3] M. Kowalczuk, Plastic Review, 4(26), 48 (2003).

[4] G. Adamus, P. Dacko, M. Musioł, W. Sikorska, M. Sobota, R. Biczak, B. Herman,

P. Rychter, K. Krasowska, M. Rutkowska, M. Kowalczuk, Polimery, 51, 539 (2006).

48


Polyurethanes from Renewable Resources as Candidates

for Friendly Environment New Materials

D. Macocinschi, D. Filip, and S. Vlad

“Petru Poni” Institute of Macromolecular Chemistry,

Aleea Gr. Ghica Voda 41 A, 700487, IASI, Romania

Because of the importance of biomaterials in medical applications, their development

has been a long-term area of research and has become one of the principal challenges to

polymer scientists. In the present study new types of polyurethane-cellulose derivative

biomaterials based on urethane prepolymers functionalized with hydroxypropylcellulose are

presented. In the literature are reported studies on materials with better haemocompatibility,

biocompatibility and amphiphilic microphase-separated domain structures [1-4]. Few

biodegradable elastomers have been synthesized, and new materials are required to meet the

need for an increasingly diverse range of physical properties. It is worthy of note that block-

polyurethanes based on cellulose derivatives were found to be biodegradable and

haemocompatibles. Biodegradable elastomers are expected to be suitable for any application

requiring the use of a flexible, elastic material, such as soft tissue engineering.

The remarkable chemical versatility characteristic to polyurethane materials combined

with polymers derived from nature like cellulose derivatives resulting in bulk and surface

properties is evidenced by means of different techniques like DSC, TGA, FT-IR, AFM,

mechanical tensile tests. The influence of various factors on the developed morphologies and

the microstructural changes is investigated. Both polyester and polyether macrodiols have

been used to prepare these polyurethanes. The aim of this study is to find also alternative

methods for improving biostability while maintaining the excellent biocompatibility and other

properties. In these applications a balance between the surface hydrophilic and hydrophobic

qualities is essential for achieving enhanced bioproperties.

Keywords : renewable resources; biodegradable polyurethanes; morphology.

____________________________________

[1]. T. Hanada, Yu-J. Li, T. Nakaya, Macromol. Chem. Phys. , 202, 97 (2001).

[2] A. Vaidya, M. K. Chaudhury, J.Colloid Interf. Sci., 249, 235 (2002)

[3] R. W. Thring, M.N. Vanderlaan, S. L. Griffin, Biomass Bioenerg, 13, 125 (1997).

[4] You-X. Wang, J. L. Robertson, W. B. Spillman Jr., R. O. Claus, Pharm Res 21, 1362 (2004).

49


Viscoelastic and Thermal Proprieties of the Biodegradable Polymer

Materials Containing Polylactide, Aliphatic-Aromatic Polyester and

Synthetic Poly[(R,S)-3-hydroxybutyrate] Received via Injection Moulding

P. Dacko1, M. Sobota

1, H. Janeczek

1, J. Dzwonkowski

2,

J. Gołębiewski2, and M. M. Kowalczuk

1

1Centre of Polymer and Carbon Materials, 41-819 Zabrze, Poland

2Institute for Plastics Processing METALCHEM, PL-87-100 Toruń, Poland

The injection moulding is one of most important technologies in the processing of plastics and of biodegradable polymer materials. In this method the material is plastified to the viscous-flow state in the plastifying system and then introduced under pressure to the form, where it solidifies or hardens at the change of the temperature. The influence of temperature and pressure during the process on plastics, especially on polymer compositions, can make essential structural changes of initial components and consequently seriously influence on proprieties of final materials.

The main goal this work was to examine the viscoelastic and thermal proprieties of biodegradable polymer materials containing the amorphous poly-lactide (PLA-b), aliphatic-aromatic copolyester of terephthalic and adipic acids and butanediol (BTA), and synthetic poly[(R,S)-3-hydroxybutyrate] (a-PHB), received via injection moulding The a-PHB (Mn = 6000, IP = 1,3) was synthesized by bulk polymerization of (R,S) – β-butyrolactone at room temperature, using tetrabutylammonium acetate as the initiator [1]. The BTA ( Mn =34000, Mw/Mn = 2,1) was obtained from BASF, and the PLA-b (GALASTIC, PABR-L-68, 12 % D(-) content units, Mn = 53000, Mw/Mn = 2,7) obtained from Galactic S.A. Both polymers were used as received.

Results, obtained by means of DMTA and DSC showed that polymer compositions received from PLA-b and BTA mixtures via injection moulding are two-phase systems. This suggestion is confirmed by presence of two maxima on the temperature dependence of the mechanical loss coefficient - tg δ (DMTA) and two glass transition temperatures Tg1 - in the negative area of temperatures and Tg2 – in the positive area of temperatures (DSC). It is characteristic that BTA and PLA-b mixtures show values of Tg1 lower than for pure BTA (Tg = -25,6 °C) in spite that Tg of PLA-b amounts 52,9 °C. Values of Tg2 practically do not change with the PLA-b content change in the composition. DSC data show that maximum degree of compatibility becomes visible at the weight ratio BTA/PLA-b equal 50/50. PLA-b mixtures with containing a small amount of a-PHB (5% and 10%) create compositions that show one glass transition temperature, and this is confirmed by presence of single peaks on the temperature dependence of tg δ.

The introduction of a-PHB to BTA/PLA-b mixtures leads to enlarged compatibility of components and to improving of their mechanical proprieties.

This research has been supported by a Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD-CT-2004-509232. The financial support of Polish Ministry of Science and Higher Education: R&D project no. R05 055 02 is also acknowledged.

Keywords: biodegradable polymer materials, compatibility, mechanical properties

____________________________________

[1] Kurcok P., Śmiga M., Jedliński Z. J. Polym. Sci. Polym. Chem. 40, 2184 (2002).

50


Biodegradation of Blown Films Based on Polylactide Acid

in Natural Conditions

Vladimir Sedlarik1, Nabanita Saha

1, Jana Bobalova

2, and Petr Saha

1

1 Polymer Centre, Faculty of Technology, Tomas Bata University in Zlin,

Nam. T. G. Masaryka 275, 76272 Zlin, Czech Republic 2 Innovation Centre, University Institute, Tomas Bata University in Zlin,

Mostni 5139, 76001 Zlin, Czech Republic

The environmental pollution by non-degradable plastic waste attracts attention to the development of biodegradable polymers made from renewable resources [1]. Polylactic acid (PLA) is polymer which fulfills these conditions. [1]. In the environment it can be degraded within less than two years in contrast to conventional plastics such as PE or PS [2]. Nowadays, the development of PLA based materials is commercially available in applications including medical items production or compostable packaging. In this work, we deal with the assessment of biodegradation course of blown film base of PLA in composting environment. The main attention is paid to mechanical properties of investigated samples and their changes during the time of biodegradation. Beside that, mass loss, and observation of structural changes of PLA films are the subsequent aims of this paper. The material investigated in this work is commercially available polymeric blend of PLA and biodegradable co-polyester Bioflex® 219F, density 1380 kg.m-3, melting point 155°C, softening temperature Vicat A 72°C. The film preparation was performed on mono-extrusion blown moulding machine at the temperature range of 170-175°C. The L/D ration was 26. The thickness of resulting film was about 45 µm. The rectangular shape specimens were cut off the film and introduced into the composting environment. The composting conditions were kept in accordance to the standard ČSN EN ISO 14855. The total time of biodegradation assessment was 6 weeks. The influence of microbial attack on mechanical properties, physico-chemical structure, mass loss and surface morphology was studied weekly. The results obtained during 6 weeks of composting indicate relatively good accessibility to biological degradation. Figure 1 shows the macroscopic surface changes of the blown films after 6 weeks of the testing. The interesting results were also found in the course of mechanical, thermal and physico-chemical properties and mass loss, which will be presented at the conference in detail.

(a) (b)

Figure 1: Optical micrographs of PLA based blown film before (a) and after 6 weeks (b) of composting

Keywords: biodegradable polyester; composting; mechanical properties; blown films Authors are grateful to the Ministry of Education, Youth and Sports of the Czech Republic for financial support (Grant No. MSM7088352101 and 1PO5ME736). ____________________________________

[1] L. Chen, X. Qui, M. Deng, Z. Hong, R. Luo, X. Chen, X. Jing, Polymer 46, 5723 (2005). [2] M. Pluta, Polymer 45, 8239 (2004).

51


Molecular Modification of Gelatine by Reaction with Isocyanates

Monica Bertoldo1, Federica Cognigni

2, Francesca Signori

2,

Simona Bronco1, and Francesco Ciardelli

1,2

1PolyLab-CNR, via Risorgimento 35, 56126 Pisa, Italy

2Dipartimento di Chimica e Chimica Industriale, Università di Pisa,

via Risorgimento 35, 56126, Pisa, Italy

Gelatine is a very common denaturated protein of collagen widely available at low cost [1].

Its chain is formed by various aminoacid residues, some of which bearing nucleophyl groups,

which can react with isocyanates. In addition, the amide groups of the protein main chain are

polarizable groups and are expected to catalyze urethane and urea group formation[2]. Several

mono- and diisocyanate derivatives were used to study the reaction of modification of

gelatine to obtain structurally modified derivatives for biomedical, adhesive, paint,

photographic and films.

In this work gelatine was successfully modified according to different routes namely

crosslinking with 1,6-diisocyanatohexane (HDI), side chain binding of hydrophobic florescent

groups with 1-naphtylisocyanate (NpI) and grafting of isocyanate terminated

polypropylenglycole monobutyl ether chains (PPG). Dimethylsulfoxide was used as reaction

solvent as, to our knowledge, is the only solvent that dissolves gelatine but does not react with

isocyanates under mild conditions.

HDI and NpI were commercial products, whereas the terminal isocyanate derivative of PPG

(PPG-NCO) was synthesized in this project. The preparative reaction was carried out with an

excess of PPG in order to minimize the amount of unreacted HDI which was then removed by

evaporation under reduced pressure at 70°C.

Gelatine was then reacted with different amount of HDI, NpI or PPG-NCO in DMSO at 40°C.

Isocyanate species went to a non detectable concentration after raction times of the order of

minutes as evidenced by FT-IR analysis of the reaction mixtures. Therefore, the presence of

somewhat autocatalytic effect on the reaction environment seemed to be confirmed.

In the case of NpI, the occurring of a quantitative bonding of naphtyl groups to gelatine was

assessed by UV-Vis spectroscopy analysis through the well detectable adsorption band of the

naphtyl group. A calibration performed with propyl 1-naphthylcarbamate allowed to quantify

the bonding yields, which could be modulated to a considerable extent on the bassi of the

reactive components molar ratios .

Modified gelatine showed a reduced hydrophilic character with respect to the pristine

proteineven if modulable solubility: in particular NpI modified gelatine is swallable but not

soluble, whereas gelatin-g-PPG is more soluble then the the pristine protein..

The three modification procedures all based on the reaction of isocyanate functionality with

recative side chains of gelatine provide useful route to biopolymer based materials with a

large variety of water swelling and solubility properties. ____________________________________

[1] B. Brodsky, J. A. Werkmeister, J. A. M. Ramshaw, in Biopolymers, (Polyamides and Complex

Proteinaceous Materials II), A. Steinbuchel, Ed. Wiley-VCH Verlag GmbH, Weinheim, Germany, 2003,

Vol. 8, 119-147.

[2] M. Bertoldo, C. Cappelli, S. Catanorchi, V. Liuzzo, S. Bronco, Macromolecules 2005, 38(4), 1385-1394

[3] M. Bertoldo, S. Bronco, T. Gragnoli, F. Ciardelli, Macromol. Biosci. in press.2007

52


Biodegradable and Compostable PLA-based Formulations

to Replace Plastic Disposable Commodities

M.-B. Coltelli1, F. Signori

2, C. Toncelli

3, C. Escrig Rondán

4,

S. Bronco3, and F. Ciardelli

2,3

1Centro Italiano Packaging and DCCI;

2DCCI-Dipartimento di Chimica e Chimica

Industriale, Università di Pisa, via Risorgimento 35-I-56126 Pisa, Italy; 3CNR-INFM-

PolyLAB Pisa and DCCI; 4AIMPLAS, C/ Gustave Eiffel, 4 València Parc Tecnològic,

46980 Paterna-Valencia, Spain

For several traditional applications, in particular those related to agriculture and fresh

food packing, the use of a 100 % biodegradable plastics could represent a convenient

alternative to polyolefin based materials. In this perspective, poly(lactic acid) (PLA), (a

biodegradable linear aliphatic polyester), is receiving much attention thanks to its peculiar

thermomechanical behavior, which makes it a possible polypropylene substitute, and its

availability from renewable resources. However, standard grade PLA presents high E-

modulus (E-Mod: 2.5-3.0 GPa) and high brittleness (elongation at break < 5%). Although the

copolymerization of lactides with various cyclic monomers resulted highly effective in the

reduction of PLA brittleness, blending of PLA (hard component) with low molecular weight

additives [1] or elastomeric-like polymers [2] (soft component) appears a more sustainable

approach to tailor the properties of the final material. In this framework, our work has been

focusing on the preparation and the characterization of binary PLA-based blends, where

poly(butylene adipate-co-terephtalate) (PBAT), a commercially available biodegradable

polyester, was selected as the soft component. Process conditions were firstly assessed, and

then thermal, rheological and mechanical behavior of the prepared blends in all the

composition range were investigated, in search of a composition with properties similar to

those of standard poly(propylene) (PP). Among the prepared blends, those richer in PLA

showed more suitable properties, mainly in terms of E-Mod and elongation at break (EaB).

Remarkably, we identified a promising PLA-based formulation to obtain a 100 %

biodegradable PP-like material. The fine tailoring of the mechanical parameters, especially in

terms of E-Mod and EaB, required to better mimic target PP behavior, was carried out by

means of different reactive blending approaches, in order to improve PLA/PBAT phase

compatibility by the promotion of PLA-PBAT block or graft copolymer synthesis during the

blending process. The PLA-PBAT block or graft copolymers are meant to dislocate at the

PLA/PBAT interfaces, thanks to their structure which combine features of the two

homopolymers, thus lowering the interfacial tension. Two approaches were investigated, e.g.

the use of a transesterification catalyst and the radical promoted grafting reaction. Indeed, the

transesterification catalyst was expected to produce macromolecules containing random

distributed short and long segments from PLA and PBAT, while the use of a peroxide initiator

was expected to provide some inter-chains grafting extension to a branched macromolecular

structure containing very long PLA and PBAT segments. Note that the addition of increasing

amount of a non toxic, biodegradable low molecular weight plasticizer as third component to

the selected blend was investigated, to further tailor mechanical performances. The obtained

results indicate that the followed approaches were successful to generate PLA-based

biodegradable polymeric blends fitting a wide spectrum of thermomechanical characteristics.

Keywords: PLA; biodegradable polymer blends; reactive blending

____________________________________

[1] I. Pillin, N. Montrelay, Y. Grohens Polymer 47, 4676 (2006).

[2] L. Jiang, M. P. Wolcott, J. Zhang, Biomacromolecules 7, 199 (2006).

53


Mass Spectrometry Studies of Cyclic Esters Ring Opening Oligomerization

in the Presence of Disperse Red 1

C. Peptu

1, V. Harabagiu

2, B.C. Simionescu

2, G. Adamus

3, and M. M. Kowalczuk

1,3

1 Institute of Chemistry and Environmental Protection, Jan Dlugosz University

of Czestochowa, 13/15 Armii Krajowej Av., 42–200 Czestochowa, Poland 2 "Petru Poni" Institute of Macromolecular Chemistry,

Aleea Grigore Ghica Voda 41A, 700487 Iasi, Romania 3 Polish Academy of Sciences, Centre of Polymer and Carbon Materials,


Azobenzene containing polymers are used as polymeric dyes, molecular probes, electrooptic

liquid crystals, and materials for nonlinear optics and optical storage [1]. One of their major

commercial applications is the preparation of ophthalmic lenses [2].

Poly(ε-caprolactone) (PCL) and polylactides (PLA) crystalline polymers are well known as

hydrophobic, biocompatible and biodegradable materials [3]. They are prepared mainly by

ring opening polymerization (ROP) of cyclic esters. The catalysts used in ROP are generally

derivatives of metals, such as Al, Sb, Sn, Ge, and might leave impurities. The bulk

polymerization without using catalysts avoids the contamination of the products, being

preferred in application where high purity is required. The polymerization in absence of metal

catalysts can be initiated by various active hydrogen containing compounds, such as amines

[4], alcohols [5], amino acids [6] or cyclodextrins [7].

The presentation deals with the synthesis and characterization of low molecular weight

poly(ε-caprolactone) and poly(D,L-lactide) end functionalized with Disperse Red 1,

considering that they could prove interesting optical applications. Well defined oligomers

were obtained by bulk polymerization initiated only by the means of hydroxyl groups.

Structural details were provided by classical characterization techniques like NMR, GPC, and

mass spectrometry - MALDI and ESI techniques. Characterization by tandem mass

spectrometry of the resulting polymer products, with respect to their structure, end-groups

content and composition, showed that these are best described as endcapped azobenzene

oligomers with linear structure.

Acknowledgment. This research project has been supported by a Marie Curie Early Stage

Training Fellowship of the European Community’s Sixth Framework Program under the

contract number MEST-CT-2005-021029.

Keywords: poly(ε-caprolactone), poly(D,L-lactide), azobenzene olygomers

____________________________________

[1] S. K. Yesodha et al.; Prog. Polym. Sci. 29, 45 (2004).

[2] R. A. Evans et al.; Nature Materials, 4, 249 (2005).

[3] A. Albertsson and I. K. Varma; Biomacromolecules, 4, 1466 (2003).

[4] W. Tian; European Polymer Journal, 39, 1935 (2003).

[5] P.Cerrai, M.Tricoli, F. Andruzzi, M. Paci; Polymer, 30, 338 (1989).

[6] J. Liu and L. Liu; Macromolecules, 37, 2674 (2004).

[7] Y. Takashima, M. Osaki, A. Harada; J. Am. Chem. Soc., 126, 13588 (2004).

54


Supramolecular Structure – a Key Parameter for Cellulose Biodegradation

Diana Ciolacu1 and Florin Ciolacu

2

1 “Petru Poni” Institute of Macromolecular Chemistry, Dept. of Chemistry-Physics of Polymers,

41A, Gr. Ghica-Voda Alley, 700487, Iasi, Romania 2 “Gh. Asachi” Technical University of Iasi, Dept. of Natural and Synthetic Polymers,

Blvd. Mangeron, 700050, Iasi, Romania

One of the major obstacles that have to be cleared for the full understanding of the

enzymatic degradation of cellulose is the influence of parameters such as accessibility,

crystallinity and supramolecular structure of the substrata.

For a better understanding of the cellulose biodegradation it was chosen three different

cellulosic substrata, like microcrystalline cellulose, cotton cellulose and spruce dissolving pulp in

order to be biodegraded. The kinetics of the enzymatic hydrolysis of these celluloses by

Trichoderma reesei has been investigated. The experiments proved the fact that both the

morphological structure and the crystalline one are crucial to the process and the ratio of the

reactions.

In this paper the effect of cellulose polymorphism on its biodegradability, was also

evaluated. It was studied the celluloses with different crystalline forms and a variety of structural

features, like cellulose I, II and III, obtained from cotton cellulose, in order to obtain the most

accessible cellulose substratum. The insoluble cellulose fraction remaining after enzymatic

hydrolysis was examined by X-ray diffraction method and it was established the degree of

crystallinity and the average crystallite size. The roentgenograms of the residues resulted after

different times of hydrolysis shown a slight increase in the crystallinity index, during the process.

This fact can be attributed both to a preference in the attack over the domains poorly organized

and also to their higher speed of hydrolysis. The enzymatic degradation is also proved by the

decrease in the degree of polymerization of hydrolyzed samples.

Keywords: enzymatic degradation, Trichoderma reesei, cellulose allomorphs, kinetic

55


Kinetics of Poly(3-hydroxybutyrate) Degradation Induced by Carboxylates

M. Kawalec1, G. Adamus

1, H. Janeczek

1, P. Kurcok

1,

M. M. Kowalczuk1, and M. Scandola

2

1 Centre of Polymer and Carbon Materials, Polish Academy of Sciences ,

34 M. Curie-Skłodowskiej St., 41-819 Zabrze, Poland 2 Department of Chemistry “G. Ciamician”, University of Bologna,

via Selmi 2, 40126 Bologna, Italy

Controlling of thermal properties of thermoplastics is of great importance from

technological point of view since thermoplastics are processed mainly in melt. Knowledge of

degradation mechanism allows one to predict and control thermal resistance of the plastic.

The control of thermal properties means also decrease of thermal stability in order to obtain

valuable short-chain products even in mild conditions.

Considering poly([R]-3-hydroxybutyrate) (PHB), which is a very well known

thermoplastic bioresorbable material, there were many papers published on its thermal

degradation mechanism [1,2] and the problem seemed to be examined thoroughly. It was

reported that the PHB thermal degradation mechanism pathway led via intramolecular cis-

elimination were trans-crotonate-terminated polymer chains and trans-crotonic acid were

generated as the main degradation products. Moreover, it was also reported that the same

degradation products were found when synthetic analogues of PHB have been degraded [3].

However, our recent studies of PHB degradation mechanism [4,5] revealed competitive

degradation reaction proceeding even at moderate temperatures which is induced by basic

agents.

In this work kinetics of degradation of poly([R,S]-3-hydroxybutyrate)/acetate, as well as

poly([R]-3-hydroxybutyrate)/acetate systems has been investigated by DSC and TG

techniques. The results have enabled the determination of the activation energy of these

processes. Moreover, the obtained results have allowed for explanation of the influence of

carboxylate groups concentration as well as the counterion size on the kinetics of poly-3-

hydroxybutyrate degradation.

The authors would like to acknowledge financial support of projects: Eureka E! 3420,

MTKD-CT-2004-509232 and Regional Stipend Fund for PhD Students under the European

Social Fund (EFS-2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD).

Keywords: degradation, kinetics of degradation, energy of activation, E1cB, thermal analysis, PHB; poly(3-

hydroksybutyrate); poly(3-hydroxyalkanoates),

____________________________________

[1] A.C. Bertoli, M.D. Schmidt, Macromol. Symp. 252, 197 (2005).

[1] N. Grassie, E.J. Murray, P.A. Holmes, Polym. Degrad. Stab. 6, 47 (1984).

[2] F.D. Kopinke, M. Remmler, K. Mackenzie, Polym. Degrad. Stab. 52, 25 (1996).

[3] P. Kurcok, M. Kowalczuk, G. Adamus, Z. Jedliński, R.W. Lenz, J. M. S.-Pure Appl. Chem. A32, 875

(1995).

[4] M. Kawalec, G. Adamus, P. Kurcok, M. Kowalczuk, , I. Foltran, L. Focarete, M. Scandola,

Biomacromolecules 8, 1053 (2007).

[5] M. Scandola, M.L. Focarete, I. Foltran, M. Kowalczuk, P. Kurcok, M. Kawalec, G. Adamus, PCT Patent

application (filed on March 20, 2006) at No. PCT/IB2006/000898.

56


Novel Biodegradable Matrices for Drug Delivery

Raluca P. Dumitriu and Cornelia Vasile

“Petru Poni” Institute of Macromolecular Chemistry, Department of Physical Chemistry,

41A Gr. Ghica Voda Alley, 700487, Iasi, Romania

Nowadays the development of biodegradable polymeric hydrogels is gaining growing

attention. Synthesis of hydrogels based on polysaccharides has attracted biomedical

researchers due to their excellent biocompatibility and biodegradability. [1] In an attempt to

obtain biodegradable materials with sensitivity to external stimuli, like pH and/or temperature,

biopolymers from renewably resources were associated with thermo-sensitive

macromolecules. [2,3,4] Such “smart” hydrogels can regulate drug release through responding

to environmental stimuli by swelling and deswelling.

New biodegradable hydrogels containing a natural polysaccharide, alginic acid and a

synthetic thermo-responsive polymer, N-isopropylacryl amide (NIPAM) were obtained and

characterized by swelling kinetic studies in different media and scanning electron microscopy

(SEM). The studies performed allowed us to ascertain that the semi-interpenetrating networks

obtained possess thermo- and pH-responsive properties dependent on composition and

crosslinking degree. SEM micrographs showed a porous structure with pores dimensions

dependent on the composition of the hydrogels.

