Absence of p,π-conjugation in the Cl2C=CHOMe molecule from data ofab initio calculations

ab initio Calculation of the Cl₂C=CHOMe molecule has been carried out with geometrical optimization in the split valence basis set in the RHF/6-31G^*//RHF/6-31G^* approximation. An analysis of the populations of the p-orbitals of the Cl atoms implies the absence of p,-conjugation between the unshared electron pairs of these atoms and the -bond. The asymmetry parameters of the electric field gradient at the³⁵Cl nuclei, calculated from the 3p-orbital populations of the Cl atoms, practically coincide with the experimental values.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2369–2372, December, 1995.The authors are grateful to G. S. Beloglazov for assistance in accomplishingab initio calculations.     

Binding Ensembles of p53-MDM2 Peptide Inhibitors by Combining Bayesian Inference and Atomistic Simulations

Designing peptide inhibitors of the p53-MDM2 interaction against cancer is of wide interest. Computational modeling and virtual screening are a well established step in the rational design of small molecules. But they face challenges for binding flexible peptide molecules that fold upon binding. We look at the ability of five different peptides, three of which are intrinsically disordered, to bind to MDM2 with a new Bayesian inference approach (MELD × MD). The method is able to capture the folding upon binding mechanism and differentiate binding preferences between the five peptides. Processing the ensembles with statistical mechanics tools depicts the most likely bound conformations and hints at differences in the binding mechanism. Finally, the study shows the importance of capturing two driving forces to binding in this system: the ability of peptides to adopt bound conformations (ΔGconformation) and the interaction between interface residues (ΔGinteraction).     

新型手性Salen双核锌配合物的分子识别研究

合成了新型手性Salen配体（H3L）及新型手性Salen双核锌配合物（主体）.通过研究主体对咪唑类客体及氨基酸酯类客体的分子识别行为,测定了这些配位反应的缔合常数.主体对咪唑类客体分子识别的缔合常数顺序为:K(Im) >K(2-MeIm) >K(2-Et-4-MeIm).主体对氨基酸酯类客体分子识别的缔合常数顺序为:K(LeuOCH3) >K(ValOCH3) >K(AlaOCH3) >K(SerOCH3),配位数均为2.主体与D、 L型氨基酸酯分子识别反应在不同温度下的缔合常数结果表明,随着温度的升高,对映选择性下降.实验发现反应体系中存在焓熵补偿关系. CD光谱的研究结果也反映了主体对不同客体识别能力的差异.     

Oxidation of 1-methylcyclobutanol by Pb(IV) and Mn(III) compounds

The main product of the reaction of 1-methylcyclobutanol with Pb(OAc)₄ in benzene is 1-phenyl-4-pentanone; the use of Mn(OAc)₃ in acetic acid gives a mixture of 2,9-decanedione and methyl propyl ketone; 1-(chloro-, bromo-, thiocyano-, or cyano)-4-pentanone is formed in the presence of the systems Pb(OAc)₄-metal halide or Mn(OAc)₃-metal halide.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2760–2763, December, 1992.     

相转移催化合成对甲氧基肉桂酸-2-乙基己酯的研究

对甲氧基肉桂酸 2 乙基己酯是一种有效的ＵＶＢ防晒剂[1 ,2 ] ,一般采用Ｃｌａｉｓｅｎ Ｓｃｈｍｉｄｔ缩合反应制得[3] ,但由于催化剂ＫＯＨ处于水相 ,对反应物不能充分起到催化作用导致产率较低[4] 。我们利用乙二醇 (ＰＥＧ)为相转移催化剂合成立体专一的反式对甲氧基肉桂酸 2 乙基己酯 ,产率提高到 72 .5 %。合成路线如下 :1　实验部分1 .1　仪器与试剂ＢＩＯ ＲＡＰＦＴ45 0红外光谱仪 ,用液膜法测试 ;Ｂｒｕｒｅｒ ＡＭ 30 0超导核磁共振仪 (溶剂ＤＣ Ｃｌ3) ;ＭＡＴ/44Ｓ ,ＧＣ ＭＳ型色质联用谱仪 ;试剂均为分析纯 ,上海化学试剂…     

Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.     

Determination of Copper at a Glassy Carbon Electrode Modified with Langmuir–Blodgett Film of p‐tert‐Butylthiacalix[4]arene

A new type of voltammetric sensor, Langmuir–Blodgett film of p‐tert‐butylthiacalix[4]arene modified glassy carbon electrode, was advanced and used for determining copper at trace levels by differential pulse stripping voltammetry. Calibration plot was found to be linear in the range of 2×10^?8 M to 5×10^?6 M; the detection limit was 2×10^?9 M. Possible recognition mechanism was also discussed. From determination of Copper in real samples (river, lake and tap water) it can be concluded that the method is rapid, sensitive in determining of copper and can be used in the analysis of natural water samples.     

4,5,6-三取代-2H-吡喃-2-酮的简便合成法

2H-吡喃-2-酮及其衍生物是有机合成的蓬要中间体。对于它们的合成已有许多报道,例如利用烯醇醚或烯醇砖醚与丁酰氯反应;羰基化合物与甲氧亚甲螭丙二酸二甲酯反应;α-苯基丙醛酸酯与丙酮的成环缩合2,6-二氯-3-三氯甲基吡啶与亚甲基丁二酸酯的反应,邻氰基苯乙炔、二苯乙二酮和丙酮的反应。但上述方法往往原料较难得到,产率较低或操作麻烦。     

Effect of Oxygen Redistribution on the Normal and Superconducting Properties of Yttrium High‐Temperature Superconductors

An anomaly is found in the vicinity of T_max 560$ K on electric resistance versus temperature curves for yttrium hightemperature superconductors of the 123 phase. Xray phase analysis suggests a structural phase transition in the vicinity of T_max due to oxygen redistribution in the mobile sublattice of this compound. Investigation of samples with Y partially replaced by Ca has shown that the structural phase transition does not depend on carrier concentration in the conduction band.     

Comparison of the Hartree-Fock,Møller-Plesset,and Hartree-Fock-Slater method with respect to electrostatic properties of small molecules

Summary The results of various quantum chemical calculations, the Hartree-Fock (HF) method, the Møller-Plesset perturbation theory (MP2), and the Hartree-Fock-Slater (HFS) method are compared. Atomic charges, dipole moments, topological properties of the electron density distribution and polarizabilities, and first hyperpolarizabilities are calculated. Atomic charges obtained with the HFS method are found to be very close to those calculated with the MP2 method, from which we conclude that the HFS method describes to some extent electron correlation effects. Performing an MP2 calculation after an HF calculation improves the molecular dipole moments considerably, yielding values close to the experimental ones. HFS calculations are computationally less demanding than MP2 and yield comparable results for the electron density distributions, dipole moments and polarizabilities.