Role of electrolyte additives on in-vitro electrochemical behavior of micro arc oxidized titania films on Cp Ti

The present work is aimed at studying the influence of electrolyte chemistry on the voltage-time (V-T) response characteristics, phase structure, surface morphology, film growth rate and corrosion properties of titania films fabricated by micro arc oxidation (MAO) on Cp Ti. The titania films were developed with a sodium phosphate based reference electrolyte comprising the additives such as sodium carbonate (Na2CO3), sodium nitrite (NaNO2) and urea (CO(NH2)(2)). The phase composition, surface morphology, elemental composition and thickness of the films were assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The corrosion characteristics of the fabricated films were studied under Kokubo simulated body fluid (SBF) condition by potentiodynamic polarization, long term potential and linear polarization resistance (LPR) measurements and electrochemical impedance spectroscopy (EIS) methods. In addition, the corrosion characteristics of the grown films were analyzed by EIS curve fitting and equivalent circuit modeling. Salt spray test (SST) as per ASTM B 117 standard was also conducted to verify the corrosion resistance of the grown films. The XRD results showed that the titania films were composed of both anatase and rutile phases at different proportions. Besides, the films grown in carbonate and nitrite containing electrolyte systems showed an enhanced growth of their rutile phase in the 1 0 1] direction which could be attributed to the modifications introduced in the growth process by the abundant oxygen available during the process. The SEM-EDX and elemental mapping results showed that the respective electrolyte borne elements were incorporated and distributed uniformly in all the films. Among all the grown films under study, the film developed in carbonate containing electrolyte system exhibited considerably improved corrosion resistance due to suitable modifications in its structural and morphological characteristics. The rate of anatase to rutile phase transformation and the rutile growth direction were strongly influenced by the abundant oxidizing species available during the film growth process. (C) 2012 Elsevier B. V. All rights reserved.

Determination of alpha(s)(M-tau(2)) from improved fixed order perturbation theory

We revisit the extraction of alpha(s)(M-tau(2)) from the QCD perturbative corrections to the hadronic tau branching ratio, using an improved fixed-order perturbation theory based on the explicit summation of all renormalization-group accessible logarithms, proposed some time ago in the literature. In this approach, the powers of the coupling in the expansion of the QCD Adler function are multiplied by a set of functions D-n, which depend themselves on the coupling and can be written in a closed form by iteratively solving a sequence of differential equations. We find that the new expansion has an improved behavior in the complex energy plane compared to that of the standard fixed-order perturbation theory (FOPT), and is similar but not identical to the contour-improved perturbation theory (CIPT). With five terms in the perturbative expansion we obtain in the (MS) over bar scheme alpha(s)(M-tau(2)) = 0.338 +/- 0.010, using as input a precise value for the perturbative contribution to the hadronic width of the tau lepton reported recently in the literature.

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

Electrochemical, phosphate hydrolysis, DNA binding and DNA cleavage properties of new polyaza macrobicyclic dinickel(II) complexes

A new class of macrobicyclic dinickel(II) complexes Ni2L1,2 B](ClO4)(4) (1-6), where L-1,L-2 are polyaza macrobicyclic binucleating ligands, and B is a N,N-donor heterocyclic base (viz. 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen)) are synthesized and characterized. The redox, catalytic, DNA binding and DNA cleavage properties were studied. They exhibit two irreversible waves in the cathodic region around E-pc = -0.95 V and E-pa = -0.85 V vs. Ag/Ag+ in CH3CN-0.1 M TBAP, respectively. The first order rate constants for the hydrolysis of 4-nitrophenylphosphate to 4-nitrophenolate by the dinickel(II) complexes 1-6 are in the range from 3.36 x 10(-5) to 10.83 x 10(-5) Ms-1. The complexes 3 and 6 show good binding propensity to calf thymus DNA giving binding constant values (K-b) in the range from 3.08 x 10(5) to 5.37 x 10(5) M-1. The binding site sizes and viscosity data suggest the DNA intercalative and/or groove binding nature of the complexes. The complexes display significant hydrolytic cleavage of supercoiled pBR322DNA at pH 7.2 and 37 degrees C. The hydrolytic cleavage of DNA by the complexes is supported by the evidence from free radical quenching and T4 ligase ligation. The pseudo Michaelis-Menten kinetic parameters k(cat) = 5.44 x 10(-2) h(-1) and K-M = 6.23 x 10(-3) M for complex 3 were obtained. Complex 3 also shows an enormous enhancement of the cleavage rate, of 1.5 x 10(6), in comparison to the uncatalysed hydrolysis rate (k = 3.6 x 10(-8) h(-1)) of ds-DNA.

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.

