Conformational characteristics of polycaproamide in dimethylacetamide containing lithium chloride

The viscosity behavior, index of refraction, and density of dilute polycaproamide solutions in DMAc containing lithium chloride have been studied. On the basis of temperature dependences of the index of refraction and the density of solutions, the θ-condition of polycaproamide solutions in DMAc containing 2.5% lithium chloride is estimated as 21.3°C. From intrinsic viscosity [η] measurements, the coefficients of swelling of a polymer coil, the mean-square distance between chain ends, and other parameters of macromolecules in solution are calculated.     

The preparation of precisely defined lithium isotope mixtures

The need for accurate (< 0.06%) isotopic blends of ⁶Liand ⁷Li is explained and their preparation is discussed. It is shown that lithium must be determined at an accuracy level better than 0.035%. Four methods — acid-base titration with hydrochloric acid or benzoic acid, and weighing as sulphate or carbonate — were tested and improved for the precise and accurate analysis of lithium hydroxide solutions. The results of these four methods for a 0.1 M solution agreed within ± 0.02%. The preparation of pure isotopically enriched lithium hydroxide solutions, with specially purified cation- and anion-exchangers, is described. The prepared products contain as little as 100 μg of other alkali metals and 50 μg of alkaline-earth metals per gram of lithium, and are sufficiently free of anions to permit accurate chemical assay of lithium. No changes in the isotopic compositions of 99% ⁶Li or 99.99% ⁷Li were detected during the treatment.     

Phase state of the polysulfone-poly(ethylene glycol)-dimethylacetamide system

Via the method of turbidity points, a fragment of the phase diagram of the polysulfone-poly(ethylene glycol) 400-dimethylacetamide three-component system was constructed. This system is a unique object with both an upper critical solution temperature and a second-order lower critical solution temperature. Viscosity characteristics and activation parameters of the viscous flow of concentrated and dilute polysulfone solutions in dimethylacetamide containing poly(ethylene glycol) were studied. An abnormal increase in the solution viscosity with temperature that precedes the phase transition was found. With the use of IR spectroscopy and the viscometry of dilute solutions, it was shown that it is possible to form additive compounds between the components in a solution.     

Imidazolium-tagged ferrocenyl diphosphanes in allylic substitution with heteroatom nucleophiles

Imidazolium-tagged ferrocenyl diphosphanes are useful ligands in palladium-catalyzed allylic substitutions with heteroatom nucleophiles. Substitution with phthalimide proceeds with high enantioselectivity (up to 92% ee) in various ionic liquids. Reaction with p-cresol as nucleophile affords allylation product in up to 62% ee, while using tolylsulfinate as a nucleophile gives a product with very little or no enantioselectivity. Under these reaction conditions, catalyst recyclability is challenging, and decrease in activity as well as enantioselectivity was observed.     

Clustering of sulfamic acid: ESI MS and theoretical study

Sulfamic acid has wide application in industry and has been suggested to act as an effective nucleation agent for the formation of aerosols and cloud particles. From the point of view of the role that sulfamic acid may play in aerosol formation, the study of its homoaggregation is important. Gas phase clustering study was performed for sulfamic acid H₃N·SO₃, (ASA), from water and methanol–water solutions, by help of a TOF‐Q spectrometer equipped with electrospray ionization source, in the negative‐ion mode. The structure and stability of the (H₃N·SO₃)_n and [(H₃N·SO₃)_n‐H]^? (n = 1–6) were studied using DFT/B3LYP/aug‐cc‐pVDZ method. The ESI MS study evidenced that both singly and doubly charged clusters are formed when the acids are electrosprayed from water solutions; they may be described as [(H₃N·SO₃)_n‐zH]^z? where z = 1 or 2. The largest identified clusters are built of 20 monomers. The theoretical studies showed that formation of higher order (ASA)_n aggregates in the gas phase is energetically profitable. In contrast with the gas phase, aqueous solution does not favor the formation of (ASA)_n aggregates. The study led to the conclusion that the ASA clusters are formed in the gas phase under the experimental conditions of the mass spectrometer. A hypothetical mechanism concerning the formation of the doubly negatively charged anionic aggregates is discussed. The obtained data suggest that small (NH₃·SO₃)_n aggregates may also contribute to formation of aerosols in heavily polluted atmospheres with relatively large NH₃ concentration. Copyright © 2015 John Wiley & Sons, Ltd.     