Fig.1. SEM micrograph of 75/25 NIPAM/ALG Fig. 2. Swelling kinetic study in various media

hydrogel . at 250C: a) twice distilled water; b) ethanol.

Keywords: biodegradable polymers; hydrogels; drug delivery

____________________________________

[1] C. Xiao, G. Zhou, Polym. Degr. Stab. 81, 297 (2003).

[2] S.Y. Kim, S.M. Cho, Y.M. Lee, S.J. Kim, J. Appl. Polym. Sci. 78, 1381 (2000).

[3] E. Marsano, E. Bianchi, A. Viscardi, Polymer 45, 157 (2004).

[4] J. Shi, N.M. Alves, J.F. Mano, Macromol. Biosci. 6, 358 (2006).

0 50 100 150 200 250

0

500

1000

1500

2000

2500

3000

3500

4000

Swelling ratio (%)

Time (min)

T = 250C

NIPAM/ALG 75/25 (a)

NIPAM/ALG 75/25 (b)

57


Divergent Synthesis of β-Cyclodextrin-Cored

Star -Poly([R,S]-3-hydroxybutyrate)

M. Michalak1, M. Kawalec

2, C. Peptu

1, P. Kurcok

1,2, and M. M. Kowalczuk

1

1 Institute of Chemistry and Environment Protection, Jan Dlugosz University,

13/15 Armii Krajowej Ave., 42-200 Częstochowa, Poland 2 Centre of Polymer and Carbon Materials , Polish Academy of Sciences,

34 M. Curie-Skłodowskiej St., 41-819 Zabrze, Poland

Poly([R,S]-3-hydroxybutyrate) is a synthetic analogue of natural polyester poly([R]-3-

hydroxybutyrate) which is produced and stored by many prokaryotic organisms as carbon and energy source [1]. The synthetic analogue can be obtained, among other ways, via ring-opening polymerization (ROP) of β-butyrolactone [2-5].

Recent work of preparation of star-poly([R,S]-3-hydroxybutyrate) have arose from a task of increasing the content of carboxylic groups of atactic poly([R,S]-3-hydroxybutyrate) while keeping polymer’s high molecular weight. Obtaining of a biodegradable, non-toxic polymer has been the second requirement for the material.

Cyclodextrins [6] are cyclic oligosaccharides which have the characteristic size of a truncated cone. Commonly, they are constituted by 6, 7 or 8 glucose rings linked to each other by a 1-4-α-glucosidic bond and they are named α-, β- and γ-cyclodextrins, respectively. Nowadays β-cyclclodextrin is produced in larger quantities and it is the cheapest available. Moreover, 7 anhydro glucose units offer total number of 21 hydroxy groups, which can be modified, per single cyclodextrin molecule. Furthermore, this hydroxycarbon is biodegradable, non-toxic and it is from renewable sources.

Thus, bearing in mind general purposes it has been contrived to prepare a star-shaped polymer by applying polycarboxylate molecules for initiation of anionic polymerization of β-butyrolactone. As the core, β-cyclodextrin polycarboxylate derivative has been chosen.

The method describes synthesis of poly(carboxysuccinate) β-cyclodextrin in similar manner as it was reported previously [7]. The degree of esterification of the derivative has been determined by potentiometric and NMR analyses (spectra prove substitution of C2-OH as well as C3-OH mainly and hardly C6-OH). After it was titrated, the final polycarboxylate derivative has been used for initiation of β-butyrolactone polymerization in DMF solution. The resulting star-poly(3-hydroxybutyrate)s have been analysed with 1H, 13C NMR, MALDI-TOF and SEC techniques after they were isolated from reaction mixtures.

The detailed data on synthesis and properties of star-poly([R,S]-3-hydroxybutyrate will be presented in this communication.

The authors would like to acknowledge financial support of project Regional Stipend Fund for PhD

Students under the European Social Fund (EFS-2.6 ZPORR No. Z/2.24/II/2.6/17/04 RFSD).

Keywords: biodegradable polymers; PHB, poly(3-hydroxybutyrate), star polymers, anionic polymerization, β-cyclodextrin

____________________________________

[1] Y. Doi, Microbial Polyesters; VCH Publishers: Weinheim, 1990. [2] L. R. Rieth, D. R. Moore, E. B. Lobkovsky, G. W. Coates, J.Am.Chem.Soc. 124, 15239(2002). [3] Z. Jedliński, P. Kurcok, M. Kowalczuk, J. Kasperczyk, Makromol. Chem. 187, 1651 (1986). [4] H. Abe, I. Matsubara, Y. Doi, Y. Hori, A. Yamaguchi Macromolecules 27, 6018 (1994). [5] P. Kurcok, M. Śmiga, Z. Jedliński, J.Polym. Sci. Polym. Chem. 40, 2184 (2002). [6] J. Szejtli, Cyclodextrin Technology; Kluwer Academic Publishers, 1988. [7] R. Dicke, Cellulose 11, 255 (2004).

58


Crystallinity and Crystalline Confinement

of the Amorphous Phase in Polylactides

Jose-Ramon Sarasua, E. Zuza, A. López-Arraiza*, N. Imaz, and E. Meaurio

University of the Basque Country (EHU-UPV), School of Engineering, Bilbao 48013, Sp. *present address: Mondragon University, MGEP, 20500 Mondragón, Sp.

In many aspects there is still a lack of understanding of the fundamentals of physical

chemistry that govern the segmental relaxation of polymer chains in both non-confined and

confined environments. Nonetheless, it is well established that constraints of polymer chains

caused by crystallinity lead to an increase in the temperature of the glass transition, for chains

find a growing hindrance to relax. Since macromolecules are longer than the crystal lamellae

are thick, they can cross the phase boundaries and cause various degrees of coupling; on weak

coupling, the dynamics of the non-crystalline segments shows usually a broadening of the

glass transition range, yet on stronger coupling the non-crystalline material may also show a

distinct glass transition, at higher temperature of the bulk amorphous phase due to a rigid

amorphous phase. [1]

Stereo-regular polylactides such as poly (L-lactide) (PLLA) or poly (D-lactide) result from

polymerization of optically pure lactides and are semicrystalline. Optically non-active

polylactides (PDLLA) can be regarded as random or atactic copolymers, show a random

moiety distribution, and are completely amorphous [2]. In this work three phases, comprising

mobile amorphous fraction (MAF, χMA), rigid amorphous fraction (RAF,χRA) and crystalline

fraction (χc) were determined in PLLA. It will be shown that RAP fraction not only elevates

Tg but also increases the dynamic fragility (m) of polylactide chains around the Tg [3]. These

results agree with reported cases in which topologycal constraints inhibit longer range

dynamics and suggest a smaller length scale of cooperativity in confined environments [4].

Figure 1

Angell’s plot of fully amorphous polylactide

(▲PDLLA) and semicrystalline polylactides

crystallized by annealing after water

quenching (● PLLA-WQA) and by slow

cooling from the melt (■ PLLA-SC).

0.90 0.92 0.94 0.96 0.98 1.00

-5

-4

-3

-2

-1

0

fragile

strong

log a

Tg/T

Keywords: polylactide, crystalline confinement; dynamic fragility.

____________________________________

[1] Wunderlich, B. Prog. Polym. Sci. 28, 383-450 (2003).

[2] Sarasua, J. R.; Prud'homme R. E.; Wisniewski, M.; Le Borgne A.; Spassky, N. Macromolecules 31, 3895

(1998); Meaurio, E.; Zuza, E.; Sarasua, J. R. Macromolecules 38, 9221 (2005).

[3] Angell, C. A. Journal of Non-Crystalline Solids 131, 13-31 (1991); Science 67, 1924 (1995).

[4] Qin, Q.; McKenna, B. Journal of Non Crystalline Solids 352, 2977-2985 (2006).

59


Liquid Crystal Template Applied for Polyimide-Cellulose

Derivative Thin Films

D. Filip, A.I. Cosutchi, C. Hulubei, and S. Ioan

“Petru Poni” Institute of Macromolecular Chemistry

Aleea Gr. Ghica Voda 41 A, 700487, IASI, Romania

Thin polyimide films are the most commonly employed liquid crystal alignment

layers. Two techniques [1] are used to produce LC alignment on polyimide films : standard

method of rubbing and polarized UV irradiation of polyimides which result in anisotropy of

the surface. Thin solid films prepared from lyotropic solutions of cellulose derivatives can be

used also as alignment layers for liquid crystals [2]. For hydroxypropylcellulose solid thin

films prepared from lyotropic solutions it was found that the band size constitutes a

controlling factor in the anisotropy of the material properties. Tailoring the surface

topography and altering the structure of polyimide enable to control orientation at the surface

which is important in adhesion properties. Spatially ordered polymer microstructures from LC

templates in a pattern-forming state is obtained. A new approach of polymerization and

patterning of thin films based on partially aliphatic polyimides is achieved. The synthesis of

the polyimides was reported previously [3]. The precursor lyotropic solution of

hydroxypropylcellulose was used as liquid crystal template. The films were exposed to UV

irradiation and the photosensitive properties have been investigated. The detailed structures

of the resulting films were studied by polarized optical microscopy, atomic force microscopy

and scanning electron microscopy.

Keywords: polyimide; liquid crystalline cellulose derivative. ____________________________________

[1] D. Andrienko, Y. Kurioz, M. Nishikawa, Y. Reznikov, J.L. West, Jpn. Appl. Phys. 39, 1217 (2000).

[2] M. H. Godinho, J. G. Fonseca, A. C. Ribeiro, L. V. Melo, P. Brogueira, Macromolecules 35, 5932 (2002).

[3] E. Hamciuc, R. Lungu, C. Hulubei, M. Bruma, J. Macromol. Sci. Part A: Pure and Appl. Chem., 43, 247

(2006).

60


Biomass Compounds with Pharmacological Applications

Iuliana Spiridon1, Maria Ichim

2 and Narcis Anghel

1

1“Petru Poni” Institute of Macromolecular Chemistry,

Grigore Ghica-Voda no. 41, Iasi, Romania 2S. C. “Bioing“ S. A.,Calea 13 Septembrie no. 105, Bucuresti, Romania

Plants vary within and among species in the types and concentrations of phytochemicals due

to variables in plant growth, soil, weather conditions and the age of the plant. Phenolic

phytochemicals are the largest category of phytochemicals and the most widely distributed in

the plant kingdom. Polyphenolic compounds, one of the most numerous and best studied

groups of plant biomass, are well known to exhibit various biological and pharmacological

effects.

It is quite possible that several of these components could contribute to the

antidepressant activity, either directly, or indirectly by making other compounds in the extract

more active or more bioavailable (this latter possibility reflects the concept known as

synergy).

In our paper, the results obtained using the polymeric compounds separated from

some biomass species to prepare a formula with therapeutic effect on nervous central system

are presented.

Keywords: polymers; polyphenols; antidepressant

61


Homo- and Copolymerization of Cyclic Aliphatic Esters

with Suppression of Transesterification

Marta Socka, Marcin Florczak, and Andrzej Duda

Centre of Molecular and Macromolecular Studies Polish Academy of Sciences,

Sienkiewicza 112, Lodz, Poland

Aliphatic polyesters [...−(CnH2nC(=O)O)m−...] become a new, emerging class of polymers

that reveal interesting properties, like biocompability, ability to hydrolytical and biological

degradation accompanied with useful mechanical and thermal parameters. Moreover, some of

those monomers and/or polymers can be obtained from the renewable resources. The most

convenient method for aliphatic polyesters synthesis is the ring-opening polymerization

(ROP) of the corresponding cyclic esters. This method provides sufficient control of

polymerization of lactones, lactides, and cyclic carbonates, giving polymers of the required

molecular weights and fitted with the desired end-groups. In the appropriately chosen

polymerization conditions the side reactions, like termination and transfer to the monomer

could be eliminated [1].

Moreover, application of initiators that bear bulky, sterically demanding ligands, such as

aromatic Schiff’s base (SB) derivatives (e.g. (R)-(−)- or (S)-(+)-2,2’-[1,1’-binaphtyl-2,2’-

diylbis-(nitrylomethylidyne)]-diphenolate aluminium isopropoxide (SBO2Al-OiPr)), leads to a

considerable suppression of the inter- and intramolecular transestrification (see e.g. papers

[2] - [4] and references cited therein) as well as disproportionation of the end-groups.

The present contribution reports on application of SBO2Al-OiPr in the controlled ROP of

ε-caprolactone (CL), L,L-lactide (LA), and cyclic carbonates (2.2-dimethyltrimethylene

carbonate (DTC) and trimethylene carbonate (TMC)).

It will be shown that SBO2Al-OiPr initiation of LA copolymerization with CL or cyclic

carbonates leads to a particularly interesting results. Namely, the corresponding diblock and

multiblock copolymers could be prepared for the first time employing the ‘living poly(LA)

block first’ synthetic route [3,4].

Keywords: aliphatic polyesters; L,L-lactide; ε-caprolactone; 2.2-dimethyltrimethylene carbonate; trimethylene

carbonate; living polymerization; block copolymers; transesterification

____________________________________

[1] A. Duda, S. Penczek, “Mechanisms of Aliphatic Polyester Formation”, in Biopolymers, Vol. 3b: Polyesters

II – Properties and Chemical Synthesis, ed. by A. Steinbüchel, Y. Doi, Wiley-VCH, Weinheim, 371 (2002).

[2] A. Duda, K. Majerska, J. Am. Chem. Soc. 126, 1026 (2004).

[3] J. Mosnacek, A. Duda, J. Libiszowski, S. Penczek, Macromolecules 38, 2027 (2005).

[4] M. Florczak, J. Libiszowski, J. Mosnacek, A. Duda, S. Penczek, Macromol. Rapid Commun. 28, 1385,

(2007).

O

O

O

H3C

H3CO

O

O

O

O

OO

H3C

CH3

O

O

( CL ) ( LA ) ( TMC ) ( DTC )

62


Acid Modification and Application of Biodegradable Polymer-Starch

Chia-I Liu and Chi-Yuan Huang

Dep.of Materials Engineering, Tatung University, No.40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan

The blends with acid hydrolysis starch present a smooth face, because acid would break the molecular chains of starch. XRD and DSC analysis also confirmed crystallinity decrease and then increase as concentration of acid increased. MFI of blends could reach to 300g/10min as additive of 0.3M CA-starch was 70wt%.

1. Experimental

1.1 Acid hydrolysis of starch with ultrasonic treatment

A different concentration of Citric acid (reagent grade)(0.1M, 0.3M, 0.5M) water were ap-plied to hydrolysis tapioca starch (food grade). The modified starch were added into tapioca starch/ glycerol the blends, and the additive was 30wt%, 50wt%, 70wt% ,separately. A sin-gle-screw extruder was employed to compound the blends at four step temperatures of 90, 100, 70, 40°C and the rotating speed was 20rpm.

2. Results and discussions

2.1. SEM observation of blends with acid hydrolysis starch: the cryo-fractured surfaces of blends presents a smooth face as the content of acid hydrolysis starch increased (Fig.1). It indicated that acid would break the molecular chains of starch and the granule of starch was easy to melt in the process [1].

2.2. DSC analysis of acid hydrolysis starch: The melting peak of 0.1M CA-starch shift to a low temperature, but the melting peak of 0.3M and 0.5M CA-starch shift to high temperature (Fig.2). It indicated that higher concentration acid would process a higher relative crystallinity. 2.3. XRD analysis of acid hydrolysis starch: The XRD pattern of 0.1M CA-starch present weak peaks but the patterns in 0.3M and 0.5M CA-starch appeared strong peaks at 2θ about 15°, 17°, 18° and 23°(Fig.3). 2.4. MFI analysis of blends with acid hydrolysis starch: the MFI of blends appear an increase as additive of acid hydrolysis starch increase. Especially, the blend with 70wt% 0.3M CA-starch, the MFI of blend could reach to 300g/10min (Fig.4).

Figure 1. SEM morphology of blends with different content of acid hydrolysis starch: 0.1M CA-starch(a)30wt% (b) 50wt% (c) 70wt%; 0.3M CA-starch (d)30wt% (e) 50wt% (f) 70wt%; 0.5M CA-starch (g)30wt% (h) 50wt%.

50 100 150 200 250

-4.0

-3.5

-3.0

-2.5

-2.0

-1.5

-1.0

-0.5

0.0

Tapioca starch

0.1M CA-starch

0.3M CA-starch

0.5M CA-starch

Heat Flow ( w/g)

Temperature (OC)

10 20 30 40 50 60 70 80 90

0

50

100

150

200

250

300

350

Tapioca starch

0.1M CA-starch

0.3M CA-starch

0.5M CA-starch

Intensity

2 theta

Fig. 2. DSC curves in different con-centration of acid hydrolysis starch.

Fig. 3. XRD curves in different con-centration of acid hydrolysis starch.

Fig. 4 .MFI curves in different con-centration of acid hydrolysis starch.

Keywords: biodegradation, acid hydrolysis, recrystallinity

____________________________________

[1] N. Atichokudomchai, S. Shobangob, S. Varavinit, Starch, 52, 283(2000).

(a) (d) (b) (c) (f) (e)

(h)

30 40 50 60 70

0

50

100

150

200

250

300

350

Hydrolysis starch

0.1M CA-starch

0.3M CA-starch

0.5M CA-starch

Melt Flow Index (g/10min)

Content (wt%)

(g) (h)

(a) (b) (c) (d) (e) (f) (g) (h)

63


Characterization of the Radical Polymeric Grafting of Hydroxylethyl

Methacrylate onto Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

Hoi-Kuan Lao

1,2, Estelle Renard

2, Valérie Langlois

2, Xaviera Pennanec

1,

Mylène Cuart1, Karine Vallee-Rehel

1, and Isabelle Linossier

1

1LBCM, EA 3884, Université de Bretagne-Sud, BP92116, 56321 Lorient Cedex, France

2SPC, ICMPE, UMR 7182, 2-8 rue Henri Dunant, 94320 Thiais, France

Polyhydroxyalkanoates (PHAs) are biosynthesized by a wide range of microorganisms

as intracellular energy and carbon storage materials. These materials have been evaluated for

a variety of medical applications, which include controlled release, surgical sutures, wound

dressings, lubricating powders, orthopaedic uses and as a pericardial substitute. However, the

surfaces of PHB and PHBHV are quite inert and hydrophobic. They have no physiological

activity which is unfavourable for adhered cell growth in tissue engineering. Therefore, as for

many polymer surfaces, the cytocompatibility should be improved by either chemical

modification with functional groups or modification of the surface topography.

Graft polymerization is a well-known method for the modification of chemical

structure to obtain properties for specific applications such as bone scaffolds [1]. Many

methods are used such as plasma, ozone treatment and gamma radiation [1-3]. In order to

improve the general wettability of the PHBHV, graft copolymerization of 2-

hydroxyethylmethacrylate (HEMA) was achieved. We have previously proposed a simple

way of grafting HEMA onto PHBHV, this synthesis was carried out in aqueous solution with

the benzoyl peroxide as chemical initiator [4].

In the framework of free radical grafting of vinylic monomer, it is generally speculate

that the graft polymerization on PHBHV is conducted by formation of primary radicals from

hydrogen abstraction of the methine protons on the PHBHV backbone, which can react with

HEMA [5]. No literature data ascertain this hypothesis. In order to determine the localization

of the grafted chains 2D 1H-NMR was carried out to elucidate the mechanism pathway.

The free radical polymerization is known to lead to broad molecular weight: the

determination of the molecular weight of the grafted chains by free radical grafting (UV,

ozone, or chemical initiation …) was not explored yet. Indeed, it is difficult to access to these

data and it is supposed to be the same order of magnitude of the homopolymer formed during

the grafting procedure. Molecular weight of the grafted chain from the degradation of the

PHBHV was characterized to ascertain the real size of the grafted PHEMA.

Enzymatic biodegradability was investigated in order to know if the grafted polymer is

still degradable.

____________________________________

[1] Grondahl, L., Chandler-Temple, A.,Trau, M., Biomacromolecules 6, 2197 (2005).

[2] Kang, I. K.,Choi, S. H.,Shin, D. S.,Yoon, S. C., Int. J. Biol Macromol. 28, 205 (2001).

[3] Ke, Y.,Wang, Y.,Ren, L.,Lu, L.,Wu, G.,Xiaofeng,Chen, C. J., J. Appl. Polym. Sci. 104, 4088 (2007).

[4] Lao, H. K.,Renard, E.,Linossier, I.,Langlois, V.,Vallee-Rehel, K., Biomacromolecules 8, 416 (2007).

[5] Chen, C.,Peng, S.,Fei, B.,Zhuang, Y.,Dong, L.,Feng, Z.,Chen, S.,Xia, H., J. Appl. Polym. Sci. 88, 659

(2003).

64


Degradation Process of Bioresorbable PGLC Terpolymers

J. Jaworska1, Y. Hu

2, J. Wei

2, J. Kasperczyk

1, P. Dobrzyński

1, and S. Li

2,3

1Centre of Polymer and Carbon Materials, Polish Academy of Sciences,

34 Str.Curie-Sklodowska, 41-808 Zabrze, Poland 2Department of Materials Science, Fudan University, Shanghai 200433, China

3Research Center on Artificial Biopolymers, Max Mousseron Institute on Biomolecules, UMR

CNRS 5247, Faculty of Pharmacy, University Montpellier I, 34093 Montpellier, France

Introduction

Bioresorbable and compatible with human tissues aliphatic polyesters undergo hydrolytic and

enzymatic degradation in biological environment to nontoxic components eliminated via the

Krebs cycle. They are considered in a variety of medical and pharmaceutical applications in

controlled drug delivery systems and in tissue engineering. In this work, we report a study on

the hydrolytic degradation of PGLC terpolymers in order to elucidate the effect of the chain

microstructure. On the basis of changes in chain microstructure the choice of appriopriate

terpolymer to desired medical application is possible.

Experimental methods

Terpolymers of glycolide, lactide, and ε-caprolactone have been prepared by the ring opening

polymerization held in a bulk using zirconium and tin initiators. Obtained terpolymers were

pressed and allowed to degrade in a phosphate buffer solution pH=7,4 in 37°C for a different

period of time. The composition and chain microstructure of obtained terpolymers and

degradation products have been determined by 1H and

13C NMR.

Results and discussion

A series of glycolide, lactide and caprolactone terpolymers, were synthesized using Zr(acac)4

or Sn(oct)2 as initiators in order to obtain various chain microstructure. The results revealed

that the degradation rate depends not only on the terpolymer composition but also on its chain

microstructure. For example in the case of high concentration of lactide units in terpolymer

chains at the beginning of degradation, longer L sequences and alternating CGC and CLC

segments in ordered domains are resistant for degradation but degradation of G-L, G-C and L-

C ‘mixed’ segments occurs faster. In consequence stable level of all monomeric units during

degradation is observed. Such stable level is noticed also in the case of high amount of

caproyl units in terpolymer chains. Alternating CGC and CLC sequences, which are resistant

for degradation, influence on the content of G and L units in polymer chain and prevent

decrease of glycolide and lactide units concentration in terpolymer chain during degradation

process.

Conclusions

Chain microstructure of terpolymer influence its degradation and can be investigated by NMR

method. According to various microstructures of the chain (random and block terpolymers)

clear differences in degradation mechanism have been observed. On the basis of changes in

chain microstructure it is possible to chose appriopriate terpolymer to desired application.

Acknowledgements Joint French-Polish CNRS-PASc. Grant No. 18256 and Regional Scholarship EFS-2.6 ZPORR No.

Z/2.24/II/2.6/17/04 RFSD

Keywords: hydrolytic degradation; bioresorbable polymers, NMR, microstructure

65


Sustainable Green Polymer Composites Based on PLA

G. Bogoeva-Gaceva1, M. Avella

2, V. Srebrenkoska

3, A. Grozdanov

1,

A. Buzarovska1, M. E. Errico

2, and G. Gentile

2

1Faculty of technology and Metallurgy, Rugjer Boskovic 16, 1000 Skopje,R.Macedonia

2Institute for Chemistry and Technologyof Polymers-ICTP,

Via Campi Flegrei 34, 80078 Pozzuoli,Napoli, Italy 3Kompozitna Oprema, Industriska bb, Prilep, R.Macedonia

In the framework of the ECO-PCCM project [http://elchem.ihtm.bg.ac.yu/ECO-PCCM/],

sustainable green polymer composites based on thermoplastic biodegradable polymer matrix

(Polylactide acid – PLA) reinforced with natural fibers (kenaf) and agricultural fillers (rice

straw) have been analyzed [1,2]. Production of green-composites has been performed by

conventional techniques, such as melt mixing (T=170 oC t=10min) and compression molding

(T=185oC t= 10min). Characterization includes analysis of mechanical behavior (tensile test,

flexural test, impact resistance), thermal stability (by TGA) and morphological analysis (by

SEM).

