Hexacoordinate triphenylantimony(V) complex with tridentate bis-(3,5-di-tert-butyl-phenolate-2-yl)-amine ligand: Synthesis,NMR and X-ray study

The oxidative addition reaction of 4,6-di-tert-butyl-N-(2-hydroxy-3,5-di-tert-butyl-phenyl)-o-iminobenzoquinone (IBQ) to triphenylantimony(III) proceeds with the migration of hydroxyl-proton to a nitrogen atom to form tridentate O,N,O′-coordinated bis-(3,5-di-tert-butyl-phenolate-2-yl)-amine ligand. In accordance with ¹H, ¹³C, DEPT NMR data, the new hexacoordinate complex [bis-(3,5-di-tert-butyl-phenolate-2-yl)-amine]triphenylantimony(V), [(AP-AP)H]SbPh₃ (1) in solution has a C_s symmetry plane leading to the equivalence of two O,N-chelate o-aminophenolato moieties. The molecular structure of 1 · acetone was studied by a single-crystal X-ray. Compound 1 was found to be air-stable both in solid and in solution. Its oxidation by PbO₂ leads to paramagnetic [4,6-di-tert-butyl-N-(3,5-di-tert-butyl-phenolate-2-yl)-o-iminobenzosemiquinolato]triphenylantimony(V), [(AP-ISQ)]SbPh₃ (2).     

Cationic Organophosphorus Chromophores: A Diamond in the Rough among Ionic Dyes

Tunable electron-accepting properties of the cationic phosphorus center, its geometry and unique preparative chemistry that allows combining this unit with diversity of π-conjugated motifs, define the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores. This Minireview summarizes the achievements in the synthesis of the π-extended molecules functionalized with P-cationic fragments, modulation of their properties by means of structural modification, and emphasizes the important effect of cation-anion interactions, which can drastically change physical behavior of these two-component systems.     

Luminescent heterometallic gold-copper alkynyl complexes stabilized by tridentate phosphine

The reactions between trinuclear gold complex tppmAu(3)Cl(3) (tppm = tris(diphenylphosphino)methane), arylacetylenes HC(2)C(6)H(4)X and Cu(+) under basic conditions result in formation of the heterometallic complexes [tppm(AuC(2)C(6)H(4)X)(3)Cu](+), X = H (1), COOMe (2), CN (3), OMe (4), NH(2) (5). These compounds belong to one structural motif and consist of the heterometallic {(AuC(2)C(6)H(4)X)(3)Cu} core stabilized by the tridentate phosphine. Compounds 1-5 were characterized by polynuclear NMR and IR spectroscopy, ESI-MS and single-crystal X-ray analysis. Luminescence properties of these complexes have been studied and revealed a substantial red shift of the emission maxima with the increase in the electron donicity of the alkynyl ligands substituents in the 550-680 nm range. The theoretical calculations of the electronic structures showed that variations of the substituents on the alkynyl ligands display very little effect on the molecular structural parameters but show appreciable influence on the orbital energies and luminescence characteristics of the compounds under study.     

Ab initio MO study of selected aluminum and boron chlorides and fluorides: Comparison with 11B NMR spectra of a tetrachloroborate melt

Molecular geometries were fully optimized for AlCl₃, AlCl₄^-, Al₂Cl₆, Al₂Cl₇^-, AlF₃, AlF₄^-, Al₂F₆, Al₂F₇^-, BCl₃, BCl₄^-, B₂Cl₆, B₂Cl₇^-, BF₃, BF₄^-, B₂F₆, and B₂F₇^-, as well as a few mixed halogen species, at the Hartree-Fock (HF) level, using basis sets from STO-3G to 6–311 + G(d). In some cases geometries were also optimized at the MP2 level. Where possible, the computed geometries were compared to known structures from electron or X-ray diffraction. The agreement between these was quite good for the neutral species, and somewhat poorer for the anions. Vibrational frequencies were calculated for all species at the HF level with the largest basis set. The geometries were characterized as minima or transition structures. Various formation reaction enthalpies were calculated; these compare well with known values. More extensive calculations on the BF₃/BF₄^- system indicate the structures and enthalpies are nearly converged with respect to basis set size and level of correlation treatment. The previously unknown species B₂Cl₇^- is predicted to be energetically stable on the basis of the calculations. Some features of the ¹¹B NMR spectra of room temperature melts consisting of mixtures of boron trichloride with 1-methyl-3-ethylimidazolium chloride are presented. These features suggest that these melts may contain small amounts of B₂Cl₇^- as an intermediate in an exchange reaction. © 1996 by John Wiley & Sons, Inc.     

Quantitative analysis of physical factors that determine the behavior of activity coefficients of electrolytes

The development of theoretical ideas on the cause and the mechanism of the change of activity coefficients is the main aim of the investigation. The model describing the interaction of hydrated ions in electrolytes is proposed. In the model the electrostatic forces between ions and change of the energy of the hydrate shell in the process of ion convergence determine ions distribution in solution. The significant factor is the dependence of dielectric permittivity on the concentration of the electrolyte and on the distance to ion. The statistical approach developed allows one to calculate the influence of principal physical factors and, on this basis, to explain the nature of curves describing the activity coefficients. The results of simulation have been tested on a large number of experimental data.     

