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11.
L. S. Zakharov G. N. Molchanova T. M. Shcherbina P. V. Petrovskii M. I. Kabachnik 《Russian Chemical Bulletin》1998,47(9):1718-1724
A number of trialkylsilylmethyl diphenyl phosphates MeRR′SiCH2OP(O)(OPh)2 (1a-e: R=Et (a), Pr (b), CF3CH2CH2 (c, e), Me3SiCH2 (d); R′=Me (a-d), Et (e)) were synthesized and their thermal rearrangement, of the 1,2-shift type, was studied. The rearrangement consists of the
migration of an alkyl group from Si atom to the methylene carbon atom and gives the corresponding silyl esters. The rate of
the rearrangement was found to increase in the order1d<1b<1a<1 (R=R′=Me)<1c corresponding to the enhancement of the total inductive effect (−I) of the substituents at the Si atom. The relative migration ability of the substituents at the Si atom, determined by GC/MS
analysis of the disiloxane fraction resulting from hydrolysis of pyrolyzed phosphates1a-e, increases in the order R=Pr<Et<CF3CH2CH2<Me≪Me3SiCH2, which differs substantially from the order in which the rate of the rearrangement of phosphates1a-d changes. The electronegativity of the migrating group affects noticeably the relative ability to migrate.
For Part 4, see Ref. 1.
Deceased.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 1767–1772, September, 1998. 相似文献
12.
近红外(NIR)光谱技术可用于表征氯仿体系中反胶团增溶水的能力. 对于C12-s-C12•2Br (s=2, 3, 4, 5, 6, 8)系列, 不论体系是否含有NaBr电解质, 由于具有较短联接链的表面活性剂易形成较大的反胶团, 其增溶水的能力随着联接链长度增加而降低. 与未含NaBr电解质的体系相比, 当体系中存在NaBr电解质时所形成的反胶团增溶水能力降低. 相似文献
13.
1 INTRODUCTION During the study of polynuclear complexes with the aim to investigate the magnetic super-exchange interaction between the adjacent metal ions bridged by a conjugation molecule[1], we have made efforts to prepare complexes bridged by 4, 5-diazafluorene-9-one azine (DAA) and found that the coordination ability of DAA is poor in the acidic solution. In order to probe the reason, DAA has been crystallized from the hydrochloric acid solution and its crystal structure has b… 相似文献
14.
15.
Lamination Design Optimization for Continuous Fiber Reinforced Composites of Variable Thicknesses北大核心CSCD 下载免费PDF全文
由于具备高的比强度、比刚度,利用连续纤维增强复合材料代替传统金属材料以实现结构轻量化正受到设计者们的广泛关注。然而,结构的复杂性给复合材料的铺层设计与优化带来了很大的挑战。针对航空用复合材料铺层设计约束多的问题,通过逐步构建设计变量准确表达结构的铺层信息。基于经典遗传算法框架,结合各设计变量特点,定义了铺层优化算法中的遗传算子,通过引入“修复”策略保证了每一代解都能满足设计约束,分布在可行域区间内。最后利用精英保留策略提高了算法的局部寻优能力,可以降低复杂复合材料结构铺层设计的计算成本。通过解决经典benchmark问题并与已有优化结果的比较,验证了前述铺层优化算法的全局、局部寻优能力,为工程实际中的复合材料铺层设计优化提供了理论支撑。 相似文献
16.
Sumitra Tavornvipas Hidetoshi Arima Fumitoshi Hirayama Kaneto Uekama Toshihiro Ishiguro Masahide Oka Kenichi Hamayasu Hitoshi Hashimoto 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):391-394
Some physicochemical and biological properties of a new branched cyclodextrin, 6-O--(4-O--d-glucuronyl)-d-glucosyl--cyclodextrin GUG--CyD) were investigated. Further, theinteraction of GUG--CyD with several drugs was studied by the solubility and spectroscopic methods, and compared with those of parent -CyD and 6-O--maltosyl--CyD(2--CyD).The hemolytic activity of GUG--CyD on rabbit erythrocytes was lower than those of -CyD and 2--CyD. GUG--CyD and 2--CyD showed negligible cytotoxicity on Caco-2 cells up to at least 0.1 M. The inclusion ability of GUG--CyD to neutral and acidic drugs was comparable to or slightly smaller than those of -CyD and 2--CyD, probably because of a steric hindrance of the branched sugar. On the other hand, GUG--CyD showed greater affinity for the basic drugs, compared with -CyD and 2--CyD, owing to the electrostatic interaction of its carboxylate anion with positive charge of basic drugs. Thus GUG--CyD may be useful as a safe solubilizing agent particularly for basic drugs. 相似文献
17.
