Compounds of molybdenum(VI) with aspartic acid: A spectrophotometric and potentiometric study of the formation and interconversion equilibria in aqueous solution

Summary Addition of Na₂MoO₄ to an excess of aspartic acid (AspH₂) can produce any of four different complexes depending on the pH, namely [MoO₃(Asp)]^2–, [Mo₂O₅(Asp)₂]^2–, [Mo₂O₄(OH)(Asp)₂]^– and [Mo₂O₄(Asp)₂]. The ranges of formation of these species with pH, the number of equivalents of acid necessary for their formation, and their stoichiometries, condensation degrees and stability constants, have been calculated by potentiometric and spectrophotometric techniques. The aspartic acid acts as a tridentate ligand in all cases.     

H‐Point Standard Addition Method Applied to Voltammetry of Microparticles. Quantitation of Dyes in Pictorial Samples

A solid‐state electrochemical application of the H‐point standard addition method (HPSAM) for quantifying two electroactive compounds, A, B, that produce strongly overlapped voltammetric peaks is described. It is based on peak current measurement in square‐wave voltammograms recorded for solid samples containing a reference compound R, upon additions of a A‐ (or B‐) containing standard compound. The method allows to the determination of the mass fraction of A and B by applying the H‐point standard addition method to solid state voltammetry. The quotients between the currents measured at two selected potentials and the peak current of R vary linearly with the mass ratio of the added standard and the reference compound, thus providing an electrochemical method for determining the content of A and B in the sample avoiding matrix effects. The method is applied to the simultaneous determination of alizarin and purpurin in madder pigments and pictorial specimens using morin as a reference material.     

3-Aryl-4-Isoquinolinone Derivatives An Efficient Oxidative Preparation

A comparative study of the oxidation of 3-aryl-4-hydroxytetrahydroisoquinolines has been carried out. A modification of the Jones conditions turn out to be the best methodology for the regioselective preparation of target 4-isoquinolinone derivatives.     

Application of the intramolecular PIFA-mediated amidation of alkynes to the synthesis of substituted indolizidinones

The construction of the title compounds has been achieved from properly substituted linear alkynylamides through the suitable combination of two key cyclization steps. First, an intramolecular PIFA-mediated alkyne amidation protocol leads to the creation of the pyrrolidinone nucleus, which under proper manipulation of the generated keto–carbonyl group permits the assembling of the indolizidinone skeleton by the introduction of a subsequent ring closing olefin metathesis step. Finally, its transformation into a series of substituted mono- and trihydroxylated indolizidinone derivatives is achieved by manipulation of the remaining unsaturated fragment under hydrogenation and dihydroxylation conditions.     

Application of the voltammetry of microparticles for dating archaeological lead using polarization curves and electrochemical impedance spectroscopy

The application of the voltammetry of microparticles methodology to date archaeological lead artifacts, based on the time-dependent formation of different layers of lead oxides, whose relative amount can be estimated from polarization curves and electrochemical impedance spectroscopy (EIS), is presented. This approach is complemented by additional data using square wave voltammetry data. Calibration of the method was performed with the help of a series of well-documented, lead pieces from the funds of different Spanish museums, covering since the 7th century BC to nowadays.     

Real hypersurfaces with constant principal curvatures in complex space forms

We present the motivation and current state of the classification problem of real hypersurfaces with constant principal curvatures in complex space forms. In particular, we explain the classification result of real hypersurfaces with constant principal curvatures in nonflat complex space forms and whose Hopf vector field has nontrivial projection onto two eigenspaces of the shape operator. This constitutes the following natural step after Kimura and Berndt?s classifications of Hopf real hypersurfaces with constant principal curvatures in complex space forms.     

A hybrid numerical-asymptotic boundary integral method for high-frequency acoustic scattering

We propose a new robust method for the computation of scattering of high-frequency acoustic plane waves by smooth convex objects in 2D. We formulate this problem by the direct boundary integral method, using the classical combined potential approach. By exploiting the known asymptotics of the solution, we devise particular expansions, valid in various zones of the boundary, which express the solution of the integral equation as a product of explicit oscillatory functions and more slowly varying unknown amplitudes. The amplitudes are approximated by polynomials (of minimum degree d) in each zone using a Galerkin scheme. We prove that the underlying bilinear form is continuous in L ₂, with a continuity constant that grows mildly in the wavenumber k. We also show that the bilinear form is uniformly L ₂-coercive, independent of k, for all k sufficiently large. (The latter result depends on rather delicate Fourier analysis and is restricted in 2D to circular domains, but it also applies to spheres in higher dimensions.) Using these results and the asymptotic expansion of the solution, we prove superalgebraic convergence of our numerical method as d → ∞ for fixed k. We also prove that, as k → ∞, d has to increase only very modestly to maintain a fixed error bound (d ∼ k ^1/9 is a typical behaviour). Numerical experiments show that the method suffers minimal loss of accuracy as k →∞, for a fixed number of degrees of freedom. Numerical solutions with a relative error of about 10⁻⁵ are obtained on domains of size for k up to 800 using about 60 degrees of freedom.     

The mechanisms of the homogeneous,unimolecular, elimination kinetics of several β‐substituted diethyl acetals in the gas‐phase

The rates of gas‐phase elimination of several β‐substituted diethyl acetals have been determined in a static system and seasoned with allyl bromide. The reactions, inhibited with toluene, are homogeneous, unimolecular, and follow first‐order law kinetics. These elimination processes involve two parallel reactions. The first parallel reaction yields ethanol and the corresponding ethyl vinyl ether. The latter product is an unstable intermediate and further decomposes to ethylene and the corresponding substituted aldehyde. The second parallel reaction gives ethane and the corresponding ethyl ester. The kinetics has been measured over the temperature range of 370–441 °C and pressure range of 23–160 torr. The rate coefficients are given by the following Arrhenius equations: The differences in the rates of ethanol formation may be attributed to electronic transmission of the β‐substituent. The comparative kinetic and thermodynamic parameters of the parallel reactions suggest two different concerted polar four‐membered cyclic transition state types of mechanisms. Copyright © 2010 John Wiley & Sons, Ltd.     

Towards a unified view of the solvatochromism of phenolate betaine dyes

An attempt has been made in order to unify the three types of solvatochromisms (negative, positive and inverted) of phenolate betaine dyes by a working model which describes them as particular cases of a general behavior. The model, based on the calculation (gas phase) of the chemical hardness of donor and acceptor fragments, was applied to 56 examples from the literature. As a result, the investigated compounds were grouped according to the sum of the hardnesses of their (non‐interacting) fragments, this sum being larger for a negative, intermediate for an inverted, and smaller for a positive solvatochromic behavior. Copyright © 2009 John Wiley & Sons, Ltd.