Bioelectrocatalysis of Acetobacter aceti and Gluconobacter roseus for current generation.

Acetobacter aceti and Gluconobacter roseus, which are known to be responsible for the spoilage of wine, are used for current generation in batch-type microbial biofuel cells and it has been shown for the first time that these two microorganisms do not require mediators for the transfer of electrons to the anode. Three biofuel cells were constructed with two cells containing the pure cultures of each of the microorganisms as the biocatalyst (A-MFC, G-MFC) and the third cell was constructed with the mixed culture of these two microorganisms as the biocatalyst (AG-MFC). The performance of the biofuel cells was evaluated in terms of open circuit voltage (OCV), fuel consumption rate, internal resistance, power output, and coulombic efficiency. The mixed culture cell (AG-MFC) exhibits a better overall performance compared to the other cells.

Electrochemical assay of the nitrate and nitrite reductase activities of Rhizobium japonicum.

This work describes an electrochemical method for the determination of the nitrate and nitrite reductase activities of Rhizobium japonicum. The advantage of the method lies in the use of whole cells for the analysis and we earlier developed this protocol for the assay of NO. The results obtained are comparable to the spectrophotometric Griess assay. As the method is based on electrochemical reduction, the commonly interfering biological components like ascorbic acid, uric acid, dopamine, etc., will not interfere with the analysis. This method can be extended to the fabrication of biosensors for nitrate and nitrite using the same principle.

CTAB-promoted prussian blue-modified electrode and its cation transport characteristics for K+, Na+, Li+, and NH4+ ions.

A Prussian blue (PB) film was deposited on a glassy carbon (GC) electrode by cyclic voltammetry in the presence of the cationic surfactant cetyltrimethylammonium bromide (CTAB). The electrode thus formed showed 4-fold enhancements in redox current and charge values in pure KCl electrolyte as well as greater stability than an electrode prepared in the absence of CTAB. This improved performance of a PB+CTAB electrode versus a PB electrode was further demonstrated using SEM, XRD, and electrochemical impedance spectroscopy (EIS) measurements. A comparative study was undertaken on the cation transport characteristics of PB and PB+CTAB electrodes for Na+, Li+, and NH4+ ions. We obtained a CV pattern for a CTAB-promoted PB film, which showed ideal Nernstian behavior at all scan rates from 5 to 140 mV s(-1). Conditions for the formation and preservation of these ideal and stable PB films are discussed. Possible mechanisms for the beneficial effects of CTAB are proposed.

Electrochemical preparation of copper-dendrimer nanocomposites: picomolar detection of Cu2+ ions.

The present work describes, for the first time, in situ electrochemical preparation of dendrimer-encapsulated Cu nanoparticles using a self-assembled monolayer of fourth-generation amine-terminated polyamidoamine (PAMAM) dendrimer as the template. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) studies of the modified surface confirmed the presence of Cu nanoparticles entrapped in dendrimer film. Au electrode modified with a monolayer of the dendrimer enables preconcentration and subsequent voltammetric detection of Cu(2+) at picomolar concentrations. Further, Cu nanoparticles in the dendrimer monolayer could be electrochemically derivatised to Cu hexacyanoferrate, which exhibits specific crystal planes, unlike the random distribution of crystal planes in bulk-formed Cu hexacyanoferrate, which is another catalytically active material for sensor applications.

Electrochemical investigations of 3-(3-thienyl) acrylic acid protected nanoclusters and planar gold surfaces.

Formation of self assembled monolayers on gold surface by thiols and disulphides is a well known phenomenon and extensive research work has been carried out in this area with envisaged applications in the area of sensors, molecular electronics, lithography, device fabrication using bottom-up approach, etc. Recently, it has been established that thiophene molecules can self assemble on gold surface due to Au-S interactions. 3-(3-thienyl) acrylic acid, a bifunctional ligand is used in this work to form self-assembled monolayers on planar gold surfaces (two dimensional assemblies) and to prepare monolayer protected gold nano clusters (three-dimensional assemblies). The electron transfer blocking properties of the two-dimensional monolayers were evaluated by using standard redox probes like ferrocyanide anions and Ruthenium hexamine cations. The functionalisation of the two-dimensional and three-dimensional assemblies has been carried out with ferrocene carboxylic acid and the functionalised monolayers were characterized by Cyclic voltammetry. The formation of thienyl acrylic acid protected nanoclusters has been verified by TEM and surface plasmon resonance absorption. It has been observed that when thiophene based ligands are used as stabilizers for the formation of metal nanoparticles, they tend to aggregate as a result of pi-pi interactions between adjacent thiophene ligands. In this case it is found that aggregation is prevented. The substituent at the thiophene ring hinders pi-pi interactions. The quantised nature of electrochemical charging of these nanoparticles has been demonstrated by differential pulse voltammetry (DPV), which exhibit peak like features (coulomb's staircase). This work also explores the possibility of using 3-(3-thienyl) acrylic acid as building blocks or spacers on planar and colloidal gold surfaces for potential applications in the field of sensors and devices.

