A study on the stereoselectivity of C,O bond formation in esterification of cyclic thiohydroxamic acids

Esterification of cyclic thiohydroxamic acids, for example, N-hydroxypyridine-2(1H)-thione, N-hydroxy-4-methylthiazole-2(3H)-thione, and N-hydroxy-4-(p-chlorophenyl)-thiazole-2(3H)-thione, occurred with inversion of configuration at the attacked stereocenter, as evident from the use of chiral alcohols, alkyl p-toluene sulfonates, and cyclic sulfates. Stereochemical analysis of enantiomerically pure O-alkyl thiohydroxamates was performed on the basis of CD-spectroscopy and chemical derivatization. The assignment of the relative configuration in cyclic O-esters was feasible via NMR spectroscopy, whereas chiral aliphatic glycolato monoesters required hydroxyl group derivatization with chloro-(4R,5R)-bis[(1R,2S,5R)-menth-1-yloxycarbonyl)]-1,3,2-dioxaphospholane for this purpose.     

Gas-phase synthesis and characterization of heteroleptic divalent germanium compounds by FVT/UV-PES

The flash vacuum thermolysis/UV photoelectron spectroscopic (FVT/UV-PES) technique has been applied for the synthesis of three cyclic germanediyls containing oxo-thio, oxo-amino, and thio-amino substitution at germanium. The three compounds (4b, 5b and 6b) were prepared from the corresponding 3,4-dimethyl-1-germacyclopent-3-enes (4a, 5a and 6a) by thermal cheletropic elimination, and the photoelectron spectra of both sets of molecules were measured. The course of the thermolysis reactions has also been confirmed by mass spectrometric methods and the results of chemical trapping experiments. The assignment of the PE spectral bands for the two series of molecules has been carried out with the aid of time dependent DFT (TD-DFT) and outer valence green’s function (OVGF) calculations. The results indicate that the strong σ-withdrawing effect of oxygen and the strong π-donating effect of nitrogen are the two main factors affecting the electronic structures of these germylene derivatives.     

Evaluation of tris(4,7-diphenyl-1,10-phenanthrolinedisulfonate)ruthenium(II) as a chemiluminescence reagent

Previous studies have suggested that tris(4,7-diphenyl-1,10-phenanthrolinedisulfonate)ruthenium(II) (Ru(BPS)₃⁴⁻) has great potential as a chemiluminescence reagent in acidic aqueous solution. We have evaluated four different samples of this reagent (two commercially available and two synthesised in our laboratory) in comparison with tris(2,2′-bipyridine)ruthenium(II) (Ru(bipy)₃²⁺) and tris(1,10-phenanthroline)ruthenium(II) (Ru(phen)₃²⁺), using a range of structurally diverse analytes. In general, Ru(BPS)₃⁴⁻ produced more intense chemiluminescence, but the oxidised Ru(BPS)₃³⁻ species is less stable in aqueous solution than Ru(bipy)₃³⁺ and produced a greater blank signal than Ru(bipy)₃³⁺ or Ru(phen)₃³⁺, which had a detrimental effect on sensitivity. Although the complex is often depicted with the sulfonate groups of the BPS ligand in the para position on the phenyl rings, NMR characterisation revealed that the commercially available BPS material used in this study was predominantly the meta isomer.     

Correlation of acoustic and optical emission signals produced at 1064 and 532 nm laser-induced breakdown spectroscopy (LIBS) of glazed wall tiles

An acoustic signal was used for the internal standardization of laser-induced breakdown spectroscopy (LIBS) of a glazed wall tile. For the LIBS analyses, 1064 nm and 532 nm wavelengths of the Nd:YAG laser were utilized. The tile was depth profiled by a single-spot ablation from the glaze into the substrate. Some lines of major elements Si(I) 252.418, Si(I) 252.851, Al(I) 257.509, Cr(I) 295.368, Al(I) 309.271 nm and Ti(II) 334.904 nm were monitored. The decrease in the optical emissions during the ablation was successfully compensated for by normalization to the square power of the acoustic signal in the interval of 290–340 nm. This approach failed for the lines between 250–270 nm. The results were the same for both lasing wavelengths despite different irradiances. The acquired profiles are in good agreement with the reference X-ray fluorescence measurement.     

Truncated ditetragonal gold prisms as nanofacet activators of catalytic platinum

We report a facile, seed-mediated method to synthesize nanoscale gold truncated ditetragonal nanoprisms (TDPs) enclosed by 12 high-index {310} facets. The method leads to the formation of nanoparticles with high size and shape monodispersity and allows for easy surfactant removal. The dependence of particle shape on the synergetic contribution of metallic ions, halide ions, and surfactant adsorbates during synthesis is described. The resulting high-index nanoparticle facets were demonstrated as efficient activators of a supported catalytic material (platinum). A Pt monolayer deposited onto the Au TDP nanofacets with sharp electrochemical signatures exhibits an enhanced catalytic activity.     

