Digital simulation of electrochemical processes involving very fast chemical reactions : Part 2. A new criterion for determining rate constants of consecutive second-order irreversible chemical reactions

Electrode reactions followed by very fast chemical reactions are considered. A simple approach, in which steady state and linear concentration profiles in the reaction layer are assumed, is proposed for the simulation of these processes when the substrate is not present in large excess. When the substrate/depolarizer mole ratio is less than one, two well-separated peaks are detected; under such conditions, working curves that enable the corresponding second-order homogeneous rate constant to be evaluated can be derived by the finite-difference simulation technique. The method is applied to elucidation of the reduction of the tetrakis(triphenylphosphine)nickel(I) complex in the presence of hydrogen ions in acetonitrile at ?30°C.     

Proteomics of gluten: mapping of the 1Bx7 glutenin subunit in Chinese Spring cultivar by matrix-assisted laser desorption/ionization

The verification of the cDNA-deduced sequence of the high molecular weight glutenin subunit 1Bx7 in Chinese Spring cultivar was achieved by direct matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) analysis of the tryptic fragments. The published sequence of the 1Bx7 subunit contains 5 Lys and 15 Arg residues but, due to the presence of three Arg-Pro bonds, which are generally resistant to cleavage by trypsin, or cleaved to a very limited extent by trypsin, 19 peptides can be predicted. The identification of the tryptic fragments was achieved by direct MALDI-MS analysis by using three different matrices (DHB, SA and HCCA) in combination with the most compatible sample preparation procedures in order to obtain the maximum sequence coverage. MALDI analysis of the 1Bx7 tryptic digest resulted in the identification of the expected peptides and additional fragments arising from non-specific cleavages; the fragments that were not detected are peptides with low mass (from 147.2 to 317.4), so we obtained a sequence coverage of 98.8%. The results reported here also indicated that the sequence of the 1Bx7 subunit from cv. Chinese Spring is different from the cDNA-deduced sequence reported in the literature; in particular, a possible insertion of the hexapeptide QPGQGQ within the sequence Gln630-Tyr725 was suggested. Finally, it is possible to rule out glycosylation of the 1Bx7 subunit, or any other post-translational modification, to within the detection limits of the method.     

Synthesis and properties of new glucocationic surfactants: model structures for marking cationic surfactants with carbohydrates

[reaction: see text] In this work, we report the synthesis of a new series of glucocationic surfactants, a class of surfactants we introduced very recently. The preparation of the surfactants is based on the synthesis of the 2-bromoethyl-2,3,4,6-tetra-O-acetyl-beta-D-glucopyranoside, whose preparation was studied in order to improve yields and stereoselectivity of this key intermediate. These glucocationic amphiphiles were prepared and studied as a model of cationic surfactants marked with a carbohydrate moiety. The use of carbohydrates as markers on cationic lipids was recently introduced to induce recognition by specific receptors, present on the surface of cell membranes. The chemicophysical characterization of these model structures can give more insight on the aggregation behavior. Conductivity and surface tension measurements were performed in order to characterize the compounds from the amphiphilic point of view. The results showed a different effect of the glucosidic moiety on the cmc value with respect to the glucopyridinium cationic surfactants. The surfactants also showed the tendency to form premicellar aggregates in solution when the hydrophobicity is raised.     

Stability boundaries, percolation threshold, and two-phase coexistence for polydisperse fluids of adhesive colloidal particles

We study the polydisperse Baxter model of sticky hard spheres (SHS) in the modified mean spherical approximation (mMSA). This closure is known to be the zero-order approximation C0 of the Percus-Yevick closure in a density expansion. The simplicity of the closure allows a full analytical study of the model. In particular we study stability boundaries, the percolation threshold, and the gas-liquid coexistence curves. Various possible subcases of the model are treated in details. Although the detailed behavior depends upon the particularly chosen case, we find that, in general, polydispersity inhibits instabilities, increases the extent of the nonpercolating phase, and diminishes the size of the gas-liquid coexistence region. We also consider the first-order improvement of the mMSA (C0) closure (C1) and compare the percolation and gas-liquid boundaries for the one-component system with recent Monte Carlo simulations. Our results provide a qualitative understanding of the effect of polydispersity on SHS models and are expected to shed new light on the applicability of SHS models for colloidal mixtures.     

Complex formation equilibria between Ag(I) and thioureas in n-propanol

Complex formation equilibria between Ag(I) and thiourea or N-alkyl-substituted thioureas have been investigated in n-propanol by potentiometry at 10 °C intervals from 5 to 50 °C. Stepwise formation of tris-coordinated AgL_n (n = 1-3) complexes has been found for the majority of the ligands. ΔH and ΔS values for the complex formation reactions have been evaluated from the dependence of ln β_n on temperature. The alkyl-substituents affect the ligand affinities in different ways in relation with the coordination level n.The reactions are exothermic with few exceptions. Enthalpy favoured complex formation with negative dependence of ΔG on temperature (ΔS > 0) have been found.The enthalpy and entropy changes for the stepwise complex formation equilibria are correlated by two linear compensative relationships with the same isoequilibrium temperature 50-51 °C.     