New ammonium surfactant-stabilized rhodium(0) colloidal suspensions: influence of novel counter-anions on physico-chemical and catalytic properties

Novel anionic species, such as hydrogen carbonate (HCO(3)(?)), fluoride (F(?)), triflate (CF(3)SO(3)(?)), tetrafluoroborate (BF(4)(?)) and chloride (Cl(?)) were investigated as new partners of water soluble N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium salts, used as a protective agent of rhodium colloids. The effect of the surfactant polar head on the micellar behavior, size and morphology of the nanospecies was studied by adapted physico-chemical experiments (surface tension measurements, dynamic light scattering, thermogravimetric and TEM analyses) and discussed in terms of strong or weak stabilization of the growing nanoparticles surface. Finally, the influence of the nanoenvironment generated by the surfactant with various counter-anions was evaluated via the hydrogenation of aromatics.     

Effect of a solvent on the solution behavior of Teflon-42 and the structure of related films

The viscosity characteristics of dilute and concentrated solutions of Teflon-42 in acetone, DMF, DMAA, N-methylpyrrolidone, and trimethyl phosphate have been studied. Films based on Teflon-42 prepared by precipitation from concentrated aqueous solutions are investigated by IR spectroscopy and X-ray analysis. The analysis of intrinsic viscosity and viscosity of concentrated solutions shows that, with respect to Teflon-42, solvent quality changes in the following order: acetone > DMF > DMAA > trimethyl phosphate ≥ N-methylpyrrolidone. Films prepared from polymer solutions in various solvents are characterized by a highly crystalline structure (the degree of crystallinity is ～70%) that involves three polymorphic modifications.     

The effect of solvents on the homopolymerization of 4-dimethylaminostyrene initiated with CCl3COOH

In the polymerization of 4-dimethylaminostyrene (DMAS) initiated with CCl₃COOH in solvents possessing different electron-donor and electron-acceptor properties and relative permittivity (c_r), the c_r value of the solvent correlates well with the polymerization rate. The greatest increase of rate of polymerization in the homogeneous system was observed in nitrobenzene. In this solvent, characteristics of the polymerization of DMAS initiated with CCl₃COOH were determined; differences between these characteristics and the rate equation for a similarly initiated polymerization of DMAS in benzene have been elucidated.     

On three-electron bonds and hydrogen bonds in the open-shell complexes [H2X2]+ for X = F, Cl, and Br

The [H2X2]+ (X = Cl, Br) formula could refer to two possible stable structures, namely, the hydrogen-bonded complex and the three-electron-bonded one. In contrary to the results published by other authors, we claim that for the F-type structures the hydrogen-bonded form is the only possible one and the [HFFH]+ complex is an artifact as its wave function is unstable. For all analyzed molecules, the IR anharmonic spectra have been simulated, which enabled a deeper analysis of other authors' published results of IR low-temperature matrix experiments. Topological atoms in molecules and electron localization function investigations have revealed that the nature of the bond in three-electron-bonded structures is similar to the covalent-depleted one in F2 or HOO molecules, but the effect of removing electrons from the bond area is stronger.     

Preparation and flocculating properties of highly substituted cationic starches of different vegetable origins

Kinetic regularities of flocculation of model kaolin suspensions by highly substituted cationic flocculants synthesized from different starches (corn, waxy corn, potato, and tapioca starches) have been studied as depending on the doses and vegetable origins of the flocculants. The rate of kaolin suspension flocculation has been found to increase with the dose of the cationic starches of all types. It has been shown that, irrespective of the dose, the highest rate of kaolin sedimentation in the model systems is observed in the presence of cationic potato starch. It has been demonstrated that cationic potato starch flocculates kaolin suspensions with concentrations of 0.1, 0.5, and 1.0% with the same efficiency. In this case, the suspensions are almost completely clarified within 2–5 min. Moreover, the dependence of the flocculating efficiency for a 0.1% model suspension on the dose of cationic starch has been found to pass through a maximum at a starch content of 1.0–5.0 mg/g of kaolin depending on the type of starch.