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101.
采用从头计算方法(HF)对几种膦铑络合物[Rh(R,R)-DIPAMP]^ ,[Rh(S,S)-CHIRAPHOS]^ ,[Rh(DIPHOS)]^ 及它们与乙基-α-乙酰胺基肉桂酸(MAC)结合形成的中间体[Rh(R,R-DIPAMP)(MAC)]^ ,[Rh(S,S-CHIRAPHOS)(MAC)]^ ,[Rh(DIPHOS)(MAC)]^ 的几何结构进行了优化,计算结果显示:(1)采用从头计算方法对含有膦铑络合物的较大催化体系的全优化计算是可行的;(2)分子构型不同的双膦配体及其所形成的膦铑络合物中大部分主要原子间的键长、键角数据相差不大,但手性的不同对膦铑络合物的部分键长、键角数据有所影响;(3)在与(MAC)形成络合物前后,双膦配体上主要原子的电荷分布变化并不显著,但金属铑原子上的电荷则显著增加,可能是MAC在与膦铑配体络合过程中有电荷向铑原子上进行了转移. 相似文献
102.
以超临界二氧化碳为溶媒,将偶氧苯分子插入到α-以及β-环糊精的分子环空洞中合成出了偶氧苯-环糊精纳米复合体。环糊精与偶氧苯的摩尔分子为1:1的混合物,放入压力30MPa、温度120℃的超临界装置中处理后,对其生成物采用红外、固体核磁共振、X-射线衍射、差热分析及化学元素分析等手段进行了分析,结果表明偶氧苯成功地插入到β-环糊精分子环空洞中形成了纳米复合体,而α-环式糊精与偶氮苯之间只是简单的物理混合物,没有形成纳米复合体。所得到的偶氮苯-β-环式糊精复合体具有通道式分子结构:二个β-环式糊精分子捕获一个偶氧苯分子,β-环式糊精的分子环空洞连成一个通道。偶氧苯插入到β-环式糊粉分子环空洞中后其热稳定性也得到大幅度提高。 相似文献
103.
对生物体内和模拟的含锰金属酶,即含锰超氧化物歧化酶(Mn—SOD)、含锰的过氧化氢酶(Mn—catalase)及含锰的光合成氧释放配合物(Mn—OEC)的结构、活性部位、催化作用机理及其模型化合物的研究进展进行了综述。 相似文献
104.
We review some results obtained by anelastic spectroscopy on H-related defects in III–V semiconductors. Anelastic measurements on InP lead to the formulation of a model explaining the conversion to the semi-insulating (SI) state. Moreover, in GaAs:Zn an extraordinarily fast relaxation rate has been measured and a possible explanation has been suggested. This results are reviewed and discussed in the light of new experiments on InP:Zn, whose spectrum shows a relaxation process similar to the one in GaAs:Zn. 相似文献
105.
106.
《Journal of Nuclear Science and Technology》2013,50(6):437-442
The structure of uranyl nitrato complex with CMPO [n-Octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide] in solid state and in non-aqueous solvents without containing free CR/IPO has been studied by using IR spectrophotometer, 13C- and 31P-NMR. The carbonyl(vcO) and phosphoryl(vpO) stretching bands of coordinated CMPO were observed at lower wavenumber than the corresponding bands of free CMPO in both the states. The 13C and 31P peaks assigned to the carbonyl carbon and phosphoryl phosphine of coordinated CMPO was detected in the lower field than that of free CMPO. From these results, it was concluded that the uranyl nitrato complex with CMPO in both the states has the structure with two nitrate and one CMPO coordinated as bidentate in the equatorial plane of uranyl ion, i.e., UO2(NO3)2·CMPO. Furthermore, the electrochemical studies of UO2(NO3)2·CMPO complex in CH3CN have been carried out using cyclic and normal pulse voltammetric methods. It was found that the UO2(NO3)2·CMPO complex is reduced to U(V) complex at around ?1.22V vs. Fc/Fc+ (ferrocene/ferrocenium) and that the resulting reductant is oxidized to U(VI) at around +0.04V vs. Fc/Fc+. 相似文献
107.