Multilocus mutation scanning for the analysis of genetic variation within Malassezia (Basidiomycota: Malasseziales)

Members of the genus Malassezia are budding yeasts, characterized by a thick cell wall. Recently, these yeasts have received attention as emerging pathogens. They are common commensals on the skin of animals and can become pathogenic under the influence of various predisposing factors. Central to studying their taxonomy, systematics, and ecology and to diagnosis is the accurate identification of species or operational taxonomic units. To overcome the limitations of current phenotypic and biochemical methods of identification, a PCR-coupled SSCP approach, utilizing sequence variation (0.4-33.5%) in short regions (approximately 250-270 bp) of the first internal transcribed spacer (ITS-1) of nuclear ribosomal DNA and the chitin synthase-2 gene (chs-2), was assessed for the identification and differentiation of different species/genotypes of Malassezia, characterized previously by DNA sequencing. Genomic DNA samples (n = 30) from Malassezia isolates cultured from canine skin scrapings were assessed by SSCP analysis of the two different genetic loci, and unequivocal delineation between genotypes and species was achieved. This SSCP approach is considered to provide a practical tool for the rapid and reliable genetic characterization of Malassezia genotypes/species from dogs and for investigating their population genetics and ecology. It will also provide a powerful tool for studies of Malassezia isolates from other animal species.     

Synthesis and characterization of hybrid borosiloxane gels as precursors for Si–B–O–C fibers

The sol–gel method has been used for the synthesis of borosilicate gels from mixtures of methyltriethoxysilane (MTES) and dimethyldiethoxysilane (DMDES) and boric acid. The use of boric acid, B(OH)₃ allows the hydrolysis and condensation of hybrid silicon alkoxides without further addition of water or catalyst. The use of difunctional silicon units, –(CH₃)₂SiO– promote the formation, during the sol–gel process, of linear oligomers which facilitate fiber drawing before gelation. Gel characterization performed by FT-IR, XRD, TG-DTA and DCS analysis indicates the formation of a mixed network with incorporation of the boron units via =B-O-Si≡ bridges. The formation of borosiloxane bonds seems favored by the presence of DMDES. SiBOC glasses were obtained after pyrolysis of the borosilicate gels in argon atmosphere at 1000 °C. TG-DTA study indicates that the ceramic yield decreases by increasing the amount of DMDES. Gel fibers were successfully prepared from convenient partially-aged solutions by hand drawing. Pyrolysis of the obtained gel fibers under argon atmosphere at 1000 °C open the possibility to produce SiBOC homogeneous glass fibers with diameter as low as 10 μm.     

Synthesis and characterization of poly(amidoamine)-platinum(II) complexes. Detailed speciation by Matrix-Assisted Laser Desorption Ionization Mass Spectrometry

MALDI and ESI-MS have been applied to the characterization of the reaction products between the labile cis-[Pt(DMSO)₂Cl₂] (1) and trans-[Pt(DMSO)₂Cl(CH₃)] (2) complexes with the simplest poly(amidoamine) ligand (PAMAM, G = 0, 1,2-diaminoethane as core). The comparison of the mass spectra of the starting G₀ and those of the metallo-dendrimers formed upon mixing of the reagents in an equimolecular ratio, and the analysis of the isotopic distribution in the ESI spectra, have revealed the formation of cationic and neutral mononuclear complexes with PAMAM as ligand, e.g., cis-[Pt(DMSO)(PAMAM)Cl]Cl or trans-(C,N)[Pt(DMSO)(PAMAM)Cl(CH₃)], together with various minor components, which have been identified as derivatives from defective structures of PAMAM. The geometry of the main products has been deduced from the values of the protons coupling constants with the isotopically abundant ¹⁹⁵Pt. The metal-to-ligand bond is restricted to the peripheral amino groups of PAMAM which shows sufficient flexibility to involve either one or two branches in the coordination bonding.     

T dependence of vibrational dynamics of water in ion-exchanged zeolites A: a detailed Fourier transform infrared attenuated total reflection study

In order to explore the influence of cation substitution on the vibrational dynamics of water molecules in zeolites, the evolution of structural properties of the O-H stretching band of water in fully hydrated Na-A and Mg-exchanged A zeolites has been studied, for different percentages of induced ion exchange, by Fourier transform infrared attenuated total reflection spectroscopy as a function of temperature. The differences revealed in the O-H stretching band shapes have been accounted by fitting the spectra as a sum of four components, corresponding to water molecules exhibiting different types of hydrogen bonding. The dependencies of the relative intensities, peak wave numbers, and bandwidths of the resolved components on temperature and Mg2+ content have been discussed. Evidence of the "structure-maker" role played by a zeolitic surface on physisorbed water, systematically enhanced by increasing the percentage of induced ion exchange, is given in the whole explored temperature range.     

Analogies between Jahn–Teller and Rashba spin physics

In developing physical theories, analogical reasoning has been found to be very powerful, as attested by a number of important historical examples. An analogy between two apparently different phenomena, once established, allows one to transfer information and bring new concepts from one phenomenon to the other. Here, we discuss an important analogy between two widely different physical problems, namely, the Jahn–Teller distortion in molecular physics and the Rashba spin splitting in condensed matter physics. By exploring their conceptual and mathematical features and by searching for the counterparts between them, we examine the orbital texture in Jahn–Teller systems, as the counterpart of the spin texture of the Rashba physics, and put forward a possible way of experimentally detecting the orbital texture. Finally, we discuss the analogy by comparing the coexistence of linear Rashba + Dresselhaus effects and Jahn–Teller problems for specific symmetries, which allow for nontrivial spin and orbital textures, respectively.