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91.
Zou JW Jiang YJ Guo M Hu GX Zhang B Liu HC Yu QS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):740-751
Ab initio calculations have been performed on a series of complexes formed between halogen-containing molecules and ammonia to gain a deeper insight into the nature of halogen bonding. It appears that the dihalogen molecules form the strongest halogen-bonded complexes with ammonia, followed by HOX; the charge-transfer-type contribution has been demonstrated to dominate the halogen bonding in these complexes. For the complexes involving carbon-bound halogen molecules, our calculations clearly indicate that electrostatic interactions are mainly responsible for their binding energies. Whereas the halogen-bond strength is significantly enhanced by progressive fluorine substitution, the substitution of a hydrogen atom by a methyl group in the CH(3)X...NH(3) complex weakened the halogen bonding. Moreover, remote substituent effects have also been noted in the complexes of halobenzenes with different para substituents. The influence of the hybridization state of the carbon atom bonded to the halogen atom has also been examined and the results reveal that halogen-bond strengths decrease in the order HC triple bond CX > H(2)C=CHX approximately O=CHX approximately C(6)H(5)X > CH(3)X. In addition, several excellent linear correlations have been established between the interaction energies and both the amount of charge transfer and the electrostatic potentials corresponding to an electron density of 0.002 au along the R-X axis; these correlations provide good models with which to evaluate the electron-accepting abilities of the covalently bonded halogen atoms. Finally, some positively charged halogen-bonded systems have been investigated and the effect of the charge has been discussed. 相似文献
92.
Lingjun Chou Yingchun Cai Bing Zhang Jianzhong Niu Shengfu Ji Shuben Li 《Reaction Kinetics and Catalysis Letters》2002,76(2):311-315
Na-Mn-W/SiO2 catalysts were prepared and their catalytic performance for oxidative coupling of methane (OCM) was evaluated in a stainless-steel microreactor at elevated pressure. The results show that a CH4 conversion of 15.1% with a C2+ selectivity of 71.8% was obtained under 750oC, 1.0×105h-1 GHSV, CH4/O2 ratio of 8 and 1.0 MPa. Moreover, 17.3% CH4 conversion with 51.6% C2 selectivity and 23.6% C3-C4 selectivity was obtained under 750oC, 2.0×105h-1 GHSV, CH4/O2 ratio of 8 and 1.0 MPa. 相似文献
93.
94.
以不同分子筛(Nonasil, MCM-22或MCM-49)为晶种, 在水热条件下以六亚甲基亚胺(HMI)为模板剂, 对纯硅沸石Nonasil(HMI)的合成进行了研究. 并且对各种合成参数, 包括晶种类型、硅源、晶化温度和Na+浓度等对Nonasil(HMI)合成的影响进行了探讨. 发现在适量的Na+存在条件下, 晶种的引入大大缩短了晶化时间; 不同类型的晶种对晶化速度有不同程度的提高. 特别是用异类晶种(如MCM-22或MCM-49)能够合成高结晶度的Nonasil(HMI). 相似文献
95.
96.
合成了甘氨酸 (Gly) 天冬氨酸 (Asp)组成的肽链Gly Asp、Gly Asp Gly Asp、Gly Asp (Gly Asp) 2 .分别将天冬氨酸及上述合成的肽链引入到聚酰胺 胺型树枝状化合物 (PAMAM)的表面 .对所得化合物进行了分子模拟 ,结果表明Gly Asp (Gly Asp) 2 肽链在PAMAM表面可形成接近于 β sheet的构象 .由实验得知 ,经Asp、Gly Asp、Gly Asp Gly Asp、Gly Asp (Gly Asp) 2 修饰的PAMAM树枝状化合物对抗坏血酸还原FeⅢ 细胞色素C(cytc)的反应有干扰作用 ,导致该反应速率下降 .这说明所合成的化合物与cytc有较好的结合能力 .特别是Gly Asp (Gly Asp) 2 修饰的PAMAM ,其与cytc的结合常数为 1 6ⅹ 1 0 5. 相似文献
97.
Here we report the first example of catalytic metallogels, which are formed irreversibly in dimethylsulfoxide via the creation of cross-linked, three-dimensional coordination polymer networks by using transition-metal ions with multiple sites available for coordination and multidentate ligands. Conformational flexibility of the ligands and slow formation of the coordination polymers apparently favor the gelation. These metallogels are stable in water and most organic solvents and can catalyze the oxidation of benzyl alcohol to benzaldehyde by using their PdII moieties as the catalytic centers. The best catalytic turnover of the metallogel is twice that of [Pd(OAc)2] under similar reaction conditions. 相似文献
98.
用乙烯为原料在双功能催化剂体系的作用下通过二聚和共聚合反应,直接合成线性低密度聚乙烯(LLDPE).所用二聚反应催化剂为钛酸正丁酯(Ti(OBu)_4),共聚催化剂为TiCl_4/MgCl_2(ZM-1催化剂).研究了二聚反应动力学行为及影响双功能催化剂体系动力学过程的一些因素.结果表明利用这两种催化剂组成双功能催化剂体系能够很方便地制得密度范围在0.90-0.93,Et/1000C在10-40的LLDPE. 相似文献
99.
Yan B Collins N Wheatley J Irving M Leopold K Chan C Shornikov A Fang L Lee A Stock M Zhao J 《Journal of combinatorial chemistry》2004,6(2):255-261
We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results. 相似文献
100.