The obtained results for the studied composites with both reinforcements, have shown

increased modulus, both tensile and flexural (EPLA/kenaf d=60mm ρ=40kg/m3 = 1,1 GPa, EPLA/kenaf

d=50mm ρ=40kg/m3 = 0,08 GPa). Tensile and flexural strength were slightly decreased. SEM

analysis indicated on the satisfied durability of the PLA polymer based composites.

Fig. 1 SEM of PLA/RS/CA “neat”

composites (75/20/5 wt%, x150).

Fig. 2 SEM of PLAx1/RS/CA composite

obtained with recycled PLA (75/20/5

wt%, x200).

Keywords: green composites; recycling; mechanical properties

____________________________________

[1] G.Bogoeva-Gaceva, D.Dimeski, Z.Manov, V.Srebrenkoska, A.Grozdanov, A.Buzarovska, M.Avella,

IUMACRO’07, IUPAC and ACS Conference on Macromolecules for a Safe, Sustainable and Healthy World 2nd

Strategic Polymer Symposium, NewYork USA , June 10-13 (2007).

[2] M.Avella, G.Bogoeva-Gaceva, A.Buzarovska, M.E.Errico, G.Gentile, A.Grozdanov, J.Appl.Polym.Sci., 104,

3192 (2007)

66


Accelerated Wound Repair by Di-O-butyrylchitin,

the Polymer for New Non-Woven Dressing Material

A. Błasińska1 and J. Drobnik

2

1Department of Fiber Physics and Textile Metrology, Technical University of Lodz,

Zeromskiego 116, 90-924 Lodz, Poland 2Department of Connective Tissue Metabolism, Medical University of Lodz,

Narutowicza 60, 90-136 Lodz, Poland.

Di-O-butyrylchitin (DBC) is the technologically friendly chitin derivative, obtained

after introduction of the two butyryl groups to chitin at position C-3 and C-6 [1,2]. Well

solubility of DBC in common solvents and high biocompatiblity makes this polymer the

good candidate for application in biological subjects [3,4]. The present study is aimed at

testing DBC action on a healing process, as well as, explaining the mechanisms of its’ effect.

Moreover, the comparison of DBC action with other dressing materials effects (butyrylchitin,

regenerated chitin and chitosan) is planned.

Experiments were made on male Wistar rats. Polypropylene nets (2cmX3cm) were

implanted subcutaneously to the rats. The implants alone served as control but in other

groups the nets were covered with the dressing material made of investigated polymers:

DBC-1 and DBC-2 with intrinsic viscosity [η]DMAc/25deg.C equal 1.75dl/g and 2.08dl/g

respectively, butyrylchitin, regenerated chitin and chitosan. Four weeks after implantation

samples were taken for biochemical analysis. DBC-dressings were showed to increase

granulation tissue weight and glicosaminoglycans content in the scar. Total collagen content

was not changed but the soluble fraction of the protein (not polymerized collagen) was

reduced. One can state the improvement of collagen polymerization by DBC. Number of

fibroblasts isolated from the wounds and cultured on DBC films was elevated but reduction

of died cells was seen. Contrary to DBC, chitosan reduced glicosaminoglycans level in the

wound and increased water content in the granulation tissue. Some general effects of DBC

were observed. Thus the polymer decreased body weight of rats and reduced body

temperature.

Beneficial effects of DBC dressings on wound repair have been documented. The most

promisable effects were obtained after application of DBC-1 with intrinsic viscosity [η]

DMAc/25deg.C=1.75 dl/g. Thus the DBC elevated the granulation tissue mass in the wound and

increased glycosaminoglycans content and polymerization of collagen level. One can explain

the observed phenomenon by direct influence of DBC on the cells in the wound (increased

cells number and weight of granulation tissue). The effects of the butyrylchitin and

regenerated chitin on repair were not better as compared to DBC (di-O-butyrylchitin).

Keywords: dibutyrylchitin; non-wovens; wound healing

____________________________________

[1] L. Szosland, G. Janowska, Method for preparation of dibutyrylchitin, Patent PL169077B1 (1996).

[2] L. Szosland, Di-O-butyrylchitin, in Chitin Handbook; Muzzarelli, R.A.A., Peter, M.G., Eds. 53-60, (1997).

[3] L. Szosland, I. Krucińska, R. Cisło, D. Paluch, J. Staniszewska-Kuś, L. Solski, M. Synthesis of

dibutyrylchitin and preparation of new textiles made from dibutyrylchitin and chitin for medical applications,

Fibres & Textiles in Eastern Europe, 9(34), 54-57 (2001).

[4] A. Chilarski, L. Szosland, I. Krucińska, A. Błasińska, R. Cisło, Non-wovens made from dibutyrylchitin as

novel dressing materials accelerating wound healing, Proceedings of 6 th International Conference of the

European Chitin Society, EUCHIS’04, Poznań, Poland (2004).

67


Characterization of Biodegradable Copolyesters Containing Aliphatic and Aromatic Repeating Units by Means of Electrospray Ionization-mass Spectrometry

after a Partial Depolymerization

Alena Šišková1, Wanda Sikorska2, Marta Musioł2 , Marek M. Kowalczuk2, and Witold J. Kowalski1

1Institute of Chemistry and Environmental Protection, Faculty

of Mathematics and Natural Sciences, Jan Dlugosz University,

13/15 Armi Krajowej, 42–200 Czestochowa, Poland 2Polish Academy of Sciences, Centre of Polymer and Carbon Materials,


Synthetic polymers are highly complex multicomponent materials. Their different

heterogeneities can be summarized in a term “molecular heterogeneity“, meaning different

aspects of molar mass, chemical composition, functionality type and molecular architecture

distribution. Among the distributed properties in the case of co- and terpolymers are, e. g.,

sequence and length of incorporation (alternating, random or block) distributions [1].

Copolyesters containing aliphatic and aromatic repeating units formed of terephthalic acid, adipic

acid and 1, 4-butanediol, (e.g., Ecoflex trade-mark series) present different degrees of (bio)-

degradability and are interesting materials for medicinal and environmental applications.

We intended to characterize these materials by means of the electrospray ionization

coupled with mass spectrometry (ESI-MS), and chromatographic methods. The first step

included a reduction of their molecular mass in order to enable the MS analysis by means of the

accessible equipment [2,3]. Depolymerization processes of selected Ecoflex samples were carried

out in selected conditions: in methanolic and aqueous solutions, at ambient and elevated

temperatures, in basic media (tetrabutylammonium hydroxide). The degradation products were

analyzed by means of steric exclusion chromatography (SEC) and the obtained fractions were

submitted to 1H NMR and ESI-MS spectrometry.

The highly reproductible partial depolymerization procedures gave rise to an assumption

that the subsequent application of ESI-MS would significantly contribute to determination of the

molecular architecture of studied polyesters.

Acknowledgement: This work was supported by the European Community, Marie Curie Actions:

MEST-CT-2005- 021029, „POLY-MS”.

Keywords: partial depolymerization; molecular size fractionation; repeating units incorporation sequence

____________________________________

[1] H. Pasch and B. Trathnigg, HPLC of polymers, Sprinter-Verlag, Berlin, Heidelberg, New York, (1999).

[2] U. Witt et.al. Biodegradation of aliphatic-aromatic copolyesters: evaluation of the final biodegradability and

ecotoxicological impact of degradation intermediates, Chemosphere 44,289-299 (2001).

[3] F. Pardal, G. Tersac, Kinetics of poly (ethylene terephthalate) glycolysis by diethylene glycol. I. Evolution

of liquid and solid phases, Polymer Degradation and Stability 91, 2840-2847 (2006).

68


Commercial Biodegradable Polymers Reinforced with Flax Fibers

Mariastella Scandola, Elisa Zini, and Maria L. Focarete

University of Bologna, “G.Ciamician” Department of Chemistry,

via Selmi 2, 40126 Bologna, Italy

Increasing environmental concern over waste disposal has recently promoted research towards

new biodegradable materials for a wide range of applications. In particular composites made of

natural fibers and biodegradable polymers are presently considered new environmentally

friendly materials suitable for lightweight structural parts [1]. At the end of their service life,

biocomposites can be completely degraded in compositing units (in specific cases also in the

environment) or alternatively they can be incinerated for energy recovery.

Two biodegradable commercial polymers were used as the matrix in biocomposite

manufacturing: a bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), NodaxTM

[average 3-hydroxyhexanoate content: 12 mol %] and cellulose acetate, CA (degree of

substitution 2.5, food-grade plasticizer content: 34 wt%), while the reinforcing fibers were flax

fibers, bleached with hydrogen peroxide in the presence of NaOH and Na2CO3. Two series of composites were prepared: long fiber (LF) and short-fiber (SF) composites. LF

composites were obtained by high temperature compression molding alternated polymer films

and fiber mats (five-layered sandwich), and contained 5mm-long fibers randomly distributed

in the plane of the sheet. Mechanical investigations of LF composites indicated that long flax

fibers are able to reinforce both polymeric matrices.

SF composites were obtained by high temperature mechanical mixing polymer and fibers,

followed by compression molding into sheets. In these composites the fibers were shortened

during processing and their length was in the range 100-220 µm. The tensile modulus of SF

composites increased, as expected, with increasing fiber content in both CA and NodaxTM

composites. The tensile strength of SF composites, instead, only increased in the CA

composites. In order to observe a reinforcing effect of the NodaxTM

copolyester, a chemical

modification (acetylation) had to be applied to the fiber surface to improve fiber-matrix

adhesion, a technique that has been previously adopted [2,3] and does not substantially affect

fiber biodegradability [4].

The NodaxTM biocomposites showed a remarkable increase of crystallization rate from the

melt, attributed to heterogeneous nucleation of the vegetable fibers, that exhibited a

transcrystalline polymer layer at their surface. From a practical standpoint, this results in

faster composite solidification and reduces processing time.

Acknowledgments: we thank Mazzucchelli 1849 s.p.a. (Castiglione Olona, Italy) and Procter and Gamble

Company (West Chester, OH, USA) for the gift of plasticized CA and of NodaxTM respectively and Linificio e

Canapificio Nazionale s.p.a for kindly providing the flax fibers.

Keywords: biocomposites; biodegradable polymers; mechanical properties; natural fibers

____________________________________

[1] A.K. Bledzki, J. Gassan, Prog. Polym. Sci. 24, 221 (1999).

[2] M. Baiardo, E. Zini, M. Scandola, Composites Part A: Appl. Sci. Manu. 35, 703 (2004).

[3] E. Zini, M. Baiardo, M. Scandola, Macromol. Biosci. 4, 286 (2004).

[4] G. Frisoni, M. Baiardo, M. Scandola, D. Lednikà, M.C. Cnockaert, J. Mergaert, J. Swings,

Biomacromolecules 2, 476 (2001).

69


Investigation of Novel Shape-Memory Polymers' Chain Microstructure

Katarzyna Gębarowska1, Janusz Kasperczyk

1, Piotr Dobrzyński

1,

Mariastella Scandola2, and Elisa Zini

2

1Centre of Polymer and Carbon Chemistry, Polish Academy of Sciences, Zabrze, Poland

2University of Bologna, Department of Chemistry, Bologna, Italy

Introduction Synthetic biodegradable lactide, glycolide and trimethylene carbonate (TMC) based

materials can possess the ability to recover from intermediate shape to primal when applying

e.g. severe temperature change. Such property is called shape-memory behaviour. [1] Shape-

memory polymers (SMP) find wide application in medical field, for instance in manufacturing

surgical pins, selfexpanding stents, etc. [2,3] The knowledge of microstructure of polymer

chain dependence with shape-memory behaviour may be crucial in elaborating the process of

obtaining material that exhibit appropriate mechanical parameters and temperature (in the

range of body temperature) of transition form intermediate to primal state.

Experimental The investigations of chain microstructure of LL-lactide/glycolide/TMC terpolymers`,

obtained on zirconium initiator (Zr(acac)4), were performed by means of 1H and

13C nuclear

magnetic resonance spectroscopy. All terpolymer`s samples differed in the initial

comonomeric unit contents.

Results Results of

1H NMR spectra enabled to calculate the content of all comonomeric units:

lactidyl LL, glycolidyl GG and carbonyl T. Much more information was obtained from 13C

NMR spectra. The most sensitive spectral region, best for detailed analysis of groups and

sequences appearing in terpolymer`s chain, were methine carbon region from lactide and

methylene carbon regions from glycolide and TMC. Therefore very detailed resonance lines

assignment was performed. Furthermore, the 13C NMR spectra allowed to evaluate percentage

molar content of long polymer blocks and mixed segments. It was found that depending on

the comonomeric unit ratio, different long blocks and mixed segments appear in terpolymer

chain microstructure.

Conclusions NMR spectroscopy is a very useful tool for analysing LL-lactide/glycolide/TMC

terpolymer`s microstructure. According to obtained results it is to state that different

monomeric unit content influences the polymer chain microstructure and, therefore, shape-

memory behaviour of investigated materials.

Acknowledgements Financial support: EU6FP Excellence – BIOMAHE, FP-6-509232

Keywords: shape-memory polymers; biodegradable materials; NMR

____________________________________

[1] Jeonga, B.; Gutowska, A.; Trends in Biotechnology 2002, 20, 305–311.

[2] Wache, H. M.; Tartakowska, D. J.. Heinrich, A. Wagner, M. H.; J. Mat. Sci.: Mat.Med. 2003, 14,109-12.

[3] Kawai, T. I in.; Plastic molded articles with shape memory property, US Patent 4, 950, 258.

70


Bioresorbable Electrospun Non-woven Scaffolds

Mariastella Scandola1, Chiara Gualandi

1, Maria L. Focarete

1,

Piotr Dobrzynski2, Michal Kawalec

2, and Piotr Wilczek

3

1 University of Bologna, Dept of Chemistry “Ciamician”, via Selmi 2, 40126 Bologna, Italy

2Centre of Polymer and Carbon Materials, M.Curie-Skłodowskiej 34, 41819 Zabrze, Poland 3Foundation for Development of Cardiac Surgery, ul. Wolnosci 345a 41800 Zabrze Poland

Polymeric scaffolds obtained by electrospinning, in the form of non-woven mats, are

promising materials for applications in the tissue engineering field [1], owing to their close

similarity to the extra-cellular matrix, in terms of topology. Electrospun porous scaffolds,

made of hydrolysable polymers, can efficiently support cell growth [1] and their

bioabsorbability in vivo may be properly designed, through an accurate tuning of the rates of

scaffold hydrolysis and tissue regeneration.

In the electrospinning process for scaffold fabrication, a careful tuning of the processing

parameters allows the obtainment of nanofibres with desired diameter and orientation. This

aspect is important because it is well known that the micro/nano-architecture of the scaffold

may affect cell behaviour.

A random copolymer of poly(lactide-co-glycolide) (PLGA, molar ratio: 50:50), synthesized

using a low-toxicity zirconium-based initiator [2], was used. Non-woven mats of PLGA were

fabricated through electrospinning, after optimization of the processing parameters (solution

composition, applied voltage, solution flow rate and needle-to-collector distance) in order to

obtain defectless fibres (average diameter of 800 nm).

Electrospun PLGA mats were subjected to an in vitro degradation study in phosphate buffer

(pH=7.4) at 37°C. The molecular weight of PLGA was found to decrease from the very

beginning of the degradation experiment, whereas the samples showed weight loss only after

20 days of exposure to buffer solution. All collected GPC curves were mono-modal, yielding

no evidence of autocatalytic effect during degradation. After 20 days also fibre morphology,

investigated by SEM analyses, began to change from smooth to porous. After 50 days the

scaffold lost about 50% of its initial weight.

In addition, endothelial cell growth supplement (ECGS) was suspended in the eletrospinning

polymer solution and nanofibrous mats were obtained. A preliminary study on the effect of

ECGS incorporation in the scaffold was conducted using mesenchymal stem cells from bone

marrow.

Keywords: scaffold; tissue engineering; electrospinning; bioabsorbable polymers

____________________________________

[1] A.G. Mikos et al., Tissue engineering, 12, 1197 (2006).

[2] P. Dobrzynski et al., Macromolecules, 34, 5090-5098 (2001).

71


Keratin Coating for Wool Fiber

Jeanette M. Cardamone

U.S. Department of Agriculture, Agricultural Research Service,

Eastern Regional Research Center,

600 East Mermaid Lane, Wyndmoor, PA 19038, USA

Keratin as the major structural fibrous protein comprising wool, hair, feathers, and nail is rich

in amino acids and cystine disulfide bonds which provide flexibility and tenacity to hair and

wool. We applied alkali to break peptide and disulfide bonds and obtained keratin protein in

the form of keratin hydrolysate (KH) and powder (KP) with molecular weight of 6 to 30 kDa.

Then we used the unaffected glutamine and lysine amino acids of the protein as sites for

enzyme-mediated crosslinking of wool, of KH and KP. We showed that keratin hydrolysate

imparted shrink-resistant properties to wool textiles; the hydrolysate application is an eco-

friendly alternative to chlorine-Hercosett treatment, which can be a source of AOX

(Adsorbable Organic Halogens). The control of the dimensional stability of wool fabric by

applying KH and KP proceeded through a mechanism involving in-situ crosslinking mediated

by transglutaminase enzyme through the formation of isopeptide linkages between glycine

and lysine residues of keratin peptide. Scanning electron and confocal fluoresence

microscopy showed keratin protein localized on the surface of wool to smooth the fiber

surface, thereby preventing the scales from interlocking. Wool material, including

hydrolysates and powders crosslinked by transglutaminase enzyme-mediation, will provide a

rich resource for the production of modified keratin-based biomaterials.

72


Films from Spruce Galactoglucomannan Blended with Poly (Vinyl

Alcohol), Corn Arabinoxylan and Konjac Glucomannan

Kirsi S. Mikkonen1,2, Madhav P. Yadav

3, Stefan Willför

4,

Kevin B. Hicks3, and Maija Tenkanen

1

1Department of Applied Chemistry and Microbiology, University of Helsinki,

P.O. Box 27, 00014 Helsinki, Finland 2Department of Food Technology, University of Helsinki,

P.O. Box 66, 00014 Helsinki, Finland 3Eastern Regional Research Center, ARS, United States Department of Agriculture,

600 East Mermaid Lane, Wyndmoor, PA 19038, USA 4Process Chemistry Centre, Åbo Akademi University, Porthansgatan 3, 20500 Åbo, Finland

O-acetyl-galactoglucomannans (GGM) are the main hemicelluloses in softwoods and

can be recovered as by-products from process water of mechanical pulping of spruce wood

[1]. GGM can be used as raw material for biodegradable films, but the tensile strength and

elongation at break of GGM films are rather low [2]. The aim of this study was to improve the

mechanical properties of GGM-based films by blending GGM with poly (vinyl alcohol)

(PVOH), corn arabinoxylan (CAX), and konjac glucomannan (KGM). In addition, thermal

behavior of the blend films was examined using dynamic mechanical analysis (DMA) and the

film structure was studied with scanning electron microscopy (SEM).

GGM was recovered from process water of thermomechanical pulping of spruce [1] and

CAX from fiber fractions from commercial corn wet milling (CFG-1) [3]. PVOH (98-99%

hydrolyzed, Mw 146,000-186,000) was from Sigma and KGM from Baoji, China. Blend

ratios of GGM to PVOH, CAX, and KGM were 1:0, 3:1, 1:1, 1:3, and 0:1. Films were

prepared by casting and drying aqueous solutions of polymer blends (10 g/l) and glycerol

(Sigma) (4 g/l). Tensile strength and elongation at break of films were determined at 21ºC and

65% RH using an updated Instron 1122 mechanical property tester (Instron Corp., Norwood,

MA, USA) with TestWorks 4 data acquisition software (MTS Systems Corp., Minneapolis,

MN, USA). Dynamic mechanical analysis was done on a Rheometrics RSA II solids analyzer

(Piscataway, NJ, USA) for film specimens dried under vacuum for 30 min prior to testing.

Images of cross-sections of freeze-fractured films were collected using a Quanta 200 scanning

electron microscope (FEI Co., Hillsboro, OR, USA).

Adding other polymers increased the elongation at break of GGM blend films. The tensile

strength of films increased with increasing amount of PVOH and KGM, but the effect of

CAX was the opposite. The mechanical properties of GGM:CAX 1:3 and 0:1 films could not

be measured, because CAX was very sensitive to changes in ambient RH and these films were

difficult to handle at 65% RH, which was used for mechanical testing. DMA showed two

separate loss modulus peaks for blends of GGM and PVOH, but a single peak for all other

films. SEM confirmed good miscibility of GGM with CAX and KGM. In contrast, for blend

films from GGM and PVOH, SEM showed phase separation. Blending GGM with KGM was

found to be an applicable way to improve the mechanical properties of GGM-based films.

Keywords: spruce galactoglucomannan; poly (vinyl alcohol); corn arabinoxylan; konjac glucomannan; films;

mechanical properties; dynamic mechanical analysis; scanning electron microscopy

____________________________________

[1] S. Willför, P. Rehn, A. Sundberg, K. Sundberg, B. Holmbom, Tappi J. 2, 27 (2003). [2] K. Mikkonen, H. Helén, R. Talja, S. Willför, B. Holmbom, L. Hyvönen, M. Tenkanen, Proceedings of the 9th European Workshop on Lignocellulosic and Pulp (EWLP), Vienna, Austria, 27-30 August 2006, 130 (2006). [3] M.P. Yadav, D.B. Johnston, A.T. Hotchkiss Jr, K.B. Hicks, Food Hydrocolloids, 21, 1022 (2007).

73


Activation of Transcription Nuclear Factor NF-κB and Induction of Inflammatory Cytokines in Immune Response on Resorbable Biomaterials

B. śywicka1, E. Zaczyńska2, A. Czarny2, S. Pielka1, J. Karaś3, and M. Szymonowicz1

1Department of Experimental Surgery and Biomaterials Research,

Wroclaw Medical University; ul. Poniatowskiego 2, 53-326 Wrocław, Poland 2Institute of Immunology and Experimental Therapy,

Polish Academy of Science, ul Weigla, Wrocław, Poland 3Institute of the Glass and Ceramics, ul Postępu 9,Warszawa, Poland

Implantation materials grafted intratissularly overtaking determined functions in the living

organism should not show unfavorable influence on the immunological system and should

disturb its homeostasis in the least possible degree. Growth of the level of inflammatory

cytokines is observed in the tissues surrounding the implant. But in pathophysiology of

implants there are not compatible data whose tissue markers play a key role in the evoked

inflammatory process. Activation of the immune response on an external stimulator requires

coordinated expression of numerous factors. So, a question appears if there are key

modulators of immune and inflammatory reaction, observation of which could be the purpose

of the more efficient estimation of biocompatibility of implantation materials. Transcription

nuclear factor NF kappa B plays the role of one of more important potential

immunoregulators. It regulates the expression of many genes connected mainly with the

course of inflammatory process, proliferation and cells differentiation including inflammatory

cytokines II-1, IL-6, TNF-α, IL-8; it is also connected with appearing of giant cells of the

foreign body type. In our study we evaluated three kinds of resorbable materials prepared on

the basis of calcium phosphate (CaSO4 .1/2H2O with 0.5%mass. KHSO4). One of them was

enhanced by poli(alchol-vinyl), with the aim to increase its mechanical resistance. The second

one was enriched with the growth activator of bone tissue tri-calcium phosphate and the third

calcium phosphate was used as control. These modifications could cause the local activation

of leukocytes to produce the mediators of inflammatory processes, which leads to long term

complications. The present study was designed to determine in vitro whether gypsum

materials treatment of leukocytes from peripheral human blood (PBL) results in changes in

activation of NF-κB and production of cytokines. The immunocytochemical localization and

expression of NF-κB in leukocytes was assessed using anti-c-Rel- antibody. The NF-κB

activation was expressed as the percentage of NF-κB(+)cells after 24 and 72 hour incubation.

