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1.
采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯. 相似文献
2.
In this study, a genetically encoded bioluminescent indicator for ERK2 dimer was developed with the split Renilla luciferase complementation method, in which the formation of ERK2 dimer induces a spontaneous emission of bioluminescence in living cells. In response to extracellular stimuli, such as epidermal growth factor (EGF) or 17β‐estradiol (E2), extracellular signal‐regulated kinase 2 (ERK2) is phosphorylated by its upstream kinase MEK, and also phosphorylates its substrates in various regions of the cell, including the nucleus. Phosphorylated ERK2 is led to form its dimer, thereby transporting itself into the nucleus. We demonstrated with the indicator that stimulation with EGF or E2 induces the formation of ERK2 dimer in living MCF‐7 cells. The dynamics of this dimer formation was examined and discussed. 相似文献
3.
Amorín M Castedo L Granja JR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6543-6551
Here we report the preparation and structural characteristics of self-assembling peptide tubelets composed of 32-membered rings formed of alternating alpha-amino acids and cis-3-aminocyclohexanecarboxylic acids. The tubelets possess a partial hydrophobic core environment, provided by the projection of the cyclohexane C2 methylene moiety into the lumen, and a Van der Waals pore diameter of about 7 A. 相似文献
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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
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Recently discovered catalytic reactions with ruthenium and lanthanide metal complexes have extended the scope of 1-alkynes as useful reagents. The specific formation of aryl-substituted (Z)-1,3-enzymes via the dimerization of HC(triple bond) CR(1) (R(1) = aryl) has been attained using dimeric lanthanide complexes, the catalytic activity of which appears to be unaffected by time. The dimerization of HC(triple bond) CR(2) (R(2) = t-Bu, SiMe(3)) catalyzed by Ru(cod)(cot)/PR(3) or RuH(2)(PPh(3))(3) produces a good yield of butatrienes (Z)R(2)CH=C=C=CHR(2) with a high degree of selectivity. Under certain conditions, HC(triple bond) C=SiMe(3) dimerizes to yield exclusively (Z)-M(3)Si-C(triple bond) C-CH=CH-SiMe(3). The hydration of HC(triple bond)CR(3) (R(3) = alkyl, aryl) catalyzed by RuCl(2)/PR'(3) or CpRuCl(PR"(3))(2) has realized the first example of anti-Markovnikov regioselectivity in an addition reaction of water that produces aldehydes R(3)CH(2)bond;CHO. The application of this reaction to propargylic alcohols has lead to their formal isomerization to alpha,beta-unsaturated aldehydes. In contrast, the addition of amines R(4)bond;NH(2) (R(4) = aryl) to HCtbond;CR(5) (R(5) = alkyl, aryl) conforms to Markovnikov's rule to produce ketimines R(5)bond;(C=NR(4))bond;CH(3) when catalyzed by a Ru(3)(CO)(12)/additive. Since the reaction can be performed in air without the need for any solvents, it enables the practical synthesis of aromatic ketimines, which are difficult to prepare by conventional methods. The synthesis of indoles using deactivated anilines is one practical application of this reaction. The mechanisms of some of these reactions have been analyzed in detail with the aid of theoretical calculations. 相似文献
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D. B. Tagiev P. S. Mamedova F. A. Abdullaeva M. K. Munshieva A. A. Turabova T. G. Takhirov 《Russian Chemical Bulletin》1992,41(11):2113-2115
The catalytic activity of Ni(II) bis-(5-thiopyrazol-4-aldiminates) was found to be related to the stereochemical flexibility of these compounds in the dimerization of propylene. The propylene conversion decreases with decreasing stereochemical flexibility of the complexes resulting from an increase in the bulk of the substituent at the coordinated nitrogen atom of the NiN2S2 chelate ring.Institute of Inorganic and Physical Chemistry, Academy of Sciences of Azerbaidjan, 370143 Baku. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2667–2670, November, 1992. 相似文献
10.
离子液体体系中1-丁烯二聚反应的研究 总被引:8,自引:0,他引:8
研究了在强酸性AlCl3/Et2AlCl/[BMIM]Cl型离子液体体系中过渡金属化合物对1-丁烯二聚反应的催化作用.结果表明,[BMIM]Cl对强酸性AlCl3/Et2AlCl催化剂催化1-丁烯高聚反应有明显的阻聚作用,并显著提高了1-丁烯二聚的选择性.在过渡金属化合物中,含镍化合物对1-丁烯二聚反应有最好的催化效果.在最佳反应条件下,1-丁烯的转化率可达95.1%,二聚产物C8烯的选择性为85.8%.同时,对1-丁烯二聚反应的机理进行了初步探讨. 相似文献