Abstract
Enzymatic glucose biosensors and biofuel cells make use of the electrochemical transduction between an oxidoreductase enzyme, such as glucose oxidase (GOx), and an electrode to either quantify the amount of glucose in a solution or generate electrical energy. However, many enzymes including GOx are not able to electrochemically interact with an electrode surface directly, but require an external electrochemical relay to shuttle electrons to the electrode. Ferrocene-modified linear poly(ethylenimine) (Fc-LPEI) redox polymers have been designed to simultaneously immobilize glucose oxidase (GOx) at an electrode and mediate electron transfer from their flavin adenine dinucleotide (FAD) active site to the electrode surface. Cross-linked films of Fc-LPEI create hydrogel networks that allow for rapid transport of glucose, while the covalently bound ferrocene moieties are able to facilitate rapid electron transfer due to the ability of ferrocene to exchange electrons between adjacent ferrocene residues. For these reasons, Fc-LPEI films have been widely used in the development of high current density bioanode materials. This chapter describes the synthesis of a commonly used dimethylferrocene-modified linear poly(ethylenimine), as well as the subsequent preparation and electrochemical characterization of a GOx bioanode film utilizing the synthesized polymer.
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References
Degani Y, Heller A (1987) Direct electrical communication between chemically modified enzymes and metal electrodes. I. Electron transfer from glucose oxidase to metal electrodes via electron relays, bound covalently to the enzyme. J Phys Chem 91(6):1285–1289. doi:10.1021/j100290a001
Degani Y, Heller A (1989) Electrical communication between redox centers of glucose oxidase and electrodes via electrostatically and covalently bound redox polymers. J Am Chem Soc 111(6):2357–2358. doi:10.1021/ja00188a091
Schuhmann W, Ohara TJ, Schmidt HL, Heller A (1991) Electron transfer between glucose oxidase and electrodes via redox mediators bound with flexible chains to the enzyme surface. J Am Chem Soc 113(4):1394–1397. doi:10.1021/ja00004a048
Struchkov YT, Andrianov VG, Sal’nikova TN, Lyatifov IR, Materikova RB (1978) Crystal and molecular structures of two polymethylferrocenes: sym-octamethylferrocene and decamethylferrocene. J Organomet Chem 145(2):213–223. doi:10.1016/S0022-328X(00)91127-6
Meredith MT, Hickey DP, Redemann JP, Schmidtke DW, Glatzhofer DT (2013) Effects of ferrocene methylation on ferrocene-modified linear poly(ethylenimine) bioanodes. Electrochim Acta 92:226–235. doi:10.1016/j.electacta.2013.01.006
Britton WE, Kashyap R, El-Hashash M, El-Kady M, Herberhold M (1986) The anomalous electrochemistry of the ferrocenylamines. Organometallics 5(5):1029–1031. doi:10.1021/om00136a033
Merchant SA, Tran TO, Meredith MT, Cline TC, Glatzhofer DT, Schmidtke DW (2009) High-sensitivity amperometric biosensors based on ferrocene-modified linear poly(ethylenimine). Langmuir 25(13):7736–7742. doi:10.1021/la9004938
Meredith MT, Kao D-Y, Hickey D, Schmidtke DW, Glatzhofer DT (2011) High current density ferrocene-modified linear poly(ethylenimine) bioanodes and their use in biofuel cells. J Electrochem Soc 158(2):B166–B174. doi:10.1149/1.3505950
Hickey DP, Halmes AJ, Schmidtke DW, Glatzhofer DT (2014) Electrochemical characterization of glucose bioanodes based on tetramethylferrocene-modified linear poly(ethylenimine). Electrochim Acta 149:252–257. doi:10.1016/j.electacta.2014.10.077
Hickey DP, Giroud F, Schmidtke DW, Glatzhofer DT, Minteer SD (2013) Enzyme cascade for catalyzing sucrose oxidation in a biofuel cell. ACS Cat 3(12):2729–2737. doi:10.1021/cs4003832
Milton RD, Wu F, Lim K, Abdellaoui S, Hickey DP, Minteer SD (2015) Promiscuous glucose oxidase: electrical energy conversion of multiple polysaccharides spanning starch and dairy milk. ACS Cat 5(12):7218–7225. doi:10.1021/acscatal.5b01777
Hickey DP, Reid RC, Milton RD, Minteer SD (2016) I. Biosens Bioelectron 77:26–31. doi:10.1016/j.bios.2015.09.013
York S, Frech R, Snow A, Glatzhofer D (2001) A comparative vibrational spectroscopic study of lithium triflate and sodium triflate in linear poly(ethylenimine). Electrochim Acta 46(10–11):1533–1537. doi:10.1016/S0013-4686(00)00749-0
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Hickey, D.P. (2017). Ferrocene-Modified Linear Poly(ethylenimine) for Enzymatic Immobilization and Electron Mediation. In: Minteer, S. (eds) Enzyme Stabilization and Immobilization. Methods in Molecular Biology, vol 1504. Humana Press, New York, NY. https://doi.org/10.1007/978-1-4939-6499-4_14
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DOI: https://doi.org/10.1007/978-1-4939-6499-4_14
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