The level of cytokines IL-6, IL-8 and TNF-α in the supernatants from leukocytes culture with

tested materials was determined by an immunoabsorbent assay (ELISA) after 24 and 72

hours. On the basis of the performed tests it was observed that calcium sulphate materials

without modifications activated nuclear factor NF-κB after 24-hour incubation (p<0.05) and

not significantly decreased its expression after 72 hours (p>0.05). Calcium sulphate materials

with addition of tri-calcium phosphate did not activate NF-κB, while calcium sulphate with

poli (alchol-vinyl) turned out toxic for leucocytes both after 24 and 72–hour incubation. The

level of IL-6, IL-8, TNF-α after stimulation for 24 and 72 hours with gypsum materials was

compared to untreated leukocytes (p<0.05). The monitoring of the stimulation of NF-κB

mediator could give us the answer about cells reaction for the new biomaterials and it could

prove to be the sensitive test for their selection.

Keywords: NF-κB, TNF-α, IL-6, IL-8, peripheral human leukocytes

74


Influence of the Gelatin-Alginate Matrixes with Calcium Lactate for the Blood Parameters Soft and Tissue Reaction

M. Szymonowicz1, B. śywicka1, S. Pielka1, L. Solski1, D. Haznar2

, and J. Pluta2

1Department of Experimental Surgery and Biomaterials Research, Medical University

Poniatowskiego 2, 50-326 Wroclaw, Poland 2Department of Drug Form Technology, Medical University

Szewska 38, 50-139 Wroclaw, Poland

Porous biodegradable matrixes for implantation are interesting drug forms in

pharmaceutical technology. Owing to their structure, sponges are likely to be used as drug

carriers of modified releasing or used in tissues engineering as a cell carrier. Introduction of

material belonging to a different species into a living organism causes systemic and local

tissue reaction with a different degree of intensity dependent on the time and size of the

contact area.

The aim of the study was to evaluate the influence of gelatin-alginate matrixes with

calcium lactate on blood hematologic parameters and the assessment of the local tissue

reaction, and biodegradation and resorption after implantation into soft tissues. Gelatin-alginate matrices in a form of a sponge were used in the study. Sponge was prepared

of mixture of gelatin and sodium alginate in 20:1 proportion with an addition of 3% of

glycerol as well cross-linking agent calcium lactate. The samples sponge were implanted into

back muscles of the rat for the following periods: 1, 2, 3, 5, 7 and 14 days. After time a blood

for analysis was collected as well as the implanted samples with surrounding tissues. In the

whole blood were designated: the value of hematocrit (Ht), hemoglobin concentration (Hb),

red cells count (RBC) and red cells indexes: mean red cell volume (MCV), mean hemoglobin

mass in red cell (MCH), mean hemoglobin concentration in red cells (MCHC). White cells

count (WBC) was also determined. Results were analyzed by use of Statistica 5.5 software.

Mean values RBC, HCT, Hb (p<0,01, p<0,001), MCV, MCH (p<0,05) and MCHC

(p<0,05, p<0,01) to 3 days reduction to control group were observed. The result values are

not higher then the reference values. The parameter values from 5 days to 14 days was in

relation to the control group values. Values WBC in the blood were close and comparable to

the values in the control group in all the times of the investigation. In the macroscopic

assessment during the post mortem there were no any changes in the implantation sites.

Collected samples were the subject of histological assessment. After 24h the strong

inflammation were observed which lasted also up to 48h after implantation. At the

implantation site the small leftovers of the sponge were noticed and exudation with the

numerous inflammatory cells. In results, after 3 and 5 days the thin layer of the connective

tissue with new, young vascularisation was formed. After 7 and 10 days the small portion of

the implanted samples were observed which were surrounded by connective tissue with

numerous fibroblasts and some lymphocytes, polymorphonuclear and plasma cells. There

were also visible collagen and single muscle fibers. The small leftovers of the sponges

surrounded by the tissue were visible until 14 days after implantation. On the basis of those all results we can stated that the sponge were surrounded and

infiltrated by the tissues and partially undergone resorption. Also we can stat that the tested

sponges did not produce the foreign body reaction.

The study was supported by the project no. 1260 of the Wroclaw Medical University.

Keywords: gelatin-alginate sponge white calcium lactate, blood parameters, implantation, soft tissue reaction,

biodegradation and bioresorbable polymers

75


Cellular Response after Stimulation of the Gelatin-Alginate Matrixes

M. Szymonowicz1, A. Marcinkowska2, B. śywicka1, S. Pielka1, A. Gamian2, D. Haznar3, and J. Pluta3

1Department of Expermental Surgery and Biomaterials Research, Medical University,

Poniatowskiego 2, 50-326 Wroclaw, Poland 2Department of Medical Biochemistry, Medical University,

50-368 Wroclaw, Chalubińskiego 10, Poland 3Department of Drug Form Technology, Medical University,

Szewska 38, 50-139 Wroclaw, Poland

Polymeric biomaterials have been used in medicine. Among the biomedical polymers

there is family of resorbable sponges. The used of scaffolds settled as specific carriers for

cells which after implantation into the system makes supporting the tissue and creates good

conditions for the tissue regeneration. The evaluation with use of cells culture are quick

sensitive tests for the assessment of the biological impurities in the tested sample. The aim of

the work was to evaluate the changes in morphology and biological cells viability after

directing its temporary contact with gelatin-alginate matrixes in testing in vitro.

Four kinds of gelatin-alginate matrixes in a form of a sponge were used in the study.

In order to obtain a form of sponge liofilization of foam originated from foaming of mixture

of sterile solution of gelatin (20%), natrium alginate (2% or 4%) and glycerol (3% or 5%)

selected in an appropriate ratio was performed. Biological material consisted of quickly

proliferinghuman carcinoma cells of the lymphoblastic T lymphoma cells Jurkat grow in the

suspension of medium, whereas epithelial lung carcinoma cells- A549 (adhering to the bed in

the culture), show the superficial growth on substrate and slowly prolifering human umbilical

vein endothelial wells – Huvec (adhering to the bed in the culture).

The cells culture were performed In culture bottles at 37 with 5%CO for 24 hours

addend. Next, cells were taken for temporary contact with sponges. The quantitative changes

in selected of cells growth fixation after 24 hours and morphological changes observed after

24, 48 hours. For this purpose the dyed methods with neutral and trypane blue were used.

Shape, adhesion to the bed, agglutination, vacuolization and lysis of the cells were

determined. Division, proliferation, colonization (to build, construct colony) ability to

reproduce and survival rate of cells were observed. Viability measured by means of MTT.

In all cultures, after 18 hours the sponges were completely dissolved, and culture

medium was clear. The cells were evaluated microscopically. No agglutination, vacuolization,

separation from the bed neither lysis of the cell’s walls were observed. Proliferation of the cell

was correct and the cells formed proper colonies. They demonstrated the proper structure,

ability to growth and no significantly different when comparing to control group. No

difference between cells after contact with sponges was observed, as well. Dead cells were

not observed. In case of Jurkat, A549, Huvec cells shoved viability comparable with control

group. Viability of those cells was over 90%. The survival rate of cells after contact with

sponges was comparable. The longest time of viability of cells after contact with sponge and

4% of natrium alginate and 3% glycerol.

On the basis of received results it was gelatin-alginate matrixes did not have anty

cytotoxicy effects.

The study was supported by the project no. 1260 of the Wroclaw Medical University.

Keywords: gelatin-alginate sponge, cells cultured, aglutynation, proliferation, viability cells.

76


Synthesis and Properties of Chitosan – Poly(ethylene glycol)

Comb Copolymers

Ričardas Makuška and Rūta Kulbokait÷

Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania

Chitosan, a naturally occurring linear cationic polysaccharide, has been widely employed as a

drug delivery system, wound dressing, anticoagulants, and scaffolds for tissue engineering

owing to its biocompatibility, biodegradability, and low toxicity. Recently prepared comb like

chitosan derivatives containing methoxy poly(ethylene glycol) (MPEG) grafts [1, 2] may find

application in household and personal care products maintaining appropriate rheological

properties and conditioning contact surfaces.

Derivatisation of chitosan with a functionalized MPEG-2000 resulted in variety of chitosan-

MPEG comb copolymers differing in graft location, degree of substitution and molecular

weight. Chitosan-2-N-MPEG comb copolymers were synthesized by reductive amination of

chitosan using MPEG aldehyde [1]. Chitosan-O-MPEG copolymers were synthesized using

MPEG iodide or MPEG dichlorotriazine as alkylating agent and silver oxide as a catalyst [2].

Oxidation of N-phthaloyl chitosan by the use of TEMPO radical led to 5-formyl-2-N-

phthaloylchitosan which was proper precursor for preparation of chitosan-6-N-MPEG [3].

A serious problem is purification of chitosan comb copolymers from unreacted MPEG. To

avoid this, the method of “click” chemistry (a copper-catalysed Huisgen reaction) was

employed which usually gives nearly quantitative yields of the main products at mild

conditions generating virtually no by-products. Azidated chitosan was prepared by reacting

azidated epichlorohydrin with chitosan. MPEG azide was made by mesylation of MPEG

followed by nucleophilic substitution using sodium azide. Alkyne containing derivatives were

synthesized by reacting MPEG or N-phthaloyl chitosan with propargyl bromide.

Chitosan-MPEG derivatives with the degree of substitution (DS) of chitosan ca. 20 % were

water soluble in a wide pH range. 2-N-PEGylated chitosans were high-molecular-weight

products (Mw up to 2 million) with the DS of chitosan varying from 23 to 89 %. Solution

viscosity of these chitosan copolymers was moderate and had tendency to decrease for the

derivatives with high DS down to 0.29 dL/g. O-substituted chitosans were the products with

low molecular weight, Mw ranging from several to twenty thousand.

Positively charged chitosan brush polyelectrolytes adsorb readily to negatively charged silica

or mica surfaces. The rate of chitosan adsorption is much higher compared to its derivatives,

though according to adsorbed amount chitosan derivatives are preponderant. The adsorption

of O-PEGylated chitosans is sufficiently large to give rise to a brush structure that generates

strong steric repulsive forces. Thus, chitosan-6-O-MPEG oligomers act as a steric stabilizer

and can be used for modification of surface properties. The adsorption layers of N-PEGylated

chitosans are heavily hydrated and much less compact than the layers of chitosan. Chitosan-2-

N-MPEG graft copolymers could be used as protein-repellent vectors [4]. Keywords: Chitosan derivatives; PEGylation; brush polyelectrolytes; “click” chemistry; chitosan adsorption.

____________________________________

[1] N. Gorochovceva et all., Eur. Polym. J., 41, 2653 (2005).

[2] N. Gorochovceva, R. Makuska, Eur. Polym. J., 40, 685 (2004).

[3] R. Makuska, N. Gorochovceva, Carbohydrate Polymers, 64, 319 (2006).

[4] Y. Zhou et all., J. Colloid Interface Sci., 305, 62 (2007).

77


Polyhydroxyalkanoate (PHA) Biosynthesis from Whey Lactose

M. Koller, P. Hesse, A. Atlić, C. Hermann-Krauss, C. Kutschera, and G. Braunegg

Graz University of Technology; Inst. of Biotechnology & Biochemical Engineering,

Petersgasse 12, A-8010 Graz, Austria

The increasing demand for polymeric compounds acting as packaging materials for

the safe distribution of goods is undisputed. Contemporary strategies for disposing of end-of-pipe plastics cause serious global problems such as increasing piles of waste. Incineration of petrol-based polymers not only generates noxious compounds, but also elevates the atmospheric CO2 concentration. This aggravates frequently discussed problems such as greenhouse effect and global warming. Recycling systems do not function as effectively as required for a real solution of the problem.

Although data for remaining amounts of mineral oil are changing quickly due to advanced methods for tracing and discharging, the reserves of fossil feed stocks are limited. In May 2005, the price per barrel of mineral oil amounted to US-$ 55; recently, this value has rocketed up to US-$ 74 (July 2007).

Utilizing alternative polymeric materials such as polyhydroxyalkanoates (PHAs) unites two major advantages: Firstly, they can be produced from renewable resources such as carbohydrates, making them independent from the availability of fossil feed stocks. Secondly, when being composted, these biopolymers undergo a biodegradation process by the action of various microbes resulting merely in CO2 and H2O, the starting materials for the photosynthetic regeneration of carbohydrates by green plants. Thus, the mass stream for carbon in the biotechnological production lines for PHAs is embedded into a closed circle. This is clearly in contrast to the life cycle of classic polymers, where carbon fixed in the bowels of earth since millions of years is converted to CO2 which is released in the atmosphere.

Because recent studies point out that PHA production from purified sugars has been optimized to a high degree, further improvement of the fermentation technologies by using cheaper carbon sources as basis feed stocks is urgently needed.The work at hand studies the utilization of whey, the major by-product from cheese and casein production, as feed stock for the biotechnological production of PHA. Whey is not only a cheap raw material, but 13500000 tons of whey per year which contain 620000 tons of lactose (D-gluco-pyranose-4-β-D-galactopyranoside) constitutes a surplus product in the EU, causing a huge disposal problem for the dairy industry. Hence, the utilization of whey lactose for PHA production unites the diminishing of a waste problem and the increase of cost-efficiency in the bioinspired production of ecologically benign materials.

The work at hand presents and compares kinetic data and polymer characteristics for three different microbial strains that turned out to be capable of PHA accumulation from whey lactose (the eubacterial species Pseudomonas hydrogenovora and Hydrogenophaga pseudoflava as well as Haloferax mediterranei). Advantages and drawbacks of the organisms as potential PHA producers from whey on industrial scale are compared. The industrial significance of the study is underlined by economic appraisals for the investigated processes. Keywords: Biodegradable polymers; Renewable resources; polyhydroxyalkanoates; whey

____________________________________

[1] G. Braunegg et al., Polym. Plast. Technol.Eng. 43(6), 1779 (2004) [2] M. Koller et al., Biomacromol. 23(5), 561 (2005) [3] M. Koller et al., Bioproc. Biosyst. Eng. 29(5-6), 367 (2006) [4] M. Koller et al., Macromol. Biosci. 15(6), 218 (2007).

78


Synthesis and Study of Chitosan – Oligosaccharide Graft Copolymers

Ugn÷ Jančiauskaite and Ričardas Makuška

Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania

Grafted brush polyelectrolytes are of immense technological importance, both for

rheology control and for modification of surface properties. The latter application includes

such vastly different areas as control of colloidal stability, non-specific protein adsorption,

cleaning applications and lubrication. Comb polyelectrolytes partially or fully made from

naturally occurring building blocks are of particular interest. The proper representatives of

such polyelectrolytes are chitosan comb copolymers combining charge regulating positively

charged backbone with flexible and affined to polysaccharides grafts of inulin or dextran. The

presence of oligomeric hydrophilic side chains is expected to influence the adsorption of the

polyelectrolytes on negatively charged surfaces, to affect the forces acting between the coated

surfaces and to have impact on the attachment of the macromolecules of proteins or

glycoproteins.

Two types of dextran containing comb polyelectrolytes were synthesized attaching

dextran-1500 (FLUKA, Mr 1500) or dextran-6000 (FLUKA, Mr 6000) to amine or C(6)-OH

groups of chitosan (FLUKA, Mr 400000). The synthesis of chitosan-N-dextran graft

copolymers was done by the method of reductive amination resulting in high-molecular-

weight products. Peculiar property of these polyelectrolytes was necessity to use freeze-

drying process in order to obtain soluble products. Degree of substitution (DS) of chitosan in

the copolymers varied from 16 to 62 %. Chitosan derivatives with higher DS had lower

intrinsic viscosity [µ], moreover, grafting of dextran-6000 resulted in lower viscosity of

aqueous solutions. Chitosan-O-dextran graft copolymers were synthesized by reacting dextran

with tosylated derivatives of N-phthaloyl chitosan. Unfortunately, deprotection of amino

group functionality in these copolymers always resulted in low-molecular-weight products.

Inulin, a known reserve carbohydrate of Cychorium intybus, consists mainly of beta (2-1)

fructosyl fructose units with normally, but not always, a glucopyranose at the reducing end

[1]. Two different methods were chosen to graft inulin oligomer (ORAFTI, Mr up to 2000) to

chitosan. The first one is EDC induced coupling between chitosan and inulin succinate the

latter being prepared by the reaction between inulin and succinic anhydride in dry DMF [2].

The second method is based on the reaction between chitosan and inulin activated with

cyanuric chloride. Graft-copolymers were purified by dialysis against water and precipitated.

Chitosan – inulin derivatives were white powders easily soluble in water possessing low

intrinsic viscosity. FTIR and 1H NMR spectra of the products were consistent with the

presumable structure of chitosan – inulin graft copolymers.

Acknowledgement: Financial support from the Lithuanian State Science and Studies Foundation (project

TECHNOSACHARIDAS, N-04/2007) is gratefully acknowledged. ORAFTI is acknowledged for a kind

donation of inulin.

Keywords: chitosan derivatives; dextran copolymers; inulin derivatives; comb polyelectrolytes.

____________________________________

[1] C.V. Stevens, A. Meriggi, K. Booten, Biomacromolecules, 2, 1 (2001)

[2] X.Y. Wu, P.I. Lee, J. Appl. Polym. Sci. 77, 833 (2000).

79


Selection of Carbon Feed Stocks for Cost-Efficient

Polyhydroxyalkanoate (PHA) Production

M. Koller, P. Hesse, A. Atlić, C. Hermann-Krauss, C. Kutschera, and G. Braunegg

Graz University of Technology; Inst. of Biotechnology and Biochemical Engineering,

Petersgasse 12, A-8010 Graz, Austria

Raw materials require the major part of biopolymer production costs; this share contributes with up to 50% to the entire process expenses. Recent studies indicate that PHA production from pure sugars such as glucose or sucrose has already been optimized to a high degree. Therefore it is of importance to enhance cost efficiency of PHA production by substituting pure substrates by cheaper carbon feed stocks or by integrating PHA production into energetically autarkic production lines of the carbon sources. Whey from dairy industry

The utilization of polluting whey combines an economic progress with solving an ecological hazard. Whey was applied as carbon source for three wild type PHA producers: Haloferax mediterranei, Ps. hydrogenovora and Hydrogenophaga pseudoflava. Among these strains, H. mediterranei constitutes an outstanding candidate for PHA production on whey. This is due to its high robustness and stability; the risk of microbial contamination during cultivation is negligible, saving a lot of energy for sterility precautions. The strain grows on whey with a max. specific growth rate µmax. of 0.11 h

-1. PHA was accumulated at a max. specific production rate of 0.08 g/g h. Conversion yield for whey to PHA amounted to 0.3 g/g. The production of PHA copolyesters without co substrates, the excellent polymer characteristics together with a cheap isolation method make the strain of special interest [1,2,3]. Raw glycerol liquid phase from Biodiesel production

H. mediterranei was also used for PHA-production on glycerol liquid phase (GLP), a side stream of the biodiesel production from plant oils and tallow, containing about 70 wt.-% glycerol. In all Europe, the total production of biodiesel is estimated for 2008 with 2,649.000 metric tons. GLP nowadays constitutes a surplus material. Its utilization leads to an enormous cost advantage compared with commercially available pure glycerol, possessing a market value of 900 € per metric ton (year 2002). On bioreactor scale, H. mediterranei was able to grow on GLP at a specific growth rate of 0,06 h-1 and produced PHA (76% of cell mass) at a specific rate of 0,08 g/g·h. The yield for PHA from glycerol was calculated with 0,23 g/g, resulting in a final concentration of 16,2 g/L PHA [1,2,3].

Sugar cane sucrose

A different approach is provided by the utilization of carbon sources that feature a considerable market value and do not constitute waste materials, but are produced within a process integrating the fabrication of the carbon substrate and PHA. This will soon be realized in the south-central region of Brazil: starting from sugar cane, saccharose, ethanol and PHB are produced by Wautersia eutropha. The needed energy for polymer production is directly available from burning bagasse, a major by product of the sugar production. Due to the autarkic energy supply and the at-house availability of the carbon source saccharose, the production costs per kilogram PHB are estimated with less than US$ 3 [3, 4]. Keywords: biodegradable polyesters; polyhydroxyalkanoates; whey; raw glycerol phase; sugar cane sucrose

____________________________________

[1] M. Koller et al., Macromol. Biosci. 15(6), 218 (2007). [2] M. Koller et al., Biomacromol. 23(5), 561 (2005) [3] M. Koller et al.,article in press [4] R. Nonato et al., Appl. Microbiol. Biotechnol.57, 1 (2001)

80


Properties and Degradation of PVA/Starch Blends

with a PVA-g-MA Compatibilizer

Wan-Ling Lu1, Chia-I Liu

2, and Chi-Yuan Huang

2

1Dep. of Raw Materials and Yarn Formation,Taiwan Textile Research Institute,Taipei,Taiwan

2Dep.of Materials Engineering, Tatung University,

No.40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan

It can enhance the strain to 100~200 % by dissolving Polyvinyl alcohol (PVA) into one or

two time water in the starch/PVA blend system. Adding a compatibilizer (MA-g-PVA) also

has a well display in the strain at the break.

1. Experimental

1.1 MA grafting polymerization onto PVA: the general experimental procedure and an

example were as follows: PVA 5g and MA 5g were dissolved in 95g DMSO after being

stirred in an atmosphere of nitrogen. The reaction temperature was adjusted as needed (such

as 60°C), then 0.5g of potassium persulfate was added as a initiator. The reaction lasted for

5h. The reaction mixture was concentrated to about 20%, and was then added to chloroform

to precipitate the polymer.

1.2 Blend: in the series A, MA and PVA were dissolved in GA with 120°C for 30min before

compounding. In series B and C, MA and PVA were dissolved individually in 300g or 150g

distilled water with 70°C for 30min before compounding. For D series, MA-g-PVA (MA

Grafting polymerization onto PVA) and PVA were dissolved in 300g distilled water with 70;

for 30min before compounding. Then, the tapioca starch and GA were mixed with above

composition.

2. Results and discussions

2.1 FTIR Spectra: FTIR spectra, Figure 1, were obtained from MA-g-PVA and PVA films by

a JASCO Micro-IR. The IR spectra showed that the characteristic peaks of –COO– at 1720

cm-1

and –C=C– at 1640 cm-1

[1] at Figure .1 could confirm MA graft onto PVA.

2.2 Tensile Strength Measurement:There was a significant distinction of tensile strength for

blends in Figure 2. The starch presented stiffness and brittleness in this blends. It was the

reason that the maximum stress of A series was much higher than those of B, C and D series

blends. Water is a good plasticizer for PVA/starch blends in this work. The strain of B series

by adding 150g water was increased above 20 times (Figure 8). Adding 300g water, the strain

of C5 was up to about 192 %.

Thinking about the graft degree of MA-g-PVA (compatibilizer), the quantity of adding

compatibilizer was converted into the amount of adding MA in the blends. The maximum

stress range between D series blends was about 1.5 MPa and the strange range between D

series blends was about 30 %.

0 2 4 6 8 10 12 14 16 18

2

4

6

8

10

12

14

16

A series

B series

C series

D series

Stress (MPa)

MA (g)

0 2 4 6 8 10 12 14 16 18

0

20

40

60

80

100

120

140

160

180

200

220

A series

B series

C series

D series

Strain (%)

MA (g)

-2 0 2 4 6 8 10 12 14 16 18

50

60

70

80

B series

C series

D series

Weight Loss (wt %)

MA (g)

Keywords: Polyvinyl alcohol (PVA)、maleic anhydride (MA), compatibilizer, MA-g-PVA, SEM micrographs.

____________________________________

[1] W. Y. Chiang, C. M. Hu, J. Appl. Polym. Sci., 30, 3895(1985).

Fig. 1.The IR spectra of (a)pure

PVA and (b)MA-g-PVA.

Fig. 2.The tensile strength

of four series starch /PVA

blends.

Fig. 3.The strain at break of

four series starch /PVA

blends.

Fig. 4.The weight loss

measurement of starch/PVA

blends.