Massimo Nespolo 《Crystallography Reviews》2017,23(4):302-303
Some statements in the review by Liu et al. [Liu Y, Liu Y, Drew GB. Comparison of calculations for interplanar distances in a crystal lattice. Cryst Rev. 2017] are corrected. The role of metric tensor to simplify calculations of interplanar spacings in crystal lattices is emphasized. 相似文献
108.
Alexander N. Orekhov Yuri V. Bobryshev Igor A. Sobenin Alexandra A. Melnichenko Dimitry A. Chistiakov 《International journal of molecular sciences》2014,15(7):12807-12841
In atherosclerosis; blood low-density lipoproteins (LDL) are subjected to multiple enzymatic and non-enzymatic modifications that increase their atherogenicity and induce immunogenicity. Modified LDL are capable of inducing vascular inflammation through activation of innate immunity; thus, contributing to the progression of atherogenesis. The immunogenicity of modified LDL results in induction of self-antibodies specific to a certain type of modified LDL. The antibodies react with modified LDL forming circulating immune complexes. Circulating immune complexes exhibit prominent immunomodulatory properties that influence atherosclerotic inflammation. Compared to freely circulating modified LDL; modified LDL associated with the immune complexes have a more robust atherogenic and proinflammatory potential. Various lipid components of the immune complexes may serve not only as diagnostic but also as essential predictive markers of cardiovascular events in atherosclerosis. Accumulating evidence indicates that LDL-containing immune complexes can also serve as biomarker for macrovascular disease in type 1 diabetes. 相似文献
109.
Liang HuJie Qin Nan ZhouYi-Fei Meng Yan XuJing-Lin Zuo Xiao-Zeng You 《Dyes and Pigments》2012,92(3):1223-1230
Metal complexes containing a new multi-sulfur atom containing 1,2-dithiolene ligand, [4′,5′:5,6] [1,4] dithiino[2,3-b] quinoxaline-1′,3′-dithiolate, have been synthesized and characterized by electrochemical measurements, IR, UV-NIR and ESR spectroscopies. X-ray structure analysis reveals that the anions of the Ni-complex derived from the new ligand form a zig-zag chain along the b axis, and the anions of Au complex of the ligand stack along the a axis while the cations occupy the holes. The Ni-complex exhibits remarkable absorption at 1082 nm (? = 15?000 dm3 mol−1 cm−1) and good solubility that render this complex as a promising near-IR dye for Q-switching neodymium lasers. The third-order non-linear optical properties of the complexes are measured by the Z-scan technique with a 6.5 ns pulsed laser at 532 nm. The Au complexes exhibit non-linear optical absorptive abilities, while the non-linear absorption of the nickel complex is negligible. All of the complexes show effective self-defocusing performance. The third-order non-linear optical susceptibilities for the Au complexes have been determined to be of the order of 10−13 esu. 相似文献
110.
Huriye Akdas-Kilig Jean-Pierre MalvalFabrice Morlet-Savary Anu SinghLoic Toupet Isabelle Ledoux-RakJoseph Zyss Hubert Le Bozec 《Dyes and Pigments》2012,92(1):681-688
Two new 4,4′-bis(donor)-6,6′-diphenyl- 2,2′-bipyridine ligands and their corresponding D2d (CuI, AgI, ZnII) octupolar metal complexes were synthesized, and their linear and nonlinear optical properties were investigated. A single crystal X-ray structure was also determined for the bis[4,4′-bis(diethylaminostyryl)-6,6′-diphenyl-bipyridine]copper(I) complex, which revealed a distorded pseudo-tetrahedral geometry. Molecular second-order nonlinear optical properties were determined for the complexes using the Harmonic Light Scatterring technique at 1.91 μm. These metallo-chromophores display large first hyperpolarizabilities β1.91 in the range of 211-340 × 10−30 esu, which increase with the Lewis acidity of the metal ion. The two-photon absorption properties of the bipyridyl ligands and related complexes were determined using either the two-photon emission method for fluorescent compounds or the open aperture Z-scan technique for non emissive ones. The complexes display red-shifted two-photon absorption bands compared to their metal-ion free chromophores, as well as a large increase of the maximum two-photon absorption cross-sections. 相似文献