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851.
Burcu Binici Dionne I. Fortenberry Kayce C. Leard Marcus Molden Nesrin Olten Sam Popwell John A. Pojman 《Journal of polymer science. Part A, Polymer chemistry》2006,44(4):1387-1395
We demonstrate for the first time spherically propagating frontal polymerization that also exhibits spin modes. We have developed an interesting system using the amine‐catalyzed Michael addition of a trithiol to a triacrylate to create a rubbery gel. The gel suppresses convection and bubble formation during front propagation. A peroxide is also present to act as a thermal initiator. The front propagates via free‐radical polymerization of the remaining triacrylate after being initiated photochemically in the center of the reactor. It is possible to prepare the rubbery gel in any shape and then initiate thermal frontal polymerization. So‐called spin modes have been observed for the first time in spherically propagating fronts in which waves of polymerization propagate on the expanding spherical front. A system using a diacrylate dissolved in dimethyl sulfoxide with added silica gel and with persulfate as the initiator supports spherical fronts but does not exhibit spin modes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1387–1395, 2006 相似文献
852.
853.
854.
An improved nearly-orthogonal structured mesh generation system with smoothness control functions 总被引:1,自引:0,他引:1
This paper presents an improved nearly-orthogonal structured mesh generation system with a set of smoothness control functions, which were derived based on the ratio between the Jacobian of the transformation matrix and the Jacobian of the metric tensor. The proposed smoothness control functions are capable of relaxing the local strong orthogonal conditions so that nearly orthogonal but smooth mesh can be achieved. Examples and applications are also investigated in this paper to demonstrate the effects of the proposed mesh generation system. 相似文献
855.
856.
Jean Nguyen David Z. Ting Cory J. Hill Alexander Soibel Sam A. Keo Sarath D. Gunapala 《Infrared Physics & Technology》2009,52(6):317-321
A limitation to the advancement of the strained-layer superlattice technology for infrared detection is unwanted high dark currents and low R0A values, especially at long-wavelengths. In this paper, we discuss dark current characteristics of LWIR InAs/GaSb type-II superlattice detectors. Comparing devices with different dominant mechanisms, a more thorough analysis at low temperatures is provided. 相似文献
857.
Sam Payne 《Discrete and Computational Geometry》2008,40(3):365-376
We express the generating function for lattice points in a rational polyhedral cone with a simplicial subdivision in terms
of multivariate analogues of the h-polynomials of the subdivision and “local contributions” of the links of its nonunimodular faces. We also compute new examples
of nonunimodal h
*-vectors of reflexive polytopes.
Supported by the Clay Mathematics Institute. 相似文献
858.
859.
Richard J Mandle Nina Stock Stephen J Cowling Rachel R Parker Sam Hart Adrian C Whitwood 《Liquid crystals》2019,46(1):114-123
Eight novel liquid crystalline materials were prepared containing highly branched terminal chains, either 2,4,4-trimethylpentyl or 3,5,5-trimethylhexyl. All materials exhibit nematic mesophases, with additional smectic (Sm) C, hexatic B and SmI phases for certain homologues. Analysis by small- and wide-angle X-ray scattering reveals continual build-up of the correlation length within the nematic phases, where we also observe splitting of the small angle peak into four lobes, indicating pretransitional Sm fluctuations. Connoscopy confirms the nematic phase to be uniaxial and optically positive. We observe that in the solid state, the molecules exist as staggered antiparallel pairs as a consequence of the sterically demanding bulky terminal group, and this would also appear to manifest in the hexatic B phase, where the layer spacing was found to be greater than the molecular length. If true, this is an example of pair formation driven by sterics rather than dipole–dipole interactions and suggests that reentrant systems driven purely by steric frustration may be found. 相似文献
860.
de Visser SP 《Journal of the American Chemical Society》2006,128(30):9813-9824
Density functional calculations on the oxygenation reaction of propene by a model for taurine/alpha-ketoglutarate dioxygenase (TauD) enzyme are presented. The oxo-iron active species of TauD is shown to be a powerful and aggressive oxidant, which is able to hydroxylate C-H bonds and epoxidize C=C bonds with low barriers. In the case of propene oxygenation, the hydroxylation and epoxidation mechanisms are competitive on a dominant quintet spin state surface. We have compared the mechanism and thermodynamics of TauD with oxo-iron heme catalysts, such as the cytochromes P450, and found some critical differences. The TauD model is found to be much more reactive toward oxygenation of substrates than oxo-iron complexes in a heme environment with much lower reaction barriers. We have analyzed this and assigned this to the strength of the O-H bond formed after hydrogen abstraction from a substrate, which is at least 10 kcal mol(-)(1) stronger in five-coordinated oxo-iron nonheme complexes than in six-coordinated oxo-iron heme complexes. Since, the metal in TauD enzymes is five-coordinated, whereas in heme-enzymes it is six-coordinated there are some critical differences in the valence molecular orbitals. Thus, in oxo-iron heme catalysts one of the antibonding pi orbitals is replaced by a low-lying nonbonding delta orbital resulting in a lower overall spin state. Moreover, heme-enzymes have an extra oxidation equivalent located on the heme, which is missing in non-heme oxo-iron catalysts. As a result, the oxo-iron species of TauD reacts via single-state reactivity on a dominant quintet spin state surface, whereas oxo-iron heme catalysts react via two-state reactivity on competing doublet and quartet spin states. 相似文献