Wavenumber [cm-1]

-C=C- 1640 cm-1

4000 400 1000 2000 3000

%T -COO- 1720 cm-1

(a)

(b)

81


Thermal and Mechanical Behaviour of a Commercial

Poly(lactid acid) Submitted to Soil Burial Test

L. Santonja-Blasco, J.D. Badia, Rosana Moriana, and A. Ribes-Greus

Instituto de Investigación en Tecnología de Materiales. Escuela Técnica Superior

de Ingeniería del Diseño. Universidad Politécnica de Valencia,

Camino de Vera s/n 46022 Valencia

The replacement of petroleum-based polymers, with biodegradable ones is an actual

goal because of the increasingly aware in the environmentally friendly materials [1]. Poly(lactic acid) (PLA) an aliphatic, biodegradable and compostable polyester, can be obtained from renewable resources such as starch to yield articles for being used in industrial packaging or in agriculture field, as mulching films. A commercial PLA, supplied by Natureworks.DDL, Minnetonka, U.S.A, was buried in soil in order to characterize non controlled further disposal when it is used in packaging and its service life when it is used as mulching film. Samples were submitted to accelerated soil burial test in a culture oven at 28 ± 0.5ºC during 690 days according to the DIN 53739 standard [2]. Samples were extracted at 0, 30, 150, 300, 450 and 690 days and thermally characterized by means of Differential Scanning Calorimetry(Mettler Toledo DSC822), HR/CR=10ºC/min from 0-200ºC, under N2 atmosphere and by Dynamic-Mechanical-Thermal Analysis experiments in a Mark IV DMTA (Rheometric Scientifics) using dual cantilever clamping by bending mode. Specimens were heated from 35 to 150ºC in isothermal mode at 2ºC/min in the frequency range:0.1-39 Hz. DSC thermograms show that when degradation time advances two melting peaks are formed at 450 days. The lamellae thickness distribution calculated by means of Thompson equation [3] is in a range from 75 to 115 Ǻ. In the curves of the samples without degradation it is observed a wide shoulder that becomes narrower when degradation time in soil advances. When 450 days are reached, the lamellae distribution is presented by two separated peaks, however at 690 days both peaks are less pronounced and the distribution is wider. DMTA spectra performed at 1 Hz have been compared, in terms of loss tangent (tan δ) and storage modulus (E’). The relaxation temperature related to glass transition has been calculated by means of the temperature at the maximum of the fitting of the experimental loss modulus (E’’) data to Fuoss-Kirkwood [4] model. During degradation in soil: E’ value increases, the temperature related to the glass transition shifts to higher temperatures and the recrystallization occurs at lower temperatures. PLA has increased its crystallinity, due to the linkages weakening in the amorphous phase. Degradation in soil improves a faster linkage of the amorphous phase of the PLA, enhancing segregation of the crystallite size distribution until 690 days when seems to be homogenised. It also provides a higher E’ increased and recrystalization is produced at lower temperatures. Acknowledges: Ministerio de Educación y Ciencia and the European Region Development Fund for the economical support through the Project CTM2004-04977/TECNO and for the concession of pre-doctoral grants FPI and FPU. Keywords: poly (lactid acid); DSC; DMA; degradation in soil ____________________________________ [1] A.-C. Albertsson, S. Karlsson, Acta Polymerica, 1995, 46, 114. [2] DIN 53739 Testing of plastics. 1984.

[3] Hoffman, J. D., Davis, G. T. & Lauritzen, J. I. in Treatise on Solid State Chemistry (ed. Hannay, N. B.) 497−614 (Plenum, 1976). [4] R.M. Fuoss, J.G. Kirkwood, J. Am. Chem. Soc. 1941, 63, 385.

82


A Thermogravimetric Approach to Study the Influence of a Biodegradation

in Soil Test to a Poly(lactic acid)

J. D. Badia, Rosana Moriana, L. Santonja-Blasco, and A. Ribes-Greus

Instituto de Tecnología de Materiales. Escuela Técnica Superior de Ingeniería del Diseño.

Universidad Politécnica de Valencia. Camino de Vera s/n, 46022, Valencia, Spain

Poly(lactic acid) (PLA) is a green polymer, due to it can be obtained from renewable

resources and can be compostable when its service life has finished. The knowledge of the

degradation mechanisms involving the disposal stage of PLA must be assessed, in order to

assure the complete life cycle of a biodegradable material.

PLA with a 3.8% of meso-lactide content samples (supplied by Natureworks.DDL,

Minnetonka, U.S.A) were submitted to accelerate soil burial test in a culture oven Heraeus 12

at 28 ± 0.5ºC during 450 days following the DIN 53739 standard[1]. Specimens extracted at 0,

30, 150, 300 and 450 were analyzed by thermogravimetry. Measures were carried out in a

Mettler-Toledo TGA/SDTA 851, from 25 to 750ºC at a heating rate of 20ºC/min, under Ar

atmosphere. The DTG temperature peak (Tpeak), the degradation onset (Ton) and endset (Tend),

as well as the activation energy of the degradation process (Ea) were selected as

characterization parameters to analyze the degradation in soil influence on poly(lactic acid).

A f (α) = (1-α) n (with n=1) degradation kinetic model was previously hypothesized to employ

the kinetics models proposed by Broido[2] and Chang[3] for calculating the Ea of the

degradation mechanism. These results were compared to the Ea values obtained by the

method developed by Coats and Redfern [4] to prove the consistence of the kinetic study.

Criado[5] mastercurves were plotted from experimental data to confirm the degradation

kinetic model assumed.

For the samples submitted to an accelerated biodegradation process, no accentuated changes

were observed at the thermal stability of the polymer. No linear trend was established for the

activation energy evolution along the degradation in soil time, evidencing an oscillating

behaviour, with an initial Ea decrease until 150 days of exposure in soil, followed by an Ea

increase until the end of the experiment.

The authors would like to acknowledge the Ministerio de Educación y Ciencia (Spanish Government) and the

European Regional Development Fund for the economical support through the Project CTM2004-

04977/TECNO and for the concession of the pre-doctoral grants through the programmes FPI and FPU.

Keywords: poly (lactic acid);biodegradation in soil; thermogravimetry; kinetic analysis ____________________________________

[1] DIN 53739 Testing of plastics. (1984).

[2] Broido, A .J.Polym.Sci. Part-2, 27,1768, (1969).

[3] Chang, W.L. , J. Appl. Polym. Sci, 53, 1759, (1994).

[4] AW. Coats, Redfern JP. Nature, 201, 68. (1964).

[5] Criado,J.M., Thermochimica Acta, ,24,86, (1978).

83


Comparative Study about the Biodegradability and the Mechanical

Performance of Different Biocomposites Based on Thermoplastic

Starch Reinforced with Cotton Fibre

Rosana Moriana, L. Santonja-Blasco , J. D. Badia, and A. Ribes-Greus

Instituto de Investigación en Tecnología de Materiales. Escuela Técnica Superior

de Ingeniería del Diseño. Universidad Politécnica de Valencia.

Camino de Vera s/n 46022 Valencia

The substitution of traditional polymeric-based composite materials with synthetic matrixes

(epoxy, unsaturated polyester, or phenolics) reinforced with fillers such as glass, carbon or

aramid fibres, by environmentally-friendly composites with a biodegradable matrix and

natural fibres is therefore considered critical, due to an increasing environmental

consciousness and demands of legislative authorities [1]. Recent advances in natural fibre

development and composite science allow improving materials from renewable sources. The

current challenge is to design materials with structural and functional stability during use,

together with enhanced degradability during disposal in landfills to reach to close the material

loop without environmental hazard [2]. The purpose of this work is to study different

composites reinforced with a cotton fibre in order to analyse the influence of the matrix

employed. Thermal Analysis has been performed to evaluate the potential applications of

these blends, their characterisation, as well as the study of their degradation processes.

The polymeric matrices are based on thermoplastic starch-based materials commercialized

under the Mater-Bi KE 03B1 and Mater-Bi NF01U trade marks, [Novamont North America

(USA)]. Cotton is the natural fibre employed as reinforcement [Yute S.L.(Spain)]. The

thermo-mechanical properties of Mater-Bi have been investigated to assess its suitability as a

matrix material for the fabrication of biocomposites, to guarantee the improvement of the

mechanical properties after reinforcing with the biofibres, and to investigate the viscoelastic

behaviour in the studied materials. The biodegradability of the unfilled matrix, the natural

fibres and the composite with 10% in weight of cotton, were simulated by an accelerated soil

burial test (DIN 53739) [3]. Thermogravimetric analysis was used to study the thermal

stability of the employed materials, to fully investigate their thermal decomposition process

and to monitor their degradation process in soil. A deep kinetic analysis of the decomposition

process has been performed, with the determination of the activation energies and the

discussion of the reaction mechanism.

The authors would like to acknowledge the Ministerio de Educación y Ciencia (Spanish Government) and the

European Regional Development Fund for the economical support through the Project CTM2004-

04977/TECNO and for the concession of the pre-doctoral grants through the programmes FPI and FPU.

Keywords: biocomposites; renewably polymers; mechanical properties; thermal analysis.

____________________________________

[1] C. Bastioli, C. Facci, Biodegradable Plastic Conference, Frankfurt. (1999).

[2] A.K. Mohanty; M. Misra; T.D. Drzal, Ed.; Natural Fibers, Biopolymers and Biocomposites, Taylor & Francis

edition, Boca Raton, (2005). [3] DIN 53739 Testing of plastics. Influence of Fungi and Bacteria. Visual Evaluation. Change in Mass and

Physical Properties, (1984).

84


Improving the Processing Ability and Mechanical Strength of Starch/PVA

Blends through Plasma and Acid Modification

Sung-Yeng Yang, Chi-Yuan Huang, and Jing-Yi Wu

Department of Materials Engineering, Tatung University,

40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan, R.O.C.

In this investigation, maleic anhydride (MA), and citric acid (CA) used as the processing

additive and plasma treatment to improve the processing ability and mechanical strength of

biodegradable starch/PVA blends were studied. The melt flow index of starch/glycerol/PVA

(300g/60g/80g) was increased from 2.3g/10min to 32.7 g/10min by adding 3g of MA and to

130 g/10min by adding MA and plasma treatment. The mechanical strength of

starch/glycerol/PVA increases from 3.48 to 6.21 MPa by adding 1.5g of MA and 1.5g of CA,

while it increases to 6.26 MPa by plasma treatment. Esterization reaction occurred when MA

was dissolved into glycerol and glycerol grafted onto plasma pretreatment PVA. This was

caused the improved compatibility between starch and PVA. Thermogravimetric analysis, x-

ray diffraction, and scanning electron microscopy were used to study the morphology during

plasma and acid modification.

Keywords: biodegradable; maleic anhydride; citric acid; starch; thermogravimetric analysis (TGA)

85


Biodegradation of Starch and PVA/Starch Blend Enhanced

by Rhizopus Arrhizus

Sung-Yeng Yang, Chi-Yuan Huang, and Jing-Yi Wu

Department of Materials Engineering, Tatung University,

40, Chung-Shan N. Rd., 3rd Sec., Taipei 104, Taiwan, R.O.C.

Biodegradation of starch and PVA/starch blend improved by Rhizopus arrhizus was

examined. PVA, tapioca starch, and PVA/starch blend were buried in soil for sixteen weeks in

order to study the different biodegradation rates among these three materials. The PVA/starch

blend consisted of PVA (20%), glycerol (15%), and native tapioca starch (65%). Burial tests

were performance in three different soil conditions: (a) general compost (b) adding fungus in

compost, and (c) adding fungus in compost after sterilization. The complete biodegradation

time of PVA/starch blend were in the order as (b) test (burial time of 10 weeks) < (c) test (12

weeks) < (a) test (16 weeks). The biodegradation of starch has the same tendency among

these burial soil conditions, but degradation time was shortening to 6, 8 and 10 weeks.

Thermogravimetric analysis, x-ray diffraction, and scanning electron microscopy were used to

determine the morphology and degradation process of each material. Overall, adding

Rhizopus arrhizus in combination with other microorganisms can initiate the biodegradation

and increase the degradation rate for starch and its blend in the burial tests.

Keywords: biodegradable; fungus; starch; thermogravimetric analysis (TGA)

86


Biodegradable Blends of Polylactide and Natural Rubber

Marcin Kowalczyk and Ewa Piorkowska



Blends of polylactide (PLA) with two poly(1,4-cis-isoprene)s, differing in molecular

weight, were prepared with the aim to improve drawability through promotion of craze

plasticity. Morphology and mechanical properties of the blends were examined. Compression

moulded and quenched films of PLA and the blends containing of 5-25 wt% of rubber were

amorphous, as it followed from DSC studies. Tg of PLA, at about 55oC, remained unaffected

by the presence of rubber. SEM, TEM and DMTA studies revealed that the blends were phase

separated, with rubber particles dispersed within PLA matrix. Tensile test, performed on an

Instron at the drawing rate of 5%/min and 50%/min, demonstrated that incorporation of

rubber decreased significantly a yield stress. Significant improvement of elongation at break

and tensile impact strength was achieved in the blends with 5 wt% of rubber. SEM and SAXS

examination of deformed specimens demonstrated that at early stages of deformation crazes

were initiated, presumably by rubbery particles. Further deformation involved also shear

banding.

Such a way of modification of PLA mechanical properties is a promising alternative to

plasticization.

Keywords: polylactide ; biodegradable blends; mechanical properties

87


Synthetic Analogues of PHA

Anionic Ring-opening Polymerization of ββββ-alkoxy Substituted ββββ-lactones

G. Adamus and M. M. Kowalczuk

Polish Academy of Sciences, Centre of Polymer and Carbon Materials,

34 M. Curie-Sklodowska St, 41-800 Zabrze, Poland

Polyhydroxyalkanoates (PHAs) are thermoplastic aliphatic polyesters produced by microorganisms as energy storage materials. They represent an interesting group of biodegradable polymers that have recently received much attention, particularly as environmentally friendly materials produced from renewable resources. Among the variety of PHAs, poly[(R)-3-hydroxybutyrate], PHB, is of particular importance.

Synthetic analogues of this biopolymer of potential industrial importance are obtainable by direct copolymerization of epoxides with carbon monoxide [1] or via ring-opening polymerization (ROP) of β-butyrolactone to isotactic, atactic (a-PHB) and syndiotactic poly-3-hydroxybutyrate. [2-6]

Recently, systematic investigations have been conducted on the catalytic synthesis of β-lactones through the carbonylation of epoxides, since epoxides are easy to synthesize, inexpensive, and readily available in an enantiomerically pure form. This specific synthetic method opens a new opportunities for exploring the utility of the β-lactones (and in particular precursors of synthetic analogues of natural poly(3-hydroxyalkanoate)s i.e. β-substituted β-lactones) as monomers for the synthesis of new polymers with desired properties. [7]

The aim of the present communication is to report the ability of novel β-alkoxy substituted β-lactones i.e.: β-(methoxymethyl)-β-propiolactone (MOMPL) and β-(ethoxymethyl)-β-propiolactone (EOMPL) to undergo anionic ROP. Polymerization was conducted in the presence of activated carboxylates i.e. supramolecular complex of potassium acetate and tetrabutylammonium acetate (Bu4N

+Ac) as well as by tetrabutylammonium hydroxide. The subtle structure of the polyesters obtained has been established on the basis of ESI-MSn experiments. Acknowledgement. This research project was supported by Polish Ministry of Science and Higher Education project No 3 T08E 022 30 and by Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth Framework Programme under the contract number MTKD-CT-2004-509232.

Keywords:; biodegradable polymers; poly(3-hydroxy-4-methoxybutyrate), poly(3-hydroxy -4-ethoxybutyrate) ____________________________________

[1] Allmendinger, M.; Eberhardt, R.; Luinstra, G.; Rieger, B. J.Am.Chem.Soc. 2002, 124, 5646. [2] (a) Zhang, Y.; Gross, R.A.; Lenz, R.W. Macromolecules 1990, 23, 3206-3212; (b) Tanahashi, N.; Doi, Y.;

Macromolecules 1991, 24, 5732-5733; (c) Hori, Y.; Suzuki, M.; Yamaguchi, A.; Nishishita, T. Macromolecules 1993, 26, 5533-5534; (d) Abe, H.; Doi, Y. Macromolecules 1996, 29, 8683-8688.

[3] Rieth, L.R.; Moore, D.R.; Lobkovsky, E.B.; Coates, G.W. J.Am.Chem.Soc. 2002, 124, 15239-15248. [4] (a) Jedliński, Z.; Kurcok, P.; Kowalczuk, M.; Kasperczyk, J. Makromol. Chem. 1986, 187, 1651-1656; (b)

Abe, H.; Matsubara, I.; Doi, Y.; Hori, Y.; Yamaguchi, A. Macromolecules 1994, 27, 6018-6025. [5] Kurcok, P.; Śmiga, M.; Jedliński, Z.; J.Polym. Sci. Polym. Chem. 2002, 40, 2184-2189. [6] (a) Kemnitzer, J.E.; McCarthy, S.P.; Gross, R.A. Macromolecules 1993, 26, 1221-1229; (b) Kricheldorf,

H.R.; Eggerstedt, S. Macromolecules 1997, 30, 5693-5697. [7] Church, T.L.; Getzler, Y.D.Y.L.; Byrne, C.M.; Coates, G.W Chemical Communications 2007, 7, 657-674.

88


Biopolymer-based Fluorescent Sensors

for Quality Control of Food Products

D. Ciechanska1, J. Wietecha

1, J. Kazimierczak

1, D. Wawro

1, and E. Grzesiak

2

1 Institute of Biopolymers and Chemical Fibres with the incorporated Pulp and Paper

Research Institute, 19/27 M. Sklodowskiej-Curie St., 90-570 Lodz, Poland 2 Institute of Dyes and Organic Products, 2/4 Chemikow St., 95-100 Zgierz, Poland

The research was aimed at development of simple and quick method for checking

microbiological quality of food, especially meat and milk products, using fluorescent

indicators.

The method consists in hydrolysis of substituted derivatives of fluorescein and rhodamine,

which, in normal conditions, show no fluorescence. Fluorescein has the absorption maximum

at 490 nm and emission maximum at 514 nm and rhodamine at 498 nm and 520nm,

respectively.

Upon the action of hydrolytic enzymes (esterases, lipases and proteases) released by active

food-deteriorating microorganisms the functional groups of fluorescein and rhodamine

derivatives will become unblocked and start emitting fluorescence. The rate of hydrolysis

reaction of various derivatives is proportional to the enzymes concentration and, therefore, to

the number and vitality of enzyme-producing microorganisms.

At the early stage of research, a wide range of fluorescent dyes derivatives such as

diacetylfluorescein, dibutyrylfluorescein, diacetyleosin, diacetylerythrosin,

dilauroylfluorescein, dibenzoylfluorescein and diacetylrhodamine has been investigated in

order to assess their suitability for sensors preparation. Based on the investigations two

selected derivatives – diacetylfluorescein (FDA) and dibutyrylfluorescein (FDB) were

deposited on surfaces of suitable polymer carriers. The progress of FDA and FDB hydrolysis

due to action of enzymes of specified activity was monitored by intensity of fluorescence

emitted by sensors under UV light source.

Fluorescein derivatives proved to be hydrolysed by both lipases and proteases but in the case

of lipases the reaction rate was significantly higher. It was also found out that

diacetylfluorescein was the most susceptible to the hydrolytic action of the above enzymes.

In vitro tests of fluorescent sensors were carried out using meat and milk samples of various

degrees of microbiological contamination, which had been previously stored for 0-5 days at

ambient temperature.

This work was carried out as part of research project Nr. 3 T09B 137 28, which has been

supported financially by the Ministry of Science and Higher Education.

89


Polyhydroxyalkanoates Production by Isolates from a Polluted Salt-lagoon

S. Povolo and S. Casella

Dipartimento di Biotecnologie Agrarie, University of Padova,

Viale dell’Università, 16, Legnaro (PD), Italy

Polyhydroxyalkanoates (PHAs) are a family of biodegradable polyesters having a

number of possible industrial applications. They are synthesised as intracellular carbon and

energy storage material by a wide variety of bacteria. The main obstacle to PHA diffusion is

its high production cost greatly depending, among others, upon the cost of the fermentation

substrate to be utilised as a carbon source. The use of agricultural waste materials could play

an important role in economic production of PHA [1]. Starch or hydrolysed starch, cellulose

and hemicellulose along with sucrose and cheese whey have been proposed as economical

sources [2]. Polymer production was studied in many bacteria and recently also in moderately

halophilic bacteria, which grow optimally with 3-15% (w/v) NaCl [3]. Nevertheless,

investigations on the phenotypic characteristics of some type strains belonging to the genus

Halomonas has revealed poly(β-hydroxybutyrate) [PHB] accumulation for several species. In

contrast to the culture requirements of extremely halophilic archaea, sodium chloride

concentrations of 0.5 and 4.5% (w/v) provided the highest cell densities and PHB

accumulation in the case of H. boliviensis [4]. The production of PHB by H. boliviensis from

hydrolyased starch and from sucrose was also described [5].

The objective of the present work was to isolate from the salt-lagoon of Sottomarina (Venice,

Italy) bacteria able to degrade different carbon sources such as glycerol and lactose and

producing PHA at the same time. Specially, we worked on the isolation of bacteria growing at

8 % (w/v) NaCl. Some isolates, were identified by 16S rDNA sequence analysis as belonging

to the genus Halomonas. Here we report preliminary results on the bacterial conversion of

glycerol and lactose to PHA by the selected isolates.

Keywords: moderate halophile; Poly(β-hydroxybutyrate) (PHB) accumulation; carbon source

____________________________________

[1] M. Koller, R. Bona, G. Braunegg, C. Hermann, P. Horvat, M. Kroutil, M. Martinz J. Neto, L. Pereira, P.

Varila. Biomacromolecules 6, 561-565 (2005).

[2] S.Y. Lee. Trends in Biotechnol. 14, 431-438 (1996).

[3] J.A. Mata, J. Martìnez-Cànovas, E. Quesada, V. Bèjar. Yt. Appl. Microbiol.25, 360-375 (2002).

[4] J. Quillaguamán, O. Delgado, B. Mattiasson, R. Hatti-Kaul Enzyme Microb. Technol. 38,148–154 (2006).

[5] J. Quillaguamàn, M. Muños, B. Mattiasson, R. Hatti-Kau. Appl. Microbiol. Biotechnol. 74, 981–986 (2007).

90


Thermal Properties for Blend of Poly[(L)-lactide]

and Highmolecular Weight Atactic Poly[(R,S)-3-hydroxybutyrate]

Michał Sobota, Henryk Janeczek, Piotr Dacko, and Marek M. Kowalczuk

Centre of Polymer and Carbon Materials, Polish Academy of Sciences,

34, Marii Sklodowskiej Curie St., 41-819 Zabrze, Poland

The field of biodegradable polymers is a fast growing area of polymer science because of

crude oil, natural gas which are sources for traditional plastics reached price level where

biodegradable polymers can be profitable at common applications instead of non-

biodegradable plastics. In addition, composting, which is used for disposal of food and yard

waste is the most suitable for the disposal of biodegradable materials. Therefore promising

oppurtiunity are appeared for packaging materials which could be prepare from biodegradable

polymers.

Polyesters such as: poly[(L)-lactide] (PLA), poly[hydroxyalkanoate] (PHA) are most popular

representants of biodegradable polymers which are applied in medical, pharmcological and

packaging industries. However biodegradable polymers are promising materials, many of

them are modified on diference ways for improve of physical properties and

processability.[1,2] One of the method modification polymer is blending of two or more

polymers, which is an attractive approach because of the low cost and simplicity.

The aim of the work is thermal investigation for melted blends of PLA and atactic poly[(R,S)-

3-hydroxybutyrate] (a-PHB) by differential scanning calorimetry (DSC). Molecular weight of

PLA (Mn= 100000, Mw/Mn= 2,0) and a-PHB (Mn= 80000, Mw/Mn= 1.2) were determined

by GPC performed in chlorofome with polystyrene standards. DSC thermograms for the

blends and pure PLA showed differences in rate of crystallization, process is accelerated by

the addition of a-PHB component. Time of isothermal (115°C) crystallization for blends after

processing decreased compare to neat PLA, even in sample which is 5% w/w a-PHB content.

Acknowledgment This work was supported by:

- Marie Curie Transfer of Knowledge Fellowship of the European Community’s Sixth

Framework Programme under the contract number MTKD-CT-2004-509232.

- Polish Ministry of Science and Higher Education: R&D project no. R05 055 02.

- Regional Fund for PhD Students (Regionalny Fundusz Stypendiów Doktoranckich) of the

European Social Fund.

____________________________________

[1] Jedliński Z, Kurcok P, Lenz RW. J Macromol Sci Pure Appl Chem 1995;A32:797.

[2] Datta R, Tsai S-P, Bonsignore P, Moon S-H, Frank JR. FEMS Microbiol Rev 1995;16:221.

