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191.
The 1205 classical isomers of fullerene C58, as well as one quasi-fullerene C58 isomer with a heptagonal ring (labeled as Cs:hept) have been investigated by the quantum chemical methods PM3, HCTH/3-21G, and B3LYP/6-31G(d). Isomer C3v:0001, which has the lowest number of adjacent pentagons, is predicted to be the most stable isomer, but the quasi-fullerene isomer Cs:hept is only 2.50 kcal mol-1 higher in energy. Systematic investigations of the electronic properties of C3v:0001 and Cs:hept find that the C3v:0001 isomer has high vertical electron affinity (3.19 eV). The nucleus-independent chemical shifts (NICS) value at the center of Cs:hept (-5.1 ppm) is more negative than that of C60 (-2.8 ppm). The NICS value at the center of the heptagonal ring in Cs:hept (-2.5 ppm) indicates weakly aromatic character. In contrast, the C58(6-) and C58(8-) ions of the C3v:0001 and Cs:hept geometries possess large aromatic character, with NICS values between -14.0 and -26.2 ppm. To clarify the thermodynamic stabilities of C58 isomers at different temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the B3LYP/6-31G(d) level. The C3v:0001 isomer prevails in a wide range of temperatures, and the Cs:hept isomer is also an important component around 2800 K. The IR spectra of C58 isomers are simulated to facilitate experimental identification of different isomers. In addition, the electronic spectra and the second-order hyperpolarizabilities are predicted by ZINDO and the sum-over-states model. The static second-order hyperpolarizability of the C3v:0001 isomer is 96.5 % larger than that of C60, and its second-order hyperpolarizabilities at external field frequencies are at least nine times larger than those of C60. 相似文献
192.
利用化学键合和“瓶中造船”方法,成功地将酒石酸钛配合物接枝到HMS(heragonal mesoporous silicas)上或包络合于微孔NaY内.FT-IR表征表明酒石酸钛在HMS上是通过与载体表面羟基发生交换作用而被固载的;在NaY载体上则是通过包络合被封装在载体的超笼内.UV-Vis可见漫反射表征表明两类固载型催化剂有着相似的钛配位环境.在催化肉桂醇环氧化反应中,HMS键合型催化剂的反应转化率比NaY包络型催化剂的高;但后者在环氧化选择性上要高于前者.回收样品的重复使用实验结果表明,两类固载型催化剂在重复使用过程中均存在不同程度的失活. 相似文献
193.
194.
Xue-qiang Yin 《Tetrahedron》2005,61(7):1839-1843
A straightforward synthesis of (1S,2R,3R,4R)-4-(6-aminopurin-9-yl)-2-hydroxymethylcyclopentane-1,3-diol (2), an isomer of aristeromycin, and its 2′-deoxy derivative 3 from readily available disubstituted cyclopentenes is presented. An antiviral analysis of 2 showed it to have significant activity versus Epstein-Barr virus (IC50 0.62 μg/mL in the Elisa assay) and to be free of cytotoxicity effects against the host cells. In a much less comprehensive antiviral analysis, 3 also was active towards Epstein-Barr (IC50 7.58 μg/mL in the Elisa assay) but this was accompanied by cellular toxicity. 相似文献
195.
A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of masstransfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performancefor hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of thetraditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersedRh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation ofhigher olefins such as 1-dodecene. 相似文献
196.
197.
Yi‐Hang Wen Xia Feng Yin‐Hua He You‐Zhao Lan Hong Sun 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):m504-m506
In the title complex, [Zn(C12H6O4)(H2O)]n, a ZnII polymer based on naphthalene‐1,8‐dicarboxylate (1,8‐nap), the ZnII atoms adopt an elongated octahedral coordination geometry. A zigzag chain is formed by μ2‐aqua ligands and μ2‐carboxylate groups of the 1,8‐nap ligands. Adjacent parallel chains are further linked by 1,8‐nap ligands, forming a twisted two‐dimensional layer structure along the (100) plane. 相似文献
198.
Li Yan Liang Shao Ping Ren Yi Quan Zheng Man Geng Lu Guangzhou Institute of Chemistry Chinese Academy of Sciences Guangzhou China Key Laboratory of Polymer Materials for Electronics Guangdong China Graduate School of the Chinese Academy of Sciences Beijing China 《中国化学快报》2007,18(2):225-228
A series of novel liquid crystalline epoxides with lateral substituents were cured with anhydrides and the cure kinetics was investigated by non-isothermal DSC technique. The results showed that the lengths of lateral substituents have great effect on the value of Ea. The curing reaction became less active, when the liquid crystalline epoxides have long lateral substituents and were controlled by diffusion at the late stage of cure. A nematic structure was observed by POM and XRD. 相似文献
199.
Wang X Yu JC Yip HY Wu L Wong PK Lai SY 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(10):2997-3004
A novel metal/semiconductor nanocomposite with catalytic and photocatalytic functions has been prepared. The new material consists of highly dispersed platinum (Pt) nanoparticles embedded in a cubic mesoporous nanocrystalline anatase (meso-nc-TiO2) thin film. The porous thin film possesses a narrow pore-size distribution and a large surface area. The diameter of the Pt cluster can be controlled to below 5 nm, and the high dispersion of these clusters gives rise to catalytic activity for the oxidation of carbon monoxide, an important reaction for automobile exhaust treatment. This novel ordered mesoporous Pt/TiO2 nanoarchitecture is also a promising photochemical material, as demonstrated by the photo-driven killing of Micrococcus lylae cells on the film. 相似文献
200.