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A glucose biosensor based on graphene-Prussian blue-chitosan composite film fabricated by electrodeposition

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https://doi.org/10.3969/j.issn.0253-2778.2019.04.002
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  • Author Bio:

    LIU Hao, male, born in 1988, master. Research field: electroanalytical chemistry. E-mail: hao0925@mail.ustc.edu.cn

  • Corresponding author: WU Shouguo
  • Received Date: 10 October 2018
  • Accepted Date: 18 December 2018
  • Rev Recd Date: 18 December 2018
  • Publish Date: 30 April 2019
    Abstract

  • Abstract

    The layer-by-layer structured composite film of graphene-Prussian blue (PB)-chitosan (CS) was fabricated on a glassy carbon electrode by three-step electrodeposition method and used for glucose sensing. Graphene nanosheets were directly deposited onto the electrode through reduction of graphene oxide by cyclic potential scanning. Then, a glucose biosensor was fabricated by electrodepositing PB nanoparticles and glucose oxidase (GOD)-chitosan hybrid film (GOD-CS) on the graphene modified electrode successively. The surface of the resulting modified electrode was characterized by electrochemical methods and scanning electron microscopy. Under optimal conditions, the biosensor shows high sensitivity (50.29 mA· L·mol-1·cm-2), low detection limit (12 μmol·L-1) and fast response time (3 s). A linear dependence of the catalytic current upon glucose concentration is obtained in a wide range from 0.02 to 10 mmol·L-1. In addition, the sensor also performs well for measuring glucose concentrations in human blood serum samples without any pretreatment.

