Effect of rehydration conditions on the catalytic activity of hydrotalcite-derived Mg-Al oxides in aldolization of acetone

Summary Mg-Al hydrotalcite-derived oxides with a varying Mg/Al molar ratio, ranging from 2.6 to 3.2, were rehydrated in the vapor phase at different temperatures (20-90°C). The catalytic performance of the materials obtained was studied in the aldol condensation of acetone. The initial activity of the rehydrated catalysts depended strongly on the Mg/Al molar ratio and the activation temperature. It was found that the re-arrangement of active sites, leading to the reconstruction of hydrotalcite-like phase, occurred during the catalytic test.     

Au gettering by Ne and Ar implantation in silicon

The gettering efficiency for Au induced by Ne⁺ and Ar⁺ implantation has been studied. The depth distribution of gettered Au as a function of annealing temperature and dose of implanted Ne⁺ and Ar⁺ ions are presented. The experiment shows that the maximum efficiency of gettering occurs when the implantation doses are comparable with amorphization dose.     

The mass spectrometric fragmentation patterns of some biologically active 1,3,4-thiadiazoles

Mass spectra of some twelve derivatives of 1,3,4-thiadiazole are reported. The fragmentation scheme of the 1,3,4-thiadiazole ring is specific and indicative as to the structure. Derivatives of 5-phenyl-1,3,4-thiadiazoles show rearrangement to isothiocyanates.     

2,6-Dialkoxy-7-methylpurines

The preparation of unsymmetrical 2,6-dialkoxy-7-methylpurines (2), and 2-alkoxy-1,7-dialkyl-6-oxo-1,6-dihydropurines (5) is described. In contrast to1 and2, a facile thermal lactim-lactam rearrangement from hypoxanthines5 and7 into xanthines6 was observed.

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2,6-Dialkoxy-7-methylpurine

Zusammenfassung Die Darstellung von unsymmetrischen 2,6-Dialkoxy-7-methylpurinen (2) und 2-Alkoxy-1,7-dialkyl-6-oxo-1,6-dihydropurinen (5) wird beschrieben. Im Gegensatz zu den Verbindungen1 und2 erfolgt die thermische Lactim-Lactam-Umlagerung der Hypoxanthine5 und7 zu den Xanthinen6 glatt.

     

Structure and UV-Vis spectroscopy of nitrosylthiolatoferrate mononuclear complexes

Density functional calculations for the [(RS)_xFe(NO)_4−x]⁻ (R=CH₃) compounds are carried out using the DFT method with the B3LYP functional. The results can be verified by the experimental data only in the case of the [(RS)₂Fe(NO)₂]⁻ complex. The experimentally characterised molecular structure of [(RS)₂Fe(NO)₂]⁻ (where (RS)₂=(SCH₂CH₂NMeCH₂CH₂CH₂NMeCH₂CH₂S) is properly reproduced by the RB3LYP method. The discrepancy between the calculated spin densities with the integral spin observed experimentally is interpreted in terms of antiferromagnetic coupling between the Fe(III) centre and the NO⁻ ligands. The theoretical analysis gives a good account of some properties observed in these compounds. In particular, the electronic spectrum calculated by the TDDFT method for [(CH₃S)₂Fe(NO)₂]⁻ is similar in shape to the experimental one, although is hypsochromically shifted. The LLCT (S_π→π^*_NO), LMCT (S_π→d) or (π^*_NO→d+S_π→d) and MLCT (d→π^*_NO) transitions are mostly responsible for absorption of the [(RS)_xFe(NO)_4−x]⁻ complexes within UV-Vis. The chemical reactivity of [(RS)₂Fe(NO)₂]⁻ is interpreted basing on the calculated effect of a polar solvent on the ligand polarity and on the character of the HOMO and LUMO orbitals.     

