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181.
Chan Sik Cho Tae Kyung Kim Bok Tae Kim Tae-Jeong Kim Sang Chul Shim 《Journal of organometallic chemistry》2002,650(1-2):65-68
Nitroarenes react with trialkylamines in the presence of a catalytic amount of a ruthenium catalyst together with tin(II) chloride dihydrate at 180 °C in an aqueous medium (toluene–H2O) to afford the corresponding quinolines in moderate to good yields. The catalytic pathway seems to be proceeded via a sequence involving initial reduction of nitroarenes to anilines, alkyl group transfer from alkylamines to anilines to form an imine, dimerization of imine, and heterocyclization. 相似文献
182.
The aggregation interaction between reduced-denatured egg white lysozymes during refolding procedure in urea solution was studied by means of reducing and non-reducing protein electrophoreses. Results of non-reducing sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) of the supernatant and aggregate precipitate formed in refolding process show that except being refolded to native egg white lysozymes, the reduced-denatured lysozymes can also form the aggregates with molecular weights (MW) being separately about 30.0 and 35.0 kD, while the reducing SDS-PAGE and the refolding results in the presence of sodium dodecyl sulphate show that these aggregates are formed chiefly through the misconnection of disulfide bonds between the reduced-denatured lysozymes, and the aggregate precipitates are formed through the non-covalent interactions between the aggregates with molecular weight being about 30.0 kD. From the results of electrophoresis and size-exclusion chromatographic analyses, it can be inferred that the aggregates with molecular weights being about 30.0 and 35.0 kD are bi-molecular and tri-molecular egg white lysozyme aggregates, respectively. And finally, a suggested refolding mechanism of reduced-denatured egg white lysozymes in urea solution was presented. 相似文献
183.
MO Yi-Rong WU Wei ZHANG Qian-ErDepartment of Chemistry Xiamen University Xiamen Fujian China 《中国化学》1995,13(1):27-32
The π electronic delocalization in trans-C4H6 and cis-C4H6 has been investigated in the frame of ab initio valence bond theory with 6-31G basis set. The result shows that the Csp2-Csp2 single bond length (1.506 A) is only about 0.024 A shorter than the Csp3-Csp3 bond, thus the central bond length shortening would be mainly due to π conjugation. The theoretical resonance energies of the trans-C4H6 and cis-C4H6 are 8.48 and 7.44 kcal/mol, respectively. 相似文献
184.
Häussermann U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(7):1471-1478
The Group 15 elements P, As, Sb, and Bi all have layered structures consisting of six-membered rings under ambient conditions and attain the body-centered cubic (bcc) structure at the highest pressures applied. In the intermediate pressure region, however, phosphorus and its heavier congeners behave profoundly differently. In this region P first attains the open packed simple cubic (sc) structure for a wide range of pressures and then transforms into the rarely observed simple hexagonal (sh) structure. For the heavier congeners complex, incommensurately modulated host-guest structures emerge as intermediate pressure structures. We investigated the high-pressure behavior of P and As by ab initio density functional calculations in which pseudopotentials and a plane wave basis set were employed. The incommensurately modulated high-pressure structure of As was approximated by a supercell. Our calculations reproduced the experimentally established pressure stability ranges of the sc and sh structures for P and the host-guest structure for As very well. We found that the sc and especially the sh structure are decisively stabilized by the admixture of d states in the occupied levels of the electronic structure. This admixture releases s-s antibonding states above the Fermi level (s-d mixing). With pressure, s-d mixing increases rapidly for P, whereas it remains at a low level for As. As a consequence, the band energy contribution to the total energy determines the structural stability for P in the intermediate pressure region, giving rise to simple packed structures. On the other hand, in the intermediate pressure region of the heavier Group 15 elements, a delicate interplay between the electrostatic Madelung energy and the band energy leads to the formation of complex structures. 相似文献
185.
变温红外光谱研究多嵌段聚氨脂脲的微相分离行为 总被引:7,自引:0,他引:7
用傅里叶变换红外光谱方法研究了热处理对由聚环氧丙烷聚醚多元醇、3.5-二乙基甲苯二胺和4,4-二苯基甲烷二异氰酸酯组成的多嵌段聚氨酯脲(SPUU)的微相分离行为的影响.从室温逐步升温到310℃的过程中,氨基甲酸酯键(UT)之间形成的氢键大量解离,而脲键(UA)之间形成的、具有平面状双分叉结构的氢键在130~200℃范围却大量生成;从310℃缓慢冷却到室温后,部分游离的UT重新形成氢键,而硬段之间形成的UA氢键的含量又有所增加.结果表明:高温热处理可以有效地提高SPUU的微相分离程度. 相似文献
186.
Takehiko Yamato Carol Pérez-Casas Shofiur Rahman Zeng Xi Mark R. J. Elsegood Carl Redshaw 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):193-197
A novel receptor possessing two complexation sites and bearing 1,3-alternate conformation based on thiacalix[4]arene, confirmed by single crystal X-ray analysis, was prepared. The tetrathiacalix[4]arene
diamide shows strong intramolecular hydrogen bonding. The binding behavior towards K+ and halides has been examined by 1H NMR titration experiments. 相似文献
187.
Clovis Peppe Paola de Azevedo Mello Rafael Pavão das Chagas 《Journal of organometallic chemistry》2006,691(11):2335-2339
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles. 相似文献
188.
V. R. Kartashov T. N. Sokolova A. Yu. Pavinskii I. V. Timofeev A. B. Radbil' 《Russian Chemical Bulletin》1995,44(12):2375-2381
The kinetics of azidomercuration of alkenes, cycioalkenes, and their derivatives with a Hg(OAc)2-NaN3 system (1 1, 1 2, and 1 3) was studied. Based on the data on the product structure and kinetic results, it was concluded that HgOAcN3 and Hg(N3)2 play the role of azidomercuration reagents. The reactions with alkenes having a strained double bond occur by a concerted scheme. With nonstrained alkenes, a multistep mechanism is realized, its first reversible step involving the formation of a mercurinium intermediate with an ion pair structure.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No.12, pp. 2479–2485, December, 1995. 相似文献
189.
Zalavutdinov Renad K. Gorodetsky Alexander E. Zakharov Andrey P. 《Mikrochimica acta》1994,114(1):533-537
This paper describes the study of chemical bonds in amorphous hydrogen rich boron/carbon (a-B/C:H) films by electron probe microanalysis. The films were deposited on Si single crystals by plasma chemical vapour deposition with a precursor-carborane (C2B10H12) in a laboratory setup. A film thickness and B/C ratio up to a value of 8000 Å and 4, respectively, have been obtained. The analysis of boron and carbon X-ray emission spectra has shown that the nearest order in the films is characterized by the coexistence of C-C, B-C and B-B bonds for B/C 1 and of B-B and B-C bonds for B/C 4. After two years exposure in air the oxygen content in the films increases from 2–5 to 15–20 at.%. 相似文献
190.
We prove that certain two-point Padé approximants occupying the diagonal of the Padé table form monotone sequences of lower and upper bounds uniformly converging to a Stieltjes function. The results can be applied to the theory of inhomogeneous media for the calculation of the bounds on the effective transport coefficients of heterogeneous materials. 相似文献