    Abstract

    The layer-by-layer structured composite film of graphene-Prussian blue (PB)-chitosan (CS) was fabricated on a glassy carbon electrode by three-step electrodeposition method and used for glucose sensing. Graphene nanosheets were directly deposited onto the electrode through reduction of graphene oxide by cyclic potential scanning. Then, a glucose biosensor was fabricated by electrodepositing PB nanoparticles and glucose oxidase (GOD)-chitosan hybrid film (GOD-CS) on the graphene modified electrode successively. The surface of the resulting modified electrode was characterized by electrochemical methods and scanning electron microscopy. Under optimal conditions, the biosensor shows high sensitivity (50.29 mA· L·mol-1·cm-2), low detection limit (12 μmol·L-1) and fast response time (3 s). A linear dependence of the catalytic current upon glucose concentration is obtained in a wide range from 0.02 to 10 mmol·L-1. In addition, the sensor also performs well for measuring glucose concentrations in human blood serum samples without any pretreatment.
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    • References(22)
  • [1]
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    KATSNELSON M I, NOVOSELOV K S, GEIM A K. Chiral tunnelling and the Klein paradox in graphene[J]. Nature Physics, 2006, 2(9): 620-625.
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    YANG W, RATINAC K R, RINGER S P, et al. Carbon nanomaterials in biosensors: Should you use nanotubes or graphene?[J]. Angewandte Chemie International Edition, 2010, 49(12): 2114-2138.
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    CHEN L, TANG Y, WANG K, et al. Direct electrodeposition of reduced graphene oxide on glassy carbon electrode and its electrochemical application[J]. Electrochemistry Communications, 2011, 13(2): 133-137.
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    NEFF V D. Electrochemical oxidation and reduction of thin films of Prussian blue[J]. Journal of the Electrochemical Society, 1978, 125(6): 886-887.
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    ITAYA K, UCHIDA I, NEFF V D. Electrochemistry of polynuclear transition metal cyanides: Prussian blue and its analogues[J]. Accounts of Chemical Research, 1986, 19(6): 162-168.
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    DELONGCHAMP D M, HAMMOND P T. Multiple-color electrochromism from layer-by-layer-assembled polyaniline/Prussian blue nanocomposite thin films[J]. Chemistry of Materials, 2004, 16(23): 4799-4805.
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    EINAGA Y, SATO O, IYODA T, et al. Photofunctional vesicles containing Prussian blue and azobenzene[J]. Journal of the American Chemical Society, 1999, 121(15): 3745-3750.
    [13]
    ITAYA K, SHOJI N, UCHIDA I. Catalysis of the reduction of molecular oxygen to water at Prussian blue modified electrodes[J]. Journal of the American Chemical Society, 1984, 106(12): 3423-3429.
    [14]
    KARYAKIN A A, KARYAKINA E E, GORTON L. The electrocatalytic activity of Prussian blue in hydrogen peroxide reduction studied using a wall-jet electrode with continuous flow[J]. Journal of Electroanalytical Chemistry, 1998, 456(1/2): 97-104.
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    WU S, LIU Y, WU J, et al. Prussian blue nanoparticles doped nanocage for controllable immobilization and selective biosensing of enzyme[J]. Electrochemistry Communications, 2008, 10(3): 397-401.
    [16]
    TAN X C, TIAN Y X, CAI P X, et al. Glucose biosensor based on glucose oxidase immobilized in sol–gel chitosan/silica hybrid composite film on Prussian blue modified glass carbon electrode[J]. Analytical and Bioanalytical Chemistry, 2005, 381(2): 500-507.
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    TAN X, LI M, CAI P, et al. An amperometric cholesterol biosensor based on multiwalled carbon nanotubes and organically modified sol-gel/chitosan hybrid composite film[J]. Analytical Biochemistry, 2005, 337(1): 111-120.
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    BHARATHI S, NOGAMI M. A glucose biosensor based on electrodeposited biocomposites of gold nanoparticles and glucose oxidase enzyme[J]. Analyst, 2001, 126(11): 1919-1922.
    [20]
    WU S, LIU J, BAI X, et al. Stability improvement of Prussian blue by a protective cellulose acetate membrane for hydrogen peroxide sensing in neutral media[J]. Electroanalysis, 2010, 22(16): 1906-1910.
    [21]
    WU S, LIU G, LI P, et al. A high-sensitive and fast-fabricated glucose biosensor based on Prussian blue/topological insulator Bi2Se3 hybrid film[J]. Biosensors and Bioelectronics, 2012, 38(1): 289-294.
    [22]
