The MNDO-PM3 study of the mechanism of nucleophilic substitution of the phenoxide anion for the nitro group in 1,3,5-trinitrobenzene and 2,4,6-trinitrotoluene in the gas phase and in polar solvents

The semi-empirical quantum chemical MNDO-PM3 calculations of the enthalpies of formation of Meisenheimerortho- andipso--complexes of 1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT) with the phenoxide anion in the gas phase and in water are performed within the framework of the point dipole model. Based on the calculated heats and activation barriers to substitution of the nitro group by the phenoxyl group in TNB and TNT, the possibility of the reactions of TNB and TNT with the phenoxide anion in water is shown. These reactions in water occurvia the S_NAr mechanism involving the correspondingipso--complex as an intermediate. In the gas phase, the S_NAr mechanism is impossible, because the reaction is strongly endothermic. In the case of TNT, the exothermic reaction of elimination of a proton from the methyl group by the phenoxide anion competes with nucleophilic substitution in a polar solvent. The activation energy calculated for this exothermic reaction is 8 kcal mol^–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 624–628, April, 1995.     

Transition state geometry in radical abstraction reactions: comparison of interatomic distances in the intersecting parabolas and Morse curves models with quantum-chemical calculations

Interatomic distances in the transition state were estimated for the reactions of radical abstraction: H^· + H₂, H^· + HCl, H^· + CH₄, N^·H₂ + NH₃, HO^· + H₂O, HO₂ ^· + HOOH, and C^·H₃ + SiH₄. The calculation was performed by the quantum-chemical density functional method or coupled clusters method (QCH), as well as by the methods of intersecting parabolas (IPM) and Morse curves (IMM), using experimental data (activation energies and reaction enthalpies). The results of the latter two methods are close to the quantum-chemical calculation and differ only by the increment a: r(IPM or IMM) = a + r(QCH), where a = –4.5·10^–12 m for IPM and a = +1.9·10^–12 m for IMM.     

气相色谱-质谱法测定茶叶中的噻嗪酮残留量

建立了气相色谱-质谱法测定茶叶中噻嗪酮残留量的方法。茶叶中残留的噻嗪酮用丙酮-正己烷混合溶剂(1∶1)提取,提取液经Envi-Carb活性碳柱和LC-Alumina N中性氧化铝柱净化,浓缩定容后,直接用气相色谱-质谱进行分析和确证,外标法定量。以HP-5MS(30m×0.25mm i. d., 0.25 μm)石英毛细管柱为分离柱,噻嗪酮的分离效果良好。方法的线性范围为0.01～1.00μg/mL,检出限为0.01mg/kg,回收率为81.6％～97.2％,相对标准偏差为3.36％～5.78％。质谱监测离子选m/z为105、140、172、305amu,其强度比约为41∶13∶29∶17。样品前处理采用微量化学技术。     

Application of symplectic algorithms to QCT calculation:H+H_2 system

The basic theory of symplectic algorithm was introduced. A comparison between Runge-Kutta method and symplectic integration method was preformed in the simulation of the long time behavior of H + H2 system on BKMP potential energy surface. Our results reveal a dis-sipative behavior in the integral of ordinary differential equation by the fourth order Runge-Kutta method, which causes incorrect simulation results in QCT calculations. However, when the symplectic integration method is applied, the dissipative behavior is not found in the same system. When the initial state is the same, the energy deviation of fourth order symplectic integral method is almost one percent of that of fourth order Runge-Kutta method in a 60000-step simulation, and that of sixth order symplectic integral method is much less. These results show that the symplectic integral methods are always the better choice in the integral calculation of the long time behavior in maintaining energy conservation.     

Structure, Stability and Vibrational Spectra of LaC_5~n(n=-1,0,+1) Clusters

用密度泛含方法研究了ＬａＣ５ｎ（ｎ＝－１，０，＋１）分子簇的结构和稳定性及振动光谱，对这个六原子体系提出了三种可能构型，点群结构为Ｃ２ｖ对称性．第一个构型为Ｌａ接在弯曲的Ｃ５链上，第二个是Ｌａ通过二个键与Ｃ５环相连第三个是Ｌａ通过一个键与Ｃ５环相连；结果表明，第一个构型即当Ｌａ接在弯曲的Ｃ５链上时能量最低．振动光谱分析指出，当ｎ＝－１时，第二个构型为局域极小值；当ｎ＝＋１时，第一个和第二个构型为局域极小值；对ｎ＝０，局域极小值没有找到．     

数均聚合度计算的教学方法

总结毛者提出的线型缩聚中当量系数的新定义及引入缩聚体系单体平均官能度的新方法，本文总结出了一套讲授数均聚合度计算问题的简单方法。     

Structural and magnetic characterization of Mn3IrGe and Mn3Ir(Si1−xGex): experiments and theory

The structural and magnetic properties of a new ternary Ir-Mn-Ge phase, Mn₃IrGe, as well as the solid solution Mn₃Ir(Si_1−xGe_x), 0?x?1, have been investigated by means of X-ray and neutron powder diffraction, magnetization measurements and first principles calculations. The crystal structure is cubic, of the AlAu₄-type (an ordered form of the β-Mn structure), Z=4, space group P2₁3, and the unit-cell dimension varies linearly with the silicon content. For all compositions, antiferromagnetic ordering is found below a critical temperature of about 225 K. The magnetic structure is noncollinear, as a result of frustrated magnetic interactions on a triangular network of Mn atoms, on which the moments rotate 120° around the triangle axes. The magnitude of the magnetic moment at 10 K is 3.39(4) μ_B for Mn₃IrGe. The theoretical calculations reproduce with very good accuracy the magnitudes as well as the directions of the experimentally observed magnetic moments.     

荧光猝灭法测定痕量镉-四碘合镉-罗丹明S-聚乙稀醇荧光猝灭体系的研究

本文首次将罗丹明S应用于镉的荧光熄灭法测定,由于PVA-124的稳定作用,克服了罗丹明类试剂常须经萃取测定操作繁杂之不足。在加入各种试剂后,直接进行水相荧光测定。方法简便、灵敏,精密度好。     

络合吸附体系吸附性的研究

本文论述了研究络合吸附体系吸附性的重要意义,较详细地讨论了各种方法,包括微分电容曲线法、交流极谱法和计时电量法等在吸附性研究和吸附量测定中的应用。     

圆二色谱中的激子手性法在有机化学中的应用

激子手性法是圆二色谱领域内,近一、二十年内发展的一种测定有机化合物绝对构型的可靠方法。本文对其基本原理及规律作一简要介绍。并以邻二醇、共轭烯酮,共轭二烯及丙烯醇为例,介绍本法在测定绝对构型中的应用。此外,本法也可用于糖类的结构研究。