Development in Synthesis,Electrochemistry, LB Moieties of Phenothiazine Based Units

A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique.     

The influence of mobile phase demixion on thin-layer chromatographic enantioseparation of ibuprofen and naproxen

In our earlier article we presented the results of tracing the enantioseparation of the two test analytes (ibuprofen and naproxen) by means of video densitometry and scanning densitometry. In that way we demonstrated an excellent performance of this combined approach to the thin-layer chromatographic detection in the area of enantioseparation. In this paper we study an impact of the four different mobile phases on the enantioseparation of the scalemic mixtures of ibuprofen and naproxen on the silica gel layers impregnated with L-arginine as chiral selector. The main component of all the investigated mobile phases is 2-propanol. Mobile phase 1 consists of pure 2-propanol, while mobile phases 2-4 contain, respectively, ca. 0.66, 1.32, and 1.98 g/L of glacial acetic acid in 2-propanol. Acetic acid is used to protonate L-arginine, as the involved retention mechanism consists of the ion pair formation between L-arginine in the cationic form and the chiral 2-arylpropionic acids (2-APAs), ibuprofen and naproxen, in the anionic form. It is shown that in the absence of glacial acetic acid no enantioseparation can be obtained. Then with adding of 0.66 g/L glacial acetic acid partial enantioseparation of the naproxen and ibuprofen antimers is obtained, with a simultaneous effect of the mobile phase demixion. With the amount of acetic acid increasing, the effect of demixion becomes increasingly perceptible. In that case the displacement effect is observed (and mathematically modeled), which results in compressing of the antimer pairs by the second front of mobile phase. The obtained results allow a deeper insight into the mechanism of enantioseparation with the two test 2-APAs. A combined impact of the crystalline chirality of silica gel and the molecular chirality of L-arginine on the vertical and the horizontal enantioseparation of ibuprofen and naproxen is also discussed.     

Diastereoselective synthesis of tetrahydrofurans via reaction of gamma,delta-epoxycarbanions with aldehydes

[reaction: see text] Hydroxymethyl-substituted tetrahydrofurans were prepared with high diastereoselectivity by reaction of the carbanion derived from 3,4-epoxybutyl phenyl sulfone with aldehydes in the presence of a mixture of lithium and potassium tert-butoxides. Initial formation of aldol-type adducts is a nondiastereoselective but reversible process; thus, subsequent formation of one main diastereoisomer is controlled by the relative rates of cyclization. The configuration of the carbon stereocenter at the oxirane ring is inverted in the course of the S(N)2 process, and two new centers are created diastereoselectively.     

The complexity of some acyclic improper colourings

In this paper we will consider acyclic bipartition of the vertices of graphs, where acyclic means that the edges whose endpoints are in different parts of the partition induce a forest. We will require that the vertices belonging to the same partition induce graphs from particular class. We will search for acyclic bipartitions of cubic and subcubic graphs.     

Absolutely summing multipliers on abstract Hardy spaces

We study summing multipliers from Banach spaces of analytic functions on the unit disc of the complex plane to the complex Banach sequence lattices. The domain spaces are abstract variants of the classical Hardy spaces generated by the complex symmetric spaces. Applying interpolation methods, we prove the Hausdorff Young and Hardy-Littlewood type theorems. We show applications of these results to study summing multipliers from the Hardy-Orlicz spaces to the Orlicz sequence lattices. The obtained results extend the well-known results for the Hp spaces.     

Oxidative nucleophilic substitution of hydrogen in nitroarenes by silyl enol ethers

Enolates generated by treatment of silyl ketene acetals and enol ethers with fluoride ion sources add to nitroarenes to produce σ^H adducts that oxidize either with KMnO₄ to give substituted nitroarenes or with dimethyldioxirane to give substituted phenols. In the latter case the oxidation results in replacement of the nitro group with a hydroxy group. It was shown that high effectiveness of these reactions is not due to stabilization of the σ^H adducts via O-silylation but due to the nature of the accompanying cation.     

The Modulus of Smoothness in Metric Spaces and Related Problems

We define a general variant of the modulus of smoothness in metric spaces and show that under mild condition it is equivalent to the K-functional of a couple of Besov type spaces which in special cases coincide with spaces defined by Korevaar and Schoen. We prove various symmetrization inequalities which involve the modulus, the K-functional and the isoperimetric estimators. We also characterize the Hajłasz-type Sobolev spaces defined not necessarily on doubling measure spaces by means of generalized Poincaré inequalities. This require to study of some variants of the Fefferman–Stein sharp functions as well as the Hardy–Littlewood maximal operators.     

Influence of sintering temperature and aging on properties of cermet Ni/8YSZ materials obtained by citric method

The anode supported cell for solid oxide fuel cell, as a modification of the traditional Ni-YSZ anode supported on electrolyte, is examined in this work. The materials obtained on the base of citric method are presented and investigated in this work. The materials consisted of 40 wt.% Ni/YSZ, 50 wt.% Ni/YSZ and 60 wt.% Ni/YSZ were obtained. The base Ni/YSZ materials are tested on the two ways: (a) aging tests and (b) sintering tests. All the materials after aging and sintering are tested by the impedance spectroscopy. The results of electrical conductivity for samples before and after aging show that only in the case of 40 wt.% Ni/YSZ, sample loses of metallic conductivity after 500 h of heating. The other samples reveal metallic conductivity even after long period of aging. The tests of sintering temperature show that this process does not affect significantly on electrical conductivity of the materials.     

Composition of extraction products from alkylated high-sulphur coals

Products of reductive and non-reductive methylation of two high-sulphur coals (Mequinenza and Illinois No. 6) have been extracted by dichloromethane. It has been established that the efficiency of the transformation of coal to the products soluble in CH₂Cl₂ is higher for coals subjected to non-reductive methylation by the Liotta method than for those after reduction in the potassium/liquid ammonia system. The extracts and the extraction residues were subjected to elemental analysis, IR spectroscopy, and AP-TPR (Atmospheric Pressure-Temperature Programmed Reduction) measurements. It has been shown that the main species undergoing extraction by CH₂Cl₂ are aliphatic compounds or aromatic structures of low degree of condensation. The effect of the extraction on the sulphur groups in coal has been discussed.