Electrocatalysis of hydrogen evolution reaction on Pt electrode surface-modified by S-2 chemisorption

Kinetic studies of hydrogen evolution reaction (HER) at the surface of Pt in alkaline conditions, reported in this paper, show that electrocatalytic activity is enhanced after adsorption of S-2 ions. EIS and steady-state polarization curve data pointed to an undoubted improvement in performance with the Pt-S cathode that was attributed to higher adsorbed hydrogen coverage. Experimental findings suggested an increase in the electronic density of the modified surface sites that may strengthen the interaction between H2O and the adsorption site and, consequently, accelerates the Volmer step. (c) 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

XPS investigation of plasma-deposited polysiloxane films irradiated with helium ions

This work describes an XPS investigation of plasma-deposited polysiloxane films irradiated with 170 keV He+ ions at fluences, Phi, ranging from 1 x 10(14) to 1 x 10(16) cm(-2). Modifications in the atomic concentrations of the surface atoms with (D were revealed by changes in the [O]/[Si], [O]/[C] and [C]/[Si] atomic ratios. Surface chemical structure modifications were evidenced by the increasing C1s peak width and asymmetry as Phi was increased, due to the formation of ether and carboxyl functionalities. Moreover, structural transformations were indicated by the positive binding energy shift of the Si2p peaks, due to the increasing Si oxidation. Correlations of the XPS data with other results from previous work on polysiloxanes illustrate the role of ion beam-induced bond breaking on the structural modifications.

Variable influence of ferric and cupric ions on Saccharomyces cerevisiae strains used in asymmetric organic synthesis.

Fe (III) and Cu (II) each at 50 mu M in four commercial strains of Saccharomyces cerevisiae induced an increase of NAD(P)(+) reduction in one strain (Turkish), but two others (Chilean and Brazilian), the presence of Fe(III) and/or Cu(II) diminished NAD(P)(+) reduction presumably due to free radicals formation inside these living cells. Suprisingly, in the American strain, Fe(III) induced a decrease and Cu (II) an increase of NAD(P)(+) reduction.

Spectroscopic studies of the Eu3+ and Er3+ ions in the fluorozirconate LaZr2F11 matrix

An investigation by optical spectroscopy of the Eu3 + and Er3 + active ions in the crystallized fluorozirconate matrix LaZr2F11 is presented. The D-5(1) --> F-7(0-5) emission lines of Eu3 + are used to extract the F-7(0-5) energy scheme and the observed extinctions permit the deduction of irreducible representations (IRREPS) associated with corresponding sub-levels in the D-2 symmetry. The crystal field analysis was carried out on a 387 x 387 basis set, comprising the F-7, D-5(1,2,3) F-5(1,2), (5)G(1,2,3) and P-3(1,2,3,4,5,6) terms of the Eu-3 (+) 4f(6) configuration. The deviation and rms are 6.8 and 7.9 cm (-1), respectively for 38 levels and ten parameters. The experimental crystal field parameters are in good agreement with the ab-initio ones. Moreover, the relative intensities of the D-5(0) --> F-7(2,3,4) emissions are well reproduced by an 'ab-initio' calculation, except for three lines. The Er3 + ions introduced in LaZr2F11, microcrystals also lie in an unique crystallographic site. A total of 31 energy levels were recorded and the crystal field analysis led to 6.6 and 7.8 cm (-1) for the deviation and rms, respectively, for nine variable parameters taken into account. The experimental CF parameters for Er3 + and Eu3 + are very similar, which seems to show that the host lattice contracts around the smaller Er3 + ion. The informations given by both Eu3 + and Eu3 + optical probes in LaZr2F11 are very consistent with the structure previously determined for the isotypic PrZr2F11 fluoride. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Fluorescence study of the interaction between metal ions and methyl methacrylate methacrylic acid copolymers in aqueous solutions: thallium(I), calcium(II), and terbium(III)

The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

The hydrogen evolution reaction on codeposited Ni-hydrogen storage intermetallic particles in alkaline medium

The hydrogen evolution reaction (HER) was studied on Ni-LaNi5 and Ni-MmNi(3.4)Co(0.8)Al(0.8) electrode materials in 1 mol dm(-3) NaOH solution. The steady-state polarization curves and electrochemical impedance spectroscopy experimental data showed a pronounced improvement in HER kinetics when these electrode materials were used. The electrochemical results are in accordance with the Volmer-Heyrovsky mechanism. The kinetic results indicate a more effective improvement in the Heyrovsky step, suggesting an electrocatalytic synergistic effect of the hyper-electronic character of the Ni and the hypo-electronic character of the rare-earth element on the electrode surface. (C) 2000 International Association for Hydrogen Energy. Published by Elsevier B.V. Ltd. All rights reserved.

Red-green-blue upconversion emission and energy-transfer between Tm3+ and Er3+ ions in tellurite glasses excited at 1.064 mu m

Red, green, and blue emission through frequency upconversion and energy-transfer processes in tellurite glasses doped with Tm3+ and Er3+ excited at 1.064 mum is investigated. The Tm3+/Er3+-codoped samples produced intense upconversion emission signals at around 480, 530, 550 and 660 nm. The 480 nm blue emission was originated from the (1)G(4)-->H-3(6) transition of the Tm3+ ions excited by a multiphoton stepwise phonon-assisted excited-state absorption process. The 5 30, 5 50 nm green and 660 mn red upconversion luminescences were identified as originating from the H-2(11/2), S-4(3/2) --> I-4(15/2) and F-4(9/2) --> I-4(15/2) transitions of the Er3+ ions, respectively, populated via efficient cross-relaxation processes and excited-state absorption. White light generation employing a single infrared excitation source is also examined. (C) 2003 Elsevier B.V. (USA). All rights reserved.

