An aqueous media based approach for the preparation of a biosensor platform composed of graphene oxide and Pt-black.

The combination of Pt nanoparticles and graphene was more effective in enhancing biosensing than either nanomaterial alone according to previous reports. Based on the structural similarities between water soluble graphene oxide (GrO(x)) and graphene, we report the fabrication of an aqueous media based GrO(x)/Pt-black nanocomposite for biosensing enhancement. In this approach GrO(x) acted as a nanoscale molecular template for the electrodeposition of Pt-black, an amorphously nanopatterned isoform of platinum metal. Scanning electron microscopy (SEM) images and energy-dispersive X-ray spectroscopy (EDS) showed that Pt-black was growing along GrO(x). The effective surface area and electrocatalytic activity towards H(2)O(2) oxidation of GrO(x)/Pt-black microelectrodes were significantly higher than for Pt-black microelectrodes. When used to prepare a bio-nanocomposite based on protein functionalization with the enzyme glucose oxidase (GOx), the GrO(x)/Pt-black microbiosensors exhibited improved sensitivity over the Pt-black microbiosensors. This suggested that the GrO(x)/Pt-black nanocomposite facilitated an increase in electron transfer, and/or minimized mass transport limitations as compared to Pt-black used alone. Glucose microbiosensors based on GrO(x)/Pt-black exhibited high sensitivity (465.9 ± 48.0 nA/mM), a low detection limit of 1 μM, a linear response range of 1 μM-2mM, and response time of ≈ 4s. Additionally the sensor was stable and highly selective over potential interferents.

[1]  D Marshall Porterfield,et al.  Non-invasive quantification of endogenous root auxin transport using an integrated flux microsensor technique. , 2010, The Plant journal : for cell and molecular biology.

[2]  S. Iijima,et al.  Open and closed edges of graphene layers. , 2009, Physical review letters.

[3]  M. Meyerhoff,et al.  Bioanalytical applications of polyion-sensitive electrodes. , 1999, Journal of pharmaceutical and biomedical analysis.

[4]  Richard G Compton,et al.  Electrocatalysis at graphite and carbon nanotube modified electrodes: edge-plane sites and tube ends are the reactive sites. , 2005, Chemical communications.

[5]  K. Hirao,et al.  Platinum nano-cluster thin film formed on glassy carbon and the application for methanol oxidation , 2007 .

[6]  Inhwa Jung,et al.  Tunable electrical conductivity of individual graphene oxide sheets reduced at "low" temperatures. , 2008, Nano letters.

[7]  J. T. Maloy,et al.  Model for the amperometric enzyme electrode obtained through digital simulation and applied to the immobilized glucose oxidase system , 1975 .

[8]  Chen-Zhong Li,et al.  Probing the Electrochemical Properties of Graphene Nanosheets for Biosensing Applications , 2009 .

[9]  Jun Liu,et al.  Glucose oxidase-graphene-chitosan modified electrode for direct electrochemistry and glucose sensing. , 2009, Biosensors & bioelectronics.

[10]  Jun Liu,et al.  Glucose biosensor based on immobilization of glucose oxidase in platinum nanoparticles/graphene/chitosan nanocomposite film. , 2009, Talanta.

[11]  R. Young,et al.  The real graphene oxide revealed: stripping the oxidative debris from the graphene-like sheets. , 2011, Angewandte Chemie.

[12]  Richard Nuccitelli,et al.  AN ULTRASENSITIVE VIBRATING PROBE FOR MEASURING STEADY EXTRACELLULAR CURRENTS , 1974, The Journal of cell biology.

[13]  Yuyan Shao,et al.  Graphene Based Electrochemical Sensors and Biosensors: A Review , 2010 .

[14]  T. Sun,et al.  Carbon nanotube composites for glucose biosensor incorporated with reverse iontophoresis function for noninvasive glucose monitoring , 2010, International journal of nanomedicine.

[15]  D. M. Porterfield,et al.  Electrochemical biosensor of nanocube-augmented carbon nanotube networks. , 2009, ACS nano.

