Stereochemistry of 1-hydroxyphosphonate-phosphate rearrangement. Retention of configuration at the phosphorus atom

1-Hydroxyphosphonate 1 in the presence of triethylamine in acetonitrile solution undergoes irreversible rearrangement to phosphate 2 and reversible retro-phospho-aldol (retro-Abramov) reaction. The X-ray structures for 1 and 2 revealed that the phosphonate-phosphate rearrangement occurs with retention of configuration at the phosphorus atom.     

Pegylated tetraarylporphyrin entrapped in liposomal membranes. A possible novel drug-carrier system for photodynamic therapy

A system of poly(ethylene glycol) bound tetraarylporphyrin entrapped in liposomal membranes was investigated. The interactions between the 5-(4-hydroxymethylphenyl)-10,15,20-tritolylporphyrin (Po) covalently attached to the poly(ethylene glycol) chain (PEG-Po), and phosphatidylcholine liposomes in the aqueous solution were studied. The adsorption of the investigated polymer to lipid vesicles was confirmed by measurements of dynamic light scattering and zeta potential. Experimental results demonstrate that the diameter of liposomes increased and the absolute value of the zeta potential decreased after addition of PEG-Po. The binding constants (K(b)) of Po chromophores to liposome in pH range from 5.2 to 9.0 were determined using fluorescence spectroscopy. The degree of binding was found to be pH-independent and the average value was 24.6 +/- 0.9 mg ml(-1). The acid-base properties of the porphyrin chromophores and their aggregation in an aqueous solution were also studied. pK values associated with imine-N protonation of the porphyrin core were found to be 2.59 and 0.68 at the ionic strength of 0.1 M. The equilibrium constant for dimerization, K(D), was found to be 5 x 10(3) M(-1).     

Invariance in a class of Bajraktarevi? means

Let I⊂R be a non-trivial interval, s:I→(0,∞) be a function, and let φ,ψ be real continuous strictly monotonic functions defined on I. We consider the equation

     

Cocrystals “Divorce and Marriage”: When a Binary System Meets an Active Multifunctional Synthon in a Ball Mill

A well-defined and stable “AB” binary system in the presence of “C” a crystalline synthon ground in a ball mill undergoes selective transformation in the solid state according to the equation AB+C→AC+B. When the amount of C is increased two times then the equation AB+2C→AC+BC is valid. The other variants are more complex. The pathway BC+A is allowed and leads to the AC and B products. The pathway AC+B is not preferred, and no transformation is observed. These non-obvious correlations were observed for cocrystal of barbituric acid (BA):thiobarbituric acid (TBA) recently reported by Shemchuk et al. (Chem. Commun. 2016 , 52, 11815–11818) in the presence of 1-hydroxy-4,5-dimethyl-imidazole 3-oxide (HIMO). This synthon shows high affinity for the BA_0.5TBA_0.5 cocrystal as well for its individual components, BA and TBA. Single-quantum, double-quantum (SQ-DQ) 2D ¹H very fast MAS NMR with a spinning rate of 60 kHz was employed as a basic and most diagnostic tool for the study of cocrystals transformations. Analysis of the experimental data was supported by theoretical calculations, including computation of the stabilization energy, E^stab, defined as the energy difference between the energy of a co-crystal and the sum of the energies of particular components in the respective stoichiometric ratios. Two mechanisms of synthon replacement have been proposed. Pathway 1 assumes a concerted mechanism of substitution. In this approach, synthon attack is synchronized in time with the departure of one of the components of the binary system. Pathway 2 implies a non-concerted process, with an intermediate stage in which three separate components are present. Evidence suggesting a preference for Pathway 2 is shown.     

Nanostructured micellar films formed via layer-by-layer deposition of photoactive polymer

Photoactive nanostructured micellar films were prepared from the amphiphilic copolymer poly(sodium styrenesulfonate- stat-2-vinylnaphthalene) (PSSS- stat-VN) and cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) or poly(allylamine hydrochloride) (PAH) on quartz and silicon substrates via layer-by-layer (LbL) electrostatic self-assembly. The macromolecules of this amphiphilic copolymer adopt a coiled micellar conformation in aqueous solution that is preserved in the films as evidenced by atomic force microscopy (AFM) and spectroscopic studies. The hydrophobic domains present in the film can serve as host sites for various organic molecules. The probe molecules reside in those isolated nanosize domains. Their aggregation and quenching of their emission is eliminated. The experiments showed a regular growth of multilayer thickness and the content of solubilized compounds in the films. Thus, a defined amount of the hydrophobic compounds of interest may be introduced into these water-processable polymeric films. Some stratification of the films was induced by the presence of stiff nanoparticle-like micelles. That makes these films an important new material for studies of photoinduced energy and electron transfer.     

Application of BDD thin film electrode for electrochemical decomposition of heterogeneous aromatic compounds

The aim of the presented study is to investigate the applicability of electrochemical oxidation of aromatic compounds containing heteroatoms, e.g. waste from production of pesticides or pharmaceutics, at a borondoped diamond (BDD) electrode. The BDD electrodes were synthesized by microwave plasma enhanced chemical vapour deposition (MW PE CVD). Investigation of the electrode surface by optical microscopy and scanning electron microscopy (SEM) confirmed that the synthesized layer was continuous and formed a densely packed grain structure with an average roughness of less than 0:5 ??m. The influence of important electrochemical parameters: current density, kind of reactor, pH or mixing operation, on the efficiency of the oxidation was investigated. The fouling of electrode??s surface caused by the deposition of organic material was observed during CV and galvanostatic experiments. At low current density the oxidation rate constant k was low, but the current efficiency was relatively high. The BDD can be used successfully to remove heterogeneous aromatic compounds existing either as molecules or cations. During 4 h of electrolysis 95% of aromatic compounds were electrochemically decomposed to mineral forms. It was observed that the influence of the initial pH on mineralization was marginal.     

A specialization of prinjective Ringel-Hall algebra and the associated Lie algebra

In the present paper we describe a specialization of prinjective Ringel-Hall algebra to 1, for prinjective modules over incidence algebras of posets of finite prinjective type, by generators and relations. This gives us a generalisation of Serre relations for semisimple Lie algebras. Connections of prinjective Ringel-Hall algebras with classical Lie algebras are also discussed.