Mercury Segregation and Diselenide Self-Assembly on Gold

We have investigated the self-assembly of didecyldiselenide on gold containing mercury using X-ray photoelectron spectroscopy, cyclic voltammetry and infrared spectroscopy. The analysis of intensity and chemical shift of selected Se, Hg, and Au photoelectron lines on samples with increasing Hg content, show that didecyldiselenide adsorption strongly contributed to segregation of bulk Hg to the surface. The voltammetry results support this conclusion and suggest the formation of Hg-Au surface amalgam. The Hg surface segregation effect must be related to the restructuring of the surface following initial adsorption, and to the strong selenophilicity of Hg. The reflectance absorbance infrared spectroscopy studies show that the molecular layer on Hg-Au substrates lacks good order.

DNA-binding and nuclease activity of1,10-phenanthroline-based thiocyanato, acetato, azido and benzoato bridged dinuclear copper(II) complexes

The mononuclear Cu(II) complex [Cu(phen)(H2O)(NO3)(2)] (1), obtained by the reaction of 1,10-phenanthroline with Cu(NO3)(2)center dot 3H(2)O in methanol solution, reacts with anionic ligands SCN-, AcO-, N-3(-) and PhCO2- in MeOH solution to form the stable binuclear complexes [Cu-2(H2O)(2)(phen)(2)(mu-X)(2)](2) (NO3)(2), where X = SCN- (2), AcO- (3), N-3(-) (4) or PhCO2- (5). The molecular structure of complex 3 was determined by single-crystal X-ray diffraction studies. These complexes were characterized by electronic, IR, ESR, magnetic moments and conductivity measurements. The electrochemical behaviour of the complexes was investigated by cyclic voltammetry. The interactions of these complexes with calf thymus DNA have been investigated using absorption spectrophotometry. Their DNA cleavage activity was studied on double-stranded pBR322 plasmid DNA using gel electrophoresis experiments in the absence and presence of H2O2 as oxidant.

DNA-binding and nuclease activity of 1,10-phenanthroline-based thiocyanato, acetato, azido and benzoato bridged dinuclear copper(II) complexes

The mononuclear Cu(II) complex [Cu(phen)(H2O)(NO3)(2)] (1), obtained by the reaction of 1,10-phenanthroline with Cu(NO3)(2)center dot 3H(2)O in methanol solution, reacts with anionic ligands SCN-, AcO-, N-3(-) and PhCO2- in MeOH solution to form the stable binuclear complexes [Cu-2(H2O)(2)(phen)(2)(mu-X)(2)](2) (NO3)(2), where X = SCN- (2), AcO- (3), N-3(-) (4) or PhCO2- (5). The molecular structure of complex 3 was determined by single-crystal X-ray diffraction studies. These complexes were characterized by electronic, IR, ESR, magnetic moments and conductivity measurements. The electrochemical behaviour of the complexes was investigated by cyclic voltammetry. The interactions of these complexes with calf thymus DNA have been investigated using absorption spectrophotometry. Their DNA cleavage activity was studied on double-stranded pBR322 plasmid DNA using gel electrophoresis experiments in the absence and presence of H2O2 as oxidant.

Durable Transition-Metal-Carbide-Supported Pt-Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. PtRu catalysts supported on MoC, WC, and Vulcan XC-72R are prepared, and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro-oxidation are studied by cyclic voltammetry. All the electro-catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide-supported electro-catalysts towards methanol electro-oxidation is found to be higher than carbon-supported catalysts before and after ADT. The study suggests that PtRu/MoC and PtRu/WC catalysts are more durable than PtRu/C. Direct methanol fuel cells (DMFCs) with PtRu/MoC and PtRu/WC anodes also exhibit higher performance than the DMFC with PtRu/C anode.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

Acenaphtho[1,2-b]quinoxaline based low band gap copolymers for organic thin film transistor applications

We report the synthesis of a novel class of low band gap copolymers based on anacenaphtho[1,2-b]quinoxaline core and oligothiophene derivatives acting as the acceptor and the donor moieties, respectively. The optical properties of the copolymers were characterized by ultraviolet-visible spectroscopy while the electrochemical properties were determined by cyclic voltammetry. The band gap of these polymers was found to be in the range 1.8-2.0 eV as calculated from the optical absorption band edge. X-ray diffraction measurements show weak pi-pi stacking interactions between the polymer chains. The hole mobility of the copolymers was evaluated using field-effect transistor measurements yielding values in the range 10(-5)-10(-3) cm(2)/Vs.

