Ferrocene in conjugation with a Fischer carbene: Synthesis, NLO, and electrochemical behavior of a novel organometallic push-pull system

Using an iterative sequence of Wittig olefination, reduction, oxidation, and condensation of an active methylene group to carbonyl, it was possible to prepare a series of organometallic push-pull molecules [(CO)(5)M=C(OCH3)(-CH=CH-)(n)(C5H4)Fe(C5H5), M = W, Cr, n = 1-4] in which ferrocene is the donor element and a Fisher carbene moeity is the acceptor group. The molecular first hyperpolarizability beta was determined by hyper-Rayleigh scattering experiments. The beta values ranged from 110 x 10(-30) to 2420 x 10(-30) esu in acetonitrile, and they are among the highest reported for organometallic molecules so far. Electrochemical measurements are consistent with the push-pull nature of these compounds.

Synthesis and Characterization of a Class of Donor-Acceptor Conjugated Molecules: Experiments and Theoretical Calculations

A class of conjugated molecules containing donor (thiophene) and acceptor (malononitrile) is synthesized by Knoevenagel condensation reaction between 2-(2,6-dimethy1-4H-pyran-4-ylidene) malononitrile and thiophene carbaldehyde containing two and three thiophene units. The resulting molecules are characterized by H-1 and C-13 NMR. We have performed UV-vis absorption, fluorescence, and cyclic voltammetry measurements on these materials. The spectroscopic and electrochemical measurements proved beyond doubt that these materials possess lowexcitation gap and are suitable for being an active material in various electronic devices. We have also performed electronic structure calculations using density functional theory (DFT) and INDO/SCI methods to characterize the ground and excited states of this class of molecules. These donor-acceptor molecules show a strong charge transfercharacter that increases with the increase in the number of thiophene rings coupled to the malononitrile acceptor moiety. We have also calculated the pi-coherence length, Stoke's shift, and effect of solvents on excited states for this class of molecules, Our theoretical values agree well with experimental results.

Tailoring of Structural Morphology of Silver Nanowires in Electrochemical Growth

Noble metal such as Ag normally exists in an fcc crystal structure. However as the size of the material is decreased to nanometer lengthscales, a structural transformation from that of its bulk state can be expected with new atomic arrangements due to competition between internal packing and minimization of surface energy. In many previous studies, it has been shown that silver nanowires (AGNWs) grown inside anodic alumina (AAO) templates by ac or dc electrochemical deposition from silver salts or complexes, adopt fcc structure and below some critical diameter ∼ 20 nm they may acquire hcp structure at low temperature. This is, however, critically dependant on the nature of confinement, as AgNWs grown inside nanotube confinement with subnanometer diameter have been reported to have fcc structure. Hence the question of the crystal structure of metal nanowires under combined influence of confinement, temperature and deposition condition remains open. In this abstract we show that the alternative crystal structures of AGNWs at room temperature can be achieved with electrochemical growth processes under specific conditions determined by the deposition parameters and nature of confinement. We fabricated AgNWs of 4H hexagonal structure with diameters 30 – 80 nm inside polycarbonate (PC) templates with a modified dc electrodeposition technique, where the nanowires were grown at deposition potentials as low as 10 mV in 2 M silver nitrate solution[1]. We call this low-potential electrodeposition (LPED) since the electrodeposition process occurs at potential much less than the standard Nernst potential (770 mV) of silver. Two types of electrodes were used – stainless steel and sputtered thin Pt film, neither of which had any influence on the crystal structure of the nanowires. EDS elemental analysis showed the nanowires to consist only of silver. Although the precise atomic dynamics during the LPED process is unclear at present, we investigated this with HRTEM (high-resolution transmission electron microscopy) characterization of nanowires grown over various deposition times, as well as electrical conductivity measurements. These experiments indicate that nanowire growth does not occur through a three-dimensional diffusion controlled process, as proposed for conventional over-potential deposition, but follow a novel instantaneous linear growth mechanism. Further experiments showed that, (a) conventional electrochemical growth at a small over-potential in a 2 mM AgNO3 solution yields nanowires with expected fcc structure inside the same PC templates, and (2) no nanowire was observed under the LPED conditions inside hard AAO templates, indicating that LPED-growth process, and hcp structure of the corresponding nanowires depend on deposition parameters, as well as nature of confinement.

Electrochemical Integration of Graphene with Light-Absorbing Copper-Based Thin Films

We present an electrochemical route for the integration of graphene with light-sensitive copper-based alloys used in optoelectronic applications. Graphene grown using chemical vapor deposition (CVD) transferred to glass is found to be a robust substrate on which photoconductive CuxS films of 1-2 mu m thickness can be deposited. The effect of growth parameters on the morphology and photoconductivity of CuxS films is presented. Current-voltage (I-V) characterization and photoconductivity decay experiments are performed with graphene as one contact and silver epoxy as the other.