The problem of amino acid complementarity and antisense peptides

The review presents three hypotheses concerning the amino acid complementarity: 1) the Mekler-Blalock antisense hypothesis; 2) the Root-Bernstein approach based on stereochemical complementarity of amino acids and anti-amino acids coded by anticodons read in parallel with the coding DNA strand; 3) Siemion hypothesis resulting from the periodicity of the genetic code. The current state of knowledge as well as the results of the implementations of these hypotheses are compared. A special attention is given to Root-Bernstein and Siemion hypotheses, which differ in only few points of the complementarity prediction. We describe methods of investigation of peptide-antipeptide pairing, including circular dichroism, mass spectrometry, affinity chromatography and other techniques. The biological applications of complementarity principle are considered, such as search for bioeffector-bioreceptor interaction systems, the influence of peptide-antipeptide pairing on the activity of peptide hormones, and the application of antipeptides in immunochemistry. The possible role of amino acid-anti-amino acid interactions in the formation of the spatial structures of peptides, proteins and protein complexes is discussed. Such problems as the pairing preferences of protein-protein interfaces, the role of the pairing in the creation of disulfide bonds and the possible appearance of such interactions in beta-structure are also examined. The main intention of the paper is to bring the complementarity problem to the attention of the scientific community, as a possible tool in proteomics, molecular design and molecular recognition.     

Adding Plasticizer Dispersible Conducting Polymer to the Ion-selective Membrane Composition – Revitalizing Single Piece Ion-selective Electrodes Concept

Typically, ion-selective electrodes used in current triggered electrochemical sensing apply a conducting polymer layer covered with an ion-selective membrane. In this work we propose an ion-selective membrane containing a dispersed conducting polymer. Thus obtained system allows elimination of the Achilles hell of heterogeneous ion-selective membranes containing solid particulates dispersed within the ion-selective polymeric membrane. The herein proposed system, even for high conducting polymer loading equal to 5 % w/w, is characterized with insensitivity towards redox interferences, as well as potentiometric detection limits, selectivity well comparable with that for other ion-selective electrodes constructions. Under voltammetric conditions, with increasing loading of the conducting polymer in the membrane cathodic peak potentials are shifted towards more negative values, yet the linear dependence of the peak potential on logarithm of concentration of the analyte in the solution is preserved.     

Immobilization of a cationic ruthenium(II) complex containing the hemilabile phosphaallyl ligand in hexagonal mesoporous silica (HMS) and application of this material as hydrogenation catalyst

The cationic ruthenium(II) complex [(η⁵-MeC₅H₄)Ru(η³-PPh₂CHCH₂)(η¹-PPh₂CHCH₂)]⁺ (1) containing the hemilabile phosphaallyl ligand in two different coordination modes has been immobilized inside the pores of aluminated hexagonal mesoporous silica HMS(Si/Al = 40) by direct ion exchange method. This material was characterized by X-ray diffraction, thermogravimetric analysis, FTIR, solid state NMR (²⁹Si, ²⁷Al), UV-Vis, and X-ray photoelectron spectroscopies. The textural properties were determined from nitrogen adsorption at 77 K. (1)/HMS(Si/Al = 40) was shown to be active and selective in the catalytic hydrogenation of phenylacetylene.     

Application of a capillary electrophoresis method for simultaneous determination of preservatives in pharmaceutical formulations

Preservatives are used to protect pharmaceutical formulations from microbial attack during the period of administration to the patient. Because of their biological activity, preservatives have to be identified and assayed according to the same rules as apply to active components. A number of methods for separation of preservatives are reported, to account for the heterogeneity of their chemical structures. A capillary electrophoretic method was devised for simple and simultaneous qualification and quantification of the preservatives most often included in pharmaceuticals, such as benzyl alcohol, parabens, phenol, m-cresol, chlorobutanol, thimerosal. After systematic method development, the electrophoretic conditions were defined as: 50 mM borate buffer pH 9.0 containing 20 mM SDS. Separations were performed at a temperature of 20 degrees C and with detection at 214 nm. Preservatives under examination can be analyzed within a 10 min run. The method was successfully validated and applied to the determination of preservatives in a number of pharmaceuticals. Results from the CE method were compared with those from reference methods.