Analytische Chemie Elektroanalytik & Sensorik
RUHR-UNIVERSITT BOCHUM 1 Perspective pentru un nou biocatod de
potenial ridicat noi proprieti ale enzimelor redox imobilizate pe
nanostructuri compozite de grafit - Wenzhi Jia, Yvonne Ackermann,
Wolfgang Schuhmann, Leonard Stoica Anal. Chem. - Elektroanalytik
& Sensorik (ELAN) Universittsstr. 150, Bochum 44780
Ruhr-University Bochum Germany Slide 2 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM Concept of
bienzymatic membrane-less biofuel cell (BFC) laccase cellobiose
dehydrogenase (CDH) Potential [mV] vs. Ag/AgCl 3M KCl -+
+150-41+450+530 E cell = 300 anode cathode e-e- e-e- e-e-
cellobiose dehydrogenase laccase lactose lactoso- lactone e-e- Os
loading H2OH2O O2O2 Stoica L. et al, Fuel Cells (2009), 9 (1),
53-62 Slide 3 Analytische Chemie Elektroanalytik & Sensorik
RUHR-UNIVERSITT BOCHUM 3 Motivation for new material electrode High
catalytic coverage: large amount of active enzyme; Large active
area of electrode: using hierarchical carboneous materials two-
generations CNTs Exploring specific properties of bio-nano
interactions. P out =E x I [E]; A; k cat, n E 0 Slide 4 Analytische
Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM I.
Large active area electrode 4 Slide 5 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 5 Graphite
electrode surface Slide 6 Analytische Chemie Elektroanalytik &
Sensorik RUHR-UNIVERSITT BOCHUM 6 Composite material: CNT/CMF onto
carbon paper Preparation: N. Li, X. Chen, L. Stoica, W. Xia, J.
Qian, J. Amann, W. Schuhmann, M. Muhler Adv. Mater. (2007), 19,
2957-2960 Slide 7 Analytische Chemie Elektroanalytik & Sensorik
RUHR-UNIVERSITT BOCHUM 7 EIS characterisation of CNT/CMF
Properties: Low ohmic resistance => no potential loss; Ratio
active/geometric area=200; Non-restrictive diffusion of enzyme
substrate. N. Li, X. Chen, L. Stoica, W. Xia, J. Qian, J. Amann, W.
Schuhmann, M. Muhler Adv. Mater. (2007), 19, 2957-2960 Slide 8
Analytische Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT
BOCHUM 8 Various supports Slide 9 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 9 Slide 10
Analytische Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT
BOCHUM II. Exploring specific bio-nano interactions 10 Slide 11
Analytische Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT
BOCHUM 11 250 results HRP-CNT Y. Yan et al., Langmuir 2005, 21,
6560-6566...only at low potentials!! Slide 12 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 12
Supervalent iron-oxo-porphyrin cation radical Document Title :
Hypervalent Iron-Oxo Porphyrin Cation Radical Formation on Reaction
of H 2 o 2 with The Cytochrome-c-Derived Heme Octapeptide
Microperoxidase-8 (Mp-8) in Aqueous-Solution Published in : JOURNAL
OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS year: 1990 issue: 2
pages: 97-98 Slide 13 Analytische Chemie Elektroanalytik &
Sensorik RUHR-UNIVERSITT BOCHUM 13 Thermodynamic potential for
reduction = +750 mV Slide 14 Analytische Chemie Elektroanalytik
& Sensorik RUHR-UNIVERSITT BOCHUM 14 Any specific
bioelectrochemistry of HRP @ these new materials? Slide 15
Analytische Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT
BOCHUM 15 Bioelectrochemistry of HRP-heme -53 mV / pH unit
PHA-pyrene-hexanoic acid Slide 16 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 16
Bioelectrocatalytic current for H 2 O 2 reduction at +600 mV Slide
17 Analytische Chemie Elektroanalytik & Sensorik
RUHR-UNIVERSITT BOCHUM 17 Optimum pH @ +400 mV vs. Ag/AgCl
Bioelectrocatalytic current for H 2 O 2 reduction at +600 mV
PHA-pyrene-hexanoic acid Slide 18 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 18
Hydrodynamic voltammogram H 2 0 2 oxidation H 2 0 2 reduction at
electrode at HRP High potential reduction of Cmp-I/II-HRP Slide 19
Analytische Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT
BOCHUM 19 Scheme of H 2 O 2 involvement H2O2H2O2 H2OH2O HRP ox HRP
red Biocathode @ +600 mV 1e - + 1e - W. Jia, S. Schwamborn, C. Jin,
W. Xia, M. Muhler, W. Schuhmann, L. Stoica PCCP 12 (2010) 10088.
Slide 20 Analytische Chemie Elektroanalytik & Sensorik
RUHR-UNIVERSITT BOCHUM 20 H 2 O 2 biosensor at +400 mV @ no O 2
involvement Amperometric responses of the HRP/PHA-CNTs/CF/GR
biosensor were recorded by additions of H 2 O 2 in N 2 -saturated
PBS (pH 7.0) at +400 mV I max = 220 A (~ 1.5 mM H 2 O 2 )K M = 320
M H 2 O 2 Slide 21 Analytische Chemie Elektroanalytik &
Sensorik RUHR-UNIVERSITT BOCHUM 21 HRP loading E appl =+300 mV
Slide 22 Analytische Chemie Elektroanalytik & Sensorik
RUHR-UNIVERSITT BOCHUM 22 Is glucose based cathode a promising
candidate? Biocathodes based on... E onset pH opt Cl - inhibition e
- / O 2 yield Laccase +6504YES4 e- Bilirubin oxidase +2006-7NO4 e-
Glucose/HRP +6007NO2 e- P out =E x I [E]; A; k cat, nE 0 Slide 23
Analytische Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT
BOCHUM 23 Conclusions 3D-hierachical carbon nanostructures: present
excellent characteristics for large active area and enhanced/novel
bioelectrocatalysis of known redox enzymes; Biocathode enzyme: Yes,
indeed, high potential biocathode functioning on glucose/oxygen is
feasible at in-vivo conditions (pH, Cl - ) Slide 24 Analytische
Chemie Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 24
Acknowledgements go to... EU-FP7 funds (project no.
FP7-NMP-2008-SMALL-2 ) to ELANOS Slide 25 Analytische Chemie
Elektroanalytik & Sensorik RUHR-UNIVERSITT BOCHUM 25 for your
attention! Thank you
