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991.
在手性金属钛催化剂存在下 ,研究了α′ 苯磺酰基 α ,β 不饱和酮与开链二烯的不对称催化环加成反应 ,讨论了α′ 苯磺酰基 α ,β 不饱和酮与开链二烯的反应活性和对映选择性 ,以高的收率和光学纯度合成了环己烯衍生物 ,并对部分产物的构型进行了鉴定 相似文献
992.
Oligomerization and Polymerization of Ethylene Initiated by a Novel Ni(Ⅱ)-Based Acetyliminopyridine Complexes as Single-Site Catalysts 下载免费PDF全文
Baojun Zhang Yanji Wang Gang Wang Jun Cao Shukun Sun Lihua Xing Yongcheng Sun Yunguang Han Hebei University of Technology Tianjin China Research Institute of Daqing Petrochemical Company Daqing Heilongjiang China College of Chemical Science Engineering China University of Petroleum Beijing China 《天然气化学杂志》2007,16(1):64-69
Novel Ni(Ⅱ)-based acetyliminopyridine complexes 1b, 2b, 3b (1-3b), which are synthesized from ligands 1a, 2a, 3a (1-3a) and [NiCl2(DME)], are suitable precursors for the catalysts that are necessary for ethylene oligomerization and polymerization reactions, activated by methylaluminoxane (MAO). The MAO-treated 1-3b presents an active catalytic center, which may oligomerize and polymerize ethylene to produce linearα-olefins and polyethylene, respectively. The molecular weight distributions of oligomers that are obtained are in good agreement with the Schulz-Flory rules for oligomers>C4. The activity of 3b-MAO complex is 6.3×107 g/(molNi·h) at 50℃. The activities and molecular weight distributions of oligomers show significant reliance on the structures of catalyst precursors. 相似文献
993.
Kim SW Oh HM Kim BS Chung HT Han WC Kim EC Kim TH Seo GS Lyou JH Nah YH Jung JC Choi SC Jun CD 《Experimental & molecular medicine》2003,35(1):53-59
Tumor target-derived soluble secretary factor has been known to influence macrophage activation to induce nitric oxide (NO) production. Since heme oxygenase-1 (HO-1) is induced by a variety of conditions associated with oxidative stress, we questioned whether soluble factor from tumor cells induces HO-1 through NO-dependent mechanism in macrophages. We designated this factor as a tumor-derived macrophage-activating factor (TMAF), because of its ability to activate macrophages to induce iNOS. Although TMAF alone showed modest activity, TMAF in combination with IFN-gamma significantly induced iNOS expression and NO synthesis. Simultaneously, TMAF induced HO-1 and this induction was slightly augmented by IFN-gamma. Surprisingly, however, induction of HO-1 by TMAF was not inhibited by the treatment with the highly selective iNOS inhibitor, 1400 W, indicating that TMAF induces the HO-1 enzyme by a NO-independent mechanism. While rIFN-gamma alone induced iNOS, it had no effect on HO-1 induction by itself. Collectively, the current study reveals that soluble factor from tumor target cells induces HO-1 enzyme in macrophages. However, overall biological significance of this phenomenon remains to be determined. 相似文献
994.