Application of voltammetric technique to the analysis of indanthrene dye in alkaline solution

The Indanthrene Olive Green B (C.I. Vat Green 3; C.I. 69500), VG3 dye, a vat dye bearing an anthraquinonoid group and a ketonic group, can be detected by differential pulse voltammetry in alkaline solution using glassy carbon electrode. on the adsorbed form the dyes are reduced into three cathodic steps at -0.54 V, -0.65 V and -0.93 V vs Ag/AgCl. The leuco form generated after previous electrolysis at controlled potential of -1 V can be detected by voltammetry due to its reoxidation peak at -0.08 V. An analytical method is proposed for determining the vat dye using modified glassy carbon electrode by electrochemical activation in alkaline medium. Linear relationship was observed between l(Pu) vs concentration from I X 10(-5) mol L-1 to 6.0 X 10(-4) mol L-1. The detection limit was calculated to be 9.3 X 10(-6) mol L-1. (c) 2005 Elsevier Ltd. All rights reserved.

PRODUCTION OF MICROBIAL ALKALINE CELLULASE AND STUDIES OF THEIR CHARACTERISTICS

In order to obtain cellulases that improve the detergency of laundry detergent products, two alkalophilic microorganims, Bacillus sp B38-2 and Streptomyces sp S36-2, were isolated from soil and compost by incubating samples in enrichment culture medium containing CMC and Na2CO3 at pH9.6. It was found that they secrete a constitutive extracellular alkaline carboxymethyl cellulase (CMCase) in high quantity. The maximum enzyme activity was observed between 48hr to 72 hr at 30-degrees-C for the Streptomyces and between 72hr to 96hr at 35-degrees-C for the Bacillus. The optimum pH and temperature of the crude enzyme activities ranged from 6.0 to 7.0 at 55-degrees-C for the Streptomyces and 7.0 to 8.0 at 60-degrees-C for the Bacillus. Two crude CMCases activities were termostable at 45-degrees-C for 1hr and the both crude enzyme activities of the Bacillus as of the Streptomyces were stable at pH 5.0 to 9.0 after pH treatments in various buffer solutions at 30-degrees-C for 24hr.

Solid-state compounds of 2-chlorobenzylidenepyruvate with some bivalent metal ions - Synthesis, characterization and thermal behaviour

Solid-state M-2-Cl-BP, where M stands for Mn, Fe, Co, Ni, Cu, Zn and Pb and 2-Cl-BP is 2-chlorobenzylidenepyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), simultaneous thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.

Energy transfer between Tm3+ and Er3+ ions in a TeO2-based glass pumped at diode laser wavelength

In this paper we investigate the energy transfer processes in TM3+/Er3+ doped telluride glass pumped at the commercial diode laser pump wavelength similar to 800 nm. Tailoring the rare-earths content in the glass matrix, seven main energy transfer channels within the doping range considered were identified, A 6-fold enhancement of the Er3+ visible frequency upconversion fluorescence at similar to 660 nm is observed due to the inclusion of Tm3+ ions. This is evidence of the relevant contribution of the route Er-1(I-4(11/2)) + Er-2(I-4(13/2)) -> Er-1(I-4(15/2)) + Er-2(F-4(9/2)) to the process. Energy migration among pumped I-4(9/2) level reducing the efficiency of the upconversion emission rate (H-3(11/2), S-4(3/2), and F-4(9/2)) is observed for Er3+ above 1.5 wt%. The rate equations regarding the observed energy transfer routes are determined and a qualitative analysis of the observed processes is reported. (c) 2006 Elsevier B.V. All rights reserved.

THE PHO-2A MUTANT OF NEUROSPORA-CRASSA WHICH IS DEFICIENT IN PI-REPRESSIBLE ALKALINE-PHOSPHATASE (EC 3.1.3.1) IS ALSO DEFECTIVE IN PI-REPRESSIBLE ACID-PHOSPHATASE (EC 3.1.3.2)

1. The mycelial Pi-repressible acid phosphatase presented p-nitrophenylphosphatase activity with negative cooperativity and Michaelian behavior when synthesized by the wild-type and pho-2A mutant strains of Neurospora crassa, respectively.2. The major acid phosphatase present in cell extracts of the pho-2A mutant of N. crassa grown in low Pi medium is more thermolabile (t1/2 = 4 min at 54-degrees-C, pH 5.4) than that of the wild strain (stable for at least 80 min at 54-degrees-C, pH 5.4).3. The pho-2A mutant of N. crassa secreted a more thermolabile acid phosphatase (t1/2 = 30 min at 50-degrees-C, pH 5.4) than the wild strain (t1/2 of at least 80 min at 50-degrees-C, pH 5.4).4. The pho-2A mutant of N. crassa synthesized a more thermolabile acid phosphatase (t1/2 = 37 min at 54-degrees-C, pH 5.4) than the wild strain in high Pi medium (t1/2 = 14 min al 54-degrees-C, pH 5.4).5. The pleiotropic nature of the pho-2 locus and its possible involvement in the mechanism of phosphatase secretion by N. crassa are proposed.