Carolin Lau

Conductive Macroporous Composite Chitosan−Carbon Nanotube Scaffolds

Multiwalled carbon nanotubes (MWCNTs) were used as doping material for three-dimensional chitosan scaffolds to develop a highly conductive, porous, and biocompatible composite material. The porous and interconnected structures were formed by the process of thermally induced phase separation followed by freeze-drying applied to an aqueous solution of 1 wt % chitosan acetic acid. The porosity was characterized to be 97% by both mercury intrusion porosimetry measurements and SEM image analysis. When MWCNTs were used as a filler to introduce conductive pathways throughout the chitosan skeleton, the solubilizing hydrophobic and hydrophilic properties of chitosan established stable polymer/MWCNT solutions that yielded a homogeneous distribution of nanotubes throughout the final composite matrix. A percolation theory threshold of approximately 2.5 wt % MWCNTs was determined by measurement of the conductivity as a function of chitosan/MWCNT ratios. The powder resistivity of completely compressed scaffolds also was measured and was found to be similar for all MWCNT concentrations (0.7-0.15 Omega cm powder resistivity for MWCNTs of 0.8-5 wt %) and almost five times lower than the 20 k Omega cm value found for pure chitosan scaffolds.

Enzymatic fuel cells: Integrating flow-through anode and air-breathing cathode into a membrane-less biofuel cell design

One of the key goals of enzymatic biofuel cells research has been the development of a fully enzymatic biofuel cell that operates under a continuous flow-through regime. Here, we present our work on achieving this task. Two NAD(+)-dependent dehydrogenase enzymes; malate dehydrogenase (MDH) and alcohol dehydrogenase (ADH) were independently coupled with poly-methylene green (poly-MG) catalyst for biofuel cell anode fabrication. A fungal laccase that catalyzes oxygen reduction via direct electron transfer (DET) was used as an air-breathing cathode. This completes a fully enzymatic biofuel cell that operates in a flow-through mode of fuel supply polarized against an air-breathing bio-cathode. The combined, enzymatic, MDH-laccase biofuel cell operated with an open circuit voltage (OCV) of 0.584 V, whereas the ADH-laccase biofuel cell sustained an OCV of 0.618 V. Maximum volumetric power densities approaching 20 μW cm(-3) are reported, and characterization criteria that will aid in future optimization are discussed.

Fabrication of macroporous chitosan scaffolds doped with carbon nanotubes and their characterization in microbial fuel cell operation

Chitosan (CHIT) scaffolds doped with multi-walled carbon nanotubes (CNT) were fabricated and evaluated for their utility as a microbial fuel cell (MFC) anodic material. High resolution microscopy verified the ability of Shewanella oneidensis MR-1 to directly colonize CHIT-CNT scaffolds. Cross-linking agents 1-ethyl-3-[3-dimethylaminopropyl] carbodimide hydrochloride (EDC), glutaraldehyde and glyoxal were independently studied for their ability to strengthen the CHIT-CNT matrix without disrupting the final pore structure. 2.5 vol% glyoxal was found to be the optimal cross-linker in terms of porosity (BET surface area=30.2 m(2) g(-1)) and structural stability. Glyoxyl and EDC cross-linked CHIT-CNT scaffolds were then studied for their ability to transfer electrons to underlying glassy carbon. Results showed an open circuit cell voltage of 600 mV and a maximum power density of 4.75 W/m(3) at a current density of 16 A/m(3) was achieved in non stirred batch mode, which compares well with published data using carbon felt electrodes where a power density of 3.5 W/m(3) at a current density of 7 A/m(3) have been reported. Additionally, CHIT-CNT scaffolds were impregnated into carbon felt electrodes and these results suggest that CHIT-CNT scaffolds can be successfully integrated with multiple support materials to create hybrid electrode materials. Further, preliminary tests indicate that the integrated scaffolds offer a robust macroporous electrode material that can be used in flow-through configurations.

A study of the flavin response by Shewanella cultures in carbon-limited environments

Mediated electron transfer has been implicated as a primary mechanism of extracellular electron transfer to insoluble electron acceptors in anaerobic cultures of the facultative anaerobe Shewanella oneidensis. In this work, planktonic and biofilm cultures of S. oneidensis exposed to carbon-limited environments trigger an electrochemical response thought to be the signature of an electrochemically active metabolite. This metabolite was detected via cyclic voltammetry for S. oneidensis MR-1 biofilms. The observed electrochemical potentials correspond to redox potentials of flavin-containing molecules. Chromatographic techniques were then used to quantify concentrations of riboflavin by the carbon-limited environmental response of planktonic S. oneidensis. Further evidence of flavin redox chemistry was associated with biofilm formation on multi-walled carbon nanotube-modified Toray paper under carbon-starved environments. By encapsulating one such electrode in silica, the encapsulated biofilm exhibits riboflavin redox activity earlier than a non-encapsulated system after media replacement. This work explores the electrochemical nature of riboflavin interaction with an electrode after secretion from S. oneidensis and in comparison to abiotic systems.

Fluorescence analysis of chemical microenvironments and their impact upon performance of immobilized enzyme

In this work the shift in fluorescence emission spectra of acrylodan, a polar sensitive fluorophore, has been used to characterize the polarity immediately surrounding cytoplasmic (cMDH) and mitochondrial malate dehydrogenase (mMDH) enzyme immobilized within three-dimensional macroporous chitosan scaffolds. The scaffolds were fabricated from solutions of fluorescently tagged enzymes mixed with deacetylated and hydrophobically modified chitosan polymer. Each solution was frozen and then freeze-dried through the process of thermally induced phase separation (TIPS). The blue shift in acrylodans emission maxima (lambda(max)) revealed a polar shift in the chemical microenvironment surrounding the enzymes when immobilized in a modified as opposed to unmodified chitosan scaffold. These results suggest that the method of hydrophobic modification of native chitosan polymer can be used to control the amphiphilic nature of the chemical microenvironment immediately surrounding the enzyme after it has been immobilized.

Microbial-enzymatic-hybrid biological fuel cell with optimized growth conditions for Shewanella oneidensis DSP-10.

In this work we present a biological fuel cell fabricated by combining a Shewanella oneidensis microbial anode and a laccase-modified air-breathing cathode. This concept is devised as an extension to traditional biochemical methods by incorporating diverse biological catalysts with the aim of powering small devices. In preparing the biological fuel cell anode, novel hierarchical-structured architectures and biofilm configurations were investigated. A method for creating an artificial biofilm based on encapsulating microorganisms in a porous, thin film of silica was compared with S. oneidensis biofilms that were allowed to colonize naturally. Results indicate comparable current and power densities for artificial and natural biofilm formations, based on growth characteristics. As a result, this work describes methods for creating controllable and reproducible bio-anodes and demonstrates the versatility of hybrid biological fuel cells.