Effect of radio frequency power and thickness on the electrochemical properties of Li2-x MnO3-y thin films

In the present work, Li2-x MnO3-y (LMO) thin films have been deposited by radio frequency (RF) reactive magnetron sputtering using acid-treated Li2MnO3 powder target. Systematic investigations have been carried out to study the effect of RF power on the physicochemical properties of LMO thin films deposited on platinized silicon substrates. X-ray diffraction, electron microscopy, surface chemical analysis and electrochemical studies were carried out for the LMO films after post deposition annealing treatment at 500 A degrees C for 1 h in air ambience. Galvanostatic charge discharge studies carried out using the LMO thin film electrodes, delivered a highest discharge capacity of 139 mu Ah mu m(-1) cm(-2) in the potential window 2.0-3.5 V vs. Li/Li+ at 100 W RF power and lowest discharge capacity of 80 mu Ah mu m(-1) cm(-2) at 75 W RF power. Thereafter, the physicochemical properties of LMO films deposited using optimized RF power 100 W on stainless steel substrates has been studied in the thickness range of 70 to 300 nm as a case study. From the galvanostatic charge discharge experiments, a stable discharge capacity of 68 mu Ah mu m(-1) cm(-2) was achieved in the potential window 2.0-4.2 V vs. Li/Li+ tested up to 30 cycles. As the thickness increased, the specific discharge capacity started reducing with higher magnitude of capacity fading.

Adsorption of human serum albumin onto gold: a combined electrochemical and ellipsometric study

Human serum albumin adsorption onto gold surfaces was investigated by electrochemical and ellipsometric methods. Albumin adsorption onto gold was confirmed by the change of the open circuit potential of gold and by the ellipsometric parameter variation during albumin immobilization. In both experiments the parameters reached stable values within 10-15 min. The albumin adsorption layer thickness measured with the ellipsometer was about 1.5 nm. The adsorption of albumin Under applied potential was also investigated and it was found that both positive and negative applied potential promote albumin adsorption. Changes in the optical parameters of bare gold and albumin adsorbed onto gold surface under applied potential were investigated with in Situ ellipsometry. The similarity and reversibility of the optical changes showed that adsorbed albumin was stable on the gold surface Under the applied potential range (-200-600 mV). The cyclic voltammograms of K3Fe(CN)(6) on the modified gold surface showed that albumin Could partly block the oxidation and reduction reaction. (C) 2004 Elsevier Inc. All rights reserved.

Electrical, electrochemical, and optical characterization of ceria films

Acceptor-doped ceria has been recognized as a promising intermediate temperature solid oxide fuel cell electrode/electrolyte material. For practical implementation of ceria as a fuel cell electrolyte and for designing model experiments for electrochemical activity, it is necessary to fabricate thin films of ceria. Here, metal-organic chemical vapor deposition was carried out in a homemade reactor to grow ceria films for further electrical, electrochemical, and optical characterization. Doped/undoped ceria films are grown on single crystalline oxide wafers with/without Pt line pattern or Pt solid layer. Deposition conditions were varied to see the effect on the resultant film property. Recently, proton conduction in nanograined polycrystalline pellets of ceria drew much interest. Thickness-mode (through-plane, z-direction) electrical measurements were made to confirm the existence of proton conductivity and investigate the nature of the conduction pathway: exposed grain surfaces and parallel grain boundaries. Columnar structure presumably favors proton conduction, and we have found measurable proton conductivity enhancement. Electrochemical property of gas-columnar ceria interface on the hydrogen electrooxidation is studied by AC impedance spectroscopy. Isothermal gas composition dependence of the electrode resistance was studied to elucidate Sm doping level effect and microstructure effect. Significantly, preferred orientation is shown to affect the gas dependence and performance of the fuel cell anode. A hypothesis is proposed to explain the origin of this behavior. Lastly, an optical transmittance based methodology was developed to obtain reference refractive index and microstructural parameters (thickness, roughness, porosity) of ceria films via subsequent fitting procedure.

Electrochemical and electron transfer investigations of copper proteins

A study of the pH and temperature dependence of the redox potentials of azurins from five species of bacteria has been performed. The variations in the potentials with pH have been interpreted in terms of electrostatic interactions between the copper site and titrating histidine residues, including the effects of substitutions in the amino acid sequences of the proteins on the electrostatic interactions. A comparison of the observed pH dependences with predictions based on histidine pK_a values known for Pseudomonas aeruginosa (Pae), Alcaligenes denitrificans (Ade), and Alcaligenes faecalis (Afa) azurins indicates that the Pae and Ade redox potentials exhibit pH dependences in line with electrostatic arguments, while Afa azurin exhibits more complex behavior. Redox enthalpies and entropies for four of the azurins at low and high pH values have also been obtained. Based on these results in conjuction with the variable pH experiments, it appears that Bordetella bronchiseptica azurin may undergo a more substantial conformational change with pH than has been observed for other species of azurin.

The temperature dependence of the redox potential of bovine erythrocyte superoxide dismutase (SOD) has been determined at pH 7.0, with potassium ferricyanide as the mediator. The following thermodynamic parameters have been obtained (T = 25°C): E°' = 403±5 mV vs. NHE, ΔG°' = -9.31 kcal/mol, ΔH°' = -21.4 kcal/mol, ΔS°' = -40.7 eu, ΔS°'_(rc) = -25.1 eu. It is apparent from these results that ΔH°', rather than ΔS°', is the dominant factor in establishing the high redox potential of SOD. The large negative enthalpy of reduction may also reflect the factors which give SOD its high specificity toward reduction and oxidation by superoxide.