91


Synthesis of Poly(aspartic acid)-b-Polylactide Block Copolymer

Ida Poljanšek, Blaž Brulc, Maja Gričar, Ema Žagar, Andrej Kržan, and Majda Žigon

National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia

The aim of our work is the preparation and study of novel functional polymers and

polymeric materials with tailored properties for application in drug delivery systems. The

research on functional polymers is oriented towards synthesis and characterization of

biodegradable and biocompatible polyesteramides as carriers for controlled drug release based

on natural monomers lactic and aspartic acids [1,2]. The current synthetic work is focused on

the block copolymers made of these two monomers because side-chain carboxylic groups

enable the formation of complexes of the copolymer with metal ions.

In this study poly(β-benzyl L-aspartate)s and their block copolymers with L,L-lactide

with varying molar mass averages and low polydispersity indices (PDI = 1.00–1.09) were

prepared. NMR and FT-IR spectroscopy was used to elucidate the products chemical

composition, and size-exclusion chromatography coupled to multi-angle laser photometer

(SEC-MALLS) was used for the determination of the absolute molar mass averages of the

products.

The benzylic protected aspartic acid N-carboxyanhydride (Asp-NCA) was chosen as

the monomer for the preparation of the polyamide block. Benzylic protection prevented side

reaction leading to branched polymers whose degree of branching could not be controlled.

Polymerization of aspartic acid NCAs was carried out in dry N,N-dimethylformamide

at room temperature and at slightly elevated temperatures (up to 40 °C) in a dry argon

atmosphere using triethylamine or n-pentylamine as the initiator. The polymerization

mechanism is strongly dependent on the initiator used since triethylamine exhibits a basic and

n-pentylamine a more nucleophilic character [3]. Molar mass averages of poly(β-benzyl L-

aspartate)s were in both cases in the order of 103–10

4 g mol

-1 (depending on the ratio of

monomer to initiator used), while polymers were practically monodisperse (PDI = 1.00–1.05).

The next step was the copolymerization of poly(β-benzyl L-aspartate) and L,L-lactide

using stannous(II) octoate as the catalyst [4]. The reactive amino end group of protected

poly(aspartate) block acts as a co-initiator. The linear block copolymers of well defined

structures were synthesized in solution in a dry nitrogen atmosphere and at temperatures

between 50 and 75°C by lactide ring-opening polymerization. The chemical composition of

the block copolymers i.e., the length of lactide block depends on the feed ratio, temperature

and time of reaction. The copolymers synthesized in this manner were linear, but those

prepared at temperatures at 65 °C and above exhibited some degree of branching due to

partial hydrolysis of pendant benzylic ester groups.

Keywords: biodegradable polymers; block-copolymers; characterization

____________________________________

[1] K. Uhrich, S. Cannizzaro, R. Langer, K. Shakesheff, Chem. Rev. 99, 3181 (1999).

[2] C. S. Ha, J. A. Gardella, Chem. Rev. 105, 4205 (2005).

[3] H. Sekiguchi, Pure Appl. Chem. 53, 1689 (1981).

[4] A. Kowalski, J. Libiszowski, R. Biela, M. Cypryk, A. Duda, S. Penczek, Macromolecules 38, 8170 (2005).

92


Compostability of Aliphatic-aromatic Copolyester and their Blends

under Natural Weather Depending Conditions

Katarzyna Krasowska1, Maria Rutkowska

1, and Marek M. Kowalczuk

2

1Gdynia Maritime University, Department of Chemistry and Industrial Commodity Science,

81-87 Morska Str., Gdynia, Poland 2Polish Academy of Sciences, 34 M. Sklodowskiej-Curie Str., Zabrze, Poland

Recently, there is growing demand of biodegradable polymers. They have acquired an

important place in modern life. Products from biodegradable polymers have been

implemented in the medical field, pharmacy, gardening, agriculture and packaging. Selective

use of biodegradable polymers in certain applications might help to reduce the environmental

impact of plastic wastes.

Generally three categories of biodegradable polymers can be distinguished: (1) natural

polymers produced by plants, animals, and microorganisms such as cellulose, starch, chitin

and polyhydroxyalkanotes, (2) synthetic polymers such as polylactide, polycaprolactone, (3)

convenient blends of natural and synthetic polymers.

Among these biodegradable polymers, polyesters are the most promising materials. On the

one hand aliphatic polyesters constitute the most attractive class of artificial polymers, which

can degrade in contact with living organisms but on the other hand aromatic polyesters exhibit

excellent material properties but proved to be almost resistant to microbial attack.

To combine good material properties with biodegradability, a new group of copolyesters have

been developed as biodegradable polymers. This group includes the aliphatic-aromatic

copolyester of 1,4-butandiol with adipic and terephtalic acids. According to DIN and ASTM

standards this polymer is biodegradable, atoxic and useful in composting process.

The development of these group of the aliphatic-aromatic copolyesters biodegradable in

natural environments is the key to solving problems caused by plastic wastes. But very often

environmental degradation can only occur in favourable environments, where the

biodegradation is expected to happen.

In this way the aim of the present study was an examination of the compostability of

copolyester of 1,4-butandiol with adipic and terephtalic acids (Ecoflex, BASF) and their

blends under natural weather depending conditions.

Environmental degradation of pure Ecoflex and and their blends such as Ecoflex/

copolyester of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV) and Ecoflex/ Ramie

woven fabric took place in the compost pile consisted of the activated sludge, burnt lime and

straw preapared under natural conditions of sewage farm

The compostability of investigated polymers under natural conditions was based on the

examination of the changes of surface and weight of polymers after degradation.

The characteristic parameters of compost were also investigated and their influence on the

rate of composting process was discussed.

The results of the present study revealed that Ecoflex and their blends are degraded in

compost with activated sludge under natural conditions. The rate of composting process

depends on the nature of environment and the kind of degraded polymer. Generally the

biodegradation rates of investigated polymers in compost with activated sludge decreased in

order: Ecoflex/PHBV>Ecoflex>Ecoflex/Ramie woven fabric.

Keywords: copolyester of 1,4-butandiol with adipic and terephtalic acids, PHBV, Ramie woven fabric, compost

with activated sludge

93


Illumination of Cellulose with Linearly Polarized Visible Light

A. Konieczna-Molenda1, M. Molenda

2, M. Fiedorowicz

1, and P. Tomasik

1

1Department of Chemistry, University of Agriculture,

Balicka 122 Str., 30-149 Cracow, Poland 2Faculty of Chemistry, Jagiellonian University,

Ingardena 3 Str., 30-060 Cracow, Poland

Cells and plants react to the polarized light [1,2]. Reports on effects of the polarized

light upon the activation of enzymes [3], enhancement rate of enzymatic hydrolysis of starch

polysaccharides [4] and rearrangement of the molecular structure of starch polysaccharides [5]

were published recently. This work provides results of our study on the changes in

physicochemical properties of cellulose induced by illumination with the polarized light.

Water suspensions of commercially available cellulose, containing long polysaccharide

chains, were illuminated with visible polarized light for 20 and 50 hrs. Another cellulose

samples suspended in water and kept in the dark served as reference. After termination of

illumination, cellulose was filtered off and dried. Crystalline structure [6], thermal properties

(DSC) [7], susceptibility to oxidation [8] and degree of polymerization (DP by viscometry) [9]

of the samples were determined. Additionally, kinetic of enzymatic as well as acid hydrolysis

of cellulose was estimated.

Illumination of cellulose with linearly polarized light (50 hrs) increased degree of

polymerization of 15%. Such effect was not observed for illuminated at shorter time as well as

for non illuminated samples. The DSC measurements indicated different water content in the

samples of illuminated and nonilluminated cellulose prepared under the same conditions. The illuminated cellulose incorporated the highest, about 18%, water content. Only for that sample

the heat effect related to water freezing was observed.

X-ray diffraction patterns demonstrated that the illumination resulted in an increase in

the cellulose crystallinity. After prolonged illumination, the cellulose was resistant to the

oxidation. Illuminated cellulose revealed lower susceptibility to enzymatic and acid-catalysed

hydrolysis

____________________________________

[1] T.Kubasowa, M.Fenyo, Z.Somosy, L.Gazso, I.Kertesz; Photochem. and Photobiol., Vol.48, No. 4, 1988,

pp. 505–509.

[2] K.M.Hartmann, A.Mollwo; Proc. Symp. Biologic Effects of Light, Basel, Switzerland, 1-3.11.1998.

[3] M.Fiedorowicz, A.Konieczna–Molenda and G.Khachatryan; Starch: – Progress in structural studies,

modifications and applications. Eds P.Tomasik, V.Yuryev, E.Bertoft, Polish Society of Food Technologist’

Małopolska Branch, 2007.

[4] M.Fiedorowicz, G.Khachatryan, A.Konieczna-Molenda, V.P.Yuryev, L.A. Wassermann; Starch:

Achievements in Understanding of Structure and Functionality. Edts.: Vladimir Yuryev, Piotr Tomasik and

Eric Bertoft . Nova Science Publishers, New York, 2006.

[5] M.Fiedorowicz, G.Chaczatrian; J. Sci. Food Agric., 2004, 84 (1), 36-42.

[6] K.Choo-Won, K.Dae-Sik, K.Seung-Yeon, M.Marquez, Yong L.J; Polymer 47 (2006) 5097-5107.

[7] A.Kochanowski, R.Dziembaj, M.Molenda, A.Izak, E.Bortel; J. Therm. Anal. Cal. 88(2) (2007) 499-502.

[8] L.M.Proniewicz, C.Paluszkiewicz, A.Wesełucha-Birczyńska, H.Majcherczyk, A.Barański, A.Konieczna;

J. Molec. Struc. 596 (2001) 163-169.

[9] A.Barański, A.Konieczna–Molenda, J.M. Łagan, L.M. Proniewicz; Restaurator 24 (2003) 36-45.

94


Poly(L-lactide) Nano- and Micro-fibers by Electrospinning:

Influence of Poly(L-lactide) Molecular Weight

W. Tomaszewski1, A. Duda

2, M. Szadkowski

1, J. Libiszowski

2, and D. Ciechańska

1

1Institute of Biopolymers and Chemical Fibres,

Sklodowskiej-Curie 19/27, 90-570 Lodz, Poland 2 Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,


Aim of the work

The present contribution aims at reporting on studies of nanofibers and nanofibrous mats

parameters obtained from poly(L-lactide)s (PLA’s) of various molecular weights.

Materials

PLA’s were prepared by the controlled ring-opening polymerization of the L.L-dilactide (LA)

monomer. The polymerization was carried out in THF as a solvent at 80°C with tin(II) bis-

octanoate (2-ethylhexanoate) as a coinitiator. For the resulting, isolated by precipitation into

methanol PLA’s, the following molecular weights (Mn, SEC, LLS detector) were determined:

22×103, 62×10

3, 132×10

3.

Preparation of fibrous mats by electrospinning

The spinning solutions contained from 1 to 12 wt-% of PLA in a solvent composed of 90/10

wt% CHCl3/DMSO mixture. The electrospinning apparatus was equipped with 12 points

spinning head sliding along a rotating tube, with diameter of about 8 cm, as collecting

electrode. The air gap and voltage were 15 cm and 20 kV, respectively. The electrospun

products were flat fibrous sheets, about 0.1 mm thick.

Analytical methods

Microscopy. The electrospun products were observed by a scanning electron microscope

Quanta 200(W), FEI Co., USA.

Thermal characterization. The thermal transitions were measured by a differential scanning

calorimeter DSC-2, Perkin-Elmer, USA.

Viscometry. The viscosity of the spinning solutions were measured by a Brookfield

viscometer

Tensile tests. The tensile properties were measured by classic (tensile tester, Instron 5544,

USA) and special ball piercing (modified Instron apparatus) methods.

Results

The nano- and micro-fibrous mats with diameters of fibers in the range from 0.1 to 1.7 µm

were manufactured by electrospinnig from solution. Molecular weights of the applied PLA’s,

viscosities of the spinning solutions, and the fibers thickness were correlated. The

microscopic, thermal and tensile characteristics of the resulting mats were examined.

This work was carried out as a part of the research project no. 3 T08E 036 29 supported by

the Ministry of Science and Higher Education, Poland

Keywords: poly(L-lactide); nanofibrous mats; electrospinning; mechanical properties

95


Biomedical Applications of Maleic Anhydride Copolymers

and Their Derivatives

Gabrielle C. Chitanu1, Irina Popescu

1,

Adina G. Anghelescu-Dogaru1, and Irina Dumistracel

2


Aleea Grigore Ghica Voda 41A, 700487, Iasi, Romania 2S. C. Antibiotice S.A. - Iasi, Valea Lupului 1, Iasi, Romania

The use of maleic anhydride copolymers or their derivatives for medical or

pharmaceutical purposes is already known, some of such applications being of current use. An

important research effort was dedicated to this topic, the pioneering results of Breslow [1] and

Maeda [2] are worthy to be mentioned as well as the contributions of Hirano and co-workers

[3], Hodnett et al. [4], Azori, Pato and co-workers [5], Rubessa and co-workers [6], Heller et

al. [7], A. Urtti and his group [8]. The application of maleic anhydride copolymers in the

biomedical and pharmaceutical topic is promoted by several advantages from which can be

mentioned their regular, reproducible chemical structure, their variable

hydrophobicity/hydrophilicity, that can be tailored by choosing the suitable comonomer, and

their chemical versatility, due to the anhydride cycle, which allows to attach different low

molecular compounds by mild reactions. Not on the last place is the pH dependent solubility

of the conjugates based on maleic anhydride copolymers, which is particularly suitable for the

controlled delivery of drugs in different segments of the gastrointestinal tract. In the first

section of our contribution all these aspects are reviewed in a systematical and organized

manner.

The second part of our work presents several of our results aiming the obtaining of

maleic anhydride (MA) copolymers based derivatives or systems for biomedical purpose.

They are described:

- Synthesis and characterization of macromolecular disinfecting systems from MA

copolymers and OH- containing disinfectants such as thymol or eugenol

- Synthesis and characterization of menthol-containing polymers for dental use

- Synthesis and characterization of amidic derivatives of MA copolymers and preparation of

microparticles loaded with bioactive molecules

- Some data on the polymer degradation in aqueous solution.

Acknowledgement The financial support of Romanian National Authority for Scientific Research, CEEX

projects no. 14/2005 and 277/2006 is gratefully acknowledged.

Keywords: bioactive polymers; polymer degradation; maleic anhydride copolymers; polymer-drug conjugates

____________________________________

[1] D. S. Breslow, Pure Appl. Chem., 46, 103 (1976).

[2] H.Maeda, Adv. Drug Delivery Rev., 6, 181 (1991).

[3] Hirano, T.; Ohashi, S.; Morimoto, S; Tsuda, K. Makromol. Chem., 187, 2815 (1986); Hirano, T.; Todoroki,

T.; Kato, S; Yamamoto, H.; Calicetti, P.; Veronese, F.; Maeda H.; Ohashi, S. J. Control. Release, 28, 203

(1994); Hirano, T.; Todoroki, T.; Morita, R.; Kato, S; Ito, Y.; Kim, K.-H.; Shukla, P. G.; Veronese, F.; Maeda

H.; Ohashi, S. J. Control. Release, 48, 131 (1997).

[4] E.M. Hodnett, A. Wai Wu, and F.A. French, Eur. J. Med. Chem., 13, 577 (1978) and subsequent papers.

[5] See for example: M. Azori, in: “Polymers in Medicine III”, ed. by C. Migliaresi, Elsevier Sci. Publishers,

B.V., Amsterdam, 1988, p. 189-199.

[6] C. Flego, M. Lovrecich, and F. Rubessa, Drug. Develop. Ind. Pharm., 14, 1185 (1988) and subsequent papers

[7] J. Heller, R.W. Baker, R.M. Gale, J.O. Rodin, J. Appl. Polym. Sci. 22, 1991 (1978).

[8] U. Finne, K. Kyyrönen, A. Urtti, J. Control. Release 10, 189 (1989).

96


Complexation of Phosphorylated Cellulose with Collagen

Dana M. Suflet1, Gabrielle C. Chitanu

1, and Viorica Trandafir

2


Aleea Grigore Ghica Voda 41A, 700487, Iasi, Romania 2National Research and Development Institute for Textile and Leather,

str. Ion Minulescu 93, sector 3, Bucuresti, Romania

Polysaccharides are of the most abundant biopolymers possessing structural diversity

and functional versatility. They are polyglucans type polymers, containing glucose repeating

units only; however a broad variety of structures appears, resulting from the stereochemistry

of the anomeric C-atom, from the regiochemistry of the glycosidic linkage and from the

pattern of branching. Chemical derivatization of polysaccharides has a determinant effect on

their macroscopic properties, such as solubility, stability, and viscosity characteristics. If the

functionalization leads to polysaccharide derivatives bearing ionic or ionizable groups they

will behave as polyelectrolytes. Among these, the strong polyelectrolytes containing

phosphoric groups can be obtained mainly by derivatization [1, 2].

Collagen is the most abundant protein in higher animals, and its function has been

considered to maintain the body skeleton. Collagen is usually employed in drug delivery

systems or as material for constructing artificial organs. The interaction of collagen with other

natural or synthetic polyelectrolytes is interesting at least from two points of view. The first

concerns the way in which the polymers interact with nonflexible protein molecules, an

understanding of which could provide a better explanation of the interaction mechanism of

polyelectrolytes with ionic colloidal particles. The second concerns the extent to which

biochemical activity is maintained in the resulting complexes, the answer to which is central

to the molecular design of composite collagen-polymer systems [3].

In this work we report original results regarding the interaction of phosphorylated

cellulose [4] with collagen in aqueous salt-free or added salt containing systems. The

collagen-phosphorylated cellulose systems were investigated firstly in aqueous solution, by

potentiometric, conductometric and turbidimetric titration, according to the recommended

procedures [2, 5, 6]. The elemental analysis, FT-IR spectra, electron microscopy and

termogravimetric method were used in characterization of complexes formed in different

conditions.

Acknowledgement: The financial support of Romanian National Authority for Scientific Research, CEEX project

no. 16/2005 is gratefully acknowledged.

Keywords: natural polymers; polysaccharides; collagen; intermacromolecular complexes

____________________________________

[1] D. Klemm, B. Philipp, T. Heinze, U. Heinze, W. Wagenknecht, Comprehensive Cellulose Chemistry, Wiley

Verlag GmbH, D-69469 Weinheim (F.R.G.), 2, 1998.

[2] H. Dautzenbeg, W. Jaeger, J. Köetz, B. Philipp, Ch. Seidel, D. Stscherbina, in Polyelectrolytes. Formation,

Characterization and Application, Hansel Publishers, Munich, 1994.

[3] A. Tsuboi, T. Izumi, M. Hirata, J. Xia, P.L. Dubin, E. Kokufuta, Langmuir, 12, 6295 (1996).

[4] M.D. Suflet, G.C. Chitanu, V.I. Popa, React. Funct. Polym., 66(11), 1240 (2006).

[5] Y. Li, P.L. Dubin, H.A. Havel, S.L. Edwards, H. Dautzenberg, Macromolecules, 28, 3098 (1995).

[6] Y.-P. Wen, P.L. Dubin, Macromolecules, 30, 7856 (1997).

97


Effect of Collagen on Sparingly Soluble Inorganic Salts Separation

Irina M. Pelin1, Gabrielle C. Chitanu

1, Viorica Trandafir

2, and Zina Vuluga

3


aleea Grigore Ghica Voda 41A, Iasi 700487, Romania 2National Research and Development Institute for Textile and Leather,

str. Ion Minulescu 93, sector 3, Bucuresti, Romania 3National Research and Development Institute for Chemistry and Petrochemistry –

ICECHIM, Splaiul IndependenŃei 202, Bucuresti, Romania

Collagen is a natural polyelectrolyte (polyampholyte) obtained by extraction from

different animal sources. It proves good properties, from which it should be mentioned

biocompatibility, bioabsorbability and hipoimmunogenicity, that make it proper in many

biomedical applications as hemostats, sealants, implant coatings, artificial skin, bone graft

substitutes, corneal shields and injectables for plastic surgery [1].

The interest in developing bone substitutes has been growing and numerous papers

describe new methods of preparation. The bones contain a carbonated and partially

substituted apatite, based on nanocrystal aggregates associated with collagen. In most cases,

collagen processing involves aqueous preparations, and the obtaining of hydroxyapatite

(HAp) takes place also in water.

In our paper we investigated the interaction in aqueous solutions between the

precursors of HAp: ammonium dihydrogen phosphate and calcium nitrate tetrahydrate, in

presence of various amounts of collagen as crystallization regulator. As mineralizing agent a

12.5% ammonium hydroxide solution was used. The influence of collagen was followed by

potentiometric, conductometric and turbidimetric titration. The particles of HAp were

characterized by FTIR spectroscopy, X-ray diffraction and scanning or transmission electron

microscopy.



Keywords: collagen, hydroxyapatite, crystallization regulators, biomaterials ____________________________________

[1] W. Friess, M. Schlapp, Eur. J. Pharm. Biopharm. 51, 259 (2001).

98


Supramolecular Systems from Natural Polymers

and Maleic Polyelectrolytes

Irina Popescu1, Marcel I. Popa

2, and Gabrielle C. Chitanu

1


Aleea Grigore Ghica Voda nr. 41-A, 700487, Iasi, Romania 2“Gh. Asachi” Technical University, Faculty of Chemical Engineering

and Environment Protection, Bd. D. Mangeron 71, Iasi, Romania

Polyelectrolyte complexes (PEC) result from the interaction of macromolecules

carrying opposite charged groups. They have been proposed for several purposes, from which

we mention the design of drug delivery systems, anticoagulant coatings, and membranes or

even as skin substitutes. The preparation of PEC from natural polymers, such as

polysaccharide or polypeptides has the additional advantage of being non-toxic,

biocompatible, and bioabsorbable.

Chitosan is a cationic polysaccharide obtained by deacetylation of chitin, which is the

major constituent of the shells of crustacean and insects. As the other natural polymers it is

renewable, highly biocompatible, very low toxic in the oral and implant administrations and

biodegradable. By derivatization or complexation of chitosan a variety of new functional

materials can be obtained.

In our work the formation of PEC by interaction between chitosan and maleic acid

copolymers (MP) as strong/weak dibasic polyanions was investigated. The salt form of maleic

acid copolymers with: vinyl acetate, N-vinylpyrrolidone, styrene and methyl methachrylate

and the hydrochloride form of chitosan were used, all macromolecular partners being

carefully purified by diafiltration and freeze-drying. The interaction of chitosan with MP in

aqueous solution was followed by potentiometric, conductometric and turbidimetric titration

by varying the polyelectrolytes concentration and the mixing order [1, 2]. The effect of the

added low molecular salt on the complex formation was also investigated. The precipitated

complexes were analysed by FT infrared spectroscopy, thermogravimetric analysis and

differential scanning calorimetry. Preliminary layer-by-layer experiments were performed to

obtain thin films from maleic polyelectrolytes and chitosan [3].

Chitosan behavior in the interaction with maleic polyelectrolytes was compared with

other natural polymers such as collagen.



Keywords: chitosan; maleic polyelectrolytes; intermacromolecular complexes; supramolecular systems

____________________________________

[1] B. Philipp, H. Dautzenberg, K.-J. Linow, J. Kötz, W. Dawydoff, Prog. Polym. Sci. 14, 91 (1989).

[2] A. F. Thünemann, M. Müller, H. Dautzenberg, J.-F. Joanny, H. Löwen, Adv. Polym. Sci. 166, 113 (2004).

[3] O. N. Oliveira, J.-A. He, V. Zucolotto, S. Balasubramanian, L. Li, H. S. Nalwa, J. Kumar, S. K. Tripathy,

“Layer by layer polyelectrolyte-based thin films for optoelectronic and photonic applications”, chapter in

“Handbook of polyelectrolytes and their applications”, Ed. By S. K. Tripathy, J. Kumar and H. S. Nalwa,

American Scientific Publishers, 2002, USA.

99


Polylactide-polyglycidol Block Copolymer as a New

Nanoparticles Forming Material

Mariusz Gadzinowski, Beata Miksa, and Stanislaw Slomkowski

Center of Molecular and Macromolecular Studies, Polish Academy of Sciences,


A novel kind of block copolymer: polyglycidol-b-polylactide was synthesized by living

anionic polymerization and used for the nanoparticles preparation. The main advantage of

using polyglycidol is presence of functional hydroxyl groups in the hydrophilic polyglycidol

chain. Synthesis includes four main steps: a) protection of glycidol hydroxyl group, b)

polymerization of protected monomer, c) extension of polyether chain by polymerization of

L-lactide initiated by active centers on the living polyglycidol chain and d) deprotection of

glycidol hydroxyl groups. Potassium tert-buthoxide has been used as an intiator.

