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61.
Ariel Fernández 《Theoretical chemistry accounts》1985,67(3):229-233
A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations. 相似文献
62.
We employ dissipative particle dynamics (DPD) to examine the self‐assembly behavior of A2‐star‐(B‐alt‐C) molecules. We successfully observe various types of hierarchical structure‐within‐structures, such as A‐formed spheres in the matrix formed by B and C alternating layers, hexagonally packed A‐formed cylinders in the matrix with B and C segregated layers, B and C alternating layers‐within‐lamellae, coaxial B and C alternating domains within hexagonally packed BC‐formed cylinders in the A‐matrix, and co‐centric BC‐alternating domains within BC‐formed spheres in the A‐matrix, by increasing the A composition. Generally speaking, the small length‐scale B and C segregated domains are in parallel to the large length‐scale structures. This hierarchical periodicity along the same axis as well as the various characteristic structures, that the A2‐star‐(B‐alt‐C) copolymers display, are quite different from those in A‐block‐(B‐graft‐C) coil‐comb copolymers. Moreover, it is interesting to find that when the copolymer chain length increases, though the hierarchical structure type is maintained, the number of small length‐scale lamellae that can form within the large length‐scale structure increases. These hierarchical structures under various compositions are reported theoretically for the first time in the copolymer systems consisting of the alternating blocks, and are in good agreement with the most recent experimental work by Matsushita and co‐workers (Macromolecules 2007 , 40, 4023). 相似文献
63.
Changes in binding affinity to catalytic antibody 6D9 of chloramphenicol phosphonate derivatives (CPDs) containing H or F were investigated by performing free energy calculations based on molecular dynamics simulations. We calculated the binding free energy, enthalpy, and entropy changes (DeltaDeltaG, DeltaDeltaH, and -TDeltaDeltaS) attributable to H-->F substitution by comparing results for CPDs containing a trifluoroacetylamino group (CPD-F) or an acetylamino group (CPD-H). The calculated DeltaDeltaG, DeltaDeltaH, and -TDeltaDeltaS values were -2.9, -6.3, and 3.5 kcal mol(-1) and close to experimental values observed for a series of similar ligands, chloramphenicol phosphonates with F and H (-1.4, -3.5, and 2.1 kcal mol(-1)). Therefore, CPD-F binds more strongly to 6D9 than does CPD-H. To clarify the origin of the large difference in DeltaDeltaG, we apportioned the calculated values of DeltaDeltaG and DeltaG for the associated and dissociated states into contributions from various atomic interactions. We found that the H-->F substitution increased the binding affinity mainly by decreasing the hydration free energy and not by increasing favorable interactions with the antibody. The decreased hydration free energy of the ligand was mainly due to unfavorable coulombic interactions between the trifluoroacetylamino group and solvent waters, which increased the free energy of the dissociated state (by about 3.7 kcal mol(-1)). Also, the trifluoroacetylamino group slightly increased the free energy level of the associated state (about 0.8 kcal mol(-1)) because favorable van der Waals interactions compensated for unfavorable coulombic interactions with antibody atoms. In addition, the enthalpy and entropy changes, DeltaDeltaH and -TDeltaDeltaS (computationally -6.3 and 3.5 kcal mol(-1)), originated mainly from a decrease in hydration free energy in the dissociated state. The CPD-F and CPD-H ligands had substantially different structures in the dissociated and complexed states. 相似文献
64.
HUA Er-BingCoordination Chemistry Institute State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangsu ChinaYANG Pin LI Qing-Shan YANG Bin-ShengInstitute of Molecular Science Shanxi University Taiyuan Shanxi China 《中国化学》1996,14(4):297-302
The effect of Cu2+ on the triple-stranded helical structure of poly(A:2I) was studied by means of circular dichroism spectral method with the help of ultraviolet spectral and ethidium bromide fluorescence probe methods. It was found that Cu2+ destabilizes the structure of the triple helix poly(A:2I) and induces its structural transformations, meanwhile, the transformations can be partially reversed by a higher NaCl concentration. The structural transformations may be expressed by the following scheme: poly(A:2I) - poly(A:I) + poly(I)- poly(A) + 2poly(I) 相似文献
65.