Synthesis and Electrochemical Characterization of LiNi0.8Co0.2O2 as Cathode Material for Aqueous Rechargeable Lithium Batteries

LiNi0.8Co0.2O2 cathode material for lithium ion batteries is synthesized by reaction under autogenic pressure at elevated temperature (RAPET) method. The simple synthesis procedure is time and energy saving, and thus is promising for commercial application. The structure and stability of the material have been characterized by means of XRD and TG-DTA. The electrochemical properties of the LiNi0.8Co0.2O2 cathode are investigated in 2 M Li2SO4 aqueous electrolyte and they are compared to that in an organic electrolyte. A battery cell consisting of LiNi0.8Co0.2O2 as cathode in 2 M Li2SO4 solution is constructed in combination with LiTi2 (PO4)(3) as anode. The cell retained almost constant discharge capacity over hundred cycles. The electrochemical impedance spectral ( EIS) studies in aqueous and nonaqueous electrolytes revealed that the mechanism of lithium ion intercalation and deintercalation processes in LiNi0.8Co0.2O2 electrode follow almost similar mechanism in both aqueous and nonaqueous electrolytes. The chemical diffusion coefficient was calculated from slow scan rate cyclic voltammetry and EIS. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.075205jes] All rights reserved.

Chemically functionalized glassy carbon spheres: a new covalent bulk modified composite electrode for the simultaneous determination of lead and cadmium

A new type of covalent bulk modified glassy carbon composite electrode has been fabricated and utilized in the simultaneous determination of lead and cadmium ions in aqueous medium. The covalent bulk modification was achieved by the chemical reduction of 2-hydroxybenzoic acid diazonium tetrafluroborate in the presence of hypophosphorous acid as a chemical reducing agent. The covalent attachment of the modifier molecule was examined by studying Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and the surface morphology was examined by scanning electron microscopy images. The electrochemistry of modified glassy carbon spheres was studied by its cyclic voltammetry to decipher the complexing ability of the modifier molecules towards Pb2+ and Cd2+ ions. The developed sensor showed a linear response in the concentration range 1-10 mu M with a detection limit of 0.18 and 0.20 mu M for lead and cadmium, respectively. The applicability of the proposed sensor has been checked by measuring the lead and cadmium levels quantitatively from sewage water and battery effluent samples.

Solution processable quinoxaline based molecular materials for organic field effect transistors

Three new solution processable quinoxaline based donor-acceptor-donor (D-A-D) type molecules have been synthesized for application in field effect transistors. These molecules were characterized by UV-visible spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and cyclic voltammetry. DFT calculation gives deeper insight into the electronic structure of these molecules. The crystallinity and morphology features of thin film were investigated using X-ray diffraction. These molecules show liquid crystalline phase confirmed by DSC and optical polarizing microscopy. Investigation of their field effect transistor performance indicated that these molecules exhibited p-type mobility up to 9.7 x 10 (4) cm(2) V (1) s (1) and on/off ratio of 10(4). (C) 2012 Elsevier B.V. All rights reserved.

Cyclopentac]thiophene oligomers based solution processable D-A copolymers and their application as FET materials

Two new solution processable, low band gap donor-acceptor (D-A) copolymers (P1 and P2) comprising a cyclopentac] thiophene (CPT) based oligomers as donors and benzoc]1,2,5] selenadiazole (BDS) and 2-dodecyl1,2,3]-benzotriazole (BTAz) as acceptors were synthesized and characterized and their field effect transistor properties were studied. The internal charge transfer interaction between the electron-donating CPT based oligothiophene and the electron-accepting BDS or BTAz unit effectively reduces the band gap in polymers to 1.3 and 1.66 eV with low lying highest occupied molecular orbital (HOMO). The absorption spectrum of P1 was found to be more red shifted than that of P2 because of incorporation of the more electron-withdrawing BDS unit. The color of neutral P1 was found to be green in both solution and film states with two major bands in the absorption spectra; however, neutral P2 revealed one dominant absorption exhibiting red color in both solution and film state which could be attributed to the less electron-withdrawing effect of the BTAz unit. The polymers were further characterized by GPC, TGA, DSC and cyclic voltammetry. P1 and P2 exhibited charge carrier mobilities as high as 9 x 10(-3) cm(2) V-1 s(-1) and 2.56 x 10(-3) cm 2 V-1 s(-1), respectively with the current on/off ratio (I-on/I-off) in the order of 10(2).

Lead ion sensor with electrodes modified by imidazole-functionalized polyaniline

Glassy carbon electrodes (GCE) and carbon paste electrodes (CPE) were modified with imidazole functionalized polyaniline with the aim to develop a sensor for lead (II) in both acidic and basic aqueous solution. The electrodes were characterized by cyclic voltammetry and differential pulse adsorptive stripping voltammetry. The limit of detections obtained with glassy carbon electrode and carbon paste electrode are 20 ng mL(-1) and 2 ng mL(-1) of lead ion, respectively. An interference study was carried out with Cd(II), As(III), Hg(II) and Co(II) ions. Cd(II) ions interfere significantly (peak overlap) and As(III) has a depressing effect on the lead signal. The influence of pH was investigated indicating that bare and modified GCE and CPE show optimum response at pH 4.0 +/- 0.05.

