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.     

白术挥发油中苍术酮氧化反应的动力学

白术挥发油;苍术酮;动力学方程;活化能;反应机理     

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．     

On-line determination of organophosphorus pesticides in water by solid-phase microextraction and gas chromatography with thermionic-selective detection

This paper describes the extraction of 49 organophosphorus pesti-cides (OPPs) from water samples using solid-phase microextraction (SPME). Three fibers, including a 15-μm XAD-coated fiber, a 85-μm polyacrylate-coated fiber, and a 30-μm polydimethylsilox-ane-coated fiber (PDMS), were evaluated here. The effects of stirring and the addition of NaCl to the sample were examined for the polyacrylate-coated fiber. The precision of the technique was examined for all three fibers and the extraction kinetics were investigated using the XAD- and polyacrylate-coated fibers. With some exceptions, the XAD- and polyacrylate-coated fibers performed better than the PDMS-coated fiber. The superiority of the XAD-nd polyacrylate-coated fiber. The superiority of the XAD- and polyacrylate-coated fibers over the PDMS-coated fibers can be attribuibuted to the aromatic functionalities of the XAD and the polar functionalities in the polyacrylate. The relatively high percent RSDs indicate that the SPME technique needs to be further refined before it can be used for anything other than screening. A more effective form of agitation than mechanical stirring may be neccessary to reduce variability and achieve a faster equilibrium between the sample and the SPME fiber.     

一种新型联萘基旋光共轭聚合物的圆二色谱和圆偏振荧光光谱

众所周知 ,聚合物的光电性质依赖于聚合物链的构象和 (或 )组成 ,通过在聚合物上引入手性单元 ,采用圆二色谱 ( CD)和圆偏振荧光光谱 ( CPL)等方法可表征聚合物结构 [1] .近年来 ,由于圆偏振光可用作光数据存储和液晶显示器背景光 [2 ] ,人们开始注重共轭聚合物圆偏振光材料的研究 .共轭聚合物的光致和电致圆偏振光的现象由一种带手性侧链的聚噻吩[3 ] 和一种带手性侧链的聚 (对苯撑乙烯 ) [4 ]产生 ,但它们的圆偏振荧光度 (用不对称因子 glum=2 ( IL-IR) / ( IL+IR)表示 ,IL 和 IR 分别指左圆偏振光强度和右圆偏振光强度 )相对较低 …     

带功能基的全氟烷基乙烯基醚的研究——4.四氟乙烯与全氟-3,6-二氧杂-4-甲基-△~7-辛基磺酰氟溶液共聚反应单体竞聚率的测定

在乙烯-四氟乙烯溶液共聚合体系研究中,我们曾编制了一个简易的计算机程序,用于测定二种单体的共聚竞聚率,这一方法计算方便,而且可以避免原先作图法中的误差,结果较为可靠。前文我们报道了四氟乙烯与两个新的全氟烷基乙烯基醚的共聚合反应,并对其中一个新单体——7,7-二氯-3-氧杂-全氟庚烯-1——与四氟乙烯的共聚进行了单体竞聚率的测定。结果表明,这一新的含氟烯醚单体的聚合活性较其它已有报道的同类单体大。为了验证这一     

A theoretical study of the structure and bonding of UOX4 (X = F, Cl, Br, I) molecules: the importance of inverse trans influence.

During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (T(c)), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions.     

Exponentially fitted symplectic methods for the numerical integration of the Schrödinger equation

The computation of the energy eigenvalues of the one-dimensional time-independent Schrödinger equation is considered. Exponentially fitted and trigonometrically fitted symplectic integrators are obtained, by modification of the first and second order Yoshida symplectic methods. Numerical results are obtained for the one-dimensional harmonic oscillator and Morse potential.AMS subject classification: 65L15Funding by research project 71239 of Prefecture of Western Macedonia and the E.U. is gratefully acknowledged.     

Simulation of aerated lagoon using artificial neural networks and multivariate regression techniques

The aim of this study was to develop an empirical model that provides accurate predictions of the biochemical oxygen demand of the output stream from the aerated lagoon at International Paper of Brazil, one of the major pulp and paper plants in Brazil. Predictive models were calculated from functional link neural networks (FLNNs), multiple linear regression, principal components regression, and partial least-squares regression (PLSR). Improvement in FLNN modeling capability was observed when the data were preprocessed using the PLSR technique. PLSR also proved to be a powerful linear regression technique for this problem, which presents operational data limitations.