Kinetics and mechanism of promoted hydrolysis of 4‐nitrophenyl acetate by zinc(II)‐tripod: Different roles of mononuclear and trinuclear species

Coordination studies on Zn(II) complexes of 1,3,5‐tri(2,5‐diazahexyl)benzene (L) show that by comparison with the non‐deprotonation of complex ZnL in a 1:1 system, the three‐dimensional complexiaton decreases the pK_a of the Zn‐bound water molecule, that is, pK_a = 7.47 for trinulclear complex Zn₃L in a 3:1 metal–ligand ratio. These two types of zinc(II) complexes have been examined as catalysts for the hydrolysis of 4‐nitrophenyl acetate (NA) in 10% (v/v) CH₃CN at 298 K, I = 0.10 mol dm^?3 KNO₃ at pH range 6.5–8.2 and 8.5–10, respectively. Kinetic studies show that the second‐order rate constants of NA‐hydrolysis catalyzed by complexes ZnL, Zn₃L, and Zn₃LH_?1 are 0.021, 0.0082, and 0.342 mol^?1 dm³ s^?1, respectively. In all the cases, the pH‐dependent observed first‐order rate constant, k_obs, shows sigmoidal pH–rate profile. The 1:1 complex ZnL–H₂O undergoes NA hydrolysis by direct rate‐determining hydrolysis to produce 4‐nitrophenol(ate) (NP^?) and ZnL(OOCCH₃); while in the 3:1 system the oxygen atom of acetic group forms a H‐bond with the Zn(II)‐bound water of the second branch of tripod indicating that the polynuclear centers are associated and bi‐functional. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 41–48 2004     

~(190)Tl的πh_(9/2)νi_(13/2)扁椭球转动带的旋称反转研究(英文)

利用能量为 1 6 7— 1 75MeV的35Cl束流 ,通过16 0 Gd(35Cl,5n)熔合蒸发反应研究了190 Tl的高自旋态能级结构 .实验建立了190 Tl基于πh9/2 　 　νi13/2 组态的转动带 .在束测量结果和194 Biα衰变的α γ测量结果确定地指定了190 Tl的πh9/2 　 　νi13/2 转动带的自旋值 .基于自旋指定 ,发现了190 Tl的πh9/2 　 　νi13/2 扁椭球转动带在低自旋时旋称反转 .这是首次在基于πh9/2 　 　νi13/2 组态的扁椭球转动带中观测到旋称反转 .考虑了质子 -中子剩余相互作用的粒子 -转子模型能够解释πh9/2 　 　νi13/2 扁椭球转动带的低自旋旋称反转 .     

递推M-估计的强收敛性

本文对u1(t)为单调递增这一比较常见的情形和在其它一些比较常见的条件 下,证明了M-估计递推算法中回归系数和散布矩阵的强相合性.     

Aggregation-dependence of Optical Properties and Fluorescence Quenching of a Water-soluble Poly（phenylene ethynylene）

In recent years, water-soluble conjugated polymers have been attained much attention as the optical platform in fluorescent chemical and biological sensors1. In comparison to the small molecule counterparts, conjugated polymers exhibit signal amplificatio…     

Optimized design of laser range finding system using the self-mixing effect in a single-mode VCSEL

An optimized design of laser range finding system using the self-mixing effect in a single-mode verticalcavity surface-emitting laser (VCSEL) is proposed. In order to improve the ranging accuracy and expand dynamic measurement range, we apply difference frequency analog phase-locked loop (PLL) instead of fast Fourier transform (FFT) to process signal, and choose the optimum triangular wave frequency fm= 500Hz and small modulation current △Ip-p = 0.28 mA to modulate single-mode VCSEL. The experiment results show that, without controlling the laser's temperature, the ranging accuracy is better than 2 mm and the measurement dynamic range is as large as 50-500 mm when the sampling time is 0.1 s and the room temperature is 0-55 ℃.     

