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1.
Holger Poths Erik Wischerhoff Rudolf Zentel Axel Sch nfeld Guido Henn Friedrich Kremer 《Liquid crystals》1995,18(5):811-818
Two new ferroelectric oligosiloxanes, a cyclic tetramer and a twin, have been synthesized. By a comparative study with their corresponding monomer and side chain polysiloxanes, the influence of oligo- and polymerization on the liquid crystalline and ferroelectric properties have been investigated. Polymerization leads to a stabilization of LC phases through increase of the clearing temperatures and suppression of crystallization. Oligomerization also leads to mesophase broadening, but, due to the low degree of polymerization, the effect is inferior to the linear polysiloxanes. The low viscosity of the oligosiloxanes ensures response times in the microsecond region, thus being comparable with their monomer and conventional LMWFLCs. It is found that polymerization increases the spontaneous polarization Ps. This is attributed to the density increase after polymerization, enhancing the inter-mesogenic interactions. The collective and local dynamics of the OFLCs are influenced differently with respect to their molecular structures. Each oligomer is already a good model for its corresponding polymer concerning the soft mode dynamics. For the local β-relaxation a similar temperature dependence of the relaxation times τ for the cyclic tetramer and for the side chain polysiloxanes is observed. The long axial rotation of the twin, having a very efficient decoupling, is significantly faster, thus resembling the monomer. 相似文献
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The rotation-tunneling spectrum of the second most stable gGg′ conformer of ethylene glycol (1,2-ethanediol) in its ground vibrational state has been studied in selected regions between 77 and 579 GHz. Compared to the study of the more stable aGg′ conformer, a much larger frequency range was studied, resulting in a much extended frequency list covering similar quantum numbers, J?55 and Ka?19. While the input data were reproduced within experimental uncertainties up to moderately high values of J and Ka larger residuals remain at higher quantum numbers. The severe mixing of the states caused by the Coriolis interaction between the two tunneling substates is suggested to provide a considerable part of the explanation. In addition, a Coriolis interaction of the gGg′ ground vibrational state with an excited state of the aGg′ conformer may also contribute. Relative intensities of closely spaced lines have been investigated to determine the signs of the Coriolis constants between the two tunneling substates relative to the dipole moment components and to estimate the magnitudes of the dipole moment components and the energy difference between the gGg′ and the aGg′ conformers. Results of ab initio calculations on the total dipole moment and the vibrational spectrum were needed for these estimates. The current analysis is limited to transitions with quantum numbers J?40 and Ka?6 plus those having J?22 and Ka?17 which could be reproduced within experimental uncertainties. The results are aimed at aiding radioastronomers to search for gGg′ ethylene glycol in comets and in interstellar space. 相似文献
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Francis J. Narcowich Joseph D. Ward Holger Wendland. 《Mathematics of Computation》2005,74(250):743-763
In this paper we discuss Sobolev bounds on functions that vanish at scattered points in a bounded, Lipschitz domain that satisfies a uniform interior cone condition. The Sobolev spaces involved may have fractional as well as integer order. We then apply these results to obtain estimates for continuous and discrete least squares surface fits via radial basis functions (RBFs). These estimates include situations in which the target function does not belong to the native space of the RBF.
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The synthesis of two new aromatic cyclic enediynes 1a and 1b using a double Wittig condensation, followed by bromination and di-dehydrobromination, is reported. The structures were determined using X-ray crystallography. The observed C(1)-C(6) distances of the enediyne moiety in the oxygen- and sulfur-containing eleven-membered rings are quite short with 3.44 and 3.50 A, respectively, indicating the highly strained nature of these compounds. Isodesmic calculations at the B3LYP/6-31G level of theory indicate a strain energy of 8.2 and 5.8 kcal/mol, respectively. Despite the highly strained ring system, the compounds were found to be stable under thermal, photochemical, and electron-transfer conditions. Using BLYP/6-311+G/BLYP/6-31G calculations, the origin of this unusual stability was traced to the high energy of the 1,4 benzyne diradicals formed via Bergman cyclization. For the radical cation, both the C(1)-C(6) and the C(1)-C(5) cyclization mode previously reported for acyclic analogues of 1 were found to be energetically prohibitive. 相似文献
10.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献