Electrochemical Detection of Bisphenol A Using Graphene-Modified Glassy Carbon Electrode

Graphene's nano-dimensional nature and excellent electron transfer properties underlie its electrocatalytic behavior towards certain substances. In this light, we have used graphene in the electrochemical detection of bisphenol A. Graphene sheets were produced via soft chemistry route involving graphite oxidation and chemical reduction. X-ray diffraction, Fourier transform infra-red (FT-IR) and Raman spectroscopy were used for the characterization of the as-synthesized graphene. Graphene exhibited amorphous structure in comparison with pristine graphite from XRD spectra. FTIR showed that graphene exhibits OH and COOH groups due to incomplete reduction. Raman spectroscopy revealed that multi-layered graphene was produced due to low intensity of the 2D-peak. Glassy carbon electrode was modified with graphene by a simple drop and dry method. Cyclic voltammetry was used to study the electrochemical properties of the prepared graphene-modified glassy carbon electrode using potassium ferricyanide as a redox probe. The prepared graphene- modified glassy carbon electrode exhibited more facile electron kinetics and enhanced current of about 75% when compared to the unmodified glassy carbon electrode. The modified electrode was used for the detection of bisphenol A. Under the optimum conditions, the oxidation peak current of bisphenol A varied linearly with concentration over a wide range of 5 x 10(-8) mol L-1 to 1 x 10(-6) mol L-1 and the detection limit of this method was as low as 4.689 x 10(-8) M. This method was also employed to determine bisphenol A in a real sample

Morphology dependent electrochemical performance of sputter deposited Sn thin films

This study deals with tailoring of the surface morphology, microstructure, and electrochemical properties of Sn thin films deposited by magnetron sputtering with different deposition rates. Scanning electron microscopy and atomic force microscopy are used to characterize the film surface morphology. Electrochemical properties of Sn thin film are measured and compared by cyclic voltammetry and charge-discharge cycle data at a constant current density. Sn thin film fabricated with a higher deposition rate exhibited an initial discharge capacity of 798 mAh g(-1) but reduced to 94 mAh g(-1) at 30th cycle. Film deposited with lower deposition rate delivered 770 mAh g(-1) during 1st cycle with improved capacity retention of 521 mAh g(-1) on 30th cycle. Comparison of electrochemical performances of these films has revealed important distinctions, which are associated with the surface morphology and hence on rate of deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Rapid sonochemical synthesis of mesoporous MnO2 for supercapacitor applications

Mesoporous MnO2 samples with average pore-size in the range of 2-20 nm are synthesized in sonochemical method from KMnO4 by using a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) as a soft template as well as a reducing agent. The MnO2 samples are found to be poorly crystalline. On increasing the amplitude of sonication, a change in the morphology of MnO2 from nanoparticles to nanorods and also change in porosity are observed. A high BET surface area of 245 m(2) g(-1) is achieved for MnO2 sample. The MnO2 samples are subjected to electrochemical capacitance studies by cyclic voltammetry (CV) and galvanostatic charge-discharge cycling in 0.1 M aqueous Ca(NO3)(2) electrolyte. A maximum specific capacitance (SC) of 265 Fg(-1) is obtained for the MnO2 sample synthesized in sonochemical method using an amplitude of 30 mu m. The MnO2 samples also possess good electrochemical stability due to their favourable porous structure and high surface area. (C) 2012 Elsevier B.V. All rights reserved.

A Durable RuO2-Carbon-Supported Pt Catalyst for PEFCs: A Cause and Effect Study

As Polymer Electrolyte Fuel Cells (PEFCs) are nearing the acceptable performance level for automotive and stationary applications, the focus on the research is shifting more and more toward enhancing their durability that still remains a major concern in their commercial acceptability. Hydrous ruthenium oxide (RuO2) is a promising material for pseudocapacitors due to its high stability, high specific-capacitance and rapid faradaic-reaction. Incorporation of carbon-supported RuO2 (RuO2/C) to platinum (Pt) is found to ameliorate both stability and catalytic activity of fuel cell cathodes that exhibit higher performance and durability in relation to Pt/C cathodes as evidenced by cell polarization, impedance and cyclic voltammetry data. The degradation in performance of Pt-RuO2/C cathodes is found to be only similar to 8% after 10000 accelerated stress test (AST) cycles as against similar to 60% for Pt/C cathodes after 7000 AST cycles under similar conditions. These data are in conformity with the Electrochemical Surface Area and impedance results. Interestingly, Pt-RuO2/C cathodes can withstand more than 10000 AST cycles with only a nominal loss in their performance. Studies on catalytic electrodes with X-ray diffraction, transmission electron microscopy and cross-sectional field-emission scanning electron microscopy reflect that incorporation of RuO2 to Pt helps mitigating aggregation of Pt particles and improves its stability during long-term operation of PEFCs. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.jes113440] All rights reserved.