In Situ Electrochemical Polymerization at Air-Water Interface: Surface-Pressure-Induced, Graphene-Oxide-Assisted Preferential Orientation of Polyaniline

In situ electrochemical polymerization of aniline in a Langmuir trough under applied surface pressure assists in the preferential orientation of polyaniline (PANI) in planar polaronic structure. Exfoliated graphene oxide (EGO) spread on water surface is used to bring anilinium cations present in the subphase to air-water interface through electrostatic interactions. Subsequent electrochemical polymerization of aniline under applied surface pressure in the Schaefer mode results in EGO/PANT composite with PANT in planar polaronic form. The orientation of PANI is confirmed by electrochemical and Raman spectroscopic studies. This technique opens up possibilities of 2-D polymerization at the air-water interface. Electrochemical sensing of hydrogen peroxide is used to differentiate the activity of planar and coiled forms of PANI toward electrocatalytic reactions.

Sensitive Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Olanzapine in Human Urine

A sensitive and selective liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed to determine olanzapine (OLZ) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C-18 column (Symmetry 3.5 mu m, 50 x 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of ammonium acetate (pH 7.8)-acetonitrile (10:90, v/v). The method was linear over a concentration range of 1-100 ngml(-1). The lower limit of quantitation was 1 ngml(-1). The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was < 11.5 %. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ngml(-1) OLZ) was within +/- 1.21 % in terms of relative errors.

Mesoporous MnO2 synthesized by hydrothermal route for electrochemical supercapacitor studies

Poorly crystalline mesoporous MnO2, which is suitable for supercapacitor studies, is synthesized from neutral KMnO4 aqueous solution by hydrothermal route. But it requires a high temperature (180 A degrees C) and also a long reaction time (24 h). Addition of a tri-block copolymer, namely, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123), which is generally used as a soft template for the synthesis of nano-structured porous materials, reduces the hydrothermal temperature to 140 A degrees C and also reaction time to 2 h. When the reaction time is increased, the product morphology changes from nanoparticles to nanorods with a concomitant decrease in BET surface area. Also, the product tends to attain crystallinity. The electrochemical capacitance properties of MnO2 synthesized under varied hydrothermal conditions are studied in 0.1 M Na2SO4 electrolyte. A specific capacitance of 193 F g(-1) is obtained for the mesoporous MnO2 sample consisting of nanoparticle and nanorod mixed morphology synthesized in 6 h using P123 at 140 A degrees C.

Determination of C-13 Chemical Shift Anisotropy Tensors and Molecular Order of 4-Hexyloxybenzoic Acid

4-Alkoxy benzoic acids belong to an important class of thermotropic liquid crystals that are structurally simple and often used as starting materials for many novel mesogens. 4-Hexyloxybenzoic acid (HBA) is a homologue of the same series and exhibits an enantiotropic nematic phase. As this molecule could serve as an ideal model compound, high resolution C-13 NMR studies of HEA in solution, solid, and liquid crystalline phases have been undertaken. In the solid state, two-dimensional separation of undistorted powder patterns by effortless recoupling (2D SUPER) experiments have been carried out to estimate the magnitude of the components of the chemical shift anisotropy (GSA) tensor of all the aromatic carbons. These values have been used subsequently for calculating the orientational order parameters in the liquid crystalline phase. The GSA values computed by density functional theory (DFT) calculations showed good agreement with the 2D SUPER values. Additionally, C-13-H-1 dipolar couplings in the nematic phase have been determined by separated local field (SLF) spectroscopy at various temperatures and were used for computing the order parameters, which compared well with those calculated by using the chemical shifts. It is anticipated that the CSA values determined for MBA would be useful for the assignment of carbon chemical shifts and for the study of order and dynamics of structurally similar novel mesogens in their nematic phases.

Electrochemical studies on Zn/nano-CeO 2 electrodeposited composite coatings

The Zn-CeO 2 composite coatings through electrodeposition technique were successfully fabricated on mild steel substrate. As a comparison pure zinc coating was also prepared. The concentration of CeO 2 nanoparticles was varied in the electrolytic bath and the composites were electrodeposited both in the presence and absence of cetyltriammonium bromide (CTAB). The performance of the CeO 2 nanoparticles towards the deposition, crystal structure, texture, surface morphology and electrochemical corrosion behavior was studied. For characterizations of the electrodeposits, the techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) were used. Both the additives ceria and surfactant polarize the reduction processes and thus influence the deposition process, surface nature and the electrochemical properties. The electrochemical experiments like potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies carried out in 3.5 wt. NaCl solution explicit higher corrosion resistance by CeO 2 incorporated coating in the presence of surfactant. © 2012 Elsevier B.V. All rights reserved.