在热压缩态中测量相位算符的涨落

利用热场动力学的方法计算了热压缩态中测量相位算符的涨落，引入了两种类型的基础量子涨落，一种是与测量相位的两个正交分量相联系，另一种是与一个测量相位分量和光子数相联系。由此，研究了热压缩压中测量相位涨落的两种压缩及其与温度的关系。     

The subgroups of the special linear group over a skew field that contain the group of diagonal matrices

For any (noncommutative) skew field T, the lattice of subgroups of the special linear group Λ=SL(n,T) that contain the subgroup Δ=SD(n,T) of diagonal matrices (with Dieudonné determinants equal to 1) is studied. It is established that for any subgroup H, Δ≤H≤Λ, there exists a uniquely determined unital net σ such that Λ(σ)≤H≤N(σ), where Λ(σ) is the net subgroup associated with the net σ and N(σ) is its normalizer in Λ. Bibliography: 11 titles. Published inZapiski Nauchnykh Seminarov POMI, Vol. 211, 1994, pp. 91–103. Translated by Bui Xuan Hai.     

Seismic response of underwater members of variable cross section

This paper is concerned with a method for solving seismic response problems of a pile of variable cross section with a tip inertia subjected to a sea bottom seismic displacement. The analysis developed here is based on an elastodynamic theory in which the effects of the continuously distributed mass and rigidity of the pile are included. The method includes use of Fourier series expansion, the Laplace transform, the transfer matrix method and the residue theorem in order to deal with the complex seismic displacement and arbitrarily shaped piles; considerable simplification of the calculations is thus achieved. The theoretical results given are applicable to seismic response problems for a pile of arbitrary shape with a tip inertia, excited by arbitrary displacements. As an application of the present theoretical results, the dynamic response has been calculated for hollow piles of curved conical shape with tip inertias and double taper beams subjected to seismic displacements.     

Copolymerization of Ethylene/1-Butene with Heterogeneous TiCl4/(α-Diimine)nickel(Ⅱ) Complex Combined Catalyst

The new type heterogeneous combined catalyst system TiCl4-(α-diimine)nickel(Ⅱ) complexes/MgCl2-SiO2/AlR3 was prepared. Ethylene and 1-butene were copolymerized with the catalysts in slurry phase. It was found that with combined catalyst, the copolymers with lower density and higher branched degree were obtained. 13CNMR results showed that in the obtained copolymers existed not only ethyl but also some other kinds of branches due to the fact that ethylene exhibits the behavior of oligomerization and copolymerization in-situ with combined catalysts.     

Synthesis and properties of processable conducting copolymers from N‐ethylaniline with aniline

Copolymers were synthesized through the chemically oxidative polymerization of N‐ethylaniline (EA) and aniline (AN) in five acid aqueous media. The polymerization yield, intrinsic viscosity, molecular weight, solubility, solvatochromism, electrical conductivity, and mechanical properties of the copolymer films were systematically studied through changes in the comonomer ratio, polymerization temperature, oxidant, oxidant/monomer ratio, and acid medium. Open‐circuit‐potential and temperature measurements of the polymerization solutions showed that the polymerization rate depended on the EA content, and the polymerization was an exothermic reaction. The resultant copolymers were characterized in detail with IR, ultraviolet–visible, and ¹H NMR spectroscopy, gel permeation chromatography, wide‐angle X‐ray diffractometry, and scanning electron microscopy. The reactivity ratios of the monomer pair were calculated from the ¹H NMR spectra of the copolymers formed at a low conversion. The polymers exhibited good solubility and interesting solvatochromism in most of the solvents and variable conductivity with the EA/AN ratio and doping state. The conductivity of the HCl‐doped copolymers increased monotonically from 5.61 × 10^?7 to 2.55 × 10^?1 S/cm with decreasing EA content from 100 to 0 mol % and showed a percolation transition between EA concentrations of 20 and 30 mol %. The EA/AN copolymers also had excellent film formability and flexibility together with high mechanical and oxygen‐enriching properties. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6109–6124, 2004