化学位移各向导性对半整数自旋四极核的2D NMR章动的影响

考察了化学位移各向异性对半整数自旋四极核2D NMR章动的影响.用数值方法对2D NMR章动实验的演化期的Hamiltonian矩阵进行对角化,然后用帐篷法进行粉末平均,获得了自旋为I=3/2、5/2、7/2和9/2的四极核在不同化学位移各向异性下的2D NMR章动谱.实验结果与理论计算符合较好.     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006     

Nitroxide‐mediated radical polymerization of 2‐(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N‐butyl acrylate

Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ～1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006     

Synthesis and application as polymer electrolyte of hyperbranched polyether made by cationic ring‐opening polymerization of 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxymethyl}‐3′‐methyl‐oxetane

A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF₃·Et₂O as initiator through cationic ring‐opening polymerization. The evidence from ¹H and ¹³C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10^?5 S/cm at room temperature and 6.3 × 10^?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006     

STRONG LAW OF LARGE NUMBERS AND ASYMPTOTIC EQUIPARTITION PROPERTY FOR NONSYMMETRIC MARKOV CHAIN FIELDS ON CAYLEY TREES

Some strong laws of large numbers for the frequcncies of occurrence of states and ordered couples of states for nonsymmetric Markov chain fields(NSMC)on Cayley trees are studied.In the proof,a new technique for the study of strong liinit theorems of Markov chains is extended to the case of Markov chain fields.The asymptotic equiparti- tion properties with almost everywhere(a.e.)convergence for NSMC on Cayley trees are obtained.     

单个波长到多个波长的变换实验

报道一种波长变换的新方法.采用此方法不需要任何泵浦光便能够直接将信号光变换成在特定谱宽内的任意多个任意波长的变换光,这对于将来的波分复用光网络提供了较大的方便.此波长变换的原理是利用色散位移光纤的非线性效应产生超连续光谱(SC)信号,由于这种SC信号携带有变换光信号,对这种连续谱进行滤波便能够得到所需要的任意频率的变换信号.此变换方式具有变换频带宽,偏振不敏感的优点。     

Theoretical analysis on waveform structures of pulse propagating in shallow water with an ideal thermocline

I.IntroductionDuetospatia1andtemporalvariabilityoftheocean-acousticenvironment,especially,theeffectsofboundaryaswel1asmediumonpropagationofacousticwavesinshal1owwater,theacousticpropagationisextrcmelycomp1icatcd.Multipathtransmissionisthebasiccharacteris-hcsofunderwatersoundchannels.Undctcrminedmultipathstructurescangreatlylimittheperformanceofunderwateracousticdetcction.However,ifthemultipathcharacteristicsofacousticpropagationinunderwatcrsoundchanne1sareknown,spaee-timeresolutionandpro-cess…     

The measurements of correlation times of molecules adsorbed on silica gel,alumina and charcoal using NOESY and MAS NMR

The correlation times (τ_c) and cross relaxation rates of toluene, dimethylformamide, tetrahydrofuran, water-acetone and water-dioxane adsorbed on silica gel, alumina and charcoal were obtained by measurements of the integrated intensities of cross and diagonal peaks in their NOESY spectra. The (τ_c) of the above mentioned systems is in the range of 10^?6?10^?9 s, much longer than that in the liquid (10^?12?10^?14 s). It was found that intramolecular rotation of toluene adsorbed on charcoal is slower than that on SiO₂, Al₂O₃ and the inversion of α and β protons in tetrahydrofuran is very fast (τ_c = 1.76×10^?9 s). The cross relaxation plays an important role in the relaxation of molecules adsorbed on solid surfaces with low electron densities.