The complex [Ru(II)(dcbpyH2)(bdmpp)NCS](PF6) (1) (where dcbpyH2 is 2,2′-bipyridine-4,4′-dicarboxylic acid, bdmpp is 2,6-bis(3,5-dimethyl-N-pyrazoyl)pyridine,) is synthesized and characterized extensively by 1H NMR and 13C NMR 1D and 2D, mass spectroscopy, cyclic voltammetry, electronic absorption spectroscopy and IR. The half-wave potential of the Ru(II)/Ru(III) redox couple was measured at E1/2=+0.795 V versus Ag/AgCl in CH3CN. The complex presents three intense metal-to-ligand charge transfer (MLCT) (dM→πL*) absorption bands centered at 383 (=21 300 M−1 cm−1), 432 (=22 400 M−1 cm−1) and 475 nm (=23 400 M−1 cm−1), respectively. The absorbance is extremely strong between 400 and 500 nm and even at 620 nm, the extinction coefficient is still high (=3768 M−1 cm−1). The strong π-acceptor property of the trans-isothiocyanate ligand compared with the Cl− ligand is probably the cause of the blue-shift observed in complex 1. These properties make the complex potentially promising for the photosensitization process. The incorporation of TiO2 photoelectrodes derivatized with this complex into a solar cell using a composite polymer/inorganic oxide solid-state electrolyte confirmed its sensitizing ability. Incident monochromatic photon-to-current conversion efficiency (IPCE) values of about 30% and overall energy conversion efficiency (η) of 1.7% were obtained. 相似文献
18.
Peter Bakó László Fenichel László Tôke 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(1):17-23
The complexing (in CHCl3) and extracting abilities of 18-crown-6 type compounds (1–15) were measured with Li, Na, K and NH4 cations. The substituents on the sugar part affected these properties significantly (K
a=103–107). Some substituents, like acetyloxy groups (3) decreased whereas others, like tosyloxy groups (10, 11) significantly increased the complexing ability and thus changed the selectivity. The compound with four tosyloxy groups (11) shows an excellent picrate salt extracting ability in a CH2Cl2-water system. 相似文献
19.
Norio Yoshino Munetoshi Morita Atsushi Ito Masahiko Abe 《Journal of fluorine chemistry》1995,70(2):187-191
Anionic surfactants having two polyfluoroalkyl chains per molecule, i.e. the sodium salt of bis(1H, 1H, 2H,2H-heptadeca-fluorodecyl)-2-sulfosuccinate, CF3(CF2)7(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)7CF3, the sodium salt of bis(1H, 1H, 2H, 2H-tridecafluoro-octyl)-2-sulfosuccinate, CF3(CF2)5(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)5CF3, and the sodium salt of bis(1H, 1H, 2H, 2H-nonafluorohexyl)-2-sulfosuccinate, CF3(CF2)3(CH2)2OCOCH2CH(SO3Na)COO(CH2)2(CF2)3CF3, have been prepared from maleic anhydride, the corresponding alcohols possessing a polyfluoroalkyl chain and sodium hydrogen sulfite. The flocculation and redispersion abilities of these surfactants for dispersed magnetic particles in water have been examined to investigate the effect of the chain length. It was found that this ability was enhanced by an increase in the chain length. The contact angles for water for pelleted surface-modified magnetite have been measured. In order to compare this ability and the contact angles, data for other fluorinated surfactant have been obtained. The Kraff point, the surface tension and the pNa of the aqueous surfactant solutions have also been measured. 相似文献
20.
创新能力是本世纪的核心竞争力,其关键是创新型人才的培养,这为理工类高校的实验教学提出了新的挑战.目前高校中的以学生为主体,教师为主导的大学生创新实验项目的实施是解决此挑战的有效途径之一.以笔者承担的系列三维立体投影物理实验的大学生创新实验项目为例,探讨了大学物理实验中的创新型人才培养模式.通过循序渐进的实验过程,引导学生自主搭建实验装置和编写控制程序,有效培养了学生的创新和实践能力,为高校实验教学改革提供了参考. 相似文献