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91.
The New Data for the Reaction of Arylenedioxy Trihalogenophosphoranes with Alkyl- and Arylacetylenes
Vladimir F. Mironov Alfiya A. Shtyrlina Ravil R. Petrov Tamara A. Baronova Fedor F. Alekseev Elena N. Varaksina 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1381-1385
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. 相似文献
92.
Vasily S. Minkov Evgeny A. Kapustin Elena V. Boldyreva 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(4):416-420
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. 相似文献
93.
Alexander P. Filippov Elena V. Belyaeva Tamara K. Meleshko Alexander V. Yakimansky 《Journal of Polymer Science.Polymer Physics》2014,52(23):1539-1546
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 相似文献
94.
95.
Elena Akhmatskaya José M. Asua 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1383-1393
Modification of the polymer–polymer interfacial tension is a way to tailor‐make particle morphology of waterborne polymer–polymer hybrids. This allows achieving a broader spectrum of application properties and maximizing the synergy of the positive properties of both polymers, avoiding their drawbacks. In situ formation of graft copolymer during polymerization is an efficient way to modify the polymer–polymer interfacial tension. Currently, no dynamic model is available for polymer–polymer hybrids in which a graft copolymer is generated during polymerization. In this article, a novel model based on stochastic dynamics is developed for predicting the dynamics of the development of particle morphology for composite waterborne systems in which a graft copolymer is produced in situ during the process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
96.
97.
Jessica Cid Dr. Jorge J. Carbó Dr. Elena Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12794-12802
Most trivalent boron reagents are electrophiles owing to the vacancy for two electrons to fill the outer orbital of boron; however, interestingly, trivalent boron compounds can change their electrophilic character to a nucleophilic character by only changing the nature of the substituents on the boron atoms. With the help of computational tools, we have analyzed the structural‐ and electronic properties of boryl fragments that were either bonded to main‐group metals or coordinated to transition‐metals/rare‐earth‐metals and we have designed a map that might help to identify certain trends. This trend map will be useful for selecting an appropriate trivalent boron compound, depending on the sought reactivity. 相似文献
98.
Viviana De Luca Paolo Digiamberardino Giovanna Di Pasquale Salvatore Graziani Antonino Pollicino Elena Umana Maria Gabriella Xibilia 《Journal of Polymer Science.Polymer Physics》2013,51(9):699-734
Smart systems adapt to the surrounding environments in a number of ways. They are capable to scavenge energy from available sources, sense and elaborate external stimuli and adequately react. Electro Active Polymers are playing a main role in the realization of smart systems for applications if fields such as bio inspired and autonomous robotics, medicine, and aerospace. This paper focus on the possibility to use Ionic Polymer Metal Composites as a class of materials relevant to the realization of post silicon smart systems. The three main aspects of this new technology, i.e., fabrication methods, modeling, and applications are described with emphasis to most recent results. Attention is given to main challenges and shortcomings to be solved for technology, modelling, and control of IPMC based devices that need to be solved before this new technology can be fully exploited in real world applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 相似文献
99.
Adrian Hernandez Santiago Salvador Rosas Castilla Albino Morales Rodriguez Elena Aleskerova Anastasia Lantushenko Viktor Kostjukov 《Molecular physics》2013,111(15):1941-1947
An approximately linear correlation has been found between the enthalpy of complexation and the area of overlap of the chromophores using published structural and thermodynamical data on the self- and hetero-association of aromatic molecules measured under similar solution conditions. This finding is consistent with the assumption that short-range van-der-Waals forces dominate over other contributions to the enthalpy of stacking of aromatic molecules. It provides a ‘model-independent’ approach for a priori estimation of the enthalpy of aromatic–aromatic stacking interactions from knowledge of the structural properties or vice versa. 相似文献
100.
Polymer-dispersed liquid crystal (PDLC) systems based on polysulfone as carrying matrix and 4-cyano-4?-pentylbiphenyl (5CB) liquid crystal (LC) were obtained as thin transparent films. The PDLC films were prepared by solvent- and thermally induced phase separation methods, with various compositions in the two components. Information on the phase separation was obtained by polarised light optical microscopy, differential scanning calorimetry and scanning electron microscopy. The PDLC composites show well-defined droplets of submicrometric size, around 650 nm for a medium content of LC and around 250 nm for a low one. The droplets show a radial configuration and a homeotropic alignment of the LC molecules within. By contact angle measurement and surface free energy calculations, it was established that self-assembling of aliphatic units of the two composite components, at droplet interface, is the driving force of the homeotropic alignment. Moreover, these data indicated the potential biocompatibility of the studied composites. The photophysical behaviour shows a better light emission of the PDLCs containing bigger droplets. 相似文献