Linear poly͑ethylenimine͒ ͑-͓CH 2 CH 2 NH͔ n -, LPEI͒ was modified by attachment of 3-͑dimethylferrocenyl͒propyl groups to ca. 17% of its nitrogen atoms ͑FcMe 2 -C 3 -LPEI͒ to form a new redox polymer for use as an anodic mediator in glucose/O 2 biofuel cells. The electrochemical properties of this polymer were compared to those of 3-ferrocenylpropyl-modified LPEI ͑Fc-C 3 -LPEI͒. When Fc-C 3 -LPEI or FcMe 2 -C 3 -LPEI was mixed with glucose oxidase and cross-linked with ethylene glycol diglycidyl ether to form hydrogels on planar, glassy carbon electrodes, limiting catalytic bioanodic current densities of up to ϳ2 mA/cm 2 at 37°C were produced. The use of dimethylferrocene moieties in place of ferrocene moieties lowered the E 1/2 of the films by 0.09 V and significantly increased electrochemical and operational stabilities. FcMe 2 -C 3 -LPEI was shown to be the more effective polymer for use in biofuel cells and, when coupled with a stationary O 2 cathode comprised of laccase and cross-linked poly͓͑vinylpyridine͒Os͑bipyridyl͒ 2 Cl 2+/3+ ͔ as a mediator, produced power densities of up to 56 W/cm 2 at 37°C. Power density increased to 146 W/cm 2 when a rotating biocathode was used. The stability of the biofuel cells constructed with FcMe 2 -C 3 -LPEI was higher than that of the cells using Fc-C 3 -LPEI.The development of fuel cells that can operate using biological catalysts and renewable fuels has gained recent attention. 1-4 Biofuel cells resemble traditional fuel cells in their fundamental operating principles ͑oxidation of a fuel to produce protons/reduction of oxygen to water͒ but differ greatly in other ways. Biofuel cells use renewable catalysts ͑microbes or enzymes͒ and are operated under mild conditions ͑usually 25 or 37°C, pH 5-7͒ relative to traditional fuel cells. The enzymes used in biofuel cells are extremely selective for their respective substrates, allowing for the removal of separator membranes and the operation of many biofuel cells in compartmentless containers. These properties make biofuel cells attractive as alternative energy sources for implantable electronic devices and other portable electronics.However, because biofuel cells use enzymes as catalysts, the stabilities of bioanodes and biocathodes can be fairly low and the highest power densities produced using single enzyme electrodes in compartmentless biofuel cells to date are only in the hundreds of microwatts per square centimeter. 5,6 In order to improve these power densities, some groups are working on complex enzyme cascades 7-9 to allow for complete oxidation of biofuels to CO 2 , and others are working with hybrid enzymatic/direct methanol fuel cells in order to increase the low power densities typically obtained from biofuel cells. 10,11 Still others are using innovative nanomaterials to enhance the connection between enzymes and electrode surfaces. [12][13][14][15][16] Because these systems are complex, are expensive, and/or use precious metal catalysts, there is a need for simple, low-cost, single enzyme bioelectrodes, especiall...
In this study, we describe the use of a sodium cholate suspension-dialysis method to adsorb the redox enzyme glucose oxidase (GOX) onto single-walled carbon nanotubes (SWNT). By this method, solutions of dispersed and debundled SWNTs were prepared that remained stable for 30 days and which retained 75% of the native enzymatic activity. We also demonstrate that GOX-SWNT conjugates can be assembled into amperometric biosensors with a poly[(vinylpyridine)Os(bipyridyl)2Cl(2+/3+)] redox polymer (PVP-Os) through a layer-by-layer (LBL) self-assembly process. Incorporation of SWNT-enzyme conjugates into the LBL films resulted in current densities as high as 440 microA/cm2, which were a 2-fold increase over the response of films without SWNTs. We also demonstrate that the adsorption pH of the redox polymer solution and the dispersion quality of SWNTs were important parameters in controlling the electrochemical and enzymatic properties of the LBL films.
We have applied a recently developed method to incorporate the self-interaction correction through Fermi orbitals to Mg-porphyrin, C60, and pentacene molecules. The Fermi-Löwdin orbitals are localized and unitarily invariant to the Kohn-Sham orbitals from which they are constructed. The self-interaction-corrected energy is obtained variationally leading to an optimum set of Fermi-Löwdin orbitals (orthonormalized Fermi orbitals) that gives the minimum energy. A Fermi orbital, by definition, is dependent on a certain point which is referred to as the descriptor position. The degree to which the initial choice of descriptor positions influences the variational approach to the minimum and the complexity of the energy landscape as a function of Fermi-orbital descriptors is examined in detail for Mg-porphyrin. The applications presented here also demonstrate that the method can be applied to larger molecular systems containing a few hundred electrons. The atomization energy of the C60 molecule within the Fermi-Löwdin-orbital self-interaction-correction approach is significantly improved compared to local density approximation in the Perdew-Wang 92 functional and generalized gradient approximation of Perdew-Burke-Ernzerhof functionals. The eigenvalues of the highest occupied molecular orbitals show qualitative improvement.
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