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291.
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
292.
The first part of the paper deals with a critical discussion of the methodical basis of essential work of fracture (EWF) concept with respect to the specimen geometry (especially the notch depth) and application to polymers. In the second part, an in situ testing device, which combines a tensile testing machine with an optical strain-field measuring system, has successfully demonstrated possibility of characterization of fracture behaviour of polystyrene-polybutadiene block copolymers and block copolymer/homopolymer blends as examples of nanostructured polymer materials. It has been shown that knowledge of the time evolution of the strain field close to the crack tips leads to a simple verification of the basic precondition for the applicability of the EWF concept, the precondition “plastic zone coalescence-before-stable crack propagation”. 相似文献
293.
Spectral quantities of cyclopropane, cyclobutane, cyclohexane, and of several derivatives, have been calculated by a semiempirical all-valence electron SCF-CI MO method. In cyclopropane, HOMO is practically localized in the carbon-frame, and LVMO is purely so. In cyclobutane, these two MO's are based on C-H bonds, while cyclohexane holds an intermediate position. Despite the overall similarity-experimental and computed-of the spectra of these molecules, assignments are non-parallel. Like cyclopropane, cyclobutane can extend conjugation, but to a diminished degree; cyclohexane behaves in this respect like an acyclic alkane. An interpretation of this gradation, in terms of the nature of high-lying MO's, is proposed. 相似文献
294.
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297.
SAPO—11分子筛用i—Pr2NH导向合成及其酸性研究 总被引:3,自引:0,他引:3
以AlPO4、H3PO4、SiO2等为原料采用单一模板剂iPr2NH合成了SAPO11分子筛,利用Avrami方程等对合成过程进行了定量描述。还利用红外(IR)、程序升温脱附(TPD)、线性丁烯骨架异构反应催化活性测试等手段表征了SAPO11的酸性。结果表明,合成过程随温度有明显变化,晶化阶段的活化能远高于核化阶段的值。可用Avrami方程的参数来表征合成过程的难易程度。分子筛中存在B酸和L酸位,主要在中等强度范围,从而对线性丁烯骨架异构反应有较好的催化活性。提高分子筛中硅含量可明显增大酸位浓度,酸强度也有轻度增强。 相似文献
298.
Jijun Qiu Weidong Yu Xiangdong Gao Xiaomin Li 《Journal of Sol-Gel Science and Technology》2007,44(3):235-239
Ordered porous TiO2 films, including TiO2 nanotube arrays, are fabricated by a sol-gel dip-coating approach via ZnO nanorod templates obtained from aqueous solution
approach. The results indicate that the morphologies of ordered porous TiO2 films have been great affected by the sol-gel dip-coating cycle number. Open-ended TiO2 nanotube arrays can be obtained in optimum dip-coating cycle numbers. The TiO2 nanotubes with the inner diameter matching well with the diameters of ZnO nanorods, are well assembled and separate each
other. When the cycle number is less than this optimum value, no intact porous TiO2 film can be obtained. As the cycle number is larger than this optimum value, an ordered porous TiO2 film with many throughout holes is formed. The evolutive mechanism of ordered porous TiO2 films is proposed. 相似文献
299.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
300.