3D Fe3S4 flower-like microspheres: high-yield synthesis via a biomolecule-assisted solution approach, their electrical, magnetic and electrochemical hydrogen storage properties

Well-defined 3D Fe3S4 flower-like microspheres were synthesized via a simple biomolecule-assisted hydrothermal process for the first time. On the basis of a series of contrast experiments, the probable growth mechanism and fabrication process of the products were proposed. The electrical conductivity property of the as-synthesized Fe3S4 sample exhibited a rectifying characteristic when a forward bias was applied for the bottom-contacted device. The magnetic properties of the products were studied as well and the results demonstrated that the products presented ferromagnetic properties related to the corresponding microstructure. In addition, we first verified that the Fe3S4 flower-like microspheres could store hydrogen electrochemically, and a discharge capacity of 214 mA h g(-1) was measured without any activation under normal atmospheric conditions at room temperature.

A novel technique for NACE coupled with simultaneous electrochemiluminescence and electrochemical detection for fast analysis of tertiary amines

A simultaneous electrochemiluminescence (ECL) and electrochemical (EC) detection scheme for NACE was presented for fast analysis of tertiary amines. Both ECL and EC signals were generated at the same Pt electrode. Triethylamine (TEA), tripropylamine (TPrA), chlorpromazine, promethazine, and dioxopromethazine (DPZ) were selected to validate NACE-ECL/EC dual detection strategy. The linear ranges for TEA and TPrA were 0.01-500 and 0.01-10 mu M with the detection limits of 8.0 and 5.0 nM (S/N=3), respectively. The RSDs (n = 6) of the migration time and the ECL intensity for 1 mu M TEA and 0.5 mu M TPrA were 0.1 and 2.8%, and 0.2 and 1.8% with theoretical plate numbers of 180 000 and 700 000 per meter, respectively. These two analytes could be separated within 92 s and the Pt electrode did not need reactivation during the experiments.

Electrochemical detector based on sol-gel-derived carbon composite material for capillary electrophoresis microchips

An on-chip disk electrode based on sol-gel-derived carbon composite material could be easily and reproducibly fabricated. Unlike other carbon-based electrodes reported previously, this detector is rigid, convenient to fabricate, and amenable to chemical modifications. Based on the stable and reproducible characters of this detector, a copper particle-modified detector was developed for the detection of carbohydrates which extends the application of the carbon-based electrode. In our experiments, the performance of the new integrated detector for rapid on-chip measurement of epinephrine and glucose was illustrated. Experimental procedures including the fabrication of this detector, the configuration of separation channel outlet and electrode verge, and the performance characteristics of this new electrochemical detector were investigated.

Effect of water on the electrochemical oxidation process of biliverdin in dimethylformamide

A systematic study has been made for the electrochemical oxidation reaction of biliverdin (BV) in pure dimethylformamide (DMF) and in DMF - H2O mixed solvent by in situ time resolved spectroelectrochemical and cyclic voltametric techniques. The experiments show that not only the oxidation of BV is promoted, the reaction mechanism is also changed from a ECEC to a ECCECC process by the introduction of water into DMF.

THE APPLICATION OF ULTRAMICROELECTRODE IN HOMOGENEOUS CATALYTIC REACTION .5. ELECTROCHEMICAL-BEHAVIOR OF MACRO-MICRO-MACRO TRIPLE AND MICRO-MICRO TWIN ELECTRODES AND THE QUASI-FIRST-ORDER HOMOGENEOUS CATALYTIC REACTION (EC') AT GENERATION/COLLECTION ELECT

A new type of macro-micro-macro triple electrode has been fabricated, the steady-state currents of solution redox species have been observed at an ultramicroband electrode by linear potential scan voltammetry, and generation/collection experiments have al

INVESTIGATION OF ELECTROCHEMICAL-BEHAVIOR OF ARS ON GC ELECTRODE BY SPECTROELECTROCHEMISTRY WITH LOPTLC

The electrochemical behavior of Alizarin Red S(ARS) on GC electrode has been studied in acidic condition by spectroelectrochemistry with LOPTLC. It was found that there are three electrochemical reactions and followed by a chemical reaction of ARS in the potential range of 1.00——0.60V. The mechanism of electrode reactions has been studied and suggested based on the informations obtained from electrochemical and insitu spectroelectrochemical experiments.

Generation of palladium clusters on Au(111) electrodes: Experiments and simulations

The properties of palladium clusters, generated with the electrochemical scanning tunneling microscope, have been investigated both by experiments and by computer simulations. The clusters are found to be larger and more stable if the tip is moved further towards the electrode surface in the generation process. The simulations suggest that the larger clusters consist of a palladium - gold mixture, which is more stable than pure palladium. Dissolution of the clusters occurs from the edges rather than layer by layer