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21.
Stanislaw Urban Krzysztof Czuprynski Roman Dąbrowski Bo Gestblom Joanna Janik Horst Kresse 《Liquid crystals》2013,40(5):691-696
Results of the dielectric studies of nine members of the nBT (4-n-alkyl-4'-thiocyanatobiphenyl, n= 2-10) homologous series in the crystal E (E) and isotropic (I) phases are presented. The dependence of the static permittivity ?s in the isotropic phase, the longitudinal relaxation times τis and τ∥, and the activation enthalpies ΔH is and ΔH ∥ on the number of carbon atoms in the alkyl chain n are analysed. A considerable increase in the retardation factor g= τ∥/τis with decreasing n is observed. The results are compared with those obtained for similar two-ring homologous series. The parameters characterizing the molecular rotations around the short axis in the E phase (τ∥ and ΔH ∥) indicate a hardening of this solid-like phase with shortening of the alkyl chain. 相似文献
22.
Benjamin A. Ellingson Matthew T. Geballe Stanislaw Wlodek Christopher I. Bayly A. Geoffrey Skillman Anthony Nicholls 《Journal of computer-aided molecular design》2014,28(3):289-298
Several submissions for the SAMPL4 hydration free energy set were calculated using OpenEye tools, including many that were among the top performing submissions. All of our best submissions used AM1BCC charges and Poisson–Boltzmann solvation. Three submissions used a single conformer for calculating the hydration free energy and all performed very well with mean unsigned errors ranging from 0.94 to 1.08 kcal/mol. These calculations were very fast, only requiring 0.5–2.0 s per molecule. We observed that our two single-conformer methodologies have different types of failure cases and that these differences could be exploited for determining when the methods are likely to have substantial errors. 相似文献
23.
Emil Pop Stanislaw Rachwal Marcus E. Brewster 《International journal of quantum chemistry》1996,60(8):1829-1834
The allylic rearrangement of trans-pinocarveol esters ( I ) to myrtenol esters ( II ), a reaction of interest in the chemistry of terpenes and cannabinoids, has been theoretically investigated. The intramolecular, cyclization-induced rearrangement results in equilibrium mixtures of the starting compounds and the products with the ratio of I vs. II in the equilibrium mixture being determined by their thermodynamic stabilities. The relative thermodynamic stabilities as reflected by calculated AM1 heats of formations (ΔHf) were determined for various I-II ester pairs. The study, in agreement with available experimental evidence, indicates that generally I , which contain an endocyclic double bond, are more stable and thus predominantly form following rearrangements. In two cases (acetate and pivalate) the stability is reversed. Calculations performed for similar structures, esters of 2-methylene cyclohexane-1-ol ( IV ) and 1-cyclohexene-1-methanol ( V ) gave similar results. Structural and electronic factors which might influence the stability of these compounds were examined. Interestingly, a correlation between thermodynamic stability and dipole moments was observed. © 1996 John Wiley & Sons, Inc. 相似文献
24.
It has previously been proposed (Ref. 1) that in the cationic vinyl polymerizations, proceeding with termination due to the collapse of ion pairs, addition of bases increases “livingness”, because of the fast convertion of the otherwise dead (within the time of polymerization) covalent species into the onium ions; these, in turn, fast convert into carbenium ions, the actually propagating species. Equilibria between carbenium ions (CH3OCH2+A− has been used as a model) and their onium counterparts ((CH3)2O taken as a model base) as well as between covalent species (CH3OCH2OSO2CF3) and the corresponding oxonium ion (with a (CH3)2O ligand) have been studied by dynamic 1H and 19F NMR. Total ionization of methoxymethyl triflate (CH3OCH2OSO2CF3) has been shown to increase indeed from 104 (-10°C) to 106 (-70°C) times when 1,0 mol·L−1 of (CH3)2O is added. Although this model system better describes polymerization of cyclic acetals than that of vinyl ethers, it shows at least qualitatively the importance of bases in ionization of covalent species, which may be responsible for reinitiation in the cationic polymerization of vinyl ethers. 相似文献
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Stanislaw Penczek Tadeusz Biela Pawel Klosinski Grzegorz Lapienis 《Macromolecular Symposia》1986,6(1):123-153
The mechanism of polymerization is discussed, in which cyclic esters of phosphoric acid, and related compounds are converted into linear macromolecules, modelling nucleic and teichoic acid backbones. Structures like deoxyribose polyphosphate and glycerol polyphosphate were prepared from the corresponding cyclic compounds. These polymerizations involve heterolytic breaking of the P-O bond in the cyclic monomer and proceed by ionic mechanism. Both 5- and 6-membered monomers have been polymerized. The thermodynamic parameters of the ring-chain interconversion were determined; the 5-membered rings polymerization is driven by the exothermicity of the ring-opening, whereas polymerization of several 6-membered rings is endothermic and allowed because of the positive change of entropy. Anionic polymerization, and particularly the pseudo(coordinate)anionic polymerization provides, in contrast to the cationic process, high-molecular-weight polymers with more uniform structure. Anionic polymerization proceeds mostly (at the applied conditions) on the macroion – -pairs. The elementary reactions consist of the nucleophilic attack of the paired macroanions on the phosphorus atom in the cyclic monomer molecule. Rate constants of the elementary reactions for the model monomers will be presented. Stereochemistry of the propagation steps is shown to be governed by the statistical ring-opening, leading to the three kinds of polymer units (head-to-tail and two symmetrical units). Apart from the ring-opening, the polyaddition of diepoxides to phosphorous and phosphoric acids is described. Finally, a few examples of preparation of models of biopolymers are given, namely poly(deoxyribose phosphate) and poly(glycerol phosphate). 相似文献
29.
Marek Gaździcki Mark I. Gorenstein Stanislaw Mrówczyński 《The European Physical Journal C - Particles and Fields》1998,5(1):129-133
The pion multiplicity per participating nucleon in central nucleus–nucleus collisions at the energies 2–15 AGeV is significantly smaller than in nucleon–nucleon interactions at the same collision energy. This effect of pion suppression is argued to appear due to the evolution of the system produced at the early stage of heavy–ion collisions towards a local
thermodynamic equilibrium and further isentropic expansion.
Received: 21 July 1997 / Revised version: 12 November 1997 / Published online: 26 February 1998 相似文献
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