Fundamental Limits on Wavelength, Efficiency and Yield of the Charge Separation Triad

In an attempt to optimize a high yield, high efficiency artificial photosynthetic protein we have discovered unique energy and spatial architecture limits which apply to all light-activated photosynthetic systems. We have generated an analytical solution for the time behavior of the core three cofactor charge separation element in photosynthesis, the photosynthetic cofactor triad, and explored the functional consequences of its makeup including its architecture, the reduction potentials of its components, and the absorption energy of the light absorbing primary-donor cofactor. Our primary findings are two: First, that a high efficiency, high yield triad will have an absorption frequency more than twice the reorganization energy of the first electron transfer, and second, that the relative distance of the acceptor and the donor from the primary-donor plays an important role in determining the yields, with the highest efficiency, highest yield architecture having the light absorbing cofactor closest to the acceptor. Surprisingly, despite the increased complexity found in natural solar energy conversion proteins, we find that the construction of this central triad in natural systems matches these predictions. Our analysis thus not only suggests explanations for some aspects of the makeup of natural photosynthetic systems, it also provides specific design criteria necessary to create high efficiency, high yield artificial protein-based triads.

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks. (C) 2007 Elsevier Ltd. All rights reserved.

Electrochemical reduction of nitroprusside on a glassy carbon electrode modified by poly-L-lysine films

The present work describes the preparation and characterization of polyelectrolyte coatings of poly-L-lysine (PLL) to modify a glassy carbon electrode and its application to the pre-accumulation of nitroprusside (NP). The effects of the coating on the electrochemical reduction of NP were investigated. The performance of the modified electrode indicates that the drug can be immobilized by electrostatic interaction and the voltammetric signal monitored at all pH values in the range of 2-12. The strong interaction between NP and PLL stabilizes the complex on the electrode surface and minimizes the chemical reaction of lost CN- ions as a subsequent reaction of electron transfer, which could improve the action mechanism of NP.

Photosynthetic characteristics of a tropical population of Nitella cernua (Characeae, Chlorophyta)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The Cathodic Cleavage of the Nitrobenzoyl Group from Protected Aliphatic Amines in N,N-Dimethylformamide

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < PH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbOx (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at PH 2.2 and potential of +2.4 V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 K PH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1 h of electrolysis the results indicated total color removal and 37% of mineralization. (c) 2004 Elsevier Ltd. All rights reserved.

Electrochemical reduction and determination of Cibacron Blue F3GA at poly-L-lysine modified glassy carbon electrode

The oxidation of a reactive dye, Cibacron Blue F3GA, CB, (C.I. 61211), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode occurs in two steps at 2.0 < pH < 10 involving one electron transfer each to the amine group leading to the imide derivative. Stable films of poly-L-lysine (PLL) in the presence of glutaraldehyde (GA) 97.5%:2.5% on glassy carbon electrode can be used to detect low levels of dye using its oxidation peak at +0.75V by voltammetry. Linear calibration graphs were obtained for the CB reactive dye, from 1.0 X 10(-6) to 1.0 X 10(-5) mol L-1 in B-R buffer, pH 2.0, using a pre-concentration off-line during 10 min. The detection limit (3 sigma/slope) was calculated to be 4.5 X 10(-8) mol L-1. Films of PLL can readily be applied for the determination of CB dye bearing aminoanthraquinone as chromophore and chlorotriazinyl as reactive group at concentrations at least 100 times lesser than using a glassy carbon electrode without modification. The method described was applied for the determination of CB dye in tap water and raw water collected from the municipal treatment plant with a recovery of 89.2% +/- 5.4 and 88.0% +/- 6.5, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

Electrochemical behavior of the N-nosyl-protected amino acids in N,N-dimethylformamide

The electrochemical reduction of serine, glycine, and leucine protected by the 4-nitrobenzenesulfonyl, group in N,N-dimethylformamide at mercury cathode occurs at two steps. The first one at -0.8 V vs. SCE, after a one-electron transfer, leads the anion radical formation that dimerizes and adsorbs at electrode. In the second step at -1.4 V, an instable dianion forms which then cleaves. The mechanism is discussed.

Electrochemical reduction of aromatic sulfinic acids in dimethylsulfoxide

The electrochemical reduction of benzenesulfinic, p-toluenesulfinic, and p-nitrobenzenesulfinic acids was studied in dimethylsulfoxide solutions. From cyclic voltammetry experiments, a chemical reaction following the first electron transfer was detected during the reduction process. A cyclic voltammetry technique using ultramicroelectrodes has provided kinetic parameters for the electron-transfer steps, from which it was possible to observe the influence of the ring substituent on the electrochemical reduction. The mechanism of the electroreduction of aromatic sulfinic acids in dimethylsulfoxide depends upon the nucleophilic attack of the radical anion produced on the starting compound during the reduction processes.

