Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P_2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P₃ via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

一阶导数吸光光度法测定碘酸钾碘盐中碘

采用一阶导数吸光光度法测定碘酸钾碘盐中碘 ,线性范围为 0～ 12 μg·ml-1,检出限为1.6μg·ml-1,对盐样进行重复测定 ,相对标准偏差≤ 1.9% ,对样品进行加标回收试验 ,回收率在 97.0 %～ 10 2 .5 % ,结果良好     

Solvothermal Synthesis and Structure Characterization of a 3D Hydrogen-bonded Copper Compound [Cu(H_2dhpmc)_2]·2H_2O

1 INTRODUCTION The controlled assembly of inorganic and coordination polymers from simple building blocks is an important challenge in the design of high- dimensionality systems. In the crystal engineering 'toolbox'[1], hydrogen bonding moieties are perhaps the implements used the most in the design of such supramolecular systems[2], and have been particularly strongly applied towards the synthesis of molecular magnetic materials[3~6]. Copper complexes play an important role in catalyzin…     

6-氨基青霉烷酸在弱碱性阴离子树脂IRA67上的吸附研究

用静态法研究了6-氨基青霉烷酸在弱碱性阴离子交换树脂IRA67上的吸附行为．在溶液pH为8．0，6-APA起始浓度介子3.00mg／m1-20．00mg／ml条件下，测定了25℃时IRA67树脂的静态交换动力学曲线、吸附等温线，并求得了IRA67树脂的平衡速率常数及吸附等温线方程．分别用Langmuir型和Frendlich型方程对IRA67树脂吸附等温线进行线性回归拟合，结果表明，6-APA在IRA67树脂上的吸附更符合Langmuir型吸附．     

Tensor products over abelian Walgebras

Tensor products of Calgebras over an abelian Walgebra are studied. The minimal Cnorm on is shown to be just the quotient of the minimal Cnorm on if or is exact.

     

The law of the solution to a nonlinear hyperbolicSPDE

Let { _s,t ,(s,t ₊ ² } be a white noise on ₊ ² . We consider the hyperbolic stochastic partial differential equation {ie863-3} The purpose of this paper is to study the law of the solution to this equation. We analyze the existence and smoothness of the density using the tools of Malliavin Calculus. Finally we prove a large deviation principle on the space of continuous functions, for the family of probabilities obtained by perturbation of the noise in the equation.This work has been partially supported by the grant of the DGICYT No. PB 930052 and the EU Science project CT 910459.     

Weak separation properties for self-similar sets

We develop a theory for self-similar sets in that fulfil the weak separation property of Lau and Ngai, which is weaker than the open set condition of Hutchinson.

     

On two--block--factor sequences and one--dependence

The distributions of two--block--factors arising from i.i.d. sequences are observed to coincide with the distributions of the superdiagonals of jointly exchangeable and dissociated arrays . An inequality for superdiagonal probabilities of the arrays is presented. It provides, together with the observation, a simple proof of the fact that a special one--dependent Markov sequence of Aaronson, Gilat and Keane (1992) is not a two--block factor.

     

Whitehead test modules

A (right -) module is said to be a Whitehead test module for projectivity (shortly: a p-test module) provided for each module , implies is projective. Dually, i-test modules are defined. For example, is a p-test abelian group iff each Whitehead group is free. Our first main result says that if is a right hereditary non-right perfect ring, then the existence of p-test modules is independent of ZFC + GCH. On the other hand, for any ring , there is a proper class of i-test modules. Dually, there is a proper class of p-test modules over any right perfect ring.

A non-semisimple ring is said to be fully saturated (-saturated) provided that all non-projective (-generated non-projective) modules are i-test. We show that classification of saturated rings can be reduced to the indecomposable ones. Indecomposable 1-saturated rings fall into two classes: type I, where all simple modules are isomorphic, and type II, the others. Our second main result gives a complete characterization of rings of type II as certain generalized upper triangular matrix rings, . The four parameters involved here are skew-fields and , and natural numbers . For rings of type I, we have several partial results: e.g. using a generalization of Bongartz Lemma, we show that it is consistent that each fully saturated ring of type I is a full matrix ring over a local quasi-Frobenius ring. In several recent papers, our results have been applied to Tilting Theory and to the Theory of -modules.

     

Abstract functions with continuous differences and Namioka spaces

Let be a semigroup and a topological space. Let be an Abelian topological group. The right differences of a function are defined by for . Let be continuous at the identity of for all in a neighbourhood of . We give conditions on or range under which is continuous for any topological space . We also seek conditions on under which we conclude that is continuous at for arbitrary . This led us to introduce new classes of semigroups containing all complete metric and locally countably compact quasitopological groups. In this paper we study these classes and explore their relation with Namioka spaces.