Calculation of the vibration–rotational transition intensities of water molecules trapped in an argon matrix: stretching O–H vibrations spectral region

The frequencies and intensities of vibration–rotational transitions of water molecules in an argon matrix were calculated for temperatures of 6 and 30 K. The rigid asymmetric top approximation was used with available literature values of the effective rotational constants in the ground and excited vibrational states. The calculations were carried out by taking into account the existence of a non-equilibrium population distribution between the rotational levels of ortho- and para-water isomers. It was assumed that the temperature relaxation of the population of rotational levels is independent of the ortho- and para-isomers. Comparison of the results of the theoretical calculations with experimental literature data shows good agreement for the majority of the rotational structure lines for symmetric and antisymmetric stretching vibrations both in the frequency values and in the values of the relative intensities.     

Novel luminescent liquid crystalline polyazomethines. Synthesis and study of thermotropic and photoluminescent properties

Novel semiflexible polyazomethines containing chromophoric units into azomethine mesogenic core have been synthesised by condensation of a flexible dialdehyde with mesogenic diamines containing fluorene, antraquinone, pyrimidine, azobenzene and benzophenone. The thermotropic behaviour of the resulting polyazomethines was assessed by differential scanning calorimetry, polarised light microscopy and investigations of the miscibility relations. While the pure polyazomethines showed a birefringent viscous texture difficult to be ascribed, by mixing with a liquid crystal dimer, clear Schlieren or marbled textures were observed, indicating a nematic mesophase. The polymers exhibited violet, blue or yellow light emission.     

The New Data for the Reaction of Arylenedioxy Trihalogenophosphoranes with Alkyl- and Arylacetylenes

The new data concerning the reaction between substituted arylenedioxy trihalogenophosphoranes and monoalkyl- or arylacetylenes are summarized. The reaction leads to formation of six-membered heterocycles-2-oxo-4-R-benzo[ e ]-1,2-oxaphosphorin-3-enes. The substituent effects in the phosphorane and acetylene molecules on the ipso -substitution and halogenation regiochemistry are discussed. The ipso -substitution of tert -butyl group on chlorine and the exchange of bromine on chlorine and iodine on hydrogen have been observed, along with formation of benzophosphorines. The interaction of tetrachloro- ortho -benzoquinone with phosphorus trichloride and arylacetylenes is proposed as a new modification of the reaction leading to the formation of benzo[ e ]-1,2-oxaphosphorines. The structures of some benzo[ e ]-1,2-oxaphosphorines are determined by the single crystal X-ray diffraction.     

Betaine 0.77‐perhydrate 0.23‐hydrate and common structural motifs in crystals of amino acid perhydrates

The title compound, betaine 0.77‐perhydrate 0.23‐hydrate, (CH₃)₃N⁺CH₂COO⁻·0.77H₂O₂·0.23H₂O, crystallizes in the orthorhombic noncentrosymmetric space group Pca2₁. Chiral molecules of hydrogen peroxide are positionally disordered with water molecules in a ratio of 0.77:0.23. Betaine, 2‐(trimethylazaniumyl)acetate, preserves its zwitterionic state, with a positively charged ammonium group and a negatively charged carboxylate group. The molecular conformation of betaine here differs from the conformations of both anhydrous betaine and its hydrate, mainly in the orientation of the carboxylate group with respect to the C—C—N skeleton. Hydrogen peroxide is linked via two hydrogen bonds to carboxylate groups, forming infinite chains along the crystallographic a axis, which are very similar to those in the crystal structure of betaine hydrate. The present work contributes to the understanding of the structure‐forming factors for amino acid perhydrates, which are presently attracting much attention. A correlation is suggested between the ratio of amino acid zwitterions and hydrogen peroxide in the unit cell and the structural motifs present in the crystal structures of all currently known amino acids perhydrates. This can help to classify the crystal structures of amino acid perhydrates and to design new crystal structures.     

Realizing the Promise—The Development of Research on Carbon Nanotubes

The present reflection on the development of research on carbon nanotubes (CNTs) stems from the publication of the report “Realizing the Promise of Carbon Nanotubes” by the US National Nanotechnology Initiative in 2015. The report is a critical assessment of the state‐of‐art of CNT research and highlights some unresolved issues related with this field. Starting from the results of this assessment, we carried out an analysis of the publications’ pool in CNTs and related domains, by exploiting bibliometric tools. We focused on the item of competition/collaboration between disciplines and nations, with the purpose of evaluating the position of chemistry (as a discipline) as well as the position of the main European countries and the European Union (EU) as a whole in the context of CNT research. The results of such analysis outline very clearly the interdisciplinary landscape wherein CNT research is situated and show the highly competitive place occupied by EU in the field.     

Solution behavior of polyimide‐graft‐polystyrene copolymers in selective solvents

A polyimide‐graft‐polystyrene (PI‐g‐PS) copolymer with a polyimide backbone and polystyrene side chains was synthesized by the “grafting from” method using styrene polymerization on a polyimide multicenter macroinitiator via ATRP mechanism. The side chain grafting density z = 0.86 of PI‐g‐PS is rather high for graft‐copolymers synthesized by the ATRP method. Molecular characteristics and solution behavior of PI‐g‐PS were studied in selective solvents using light scattering and viscometry methods. In all solvents, the backbone tends to avoid contact with a poor solvent. To describe the conformation and hydrodynamic properties of PI‐g‐PS macromolecules in thermodynamically good solvents for side chains and PI‐g‐PS, the wormlike spherocylinder model is used. Macromolecules of the studied graft‐copolymer are characterized by high equilibrium rigidities (Kuhn segment length >20 nm). In Θ‐conditions, PI‐g‐PS macromolecules may be modeled by a rigid prolate ellipsoid of revolution with a low asymmetry form and a collapsed backbone as the ellipsoid core. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1539–1546     

Toward Fluorescence‐Based High‐Throughput Screening for Enantiomeric Excess in Amines and Amino Acid Derivatives

A highly accurate and reliable screening method for enantiomeric excess of amine derivatives in the presence of water is reported. The fluorescence‐based screening system has been realized by self‐assembly of chiral diol‐type dyes (BINOL, VANOL and VAPOL), 2‐formylphenylboronic acid, and chiral amines forming iminoboronate esters. The structure and chirality of the amine analytes determine the stability of the diastereomeric iminoboronate esters, which in turn display differential fluorescence. The fluorescence signal reflects the enantiomeric purity of the chiral amines and was utilized in high‐throughput arrays. The arrays were able to recognize enantiomeric excess of amines, amino esters, and amino alcohols. In addition to qualitative analysis, quantitative experiments were successfully performed. Studies of the role of additives such as water or citrate were carried out to gain insight into the stability of the iminoboronate esters. It is shown that the above additives destabilize less stable esters while the stable esters remain unchanged. Thus, the presence of water and citrate leads to increased difference between the diastereomeric iminoboronates and contributes to the enantiodiscrimination of the chiral amines.     

Unexpected formation of dinaphthoaza-17-crown-5 ether containing γ-aminopiperidine subunit

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A transmission problem on a polygonal partition: regularity and shape differentiability

We consider a transmission problem on a polygonal partition for the two-dimensional conductivity equation. For suitable classes of partitions we establish the exact behaviour of the gradient of solutions in a neighbourhood of the vertexes of the partition. This allows to prove shape differentiability of solutions and to establish an explicit formula for the shape derivative.