Simultaneous determination of quinoline and pyridine compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion-exchange resin (Amberlyte IR - 120 H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for quinoline (-1.95 V) and pyridine (-2.52 V) vs. Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300 mg L-1 and a limit of detection (LOD) of 5.05 and 0.25 mu g L-1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0 +/- 0.3 and 33.0 +/- 0.7 mg L-1 and in diesel samples yielded 80.3 +/- 0.2 and 131 +/- 0.4 mg L-1, respectively. Spike recoveries were 94.4 +/- 0.3% and 10 +/- 0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests.

Electroreduction of benznidazole in dimethylsulfoxide

The electrochemical behavior of benznidazole has been investigated in dimethylsulfoxide by cyclic voltammetry and controlled-potential electrolysis. The reduction occurs in two one-electron steps, where the first electron transfer corresponds to the reversible formation of the radical anion followed by a slow chemical reaction. The second electron transfer is attributed to the reduction of the radical anion to a dianion by an electrodic process involving a Very fast cleavage of the dianion with the formation of a lactam derivative as the principal product of reduction in aprotic medium. (C) 2001 the Electrochemical Society. All rights reserved.

Simultaneous determination of neutral nitrogen compounds in gasoline and diesel by differential pulse voltammetry

The presence of trace neutral organonitrogen compounds as carbazole and indole in derivative petroleum fuels plays an important role in the car's engine maintenance. In addition, these substances contribute to the environmental contamination and their control is necessary because most of them are potentially carcinogenic and mutagenic. For those reasons, a reliable and sensitive method was proposed for the determination of neutral nitrogen compounds in fuel samples, such as gasoline and diesel using preconcentration with modified silica gel (Merck 70-230 mesh ASTM) followed by differential pulse voltammetry (DPV) technique on a glassy carbon electrode. The electrochemical behavior of carbazole and indole studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF(4) 0.1 mol L-1) for indole (-2.27 V) and carbazole (-2.67 V) versus Ag vertical bar AgCl vertical bar KClsat reference electrode. The proposed DPV method showed a good linear response range from 0.10 to 300 mg L-1 and a limit of detection (L.O.D) of 7.48 and 2.66 mu g L-1 for indole and carbazole, respectively. The results showed that simultaneous determination of indole and carbazole presents in spiked gasoline samples were 15.8 +/- 0.3 and 64.6 +/- 0.9 mg L-1 and in spiked diesel samples were 9.29 +/- 1 and 142 +/- 1 mg L-1, respectively. The recovery was evaluated and the results shown the values of 88.9 +/- 0.4 and 90.2 +/- 0.8% for carbazole and indole in fuel determinations. The proposed method was also compared with UV-vis spectrophotometric measures and the results obtained for the two methods were in good agreement according to the F and t Student's tests. (C) 2007 Elsevier B.V. All rights reserved.

The electrochemical cleavage of the nitrobenzoyl group from butyl nitrobenzoates in N,N-dimethylformamide

The applicability of the nitrobenzoyl group [NO2C6H4CO-] to protecting the functional hydroxyl group was investigated through study of the electrochemical behaviour of the butyl 4-, 3- and 2-nitrobenzoate compounds. These isomers are reduced in two cathodic steps. The first, at potentials of ca. -0.9 V vs. SCE, is attributed to the formation of rather stable anion radicals, involving one-electron transfer. The second, at potentials of ca. -1.7 V vs. SCE, occurs with a two-electron transfer in an ECE process, in which the dianion produced undergoes scission of the C-O bond giving n-butanoate ions with high yields (similar to 80%)

Langmuir-Blodgett films incorporating an ionic europium complex

Langmuir-Blodgett (LB) technique is a powerful tool to fabricate ultrathin films with highly ordered structures and controllable molecular array for efficient energy and electron transfer, allowing the construction of devices at molecular level. One method to obtain LB films consists in the mixture of classical film-forming molecules, for example Stearic Acid (SA) and functional metal complex. In this work NH(4)[Eu(bmdm)(4)], where the organic ligand bmdm is (butyl methoxy-dibenzoyl-methane) or (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione) was used to build up Langmuir and LB films. Langmuir isotherms were obtained from (i) NH(4)[Eu(bmdm)(4)] complex and (ii) NH(4)[Eu(bmdm)(4)]/SA (1:1). Results indicated that (i) form multilayer structure; however the surface pressure was insufficient to obtain LB films, and (ii) can easily reproduce and build LB films. The dependence of number of layers in the UV absorption spectra suggest that the complex did not hydrolyze or show decomposition, UV spectral differences observed between the solution and the LB film indicate that the complex has a highly ordered arrangement in the film and the complex has an interaction with SA. Excitation spectra confirm a ligand-europium energy transfer mechanism. The transition lines of Eu(3+) ion were observed in emission spectra of all films, the photoluminescence spectra indicate a fluorescence enhanced effect with the number of LB layers. (C) 2009 Elsevier B.V. All rights reserved.

Capacitance Spectroscopy: A Versatile Approach To Resolving the Redox Density of States and Kinetics in Redox-Active Self-Assembled Monolayers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)