RESUMEN
Miniature, self-contained biodevices powered by biofuel cells may enable a new generation of implantable, wireless, minimally invasive neural interfaces for neurophysiological in vivo studies and for clinical applications. Here we report on the fabrication of a direct electron transfer based glucose/oxygen enzymatic fuel cell (EFC) from genuinely three-dimensional (3D) nanostructured microscale gold electrodes, modified with suitable biocatalysts. We show that the process underlying the simple fabrication method of 3D nanostructured electrodes is based on an electrochemically driven transformation of physically deposited gold nanoparticles. We experimentally demonstrate that mediator-, cofactor-, and membrane-less EFCs do operate in cerebrospinal fluid and in the brain of a rat, producing amounts of electrical power sufficient to drive a self-contained biodevice, viz. 7 µW cm(-2) in vitro and 2 µW cm(-2) in vivo at an operating voltage of 0.4 V. Last but not least, we also demonstrate an inductive coupling between 3D nanobioelectrodes and living neurons.
Asunto(s)
Fuentes de Energía Bioeléctrica , Encéfalo/metabolismo , Electrodos , Nanoestructuras , Neuronas/metabolismo , Animales , Técnicas Biosensibles/instrumentación , Técnicas Biosensibles/métodos , Técnicas Electroquímicas , Femenino , Glucosa/metabolismo , Oro , Microelectrodos , Microscopía de Fuerza Atómica , Nanoestructuras/química , Nanoestructuras/ultraestructura , Consumo de Oxígeno , RatasRESUMEN
A microscale membrane-less biofuel cell, capable of generating electrical energy from human lachrymal liquid, was developed by utilizing the ascorbate and oxygen naturally present in tears as fuel and oxidant. The biodevice is based on three-dimensional nanostructured gold electrodes covered with abiotic (conductive organic complex) and biological (redox enzyme) materials functioning as efficient anodic and cathodic catalysts, respectively. Three-dimensional nanostructured electrodes were fabricated by modifying 100 µm gold wires with 17 nm gold nanoparticles, which were further modified with tetrathiafulvalene-tetracyanoquinodimethane conducting complex to create the anode and with Myrothecium verrucaria bilirubin oxidase to create the biocathode. When operated in human tears, the biodevice exhibited the following characteristics: an open circuit voltage of 0.54 V, a maximal power density of 3.1 µW cm(-2) at 0.25 V and 0.72 µW cm(-2) at 0.4 V, with a stable current density output of over 0.55 µA cm(-2) at 0.4 V for 6 h of continuous operation. These findings support our proposition that an ascorbate/oxygen biofuel cell could be a suitable power source for glucose-sensing contact lenses to be used for continuous health monitoring by diabetes patients.
Asunto(s)
Fuentes de Energía Bioeléctrica , Técnicas Biosensibles/métodos , Lentes de Contacto , Glucosa/análisis , Miniaturización/métodos , Fuentes de Energía Bioeléctrica/tendencias , Técnicas Biosensibles/tendencias , Lentes de Contacto/tendencias , Humanos , Masculino , Lágrimas/químicaRESUMEN
A flexible electrochemical micro(bio)sensor has been designed for determination of several biological compounds, specifically, ascorbate, dopamine, and glucose, in human lachrymal liquid (tears). The microsensor for simultaneous determination of ascorbate and dopamine concentrations was based on a gold microwire modified with the tetrathiafulvalen-7,7,8,8-tetracyanoquinodimethane complex as a catalyst. To monitor glucose concentration in tears, glucose dehydrogenase was immobilized on a gold microwire modified with carbon nanotubes and an osmium redox polymer. A capillary microcell was constructed for sampling tears. The cell had a working volume of 60-100 nL with a sampling deviation of 6.7%. To check if the microcell was properly filled with buffer or tear sample, a control electrode was introduced into the construction. The electrode was used to measure the electrical resistance of a fully filled nanovolume cell. The mechanical flexibility is one of the most important features of the prototype and allowed direct collection of tears with minimized risk of damage to the eye.
Asunto(s)
Ácido Ascórbico/análisis , Técnicas Biosensibles/instrumentación , Dopamina/análisis , Técnicas Electroquímicas/instrumentación , Glucosa/análisis , Lágrimas/química , Catálisis , Enzimas Inmovilizadas/química , Diseño de Equipo , Glucosa Deshidrogenasas/química , Oro/química , Humanos , Masculino , Nanotubos de Carbono/química , Nitrilos/química , Tamaño de la MuestraRESUMEN
Here we present unequivocal experimental proof that microscale cofactor- and membrane-less, direct electron transfer based enzymatic fuel cells do produce significant amounts of electrical energy in human lachrymal liquid (tears). 100 µm diameter gold wires, covered with 17 nm gold nanoparticles, were used to fashion three-dimensional nanostructured microelectrodes, which were biomodified with Corynascus thermophilus cellobiose dehydrogenase and Myrothecium verrucaria bilirubin oxidase as anodic and cathodic bioelements, respectively. The following characteristics of miniature glucose/oxygen biodevices operating in human tears were registered: 0.57 V open-circuit voltage, about 1 µW cm(-2) maximum power density at a cell voltage of 0.5 V, and more than 20 h operational half-life. Theoretical calculations regarding the maximum recoverable electrical energy can be extracted from the biofuel and the biooxidant, glucose and molecular oxygen, each readily available in human lachrymal liquid, fully support our belief that biofuel cells can be used as electrical power sources for so called smart contact lenses.