[16]  M. Pumera,et al.  A mechanism of adsorption of beta-nicotinamide adenine dinucleotide on graphene sheets: experiment and theory. , 2009, Chemistry.

[17]  Jacek Klinowski,et al.  A new structural model for graphite oxide , 1998 .

[18]  Suxia Zhang,et al.  Covalent attachment of glucose oxidase to an Au electrode modified with gold nanoparticles for use as glucose biosensor. , 2005, Bioelectrochemistry.

[19]  W. Heineman,et al.  Cyclic voltammetry experiment , 1983 .

[20]  Chia-Liang Sun,et al.  The simultaneous electrochemical detection of ascorbic acid, dopamine, and uric acid using graphene/size-selected Pt nanocomposites. , 2011, Biosensors & bioelectronics.

[21]  Guo-Li Shen,et al.  In situ synthesis of palladium nanoparticle-graphene nanohybrids and their application in nonenzymatic glucose biosensors. , 2011, Biosensors & bioelectronics.

[22]  D Marshall Porterfield,et al.  Oscillatory glucose flux in INS 1 pancreatic β cells: a self-referencing microbiosensor study. , 2011, Analytical biochemistry.

[23]  E. S. McLamore,et al.  A self-referencing glutamate biosensor for measuring real time neuronal glutamate flux , 2010, Journal of Neuroscience Methods.

[24]  E. McLamore,et al.  Non‐invasive self‐referencing electrochemical sensors for quantifying real‐time biofilm analyte flux , 2009, Biotechnology and bioengineering.

[25]  D. Luss,et al.  Local Particle-Liquid Mass Transfer Fluctuations in Mixed-Phase Cocurrent Downflow through a Fixed Bed in the Pulsing Regime , 1979 .

[26]  Zhuang Li,et al.  Graphene–Pt nanocomposite for nonenzymatic detection of hydrogen peroxide with enhanced sensitivity , 2011 .

[27]  Junwu Zhu,et al.  Bioinspired Effective Prevention of Restacking in Multilayered Graphene Films: Towards the Next Generation of High‐Performance Supercapacitors , 2011, Advanced materials.

[28]  Jacek Klinowski,et al.  Structure of Graphite Oxide Revisited , 1998 .

[29]  R. Ruoff,et al.  The chemistry of graphene oxide. , 2010, Chemical Society reviews.

[30]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[31]  Susumu Kuwabata,et al.  Preparation of selective micro glucose sensor without permselective membrane by electrochemical deposition of ruthenium and glucose oxidase , 2007 .

[32]  J. L. House,et al.  Immobilization Techniques to Avoid Enzyme Loss from Oxidase-Based Biosensors: A One-Year Study , 2007, Journal of diabetes science and technology.

[33]  E S McLamore,et al.  A self referencing platinum nanoparticle decorated enzyme-based microbiosensor for real time measurement of physiological glucose transport. , 2011, Biosensors & bioelectronics.

[34]  B. Ogorevc,et al.  Response Behavior of Amperometric Glucose Biosensors Based on Different Carbon Substrate Transducers Coated with Enzyme-Active Layer: A Comparative Study , 2009 .

[35]  Shen-ming Chen,et al.  Amperometric glucose sensor based on glucose oxidase immobilized on gelatin-multiwalled carbon nanotube modified glassy carbon electrode. , 2011, Bioelectrochemistry.

[36]  Y. Morita,et al.  A study on the glutaraldehyde activation of hydrophilic gels for immobilized enzymes. , 1988, Biotechnology and bioengineering.

[37]  Joseph Wang.  Carbon‐Nanotube Based Electrochemical Biosensors: A Review , 2005 .

[38]  D Marshall Porterfield,et al.  A comparative study of enzyme immobilization strategies for multi-walled carbon nanotube glucose biosensors , 2011, Nanotechnology.

[39]  S. Stankovich,et al.  Graphene-based composite materials , 2006, Nature.