Chalcogenide based all-solid-state thin electroplated ion-selective membrane for Hg(II) flow-injection determinations

The response to Hg(II) of a thin all-solid-state Te-doped silver chalcogenide membrane, described by the general formula Ag₂ + δSe_{1 − x}Te_x, which has been electrochemically prepared following a previously proposed approach, has been investigated. The kinetics of formation of the membrane's secondary dynamic response to Hg(II) has been successfully combined with the precise timing and transient signal, typical for flow-injection (FI) measurements, in developing a sensitive and reliable mercury FI detector. Under optimized stream conditions it exhibits a linear Nernstian response, with a double slope of the calibration graph of 59 mV dec⁻¹, over the mercury(II) concentration range 10⁻⁶ − 10⁻³ M, the typical sample throughput amounting to about 70 samples per hour. The observed chemical amplification of the signal is due to the specificity of the processes dominating the initial step in formation of the steady-state signal of the membrane to mercury. The analytical performance of the Hg(II) FI detector, as regards sensitivity, reproducibility, selectivity and long-term stability has been thoroughly investigated. The exact procedure for membrane electrodeposition is given and the potential of the proposed approach as a cost-effective way for preparing chalcogenides of unique structure and properties has been outlined in the above context.     

Obtaining 4-vinylphenols by decarboxylation of natural 4-hydroxycinnamic acids under microwave irradiation

4-Vinylphenols, useful compounds for industrial applications, were obtained by decarboxylation of 4-hydroxycinnamic acids under microwave irradiation in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as base and basic aluminum oxide as solid support. The reactions were fast (15-30 min). The selective extraction of the final products with ethyl acetate avoids chromatographic purifications. The conversions are quantitative and the yields are satisfactory. Only the unstable 4-vinylcatechol was obtained in moderate yield. This procedure was successfully extended to a natural sample of ferulic acid extracted from wheat bran to get the corresponding 4-vinylguaiacol, a FEMA GRAS (Flavor and Extract Manufacturer's Association; General Regarded as Safe) approved flavoring agent.     

Derivatization of 1-phenyl substituted 4-amino-2-benzazepin-3-ones: evaluation of Pd-catalyzed coupling reactions

Several Pd-catalyzed reactions were explored to further functionalize the bromo-substituted 4-amino-1,2,4,5-tetrahydro-2-benzazepin-3-one scaffold (Aba). We report in this paper suitable reaction conditions for Suzuki, Buchwald-Hartwig, and Heck reactions. The substitution pattern of the starting aminobenzazepinone turned out to be crucial for the success of these transition metal-catalyzed reactions, which often required modifications of standard literature procedures. The Pd-catalyzed methods provide access to novel substitution patterns of the Aba scaffold.     

The Matsumoto-Yor property and the structure of the Wishart distribution

This paper establishes a link between a generalized matrix Matsumoto-Yor (MY) property and the Wishart distribution. This link highlights certain conditional independence properties within blocks of the Wishart and leads to a new characterization of the Wishart distribution similar to the one recently obtained by Geiger and Heckerman but involving independences for only three pairs of block partitionings of the random matrix.In the process, we obtain two other main results. The first one is an extension of the MY independence property to random matrices of different dimensions. The second result is its converse. It extends previous characterizations of the matrix generalized inverse Gaussian and Wishart seen as a couple of distributions.We present two proofs for the generalized MY property. The first proof relies on a new version of Herz's identity for Bessel functions of matrix arguments. The second proof uses a representation of the MY property through the structure of the Wishart.