Polymerizations were carried on in THF. Copolymer blocks lengths were determined by 1H-NMR spectroscopy and a very good agreement between calculated (assuming quantitative

initiation and complete monomer conversion) and measured molecular weight of blocks was

observed. In water macromolecules of all synthesized polyglycidol-b-polylactides (with

various molecular weight: PGL4000-PLA3000, PGL2000–PLA3000, PGL4000-PDLA3000)

did self-assembly into nanoparticles with diameters ranging from 22 to 31 nm. There was

developed a method for preparation of polyglycidol-b-polylactide loaded with ovalbumin

(OVA). This method consists on dialysis of copolymer and ovalbumin solution in DMSO

carried on against water. Diameter of nanoparticles with OVA was equal 31 nm. The high

loading with OVA (from 77-200 mg protein per gram of nanoparticles, depending on the

PGL/PLA ratio in the copolymer chain) has been achieved.

100


Structure Evolution in Amorphous Poly(L/DL-lactide)

upon Plain Strain Compression

Miroslaw Pluta and Andrzej Galeski



Plastic deformation of amorphous, thermally non-crystallizable poly(L/DL-lactide) 70/30 (P(L/DL)LA) was induced by a plain strain compression in a channel-die at different temperatures, above Tg from 60

oC to 90oC. Samples undeformed (reference) and deformed to different compression ratios (CR), from 4.6 to 23.0, were studied by an X-ray diffraction, thermally modulated differential scanning calorimetry, light microscopy and mechanical methods – viscoelastic and tensile tests. The effects of the compression ratios and deformation temperatures on the final structure and properties of the P(L/DL)LA were evaluated. It was revealed that plastic deformation transformed of an amorphous P(L/DL)LA (thermally non-crystallizable), to a crystalline fibrillar texture oriented in the flow direction. Fibrillar texture was formed in spite of the tendency of the plane strain compression to form single crystal-like texture. The crystallite size in the transverse direction was small, up to 90 Å at the highest CR. No evidence of lamellar organization and features of supermolecular structure were detected by SAXS and light microscopy, respectively. The oriented samples exhibited low crystallinity degree at the level of 6-9% at the highest CR. The main transformation mechanism was shear and orientation induced crystallization. The crystalline phase was in the α crystallographic modification of poly(lactide) typically formed in more stereoregular poly(lactide) by thermal treatment. The glass transition increased with the increase of CR reflecting the increase of orientation of the polymer chains. Tensile strength of deformed samples were improved considerably in comparison to the reference sample.

101


Structure and Physical Properties of PLA/Calcium Sulfate Composites

Miroslaw Pluta

1, Marius Murariu

2, Amália Da Silva Ferreira

3,

Michaël Alexandre2, Andrzej Galeski

1, and Philippe Dubois

3

1Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences,

Sienkiewicza 112, 90-363 Lodz, Poland 2Materia Nova asbl, Parc Initialis, Av. Nicolas Copernic 1, B-7000 Mons, Belgium

3Centre of Innovation and Research in Materials & Polymers (CIRMAP), Laboratory of Polymeric

and Composite Materials (LPCM), University of Mons-Hainaut, Académie Universitaire Wallonie-

Bruxelles, Place du Parc 20, B-7000 Mons, Belgium

Starting from calcium sulfate (gypsum) as fermentation by-product of lactic acid production

process, high performance composites have been produced by melt-blending polylactide

(PLA, L/D isomer ratio of 96 : 4) and beta - anhydrite II (AII) filler i.e., calcium sulfate

hemihydrate previously dehydrated at 500 °C. Characterized by attractive mechanical and

thermal properties due to good filler dispersion throughout the polyester matrix, these

composites are interesting for potential use as biodegradable rigid packaging. Physical

characterization of selected composites filled with 20 and 40 wt% AII has been performed

and compared to processed unfilled PLA with similar amorphous structure. State of dispersion

of the filler particles and interphase characteristic features have been investigated using light

microscopy (LM) and scanning electron microscopy (SEM). Addition of AII did not decrease

PLA thermal stability as revealed by thermogravimetry analyses (TGA) and allowed reaching

a slight increase of PLA crystallizability during melt-crystallization and upon heating from

the glassy, amorphous state (DSC). It was found by thermo-mechanical measurements

(DMTA) that the AII filler increased pronouncedly storage modulus (E’) of the composites in

comparison with PLA in a broad temperature range: e.g. addition of 40 wt% AII increased E’

more than 90% at 25 °C, and surprisingly, more than 200% at 80 °C. The X-ray investigations

showed stable/unchanged crystallographic structure of AII during processing with molten

PLA and in the composite system. The notable thermal and mechanical properties of PLA–

AII composites are accounted for by the good filler dispersion throughout the polyester matrix

confirmed by morphological studies, system stability and favourable interactions between

components.

102


Materials of Functional Properties Based on Biodegradable Polymers

M. Kozlowski, A. Iwanczuk, A. Kozlowska, and S. Frackowiak

Wroclaw University of Technology, Wybrzeze Wyspianskiego 27, 50-370 Wroclaw, Poland

Modern plastic materials constitute frequently polymer blends and composites obtained

by mixing polymers with fillers, adhesion promoters, processing aids etc. Incorporation of

such additives brings about a novel properties to a matrix polymer, thus broadening a field of

possible applications. Recent shortages in the petrochemical products delivery and high oil

prices caused a revival of renewable resources, which is higly advantageous for a sustainable

development. Polymers and fillers deriving from agriculture recently have focused substantial

interest of the research teams and industry. Thermoplastic composites with natural fibers

(biocomposites) have been increasingly used in automotive industry, insulating materials and

in constructions. Further modification may be obtained by addition of functional fillers.

Properties of biodegradable polymers filled with natural fibers and flame retardants have been

presented in this paper.

Polylactic acid (PLA) and poly(hydroxybutyrate) (PHB) were used as matrix polymers,

whereas flax (F) and hemp fibers (H) were used for reinforcement. Different flame retardants

(FR) were used for modification of the fire resistance of biocomposites. Flammability was

evaluated by UL 94 horizontal and vertical Bunsen burner tests according to IEC 6007 and

IEC 60695. Mechanical properties of biocomposites were tested by means of the tensile and

bending methods. Selected results have been presented in Table 1 and Table 2.

Table 1. Horizontal burn method

Material Burning time

(0-25 mm), min

Behaviour Class

PLA

PLA/F30/20FR

PLA/H30/20FR

PLA/H30/20FR/10M

PLA/H30/20FR/20M

PLA/H30/20FR/30M

0:16

1:45

0:02

1:00

2:20

1:20

burning, flaming drips, cotton ignition

burning stops, no flaming drips





HB

HB

HB

HB

HB

Table 2. Vertical burn method

Material Burning time

(50 mm), sec

Behaviour Class

PLA

PLA/F30/20FR

PLA/H30/20FR

PLA/H30/20FR/10M

PLA/H30/20FR/20M

PLA/H30/20FR/30M

5

0

0

20

15

40

buring intensively, flaming drips, cotton ignition

no flaming drips

no flaming drips

no flaming drips

no flaming drips

no flaming drips

-

V-0

V-0

V-1

V-1

V-1

Acknowledgements

This research was financially supported by FP6-IP-SME Project 515769-2 BIOCOMP.

Keywords: biodegradable polymers; fire resistance; mechanical properties

103


Influence of Gamma-radiation on PCL/PHB Blends

D. Babic1, Z. Kacarevic-Popovic

1, G. Mikova

2, and I. Chodak

2

1Institute of Nuclear Sciences Vinca, Laboratory Gamma, Belgrade, Serbia 2Polymer Institute of the Slovak Academy of Sciences, Bratislava, Slovakia

The influence of high energy radiation to polymer blend made of polycaprolactone (PCL) and

polyhydroxybutyrate (PHB) was studied.

The PCL/PHB blend was prepared in 50:50 component ratio with different amounts of

triallylcyanurate (TAC) up to 5%.

The samples have been irradiated with the radiation doses of 25 and 50 kGy with the Co-60

gamma rays.

Mechanical properties were studied by stress-strain measurements. Heat properties and

supermolecular structure were followed by thermal characterization with DSC method.

Molecular structure was characterized by FTIR. Changes in structural and mechanical

properties are correlated with the influence of TAC content and absorbed radiation dose. The

effects to end-use properties of this material were discussed. As this material is of interest for

use in biodegradable application the changes of biodegradability of the radiation treated

blends has been followed as well.

104


Synthesis and Properties Evaluation of a New Class

of Degradable Polymers: Poly(vinyl-co-ester)s

Seema Agarwal and Liqun Ren

Philipps Universitaet Marburg,

Hans-Meerwein Strasse, 35032 Marburg, Germany

Generally, a high molecular weight polymer based on the C-C backbone like vinyl polymers

tends to be resistant to hydrolysis, oxidative cleavage, resistant to the enzymatic attack etc.

and are therefore not (bio)degradable, whereas heteroatom-containing polymer backbones

confer (bio)degradability. In this work efforts have been made to bring degradable ester

linkages onto the poly vinyl polymer backbones like poly (methyl methacrylate)(PMMA)

and poly(N-isopropyl acrylamide)(PNIPAAM) for the generation of new class of degradable

materials poly(vinyl-co-ester)s. A combination of radical ring-opening polymerisation of

cyclic ketene acetals and conventional free-radical polymerisation of vinyl monomers have

been utilised for bringing ester linkages onto the C-C backbones. An in sight into the

microstructure of the resulting materials is achieved using different 1D and 2D NMR

techniques. The introduction of ester linkages generated different new materials with a range

of properties like varied lower critical solution temperatures (LCSTs), improved thermal

stability, elasticity etc. besides making them degradable thereby increasing their utility areas

for various biomedical applications. Synthesis, characterization and properties of some new

materials like (poly(MMA-co-ester)s and poly(NIPAAM-co-ester)s will be presented.

105


Dynamic-Mechanical and Thermal Properties of Biodegradable Composites

from Polylactic Acid (PLA) Reinforced with Wood Fibres

A. Gregorova and R. Wimmer

Green Composites Group, Universität für Bodenkultur Wien,

Peter Jordanstrasse 82, 1190 Vienna, Austria

Biodegradable polymers have received an increased interest for utilization due to

increasing environmentally aware consumers, increased price of crude oil and global

warming. Nowadays, biodegradable polymers are used with a number of applications, such as

therapeutic aids, medicines, coatings, food products and packaging materials. Poly(lactic acid)

(PLA) is a biodegradable hydrolysable aliphatic polyester of lactic acid, which can be

obtained from renewable resources. PLA is becoming increasingly popular as a biodegradable

engineering plastic due to its high mechanical strength, and easy to process compared to other

biopolymers. However, the addition of plasticizers is necessary because of rigidity and

brittleness f PLA.

The goal of this work was to compare the dynamic-mechanical and thermal properties

of 5% softwood and hardwood filled PLA films prepared by solution casting method in

chloroform. Softwood and hardwood fibres with particles from 100-500 µm were modified by

various methods such as hydrolysis, esterification, oligoesterification, NaOH impregnation,

and silane impregnation.

Dynamic-mechanical-analysis (DMA) and differential-scanning-calorimetry (DSC)

showed that different types of wood fibres modification have a tremendous effect on the

results in terms of changes in storage and loss moduli, as well as crystallinity.

Keywords: biodegradable polymers; wood fibres, dynamic-mechanical properties, differential scanning

calorimetry

106


New Derivatives of Methyl Oleate

Tarik Eren and Banu Taslica

Department of Chemistry, Bogazici University, Bebek, Istanbul, 34342, Turkey

Abstract: The purpose of this work is to synthesize new free radically polymerizable

monomers based on methyl oleate. The chemistry consists of reaction of the unsaturated fatty

ester with N-bromosuccinimide (NBS) in the presence of excess amount of a nucleophile. The

nucleophiles used were acrylic acid (1), methacrylic acid (2), methacrylamide (3) and maleic

acid-mono(dibutylamine) salt (4). Monomers are the addition products of bromine and the

nucleophile to the oleate double bond. These new monomers were characterized by

spectroscopic techniques. New phosphonate derivative of methyl oleate was also synthesized.

Bromoacrylated methyl oleate was reacted with trimethyl phosphite (TMP) by Arbuzov

reaction to produce the phosphonate (5) derivative. 1,4- addition of TMP to the acrylate

double bonds of bromoacrylated methyl oleate was observed as main product instead of the

expected Michaelis-Arbuzov product.

COOCH3

OH

O

O

OH

O

NH2

HO

O

O

O

H3N C4H9 2

NBS, RT, 1 day

NBS, RT, 1 day

NBS, RT, 6 h, Acetone

1. NBS, RT,

1 day, CH2Cl2

2. H

[1]

[2]

[3]

[4]

COOCH3

Br

X

O

CO

HC CH2

O

CO

C CH2

CH3

NH

CO

C CH2

CH3

O

CO

HC CHC OH

O

[1] [2] [3] [4]

X

Fig. Synthesis of new derivatives of 10-bromo, 9-acrylate methyl stearate (1); 10-bromo, 9-

methacryloxy methyl stearate (2); 10-bromo, 9-methacrylamido methyl stearate (3); mono-9-

(10-bromo methyl stearate)yl ester (4) (corresponding regioisomers are not shown).

107

AUTHOR INDEX

Aa van der L. J. 25 (I-10)Adamus G. 35 (P-02), 54 (P-21), 56 (P-23),

88 (P-55)Agarwal S. 30 (I-15), 105 (P-72)Albertsson A.-C. 15 (I-02)Alexandre M. 17 (I-04), 102 (P-69)Anghel N. 61 (P-28)Anghelescu-Dogaru A. G. 96 (P-63)Atlic A. 28 (I-13), 78 (P-45), 80 (P-47)Avella M. 66 (P-33)Babic D. 104 (P-71)Badia J. D. 82 (P-49), 83 (P-50), 84 (P-51)Bawa S. S. 42 (P-09)Bertoldo M. 21 (I-07), 52 (P-19)Błasinska A. 67 (P-34)Bobalova J. 51 (P-18)Bogoeva-Gaceva G. 66 (P-33)Bonnaud L. 17 (I-04)Borsali R. 22 (I-08)Bourdiot U. 30 (I-15)Braunegg G. 28 (I-13), 78 (P-45), 80 (P-47)Bronco S. 21 (I-07), 52 (P-19), 53 (P-20)Brulc B. 92 (P-59)Buzarovska A. 66 (P-33)Cardamone J. M. 72 (P-39)Casella S. 90 (P-57)Chardhuri J. B. 38 (P-05)Chen Y. 30 (I-15)Chiellini E. 27 (I-12)Chitanu G. C. 96 (P-63), 97 (P-64), 98 (P-65),

99 (P-66)Chodak I. 104 (P-71)Ciardelli F. 21 (I-07), 52 (P-19), 53 (P-20)Ciechanska D. 89 (P-56), 95 (P-62)Ciolacu D. 55 (P-22)Ciolacu F. 55 (P-22)Cognigni F. 52 (P-19)Coltelli M.-B. 21 (I-07), 53 (P-20)Cosutchi A. I. 60 (P-27)Cuart M. 64 (P-31)Czarny A. 74 (P-41)Da Silva Ferreira A. 17 (I-04), 102 (P-69)Dacko P. 48 (P-15), 50 (P-17), 91 (P-58)Davidson M. G. 38 (P-05)Dersch R. 30 (I-15)Dijkstra P. J. 25 (I-10)Dobrzynski P. 65 (P-32), 71 (P-38), 70 (P-37)Drobnik J. 67 (P-34)Dubois P. 17 (I-04), 102 (P-69)Duda A. 16 (I-03), 62 (P-29), 95 (P-62)

Dumistracel I. 96 (P-63)Dumitriu R. P. 57 (P-24)Duncianu C. 45 (P-12)Dzwonkowski J. 50 (P-17)El Fray M. 34 (P-01)Ellis M. J. 38 (P-05)Erberich M. 26 (I-11)Eren T. 107 (P-74)Errico M. E. 66 (P-33)Faÿ F. 47 (P-14)Feijen J. 25 (I-10)Fiedorowicz M. 32 (I-17), 94 (P-61)Filip D. 49 (P-16), 60 (P-27)Florczak M. 62 (P-29)Focarete M. L. 69 (P-36), 71 (P-38)Frackowiak S. 103 (P-70)Gadzinowski M. 100 (P-67)Galeski A. 18 (I-05), 101 (P-68), 102 (P-69)Gamian A. 76 (P-43)Garnaik B. 46 (P-13)Gensheimer M. 30 (I-15)Gentile G. 66 (P-33)Gebarowska K. 70 (P-37)Gnanou Y. 22 (I-08)Gołebiewski J. 50 (P-17)Gregorova A. 106 (P-73)Greiner A. 30 (I-15)Gricar M. 92 (P-59)Gross R. A. 20 (I-06)Grozdanov A. 66 (P-33)Grzesiak E. 89 (P-56)Gualandi C. 71 (P-38)Hans M. 26 (I-11)Harabagiu V. 54 (P-21)Haznar D. 75 (P-42), 76 (P-43)Hermann-Krauss C. 78 (P-45), 80 (P-47)Hesse P. 78 (P-45), 80 (P-47)Hicks K. B. 73 (P-40)Hiemstra C. 25 (I-10)Houga C. 22 (I-08)Höcker H. 37 (P-04)Hu Y. 65 (P-32)Huang C.-Y. 63 (P-30), 81 (P-48), 85 (P-52),

86 (P-53)Hulubei C. 60 (P-27)Ichim M. 61 (P-28)Imaz N. 59 (P-26)Ioan S. 60 (P-27)Iversen T. 39 (P-06)Iwanczuk A. 103 (P-70)

108

Janeczek H. 50 (P-17), 56 (P-23), 91 (P-58)Janèiauskaite U. 79 (P-46)Jaworska J. 65 (P-32)Jin R. 25 (I-10)Jones M. D. 38 (P-05)Kacarevic-Popovic Z. 104 (P-71)Karas J. 74 (P-41)Kasperczyk J. 65 (P-32), 70 (P-37)Kavaliauskaite R. 41 (P-08)Kawalec M. 56 (P-23), 58 (P-25), 71 (P-38)Kazimierczak J. 89 (P-56)Keul H. 26 (I-11)Klee D. 37 (P-04)Klimaviciute R. 41 (P-08)Koller M. 28 (I-13), 78 (P-45), 80 (P-47)Konieczna-Molenda A. 94 (P-61)Kowalczuk M. M. 29 (I-14), 35 (P-02), 48 (P-15),

50 (P-17), 54 (P-21), 56 (P-23), 58 (P-25),68 (P-35), 88 (P-55), 91 (P-58), 93 (P-60)

Kowalczyk M. 87 (P-54)Kowalski W. J. 68 (P-35)Kozlowska A. 103 (P-70)Kozlowski M. 103 (P-70)Krasowska K. 93 (P-60)Kržan A. 92 (P-59)Kulbokaitë R. 77 (P-44)Kurcok P. 56 (P-23), 58 (P-25)Kutschera C. 28 (I-13), 78 (P-45), 80 (P-47)Langlois V. 64 (P-31)Lao H.-K. 64 (P-31)Lemeins J.-F. 22 (I-08)Lemstra P. J. 24 (I-09)Li S. 65 (P-32)Libiszowski J. 95 (P-62)Lindström M. 39 (P-06)Linossier I. 47 (P-14), 64 (P-31)Liu C.-I. 63 (P-30), 81 (P-48)López-Arraiza A. 59 (P-26)Lu W.-L. 81 (P-48)Macocinschi D. 49 (P-16)Makuška R. 77 (P-44), 79 (P-46)Malhotra B. D. 42 (P-09)Marcinkowska A. 76 (P-43)Meaurio E. 59 (P-26)Meyer J. 26 (I-11)Michalak M. 58 (P-25)Mikkonen K. S. 73 (P-40)Mikova G. 104 (P-71)Miksa B. 100 (P-67)Mishra A. P. 40 (P-07)Moczek Ł. 31 (I-16)Moeller M. 26 (I-11)

Molenda M. 94 (P-61)Molenda-Konieczny A. 32 (I-17)Moriana R. 82 (P-49), 83 (P-50), 84 (P-51)Murariu M. 17 (I-04), 102 (P-69)Musioł M. 48 (P-15), 68 (P-35)Narayan R. 14 (I-01)Nilsson H. 39 (P-06)Nowakowska M. 31 (I-16)Olsson A. 39 (P-06)Pandey A. 46 (P-13)Pelin I. M. 98 (P-65)Pennanec X. 64 (P-31)Peptu C. 54 (P-21), 58 (P-25)Piegat A. 34 (P-01)Pielka S. 74 (P-41), 75 (P-42), 76 (P-43)Piorkowska E. 18 (I-05), 87 (P-54)Pluta J. 75 (P-42), 76 (P-43)Pluta M. 17 (I-04), 18 (I-05), 101 (P-68),

102 (P-69)Poljanšek I. 92 (P-59)Popa M. I. 99 (P-66)Popescu I. 96 (P-63), 99 (P-66)Povolo S. 90 (P-57)Ren L. 105 (P-72)Renard E. 64 (P-31)Ribes-Greus A. 82 (P-49), 83 (P-50), 84 (P-51)Rondán C. E. 53 (P-20)Rutkowska M. 93 (P-60)Rychter P. 35 (P-02)Rydz J. 48 (P-15)Saha N. 51 (P-18)Saha P. 51 (P-18)Santonja-Blasco L. 82 (P-49), 83 (P-50),

84 (P-51)Sarasua J.-R. 59 (P-26)Scandola M. 56 (P-23), 69 (P-36), 70 (P-37),

71 (P-38)Sedlarik V. 51 (P-18)Signori F. 21 (I-07), 52 (P-19), 53 (P-20)Sikorska W. 48 (P-15), 68 (P-35)Simionescu B. C. 54 (P-21)Singh S. P. 42 (P-09)Slomkowski S. 36 (P-03), 100 (P-67)Sobota M. 48 (P-15), 50 (P-17), 91 (P-58)Socka M. 62 (P-29)Solski L. 75 (P-42)Sosnowski S. 36 (P-03)Spiridon I. 61 (P-28)Spychaj S. 43 (P-10)Spychaj T. 43 (P-10), 44 (P-11)Srebrenkoska V. 66 (P-33)Suflet D. M. 97 (P-64)Szadkowski M. 95 (P-62)

109

Szczubiałka K. 31 (I-16)Szymonowicz M. 74 (P-41), 75 (P-42), 76 (P-43)Šišková A. 68 (P-35)Taslica B. 107 (P-74)Taton D. 22 (I-08)Tenkanen M. 73 (P-40)Tiwari A. 40 (P-07), 42 (P-09)Tomasik P. 32 (I-17), 94 (P-61)Tomaszewski W. 95 (P-62)Toncelli C. 53 (P-20)Trandafir V. 97 (P-64), 98 (P-65)Vallee-Rehel K. 64 (P-31)Vallée-Réhel K. 47 (P-14)Vasile C. 45 (P-12), 57 (P-24)Vidovic E. 37 (P-04)Vlad S. 49 (P-16)Vuluga Z. 98 (P-65)Wawro D. 89 (P-56)Wei J. 65 (P-32)Wendorff J. H. 30 (I-15)Wietecha J. 89 (P-56)

Wilczek P. 71 (P-38)Willför S. 73 (P-40)Wilpiszewska K. 43 (P-10), 44 (P-11)Wimmer R. 106 (P-73)Wozniak P. 36 (P-03)Wu J.-Y. 85 (P-52), 86 (P-53)Wu X. 38 (P-05)Yadav M. P. 73 (P-40)Yang S.-Y. 85 (P-52), 86 (P-53)Zaczynska E. 74 (P-41)Zampano G. 21 (I-07)Zapotoczny S. 31 (I-16)Zemaitatitis A. 41 (P-08)Zhong Z. 25 (I-10)Zhou W. 25 (I-10)Zini E. 69 (P-36), 70 (P-37)Zuza E. 59 (P-26)Zywicka B. 74 (P-41), 75 (P-42), 76 (P-43)Žagar E. 92 (P-59)Žigon M. 92 (P-59)

