Enzymatic biosensing by covalent conjugation of enzymes to 3D-networks of graphene nanosheets on arrays of vertically aligned gold nanorods: Application to voltammetric glucose sensing
- 163 Downloads
The authors demonstrate efficient direct electron transfer from the enzyme glucose oxidase to vertically aligned gold nanorods with a diameter of ~160 nm and a length of ~2 μm that are covalently linkage to a 3-dimensional network of reduced graphene oxide nanosheets. The assembly can be prepared by a 2-step electrochemical procedure. This hybrid structure holds the enzyme in a favorable position while retaining its functionality that ultimately provides enhanced performance for enzymatic sensing of glucose without utilizing mediators. The nanorod assembly was applied to the voltammetric detection of glucose. Figures of merit include an electrochemical sensitivity of 12 μA·mM−1·cm−2 (obtained from cathodic peak current at a voltage of −0.45 V vs. Ag/AgCl), a 3 μM detection limit (at signal/noise = 3), and a wide linear range (0.01–7 mM). The hybrid nanostructure has a heterogeneous electron transfer rate constant (ks) of 2.9 s−1. The high electrochemical activity is attributed to the synergistic effect of a large active surface and an enhanced electron transfer efficiency due to covalent amide linkage.
KeywordsBiosensor Carbon nanostructures Reduced graphene oxide Nanosheets Glucose oxidase Electrochemistry Differential Pulse Voltammetry (DPV)
This work was supported by the Grant Program of Sharif University of Technology (No. G930305) and Iran National Science Foundation (INSF No. 95-S-48740).
Compliance of ethical standards
All utilized procedures were in accordance with relevant guidelines and regulations of the Sharif University of Technology. The work has been approved by the ethical committee and all the patients signed an informed consent form.
Conflicts of interest
There are no conflicts to declare.
- 3.Hasan A, Nurunnabi M, Morshed M, Paul A, Polini A, Kuila T, Al Hariri M, Lee Y-K, Jaffa AA (2014) Recent Advances in Application of Biosensors in Tissue Engineering. Biomed res int 2014 (Article ID 307519):1–18 doi: https://doi.org/10.1155/2014/307519
- 5.Mani V, Devadas B, Chen S-M (2013) Direct electrochemistry of glucose oxidase at electrochemically reduced graphene oxide-multiwalled carbon nanotubes hybrid material modified electrode for glucose biosensor. Biosens Bioelectron 41:309–315. https://doi.org/10.1016/j.bios.2012.08.045 CrossRefGoogle Scholar
- 9.García-Carmona L, Moreno-Guzmán M, Martín A, Martínez SB, Fernández-Martínez AB, González MC, Lucio-Cazaña J, Escarpa A (2017) Aligned copper nanowires as a cut-and-paste exclusive electrochemical transducer for free-enzyme highly selective quantification of intracellular hydrogen peroxide in cisplatin-treated cells. Biosens Bioelectron 96:146–151. https://doi.org/10.1016/j.bios.2017.04.048 CrossRefGoogle Scholar
- 13.Luong JH, Glennon JD, Gedanken A, Vashist SK (2017) Achievement and assessment of direct electron transfer of glucose oxidase in electrochemical biosensing using carbon nanotubes, graphene, and their nanocomposites. Microchim Acta 184(2):369–388. https://doi.org/10.1007/s00604-016-2049-3 CrossRefGoogle Scholar
- 23.de Jesus CG, Lima D, dos Santos V, Wohnrath K, Pessôa CA (2013) Glucose biosensor based on the highly efficient immobilization of glucose oxidase on layer-by-layer films of silsesquioxane polyelectrolyte. Sens Actuators B: Chem 186:44–51. https://doi.org/10.1016/j.snb.2013.05.063 CrossRefGoogle Scholar
- 24.Sehat AA, Khodadadi AA, Shemirani F, Mortazavi Y (2015) Fast immobilization of glucose oxidase on graphene oxide for highly sensitive glucose biosensor fabrication. Int J Electrochem Sci 10(20145):272–286Google Scholar
- 28.Rabti A, Argoubi W, Raouafi N (2016) Enzymatic sensing of glucose in artificial saliva using a flat electrode consisting of a nanocomposite prepared from reduced graphene oxide, chitosan, nafion and glucose oxidase. Microchim Acta 183(3):1227–1233. https://doi.org/10.1007/s00604-016-1753-3 CrossRefGoogle Scholar
- 30.Devasenathipathy R, Mani V, Chen S-M, Huang S-T, Huang T-T, Lin C-M, Hwa K-Y, Chen T-Y, Chen B-J (2015) Glucose biosensor based on glucose oxidase immobilized at gold nanoparticles decorated graphene-carbon nanotubes. Enzyme Microb Technol 78:40–45. https://doi.org/10.1016/j.enzmictec.2015.06.006 CrossRefGoogle Scholar
- 32.Kumar-Krishnan S, Hernandez-Rangel A, Pal U, Ceballos-Sanchez O, Flores-Ruiz FJ, Prokhorov E, Arias de Fuentes O, Esparza R, Meyyappan M (2016) Surface functionalized halloysite nanotubes decorated with silver nanoparticles for enzyme immobilization and biosensing. J Mater Chem B 4(15):2553–2560. https://doi.org/10.1039/C6TB00051G CrossRefGoogle Scholar