Han H Langley DR Rangan A Hurley LH 《Journal of the American Chemical Society》2001,123(37):8902-8913
G-quadruplex DNA presents a potential target for the design and development of novel anticancer drugs. Because G-quadruplex DNA exhibits structural polymorphism, different G-quadruplex typologies may be associated with different cellular processes. Therefore, to achieve therapeutic selectivity using G-quadruplexes as targets for drug design, it will be necessary to differentiate between different types of G-quadruplexes using G-quadruplex-interactive agents. In this study, we compare the interactions of three cationic porphyrins, TMPyP2, TMPyP3, and TMPyP4, with parallel and antiparallel types of G-quadruplexes using gel mobility shift experiments and a helicase assay. Gel mobility shift experiments indicate that TMPyP3 specifically promotes the formation of parallel G-quadruplex structures. A G-quadruplex helicase unwinding assay reveals that the three porphyrins vary dramatically in their abilities to prevent the unwinding of both the parallel tetrameric G-quadruplex and the antiparallel hairpin dimer G-quadruplex DNA by yeast Sgs1 helicase (Sgs1p). For the parallel G-quadruplex, TMPyP3 has the strongest inhibitory effect on Sgs1p, followed by TMPyP4, but the reverse is true for the antiparallel G-quadruplex. TMPyP2 does not appear to have any effect on the helicase-catalyzed unwinding of either type of G-quadruplex. Photocleavage experiments were carried out to investigate the binding modes of all three porphyrins with parallel G-quadruplexes. The results reveal that TMPyP3 and TMPyP4 appear to bind to parallel G-quadruplex structures through external stacking at the ends rather than through intercalation between the G-tetrads. Since intercalation between G-tetrads has been previously proposed as an alternative binding mode for TMPyP4 to G-quadruplexes, this mode of binding, versus that determined by a photocleavage assay described here (external stacking), was subjected to molecular dynamics calculations to identify the relative stabilities of the complexes and the factors that contribute to these differences. The DeltaG(o) for the external binding mode was found to be driven by DeltaH(o) with a small unfavorable TDeltaS(o) term. The DeltaG(o) for the intercalation binding model was driven by a large TDeltaS(o) term and complemented by a small DeltaH(o) term. One of the main stabilizing components of the external binding model is the energy of solvation, which favors the external model over the intercalation model by -67.94 kcal/mol. Finally, we propose that intercalative binding, although less favored than external binding, may occur, but because of the nature of the intercalative binding, it is invisible to the photocleavage assay. This study provides the first experimental insight into how selectivity might be achieved for different G-quadruplexes by using structural variants within a single group of G-quadruplex-interactive drugs. 相似文献
995.
996.
定标粒子理论预测乙醇-水体系汽液平衡盐效应 总被引:6,自引:0,他引:6
测定了70℃下3个1-1型电解质(NaCl、NaBr、KCl)在各种不同浓度的乙醇-水体系中的汽液平衡盐效应参数,并给出用定标粒子理论计算盐效应参数的方法。硬球作用项采用Masterton-Lee方程,软球作用项采用胡英的径向分布函数。分子间力在Lennard-Jones位能函数基础上计入偶极-偶极、偶极-诱导偶极、电荷-偶极、电荷-诱导偶极的贡献,其中离子-分子间的静电作用项仅限于规则排列的第一配位圈之内。将混合溶剂的局部介电常数视为液相浓度的函数,函数关系由实验拟合。在乙醇浓度变化的很大范围内,3个体系的预测与实验结果基本相符。 相似文献
997.
Fifteen isomers of [Si,N,C,O]2+ system are obtained at UB3LYP/6-311G(d) and UCCSD(T)/6-311+G(2df) (single-point) levels. The analyses are made for predicting the structures of optimized isomers, while ionic fragments with lower energies are suggested. The calculated results indicate that linear isomer SiNCO2+(2Π) is thermodynamically the most stable species in [Si,N,C,O]2+ system, followed by linear SiOCN2+ (2Π), SiCNO2+ (2Π), and SiC(NO) (2A) with NCO three-membered ring. The order of stability of several kinetically stable isomers is SiNCO2> SiCNO2+ (2Π)>SiOCN2+>SiC(NO)2+>OSiNC2+ (2Π). The obtained results by analyzing the isomerizations and ionic fragment patterns show that the signal peaks of [Si,N,C,O]2+ are attributed to the contribution of linear SiNCO2+ species, which is metastable and can dissociate to the ionic fragments in the mass spectrometry experiments. 相似文献
998.
999.
ShiGuoSUN XiaoJunPENG MingWenFAN YongQianXU LeiSHI LiChengSU 《中国化学快报》2004,15(8):965-968
Two novel rhenium(I) 2, 2′-bipyridyl complexes, [(4,4′-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4′-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4′-di-COOEt-bipy) Re (CO)3 (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN. 相似文献
1000.
含八齿苦味酸根的超分子苦味酸钾的合成和结构 总被引:1,自引:0,他引:1
A supramolecular complex, [Kpic]n (pic- is picratol, (NO2)3C6H2O-), has been synthesized unexpectedly in acetone solution, and characterized by elemental analysis, IR and X-ray crystallography. In the complex, the K+∶pic- is 1∶1, and one K(Ⅰ) ion is surrounded by six picrate anions, one picrate anion can coordinate to six K(Ⅰ) ions. The coordination number of every potassium atom is eight. Interestingly, the picratol adopts an eight-coordinated ideal mode unreported. CCDC: 630627. 相似文献