PEDOT-Au nanocomposite films for electrochemical sensing of dopamine and uric acid.

In this work, conducting polymer impregnated gold nanoparticles are synthesized through a sequence of chemical and electrochemical routes. The nanocomposite film is characterized using UV-vis, FTIR spectroscopy, and SEM techniques to study the formation of oxidized PEDOT and Au0. The advantages of these films are demonstrated for sensing biologically important compounds such as dopamine and uric acid in presence of excess ascorbic acid, one of the major interferants in the detection of DA and UA (mimicking the physiological conditions), with superior selectivity and sensitivity when compared to the polymer film alone. Simultaneous determination is realized at 115 mV and 246 mV for DA and UA, respectively. The PEDOT matrix is recognized to be responsible for the peak separation (selectivity) while also favouring catalytic oxidation of the above compounds and the nanometer-sized gold particles allow nanomolar sensing of DA and UA (sensitivity). Thus, it is possible to detect nanomolar levels of DA and UA in presence of excess of AA. The combined effect of Au nanoparticles and the PEDOT matrix is rationalized that the Aunano surrounded by a "hydrophobic sheath (PEDOT)" tending to reside within these hydrophobic regions of PEDOT, thus favouring the selectivity and sensitivity of the DA/UA detection. This new generation of nanocomposites is expected to enhance the value of electroanalytical techniques, as it is possible to tune their properties suiting the analytical needs.

Direct electron transfer with yeast cells and construction of a mediatorless microbial fuel cell.

The direct electron transfer exhibited by the yeast cells, Hansenula anomala has been demonstrated using the electrochemical technique cyclic voltammetry by immobilizing the microorganisms by two different methods viz., physical adsorption and covalent linkage. The analysis of redox enzymes present in the outer membrane of the microorganisms has been carried out in this work. This paper demonstrates that yeast cells with redox enzymes present in their outer membrane are capable of communicating directly with the electrode surface and contribute to current generation in a mediatorless biofuel cells. The efficiency of current generation has been evaluated using three anode materials.

Templated synthesis of silver nanowires based on the layer-by-layer assembly of silver with dithiodipropionic acid molecules as spacers.

The layer-by-layer assembly of silver nanoclusters with 3,3'-dithiodipropionic acid (DTDPA) as spacers was prepared through self-assembly on a gold foil and has been characterized by cyclic voltammetric and AFM techniques. The DTDPA molecules acting as spacers between the layers of silver serve as molecular interconnects for the four layers prepared in this work. The organization of layers was found to decrease with an increase in the number of layers. The layer-by-layer assembly of silver clusters motivated us to prepare silver nanowires stabilized by the bifunctional molecules DTDPA through template synthesis using cellulose nitrate membranes. The nanostructures formed by this method were characterized by SEM, TEM, AFM, FTIR, CV, and photoluminescence studies. It is observed that the DTDPA molecules, instead of forming molecular interconnects, protect the structures by self-assembling themselves along the edges of the nanostructures. The concept of self-assembly protecting the nanostructures is demonstrated in this work.

A Combined Surface-Enhanced Raman-X-Ray Photoelectron Spectroscopic Study of 2-mercaptobenzothiazole Monolayers on Polycrystalline Au and Ag Films.

The monolayers of 2-mercaptobenzothiazole (MBT) on polycrystalline Au and Ag films have been studied by surface-enhanced Raman (SERS) and X-ray photoelectron (XPS) spectroscopies. Whereas MBT adsorbs with its molecular plane flat on Ag, its plane is perpendicular on Au. This difference in adsorbate geometry is manifested as differences in the intensities of certain vibrational peaks in the Raman spectra. Ab initio molecular orbital (MO) calculations suggest that MBT adsorbs on Au in the thione form and on Ag in the thiol form. The monolayers are stable up to a temperature of 473 K, much higher than most of the self-assembled monolayers (SAMs) studied so far. The adsorption geometry does not undergo any significant change when the monolayers are heated, although minor changes are observed in the SER spectra of the Ag monolayer. Raman intensities of all the bands increase with heating, and the enhanced intensity is preserved even after cooling. This is attributed to monolayer-induced coalescence of gold islands leading to the formation of an extended self-assembly. XPS studies confirm chemisorption, although structural details are not manifested. Copyright 1999 Academic Press.