    CHIU J Y, YU C M, YEN M J, et al. Glucose sensing electrodes based on a poly (3, 4-ethylenedioxythiophene)/Prussian blue bilayer and multi-walled carbon nanotubes[J]. Biosensors and Bioelectronics, 2009, 24(7): 2015-2020.)
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    [1]
    SULAK M T, GKDO?値AN , GLCE A, et al. Amperometric glucose biosensor based on gold-deposited polyvinylferrocene film on Pt electrode[J]. Biosensors and Bioelectronics, 2006, 21(9): 1719-1726.
    [2]
    SCHEDIN F, GEIM A K, MOROZOV S V, et al. Detection of individual gas molecules adsorbed on graphene[J]. Nature Materials, 2007, 6(9): 652-655.
    [3]
    KANG X, WANG J, WU H, et al. Glucose oxidase–graphene–chitosan modified electrode for direct electrochemistry and glucose sensing[J]. Biosensors and Bioelectronics, 2009, 25(4): 901-905.
    [4]
    KATSNELSON M I, NOVOSELOV K S, GEIM A K. Chiral tunnelling and the Klein paradox in graphene[J]. Nature Physics, 2006, 2(9): 620-625.
    [5]
    RAMANATHAN T, ABDALA A A, STANKOVICH S, et al. Functionalized graphene sheets for polymer nanocomposites[J]. Nature Nanotechnology, 2008, 3(6): 327-331.
    [6]
    YANG W, RATINAC K R, RINGER S P, et al. Carbon nanomaterials in biosensors: Should you use nanotubes or graphene?[J]. Angewandte Chemie International Edition, 2010, 49(12): 2114-2138.
    [7]
    PUMERA M, AMBROSI A, BONANNI A,et al. Graphene for electrochemical sensing and biosensing[J]. TrAC Trends in Analytical Chemistry, 2010, 29(9): 954-965.
    [8]
    CHEN L, TANG Y, WANG K, et al. Direct electrodeposition of reduced graphene oxide on glassy carbon electrode and its electrochemical application[J]. Electrochemistry Communications, 2011, 13(2): 133-137.
    [9]
    NEFF V D. Electrochemical oxidation and reduction of thin films of Prussian blue[J]. Journal of the Electrochemical Society, 1978, 125(6): 886-887.
    [10]
    ITAYA K, UCHIDA I, NEFF V D. Electrochemistry of polynuclear transition metal cyanides: Prussian blue and its analogues[J]. Accounts of Chemical Research, 1986, 19(6): 162-168.
    [11]
    DELONGCHAMP D M, HAMMOND P T. Multiple-color electrochromism from layer-by-layer-assembled polyaniline/Prussian blue nanocomposite thin films[J]. Chemistry of Materials, 2004, 16(23): 4799-4805.
    [12]
    EINAGA Y, SATO O, IYODA T, et al. Photofunctional vesicles containing Prussian blue and azobenzene[J]. Journal of the American Chemical Society, 1999, 121(15): 3745-3750.
    [13]
    ITAYA K, SHOJI N, UCHIDA I. Catalysis of the reduction of molecular oxygen to water at Prussian blue modified electrodes[J]. Journal of the American Chemical Society, 1984, 106(12): 3423-3429.
    [14]
    KARYAKIN A A, KARYAKINA E E, GORTON L. The electrocatalytic activity of Prussian blue in hydrogen peroxide reduction studied using a wall-jet electrode with continuous flow[J]. Journal of Electroanalytical Chemistry, 1998, 456(1/2): 97-104.
    [15]
    WU S, LIU Y, WU J, et al. Prussian blue nanoparticles doped nanocage for controllable immobilization and selective biosensing of enzyme[J]. Electrochemistry Communications, 2008, 10(3): 397-401.
    [16]
    TAN X C, TIAN Y X, CAI P X, et al. Glucose biosensor based on glucose oxidase immobilized in sol–gel chitosan/silica hybrid composite film on Prussian blue modified glass carbon electrode[J]. Analytical and Bioanalytical Chemistry, 2005, 381(2): 500-507.
    [17]
    TAN X, LI M, CAI P, et al. An amperometric cholesterol biosensor based on multiwalled carbon nanotubes and organically modified sol-gel/chitosan hybrid composite film[J]. Analytical Biochemistry, 2005, 337(1): 111-120.
    [18]
    GAO X, WEI W, YANG L, et al. Simultaneous determination of lead, copper, and mercury free from macromolecule contaminants by square wave stripping voltammetry[J]. Analytical Letters, 2005, 38(14): 2327-2343.
    [19]
    BHARATHI S, NOGAMI M. A glucose biosensor based on electrodeposited biocomposites of gold nanoparticles and glucose oxidase enzyme[J]. Analyst, 2001, 126(11): 1919-1922.
    [20]
    WU S, LIU J, BAI X, et al. Stability improvement of Prussian blue by a protective cellulose acetate membrane for hydrogen peroxide sensing in neutral media[J]. Electroanalysis, 2010, 22(16): 1906-1910.
    [21]
    WU S, LIU G, LI P, et al. A high-sensitive and fast-fabricated glucose biosensor based on Prussian blue/topological insulator Bi2Se3 hybrid film[J]. Biosensors and Bioelectronics, 2012, 38(1): 289-294.
    [22]
    CHIU J Y, YU C M, YEN M J, et al. Glucose sensing electrodes based on a poly (3, 4-ethylenedioxythiophene)/Prussian blue bilayer and multi-walled carbon nanotubes[J]. Biosensors and Bioelectronics, 2009, 24(7): 2015-2020.)
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