ZnO and ZnO/polyglycine modified carbon paste electrode for electrochemical investigation of dopamine

Present work describes the characterization of commercially available ZnO and its electrochemical investigation of dopamine in the presence of ascorbic acid. ZnO was characterized by powder XRD, UV-visible absorption, fluorescence, infrared spectroscopy and scanning electron microscopy. The carbon paste electrode was modified with ZnO and ZnO/polyglycine for further electrochemical investigation of dopamine. The modified electrode shows good electrocatalytic activity towards the detection of dopamine with a reduction in overpotential. The ZnO/polyglycine modified carbon paste electrode (CPE/ZnO/Pgl) shows excellent electrochemical enhancement of peak currents for both dopamine (DA) and ascorbic acid (AA) and for simultaneous detection of DA in the presence of high concentrations of AA with 0.214 V oxidation peak potential differences between them at pH 7.4. From the scan rate variation and concentration, the oxidation of DA and AA was found to be adsorption-controlled. The use of CPE/ZnO/Pgl is demonstrated for the detection of DA in blood serum and injection samples. This journal is © The Royal Society of Chemistry 2012.

H-1, C-13, N-15 assignment and secondary structure determination of glutamine amido transferase subunit of gaunosine monophosphate synthetase from Methanocaldococcus jannaschii

Sequence specific resonance assignments have been obtained for H-1, C-13 and N-15 nuclei of the 21 kDa (188 residues long) glutamine amido transferase subunit of guanosine monophosphate synthetase from Methanocaldococcus jannaschii. From an analysis of H-1 and C-13(alpha), C-13(beta) secondary chemical shifts, (3) JH(N)H(alpha) scalar coupling constants and sequential, short and medium range H-1-H-1 NOEs, it was deduced that the glutamine amido transferase subunit has eleven strands and five helices as the major secondary structural elements in its tertiary structure.

Optical, electrochemical and morphological investigations of poly (3,4-propylenedioxythiophene)-sultone (PProDOT-S) thin films

In this paper, we have carried out thin film characterization of poly(3,4-propylenedioxythiophene)-sultone (PProDOT-S), a derivative of electrochromic poly(3,4-propylenedioxythiophene) (PProDOT). PProDOT-S was deposited onto transparent conducting oxide coated glass substrates by solution casting method. Single wavelength spectrophotometry is used to monitor the switching speed and contrast ratio at maximum wavelength (lambda (max)). The percentage transmittance at the lambda (max) of the neutral polymer is monitored as a function of time when the polymer film is repeatedly switched. This experiment gives a quantitative measure of the speed with which a film is able to switch between the two states i.e. the coloured and the bleached states. PProDOT-S films were switched at a voltage of 1 center dot 9 V with a switching speed of 2 s at lambda (max) of 565 nm and showed a contrast of similar to 37%. Cyclic voltammetry performed at different scan rates have shown the characteristic anodic and cathodic peaks. The structural investigations of PProDOT-S films by IR spectra were in good agreement with previously reported results. Raman spectra of PProDOT-S showed a strong Raman peak at 1509 cm (-aEuro parts per thousand 1) and a weak peak at 1410 cm (-aEuro parts per thousand 1) due to the C = C asymmetric and symmetric stretching vibrations of thiophene rings. The morphological investigations carried out by using scanning electron microscope (SEM) of polymer films have shown that these polymers are found to be arranged in dense packed clusters with non-uniform distribution having an average width and length of 95 nm and 160 nm, respectively.

A new method for fracture toughness determination of graded (Pt,Ni)Al bond coats by microbeam bend tests

A novel method is proposed for fracture toughness determination of graded microstructurally complex (Pt,Ni)Al bond coats using edge-notched doubly clamped beams subjected to bending. Micron-scale beams are machined using the focused ion beam and loaded in bending under a nanoindenter. Failure loads gathered from the pop-ins in the load-displacement curves combined with XFEM analysis are used to calculate K-c at individual zones, free from substrate effects. The testing technique and sources of errors in measurement are described and possible micromechanisms of fracture in such heterogeneous coatings discussed.

An Exfoliated Graphite-Based Bisphenol A Electrochemical Sensor

The use of an exfoliated graphite (EG) electrode in the square wave voltammetric detection of bisphenol A (a model phenolic pollutant) in water, whereby the phenolic electrode fouling challenge is mitigated, is described. The oxidation peak of BPA was observed at about 0.45 V in phosphate buffer solution at pH 10. The current response exhibited a linear relationship with the concentration over a range from 1.56 mu M-50 mu M. The detection limit was calculated to be 0.76 mu M. The EG electrode surface was renewed after each measurement with excellent reproducibility. A real sample application was also investigated.