Chemosensors and biosensors based on polyelectrolyte microcapsules containing fluorescent dyes and enzymes

The concept of enzyme-assisted substrate sensing based on use of fluorescent markers to detect the products of enzymatic reaction has been investigated by fabrication of micron-scale polyelectrolyte capsules containing enzymes and dyes in one entity. Microcapsules approximately 5 μm in size entrap glucose oxidase or lactate oxidase, with peroxidase, together with the corresponding markers Tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) dichloride (Ru(dpp)) complex and dihydrorhodamine 123 (DHR123), which are sensitive to oxygen and hydrogen peroxide, respectively. These capsules are produced by co-precipitation of calcium carbonate particles with the enzyme followed by layer-by-layer assembly of polyelectrolytes over the surface of the particles and incorporation of the dye in the capsule interior or in the multilayer shell. After dissolution of the calcium carbonate the enzymes and dyes remain in the multilayer capsules. In this study we produced enzyme-containing microcapsules sensitive to glucose and lactate. Calibration curves based on fluorescence intensity of Ru(dpp) and DHR123 were linearly dependent on substrate concentration, enabling reliable sensing in the millimolar range. The main advantages of using these capsules with optical recording is the possibility of building single capsule-based sensors. The response from individual capsules was observed by confocal microscopy as increasing fluorescence intensity of the capsule on addition of lactate at millimolar concentrations. Because internalization of the micron-sized multi-component capsules was feasible, they could be further optimized for in-situ intracellular sensing and metabolite monitoring on the basis of fluorescence reporting.     

Reaction of tetrahydrofurfuryl alcohol with dimethylamine and/or hydrogen

Conclusions 1-Pentanol, 1-dimethylaminopentane or 4-penten-1-o1, 1-pentanol, and 1,5-pentanediol are the major products of the hydroamination of tetrahydrofurfuryl alcohol by dimethylamine and the hydrogenation of this alcohol on a promoted, fused reduced iron catalyst.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2847–2849, December, 1987.The authors express their gratitude to V. G. Zaikin and A. I. Mikaya for assistance in interpreting the mass spectral data.     

Effect of the structure of titanium–magnesium catalysts on the morphology of polyethylene produced

The structure and formation of polyethylene (PE) particles on supported titanium–magnesium catalysts having different structural characteristics (sizes of microcrystallites, mesopores, and subparticles) were studied for the first time. Scanning electron microscopy was used to identify structural elements of the polymer particles formed over such catalysts and to reveal morphological changes in the growing polymer particles when the yield was increased from approximately 0.2 g PE/g catalyst to approximately 13 kg PE/g catalyst. A relationship was found between structural characteristics of the porous catalyst particles, morphology of the nascent polymer particles, and bulk density of the polymer powder. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2298–2308     

Methyl methacrylate particles with amino groups on the surface: Colloid stability and sorption of biologically active substances

The present article investigates the influence of dispersion medium on the aggregate stability of cross-linked poly-(methyl methacrylate) particles on the surface layer of which aliphatic amino groups are localized. It is shown that particle size depends on the ionic strength of dispersion medium. The research determines the optimal content of cross-linked agent, ethylene glycol dimetharylate that results in the formation of cationic particles being stable in saline. Particle modification is performed by bovine serum albumin and luminophore fluorescein 5(6)-isothiocyanate. Protein sorption is observed not to influence luminescent properties of the particles. It is also determined that due to the aggregate stability of particles obtained from 5?wt% of ethylene glycol dimethacrylate in saline, the monodispersity and the absence of inversion of zeta potential in wide pH range is retained, such particles may be considered as perspective carriers of biologically active substances.     

Large Eddy Simulation of the vortex end in reverse-flow centrifugal separators

The present work is a study of the gas-flow phenomenon known as the “end of the vortex” (EoV), which spontaneously occurs at the lower end, or under, reverse-flow centrifugal separators such as cyclones or swirl tubes. Different CFD models of swirl tubes have been built to study and analyse this phenomenon in detail. The present numerical work is based on—and compared with—previous experimental observations of this phenomenon. The numerical models were built in complete agreement with the geometrical configurations and operating conditions used in these earlier experimental studies [1]. Two different configurations of swirl tubes were analyzed. One configuration was an in principle long tube with variable length in which the dependence on the vessel length of the behaviour of the vortex core in a simple, well-defined geometry was studied. The other configuration was equipped with a wide “dust collection vessel” at the bottom, the depth of which was varied, to study the behaviour of the vortex core in a widely-used geometry. 3-D LES simulations were carried out using the commercial CFD package Star-CD. The bending of the vortex core to the wall of the vessel and its precessional motion, constituting the phenomenon of the EoV, was seen in both configurations, and the obtained results are in very good agreement, both qualitatively and to an extent quantitatively, with previous experimental results [1].