Bond dissociation of the dipeptide dialanine and its derivative alanine anhydride induced by low energy electrons

Dissociative electron attachment to dialanine and alanine anhydride has been studied in the gas phase utilizing a double focusing two sector field mass spectrometer. We show that low-energy electrons (i.e., electrons with kinetic energies from near zero up to 13 eV) attach to these molecules and subsequently dissociate to form a number of anionic fragments. Anion efficiency curves are recorded for the most abundant anions by measuring the ion yield as a function of the incident electron energy. The present experiments show that as for single amino acids (M), e.g., glycine, alanine, valine, and proline, the dehydrogenated closed shell anion (M-H)(-) is the most dominant reaction product. The interpretation of the experiments is aided by quantum chemical calculations based on density functional theory, by which the electrostatic potential and molecular orbitals are calculated and the initial electron attachment process prior to dissociation is investigated.     

Spatial econometric approach to the EU regional employment process

This paper deals with the estimation of spatial econometric models of employment rate across 259 NUTS 2 (Nomenclature of Units for Territorial Statistics) regions of the European Union in 2018 regarding different region-specific factors. Since, spatial autocorrelation and spatial heterogeneity often occur jointly, the paper is oriented at verification of two hypotheses. Hypothesis 1 related to the existence of the spatial autocorrelation, i.e., that the regional employment process is not a spatially isolated process, was confirmed. Based on the estimation of Spatial Durbin Model, direct, indirect and total spatial impacts were quantified and verified. The results proved the significant impact of neighbouring regions for GDP and compensation of employees variables in explaining regional employment rate. Significant influence of factors like educational attainment level and population density seems to be limited only to the particular region. Hypothesis 2 reflected the existence of the spatial heterogeneity. Based on the geographically weighted regression the assumption of spatial variability of the model parameters was also verified. The regional employment in the EU seems to be affected by both spatial effects and the presented approaches thus represent two different insights into the complex spatial character of the modelled process.

     

Two polymorphs of bis(2‐carbamoylguanidinium) fluorophosphonate dihydrate

Two polymorphs of bis(2‐carbamoylguanidinium) fluorophosphonate dihydrate, 2C₂H₇N₄O⁺·FO₃P²⁻·2H₂O, are presented. Polymorph (I), crystallizing in the space group Pnma, is slightly less densely packed than polymorph (II), which crystallizes in Pbca. In (I), the fluorophosphonate anion is situated on a crystallographic mirror plane and the O atom of the water molecule is disordered over two positions, in contrast with its H atoms. The hydrogen‐bond patterns in both polymorphs share similar features. There are O—H...O and N—H...O hydrogen bonds in both structures. The water molecules donate their H atoms to the O atoms of the fluorophosphonates exclusively. The water molecules and the fluorophosphonates participate in the formation of R⁴₄(10) graph‐set motifs. These motifs extend along the a axis in each structure. The water molecules are also acceptors of either one [in (I) and (II)] or two [in (II)] N—H...O hydrogen bonds. The water molecules are significant building elements in the formation of a three‐dimensional hydrogen‐bond network in both structures. Despite these similarities, there are substantial differences between the hydrogen‐bond networks of (I) and (II). The N—H...O and O—H...O hydrogen bonds in (I) are stronger and weaker, respectively, than those in (II). Moreover, in (I), the shortest N—H...O hydrogen bonds are shorter than the shortest O—H...O hydrogen bonds, which is an unusual feature. The properties of the hydrogen‐bond network in (II) can be related to an unusually long P—O bond length for an unhydrogenated fluorophosphonate anion that is present in this structure. In both structures, the N—H...F interactions are far weaker than the N—H...O hydrogen bonds. It follows from the structure analysis that (II) seems to be thermodynamically more stable than (I).     

Application of heptapeptides containing D-amino acid residues immobilized to magnetic particles and Sepharose for the study of binding properties of gastric aspartic proteases

Synthetic heptapeptides containing D-amino acid residues and differing in the content of L-phenylalanine and L-tyrosine residues and their position (Val-D-Leu-Pro-Tyr-Phe-Val-D-Leu, Val-D-Leu-Pro-Tyr-Tyr-Val-D-Leu, Val-D-Leu-Pro-Phe-Tyr-Val-D-Leu) were immobilized to two types of carriers: glyoxal-activated magnetic agarose particles and CNBr-activated Sepharose. In both cases, peptides were immobilized via their terminal amino group. Immobilized peptides were used for the study of binding properties of two gastric aspartic proteases (porcine pepsin A and rat pepsin C). Porcine pepsin A was adsorbed to all studied peptide-modified magnetic carriers, while rat pepsin C interacted with immobilized ligands only slightly. Similar results were obtained in affinity chromatographic experiments using heptapeptides immobilized to Sepharose.