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LIST OF PARTICIPANTS

Adamus Grazyna, Dr.Polish Academy of Sciences, Centre of Polymer and CarbonMaterials34 M. Curie-Sklodowska St; 41-800 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077; Fax: +48-32-2712969Agarwal Seema, Dr.Philipps universitaet Marburg; Department of ChemistryHans-Meerwein Strasse; 35032 Marburg; GERMANYE-mail: [email protected]: +49-6421-2825755; Fax: +49-6421-2825785Albertsson Ann-Christine, Prof.KTH, Royal Institute of Technology; Department of PolymerTechnologyS-100 44 Stockholm; SWEDENE-mail: [email protected]: +46-8-7908274; Fax: +46-8-7908274Babic Dragan, Dr.Institute of Nuclear Sciences Vinca; Laboratory of RadiationChemistry and PhysicsMike Petrovica Alasa 12-14; 11001 Belgrade; SERBIAE-mail: [email protected]: +381-11-2453986; Fax: +381-11-3440100Blasinska Anna, Dr.Technical University of Lodz; Department of Fiber Physics andTextile MetrologyZeromskiego 116; 90-924 Lodz; POLANDE-mail: [email protected] Gerhard, Prof.Technische Universität Graz; Institut für BiotechnologiePetersgasse 12; 8010 Graz; AUSTRIAE-mail: [email protected]: +43-316-8738412; Fax: +43-316-8738412Brulc Blaž, Mr.National Institute of Chemistry; Laboratory of PolymerChemistry and TechnologyHajdrihova 19; 1000 Ljubljana; SLOVENIAE-mail: [email protected]: +386-1-4760207Cardamone Jeanette M, Dr.U.S. Department of Agriculture; Fats, Oils and AnimalCoproducts Research Unit600 E. Mermaid Lane; 19038 Wyndmoor; UNITED STATESE-mail: [email protected]: +215-2336680; Fax: +215-2336795Chen Su-Chen, Ms.Taiwan Textile Research Institute; Department of Raw Materialsand Yarn FormationNo.6, Chengtian Rd., Tucheng; 23674 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected]: +886-22670321 ext.223Chiellini Emo, Prof.Universita di Pisa; Dip. Chimica e Chimica IndustrialeVia Risorgimento 35; 56126 Pisa; ITALYE-mail: [email protected]: +39-50-2219299; Fax: +39-50-2219299Chitanu Gabrielle Charlotte, Dr.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299

Chodak Ivan, Prof.Polymer Institute, Slovak Academy of Sciences; ComositeThermoplasticsDubravska 9; 84236 Bratislava; SLOVAKIAE-mail: [email protected]: +421-2-54771603

Ciardelli Francesco, Prof.University of Pisa; Department of Chemistry and IndustrialChemistryvia Risorgimento, 35; 56126 Pisa; ITALYE-mail: [email protected]: +39-050-2219229; Fax: +39-050-2219229

Ciechanska Danuta, Dr.Institute of Biopolymers and Chemical Fibres with theIncorporated Pulp and Paper Research InstituteSklodowskiej-Curie 19/27; 90-570 Lodz; POLANDE-mail: [email protected]: +48-42-6376510; Fax: +48-42-6376501

Ciolacu Diana Elena, Dr.Petru Poni Institute of Macromolecular Chemistry; Chemistry -Physics of PolymersGrigore-ghica Voda Alley, 41A; 700487 Iasi; ROMANIAE-mail: [email protected]

Dacko Piotr, Dr.Centre of Polymer and Carbon MaterialsM. Curie-Skłodowskiej 34; 41-819 Zabrze; POLANDE-mail: [email protected]

Davidson Matthew G, Prof.University of Bath; Department of ChemistryClaverton Down; BA27AY Bath; UNITED KINGDOME-mail: [email protected]: +44-1225-386443

Dubois Philippe, Prof.Université de Mons-HainautPlace du Parc, 20; B-7000 Mons; BELGIUME-mail: [email protected]: +32-65-373480; Fax: +32-65-373480

Duda Andrzej, Prof.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Department of Polymer ChemistrySienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6819815; Fax: +48-42-6847126

Dumitriu Raluca Petronela, Ms.Romanian Academy, "Petru Poni" Institute of MacromolecularChemistry; Physical Chemistry of PolymersGr. Ghica Voda Alley, 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299

Duncianu Catalina Natalia, Ms.Institute of Macromolecular Chemistry Petru Poni; Departmentof Physical Chemistry of PolymersGr. Ghica Voda Alley 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299

Dworak Andrzej, Prof.Polish Academy of Sciences; Institute of Coal ChemistrySowinskiego 5; 44-121 Gliwice; POLANDE-mail: [email protected]: +48-32-2380780; Fax: +48-32-2380780

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El Fray Miroslawa, Prof.Szczecin University of Technology; Polymer InstitutePulskiego 10; 70-322 Szczecin; POLANDE-mail: [email protected]: +48-91-4494828; Fax: +48-91-4494098

Fay Fabienne, Dr.Université Bretagne Sud; Laboratoire de Biotechnologie etchimie MarineCentre de Recherche BP92116; 56321 Lorient; FRANCEE-mail: [email protected]

Feijen Jan, Prof.University of Twente; Institute for BioMedical TechnologyP.O. Box 217;; 7500 AE Enschede; NETHERLANDSE-mail: [email protected]: +31-53-4893367; Fax: +31-53-4893367

Filip Daniela, Dr.Institute of Macromolecular Chemistry; Physical Chemistry ofPolymersAleea Gr. Ghica Voda 41 A; 700487 Iasi; ROMANIAE-mail: [email protected]

Florjanczyk Zbigniew, Prof.Warsaw University of Technology; Department of PolymerChemistry and Technology, Faculty of ChemistryNoakowskiego 3; 00-664 Warsaw; POLANDE-mail: [email protected]: +48-22-2347303; Fax: +48-22-2347303

Forstner Reinhard, Dr.Upper Austrian Research G.m.b.HFranz-Fritsch-Strasse 11; 4600 Wels; AUSTRIAE-mail: [email protected]: +43-7242-20881022; Fax: +43-7242-20881020

Gadzinowski Mariusz, Dr.Center of Molecular and Macromolecular Studies PolishAcademy of Sciences; Department of Engineering of PolymerMaterialsSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6803235

Galeski Andrzej, Prof.Centre of Molecular and Macromolecular Studies; olymerPhysics DepartmentSienkiewicza 112; 90363 Lodz; POLANDE-mail: [email protected]: +48-42-6803250; Fax: +48-42-6803261

Garnaik Baijayantimala, Dr.National Chemical Laboratory; Polymer Science andEngineering DivisionDr.Homi Bhabha Road; 411008 Pune; INDIAE-mail: [email protected]: +91-20-25902071 ext.2071; Fax: +91-20-25902615ext.2615

Gebarowska Katarzyna, Ms.Centre of Polymer and Carbon Materials Polish Academy ofSciencesSkłodowskiej-Curie 34; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-60983359

Gnanou Yves, Dr.Université Bordeaux I; Laboratoire de Chimie des PolymèresOrganiques (LCPO-CNRS)16, ave Pey-Berland; 33607 Pessac; FRANCEE-mail: [email protected], [email protected]: +33-5-40006987; Fax: +33-5-40006987

Gregorova Adriana, Dr.Universität für Bodenkultur Wien; Institut für HolzforschungPeter-Jordan-Straße 82; A-1190 Wien; AUSTRIAE-mail: [email protected]

Greiner Andreas, Prof.Universitat Marburg; Materials Science CenterHans-Meerwein-Strasse, Gebäude H; D-35032 Marburg;GERMANYE-mail: [email protected]: +49-6421-2825573; Fax: +49-6421-2825573

Gross Richard A., Prof.The Polytechnic University; Department of Chemical andBiological SciencesSix Metrotech Center; NY 11201 Brooklyn; UNITED STATESE-mail: [email protected]: +718-2603984; Fax: +718-2603984

Grozdanov Anita, Dr.Faculty of Technology and Metallurgy; Department of PolymerEngineeringRugjer Boskovic 16; 1000 Skopje; MACEDONIAE-mail: [email protected]: +389-2-3064588 ext.237; Fax: +389-2-3065389

Gulle Heinz, Dr.Baxer Aktiengesellschaft; R&D Biosurgery Fibrin PlatformIndustriestrasse 67; 1220 Vienna; AUSTRIAE-mail: [email protected]: +43-1-20100259Haan Robert, Mr.Purac Biochem bv; Process TechnologyArkelsedijk 46; 4206AC Gorinchem; NETHERLANDSE-mail: [email protected]: +31-183-695695; Fax: +31-183-695607

Ichim Maria, Dr.Institutul De Inginerie, Biotehnologie Si Protectia MediuluiProf. Ion Bogdan nr.10; 010539 Bucuresti; ROMANIAE-mail: [email protected]: +40-21-2113754; Fax: +40-21-2102659

Iversen Tommy, Dr.STFI-PackforskDrottning Kristinas väg 61; SE-11486 Stockholm; SWEDENE-mail: [email protected]: +46-8-6767000 ext.210; Fax: +46-8-4115518

Janciauskaite Ugne, Ms.Vilnius University; Polymer ChemistryNaugarduko 24; LT-03225 Vilnius; LITHUANIAE-mail: [email protected]: +370-5-2337811; Fax: +370-5-2330987

Jaworska Joanna, Ms.Polish Academy of Sciences; Centre of Polymer and CarbonMaterialsSklodowskiej-Curie 34; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2712214 ext.164Kawalec Michal, M.Sc.Centre of Polymer and Carbon Materials Polish Academy ofSciences34, Marii Skłodowskiej-Curie St.; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077 ext.121Klimaviciute Rima, Dr.Kaunas University of Technology; Organic TechnologyRadvilenu 19; LT-50524 Kaunas; LITHUANIAE-mail: [email protected]: +370-37-456081; Fax: +370-37-456081

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Koller Martin, Dr.Graz University of Technology; Institute of Biotechnology andBiochemical EngineeringPetersgasse 12; 8010 Graz; AUSTRIAE-mail: [email protected]: +43-316-8738905

Konieczna-Molenda Anna, Dr.University of Agriculture; Department of ChemistryBalicka 122; 30-149 Cracow; POLANDE-mail: [email protected]

Kowalczuk Marek M., Prof.Centre of Polymer and Carbon Materials, Polish Academy ofSciencesM. Curie-Sklodowskiej 34; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077; Fax: +48-32-2716077

Kowalczyk Marcin, M.Sc.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Polymer PhysicsSienkiewicza 112; 90363 Lodz; POLANDE-mail: [email protected]: +48-42-6803237

Kowalski Witold J., Prof.Jan Długosz University, Faculty of Mathematics and NaturalSciences; Institute of Chemistry and Enivironmental ProtectionArmii Krajowej 13/15; PL-42-200 Czestochowa; POLANDE-mail: [email protected]: +48-502-616458

Kozlowska Anna, Dr.Wroclaw University of TechnologyWybrzeze Wyspianskiego 27; 50-370 Wroclaw; POLANDE-mail: [email protected]: +48-71-3206216

Kozlowski Marek, Prof.Wroclaw University of Technology; Faculty of EnvironmentalEngineeringWybrzeze Wyspianskiego 27; 50-370 Wroclaw; POLANDE-mail: [email protected]: +48-71-3206538; Fax: +48-71-3282980

Krasowska Katarzyna, Dr.Gdynia Maritime University; Department of Chemistry andIndustrial Commodity ScienceMorska 81-87; 81-225 Gdynia; POLANDE-mail: [email protected]: +48-58-6901367; Fax: +48-58-6206701

Krucinska Izabella, Prof.Technical University of Lodz; Textile Engineering and MarketingZeromskiego 116; 90-924 Lodz; POLANDE-mail: [email protected], [email protected]: +48-42-6313300; Fax: +48-42-6313300

Krzan Andrej, Dr.National Institute of Chemistry; Laboratory for PolymerChemistry and Technology;Hajdrihova 19, POB 660; 1001 Ljubljana; SLOVENIAE-mail: [email protected]: +386-1-4760204; Fax: +386-1-4760204

Kurcok Piotr, Dr.Centre of Polymer and Carbon Materials, Polish AcademySciences34, Marii Sklodowskiej Curie St.; 41-819 Zabrze; POLANDE-mail: [email protected]: +48-32-2716077 ext.261; Fax: +48-32-2712969

Lao Hoi-Kuan, Dr.LBCM - Laboratoire de Biotechnologie et Chimie Marine;Universite de Bretagne SudRue Saint Maude; 56321 Lorient; FRANCEE-mail: [email protected]: +33-2-97874594Lee Chia, Ms.Tatung UniversityNo. 40, Cung-Shan N. RD., Sec. 3; 10453 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected] Piet J., Prof.Eindhoven University of Technology; Polymer TechnologyPO Box 513, Helix STO 0.37; 5600 MB Eindhoven;NETHERLANDSE-mail: [email protected]: +31-40-2473650; Fax: +31-40-2473650Liu Chia-I, Ms.Tatung University; Department of Materials Engineering40, Chung-Shan N. Rd.,3rd Sec.; 10453 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected] Wan-Ling, Dr.Taiwan Textile Research Institute; Raw Materials and YarnFormationNo.6 Chengtian Rd.; 23674 Tucheng; TAIWAN, PROVINCE OFCHINAE-mail: [email protected]: +886-2-22670321 ext.245Macocinschi Doina, Dr.Institute of Macromolecular Chemistry; Physical Chemistry ofPolymersAleea Gr. Ghica Voda 41 A; 700487 Iasi; ROMANIAE-mail: [email protected] Ricardas, Prof.Vilnius University; Polymer ChemistryNaugarduko 24; LT-03225 Vilnius; LITHUANIAE-mail: [email protected]: +370-5-2337811; Fax: +370-5-2330987Meyer Sibylle, Ms.Wiley-VCH VerlagBoschstrasse 12; 69469 Weinheim; GERMANYE-mail: [email protected] Kirsi, M.Sc.University of Helsinki; Department of Applied Chemistry andMicrobiologyLatokartanonkaari 11; 00014 Helsinki; FINLANDE-mail: [email protected]: +358-9-19158417; Fax: +358-9-19158475Mishra Astbhuja Prasad, Dr.Ministry of Science and Technology; Department of Scienceand TechnologyTechnology Bhawan, New Maharauli Road; 110016 New Delhi;INDIAE-mail: [email protected]: +91-11-26590325Moeller Martin, Prof.DWI an der RWTH Aachen e. V.Pauwelsstrasse 8; 52074 Aachen; GERMANYE-mail: [email protected]: +49-241-8023300; Fax: +49-241-8023301Nadolny Andrzej J., Dr.Scientific Centre of the Pol. Acad. Sci. in ViennaBoerhaavegasse 25; 1030 Wien; AUSTRIAE-mail: [email protected]: +43-1-7135929 ext.303

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Narayan Ramani, Prof.Michigan State University; Chemical Engineering Division2527 Engineering Building; MI 48824-122 East Lansing;UNITED STATESE-mail: [email protected]: +517-4320775; Fax: +517-4320775

Nilsson Helena, M.Sc.STFI-Packforsk; Packaging and LogisticsDrottning Kristinas väg 61; 11486 Stockholm; SWEDENE-mail: [email protected]: +46-8-6767253

Nowakowska Maria, Prof.Jagiellonian University; Department of Physical Chemistry andElectrochemistry, Faculty of ChemistryIngardena 3; 30-060 Krakow; POLANDE-mail: [email protected]: +48-12-6632050; Fax: +48-12-6632050

Pandey Asutosh Kumar, Mr.National Chemical Laboratory; Polymer ChemistryDr.Homi Bhabha Road; 411008 Pune; INDIAE-mail: [email protected]: +91-20-25902071 ext.2071

Pelin Irina Mihaela, Ms.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299

Penczek Stanislaw, Prof.Centre of Molecular and Macromolecular Studies, PolishAcademy of SciencesSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6819815; Fax: +48-42-6819815

Peptu Cristian, M.Sc.Institute of Chemistry and Environmental Protection JanDlugosz Czestochowa13/15 Armii Krajowej Av.; 42-200 Czestochowa; POLANDE-mail: [email protected]

Piorkowska Ewa Malgorzata, Prof.Centre of Molecular and Macromolecular Studies; PolymerPhysics DepartmentSienkiewicza 112; 90363 Lodz; POLANDE-mail: [email protected]: +48-42-6803223; Fax: +48-42-6803261

Pluta Miroslaw, Dr.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Department of Polymer PhysicsSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6803237; Fax: +48-42-6847126

Popescu Irina, Ms.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299

Povolo Silvana, Dr.Universita degli Studi di Padova; Biotechnologie AgrarieViale dell’Universita, 16; 35020 Legnaro; ITALYE-mail: [email protected]: +39-49-8272926; Fax: +39-49-8272929

Rapa Maria, Ms.Commercial Society Incerplast S.A.; Research DevelopmentZiduri Mosi 23; 021203 Bucuresti; ROMANIAE-mail: [email protected]: +40-21-2525250Raquez Jean-Marie, Dr.University of Mons-Hainaut/Materia Nova; Laboratory ofPolymeric Composites and MaterialsPlace du Parc 20; 7000 Mons; BELGIUME-mail: [email protected]: +32-65-373771Rokicki Gabriel, Prof.Warsaw University of Technology; Department of PolymerChemistry and Technology, Faculty of Chemistryul. Noakowskiego 3; 00-664 Warszawa; POLANDE-mail: [email protected]: +48-22-2347562; Fax: +48-22-2347562

Rutkowska Maria, Prof.Gdynia Maritime University; Department of ChemistryMorska 83; 81-225 Gdynia; POLANDE-mail: [email protected]: +48-58-6901585; Fax: +48-58-6206701

Rychter Piotr, M.Sc.Chemistry and Environmental Protection; Mathematics andEnvironmentArmii Krajowej Av., 13/15; 42-200 Czestochowa; POLANDE-mail: [email protected]: +48-34-3615154; Fax: +48-34-3665322

Sahli Stefan, Dr.Sika Technology AG; Corporate Research and AnalyticsTüffenwies 16; 8048 Zürich; SWITZERLANDE-mail: [email protected]: +41-44-4365827; Fax: +41-44-4365850

Santonja-Blasco Laura, Ms.Universidad Politecnica ValenciaCamino De Vera S/n; 46022 Valencia; SPAINE-mail: [email protected]: +34-96-3879817 ext.71806Sarasua Jose-Ramon, Prof.University of the Basque Country; Materials ScienceETS Ingenieria Bilbao, Alameda de Urquijo s/n; 48013 Bilbao;SPAINE-mail: [email protected]: +34-94601427; Fax: +34-94601418

Scandola Mariastella, Prof.University of Bologna; G. Ciamician Chemistry DepartmentVia Selmi 2; 40126 Bologna; ITALYE-mail: [email protected] Vladimir, Dr.Faculty of Technology, Tomas Bata University in Zlín; PolymerCentreT.G. Masaryka 275; 76272 Zlín; CZECH REPUBLICE-mail: [email protected]: +420-57603801; Fax: +420-57603144

Signori Francesca, Dr.University of Pisa; Dipartimento di Chimica e ChimicaIndustrialevia Risorgimento 35; I-56126 Pisa; ITALYE-mail: [email protected]: +390-50-2219212; Fax: +390-50-2219320

Sikorska Wanda, Dr.Centre of Polymer and Carbon MaterialsM.C.-Skłodowskiej 34; 41-819 Zabrze; POLANDE-mail: [email protected]

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Slomkowski Stanislaw, Prof.Centre of Molecular and Macromolecular Studies, PolishAcademy of SciencesSienkiewicza 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6826537; Fax: +48-42-6826537Sobota Michal, M.Sc.Centre of Polymer and Carbon Materials, Polish Academy ofSciences34, Marii Sklodowskiej Curie St. Poland; 41-819 Zabrze;POLANDE-mail: [email protected]: +48-32-2716077 ext.121Socka Marta, M.Sc.Centre of Molecular and Macromolecular Studies, PolishAcademy of Sciences; Department of Polymer ChemistrySienkiewicza, 112; 90-363 Lodz; POLANDE-mail: [email protected]: +48-42-6803219 ext.219Spiridon Iuliana, Dr.Petru Poni Institute of Macromolecular Chemistry; NaturalPolymersAleea Gr. Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299Spychaj Tadeusz, Prof.Szczecin University of Technology; Polymer InstitutePulaskiego 10; 70-322 Szczecin; POLANDE-mail: [email protected]: +48-91-4494684; Fax: +48-91-4494685Stanford John L., Prof.University of Manchester; School of MaterialsGrosvenor Street; m17hs Manchester; UNITED KINGDOME-mail: [email protected]: +44-161-2003573Stepto Robert F., Prof.University of Manchester and UMIST; Polymer Science andTechnology GroupGroswenor St.; M1 7HS Manchester; UNITED KINGDOME-mail: [email protected] Dana Mihaela, Dr.Petru Poni Institute of Macromolecular Chemistry Iasi; Bioactiveand Biocompatible Polymers DepartmentAleea Grigore Ghica Voda 41A; 700487 Iasi; ROMANIAE-mail: [email protected]: +40-232-217454; Fax: +40-232-211299Szymonowicz Maria, Dr.Wrocław Medical University; Department of ExperimentalSurgery and Biomaterials ResearchPoniatowskiego 2; 50-326 Wroclaw; POLANDE-mail: [email protected]: +48-71-7840135Šišková Alena, M.Sc.Jan Dlugosz University, Faculty of Mathematiscs and NaturalSciences; Institute of Chemistry and Environmental ProtectionArmii Krajowej 13/15; PL-42-200 Czestochowa; POLANDE-mail: [email protected] Banu, M.Sc.Bogazici University; Department of ChemistryBebek; 34342 Istanbul; TURKEYE-mail: [email protected]: +90-212-3587572; Fax: +90-212-2872467Tiwari Ashutosh, Dr.National Physical Laboratory; Division of Engineering MaterialsDr. K. S. Krishnan Road; 110012 New Delhi; INDIAE-mail: [email protected]: +91-11-32507819

Tomasik Piotr, Prof.Agricultural University in Krakow; Department of ChemistryBalicka 122; 30-149 Krakow; POLANDE-mail: [email protected]: +48-12-6624335; Fax: +48-12-6624335Vairon Jean-Pierre, Prof.Université Pierre et Marie Curie; UMR 7610 - Chimie DesPolymeresCase 185, 4 Place Jussieu; F-75252 Paris Cédex 05; FRANCEE-mail: [email protected]: +33-1-44275502; Fax: +33-1-44275502Vidovic Elvira, Dr.University of Zagreb; Faculty of Chemical EngineeringMarulicev trg, 19; 10000 Zagreb; CROATIAE-mail: [email protected]: +385-1-4597128; Fax: +385-1-4597142Weber Hedda, Dr.Competence Centre Wood; Wood and Pulp ChemistryWerkstrasse 2; 4860 Lenzing; AUSTRIAE-mail: [email protected]: +43-7672-7013181; Fax: +43-7672-9183181Woldum Henriette Sie, M.Sc.Chew Tech I/SDandyvej 19; DK-7100 Vejle; DENMARKE-mail: [email protected] Pawel, M.Sc.Centre of Molecular and Macromolecular Studies, PolishAcademy of Science; Department of Engineering of PolymerMaterialsSienkiewicza, 112; 90-363 Lodz; POLANDE-mail: [email protected] Xujun, Mr.University of Bath; Center for Regenerative Medicine,Department of Chemical Engineering& Department ofChemistryClaverton Down; BA27AY Bath; UNITED KINGDOME-mail: [email protected] Jing-Yi, Ms.Tatung University; Department of Materials EngineeringChung-Shan N. Rd., 3rd Sec.; 10452 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected]: +886-2-25925252; Fax: +886-2-25866050Yang Sung-Yeng, Mr.Tatung University40, Chung-Shan N. Rd., 3rd Sec.; 10453 Taipei; TAIWAN,PROVINCE OF CHINAE-mail: [email protected] Boris, Mr.Postnova Analytics GmbHMax-Planck-Str. 14; 86899 Landsberg am Lech; GERMANYE-mail: [email protected]: +49-8191-428181; Fax: +49-8191-428175

Zuchowska Danuta, Prof.Wroclaw University of Technology; Faculty of ChemistryWybrzeze S. Wyspianskiego 27; 50-370 Wroclaw; POLANDE-mail: [email protected]: +48-71-3203633; Fax: +48-71-3203633

Zywicka Bogusława, Dr.Wroclaw Medical University; Department of ExperimentalSurgery and Biomaterials ResearchPoniatowskiego 2; 53-326 Wrocław; POLANDE-mail: [email protected]: +48-71-7840136

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International Conference (Bio)Degradable Polymers from ... · International Conference (Bio)Degradable Polymers from Renewable Resources Vienna, November 18 – 21, 2007 ... degradable