Mosstafa Kazemi 《合成通讯》2020,50(13):1899-1935
AbstractCatalysis research under magnetically recoverable nanocatalysts is a well-known topic in organic synthesis. In recent times, catalysis research has clearly experienced a renaissance in the area of utility of ferrite nanoparticles based on their ability to recovery and reusability. In this review, the focus is on the fabrication, characterization and of application the MFe2O4 (M=Co, Cu, and Ni) nanocatalysts in synthesis of heterocyclic structural scaffolds. 相似文献
66.
V. V. Sharutin O. K. Sharutina L. G. Mel'nikova G. K. Fukin L. N. Zakharov A. I. Yanovsky Yu. T. Struchkovdt 《Russian Chemical Bulletin》1996,45(8):1977-1980
Tetraphenylantimony hydrogen phthalate, Ph4SbOC(O)C6H4000H-o, was prepared by the reaction of pentaphenylantimony with phthalic acid. According to the data of X-ray structural analysis, the resulting compound is a trigonal-bipyramidal complex of antimony with three phenyl groups in equatorial positions; the fourth phenyl group and the carboxyl fragment are in axial positions. The CSbO angle is 177.5(1)° the Sb-C(Ph)eq and Sb-C(Ph)ax distances are 2.099(4)-2.177(4) A and 2.129(4) A, respectively. The H atom of the free carboxyl group and the carbonyl O atom of another carboxylate group form an intramolecular hydrogen bond.DeceasedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2082–2085, August, 1996. 相似文献
67.
The molecular structure of Ph3CSSC(S)SCPh3 · CS2 has been determined by X-ray structural analysis. The substance crystallizes in the triclinic crystal system [a = 884.9(2) pm, b = 1 039.5(2) pm, c = 2 064.6(3) pm, α = 75.86(1)°, β = 79.83(2)°, γ = 77.31(5)°, Z = 2, space group P1 ]. The CS3 group is planar; the S? S-bond (201.4 pm) forms an angle of 5.7° with the CS3 plane. The torsional angle CSSC equals 96.3°. (Ph3C)2CS4 was obtained by reaction of TosNSCl2 (Tos = p-MeC6H4SO2) with Ph3CSH in CS2 in the presence of triethylamine. The reaction mechanism is discussed. 相似文献
68.
Gadolinium dicyanamide dihydrate Gd[N(CN)2]3 · 2 H2O was prepared by ion exchange in aqueous solution followed by evaporation of the solvent at room temperature. Gd[N(CN)2]3 · 2 H2O was characterized by single‐crystal structure analysis, FTIR spectroscopy and DSC analysis. In the crystal there are three crystallographically independent [N(CN)2]? ions and Gd3+ which are coordinated by six N atoms from six different [N(CN)2]? ions and two O atoms from two water molecules forming an irregular quadratic antiprism. Four H bonds have been identified in the structure of Gd[N(CN)2]3 · 2 H2O, two of them running to terminal N atoms and two to the bridging N atoms of dicyanamide ions (Gd[N(CN)2]3 · 2 H2O: P21/n (no. 14), a = 7.4845(15) Å, b = 11.529(2) Å, c = 13.941(3) Å, β = 93.98(3)°, Z = 4, 1948 reflections, 175 parameters, R1 = 0.0493). The DSC analysis indicates that Gd[N(CN)2]3 · 2 H2O looses the crystal water at temperatures around 130 – 140 °C forming anhydrous Gd[N(CN)2]3, the structure of which has been refined by the Rietveld method based on X‐ray powder diffraction data. Gd[N(CN)2]3 was found to be isotypic with Ln[N(CN)2]3 (Ln = La, Ce, Pr, Nd, Sm and Eu) which previously have been described in the literature. 相似文献
69.
70.
双质谱测定地卟啉取代基组成的解析方法及其应用 总被引:2,自引:0,他引:2
根据卟啉标样的双质谱特征,建立一种计算卟啉环上取代基组成的方法。卟啉的平均分子结构简式衡量其取代基的组成,尤其对地质体中相同碳数的卟啉“混合物”大环外取代基的构成十分有效。 相似文献