MMA在均相和非均相离子液体中的ATRP反应

分别以1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim]PF6）和氯化1-烯丙基-3-甲基咪唑（[Amim]Cl）为反应介质,研究了MMA在均相体系（[Bmim]PF6）和非均相体系（[Amim]Cl）中的原子转移自由基聚合（ATRP）反应。结果表明：两种离子液体中反应均呈现一级反应特征,用四氯化碳作引发剂比用氯化苄（Bz...     

粤航一号稻米及其亲本抗性淀粉含量的测定与比较

为确定航天品种功能稻米——粤航一号抗性淀粉含量,给临床观察膳食干预后果判断提供实验参考数据,并了解航天育种对该品种大米抗性淀粉含量的影响,用Goni测定方法测定了粤航一号、富硒粤航一号、长丝占、粳籼89 4种稻米的抗性淀粉含量。结果表明,粤航一号、富硒粤航一号、长丝占、粳籼89 4种稻米的抗性淀粉含量分别是(0.30±0.11)%、(0.47±0.37)%、(0.31±0.66)%、(0.36±0.62)%。可见粤航一号与亲本长丝占,及与富硒品种富硒粤航一号,和非航天品种优质大米粳籼89在抗性淀粉含量上无差异,航天育种对该品种稻米抗性淀粉生成遗传特征无影响。     

Superfast electrophoresis of electron-type conducting particles

The features of concentration polarization caused by electric current through a unipolar conductive particle are considered. The peculiarities of the formation of an induced space charge near a particle with electron-type conductivity are analysed. It has been shown that the theoretical values of electrophoretic velocity for these particles are essentially smaller than those calculated for particles with ion-type conductivity.A new method to observe the superfast electrophoresis is developed. The electrophoretic velocity of graphite and activated carbon particles of different size (diameter, 200–500 μm) displaced in distilled water and electrolyte solutions in strong electric fields (100–500 V cm⁻¹) was measured. It is shown that, in contrast to classical electrophoresis, the electrophoretic mobility of such particles increases with the particle size and the external field strength. The experimental and theoretical results are compared. The discrepancy between theory and experiment is analysed.     

On the choice of active space orbitals in MCSCF calculations

We describe a procedure which may be used to aid selection of the active space in multiconfigurational self-consistent field (MCSCF) calculations for general chemical systems. Starting from a restricted Hartree-Fock calculation, we define a hierarchy of interacting virtual orbitals for every occupied orbital. The most strongly interacting orbitals are then taken to constitute the active space in a configuration interaction (CI) calculation. The natural orbital occupation numbers obtained from the CI calculation are then used to choose the active space to be used in a subsequent MCSCF calculation. We illustrate our method on a number of systems (Li₂, B₂, C₂, carbonyl oxide and the transition state for oxidation of H₂S by dioxirane). In all these cases, ‘intuitive’ active spaces are inadequate, as are active spaces derived from the natural orbitals of unrestricted Hartree-Fock calculations.     

硼原子的键合形式对硼酸盐晶体非线性光学行为的影响

在几种具有典型复杂结构的硼酸盐晶体中 ,从硼原子的键合形式出发讨论了不同键合情况下的B—O键对硼酸盐晶体的非线性光学行为的具体影响。结果表明 ,晶体中B—O键的键合形式是制约硼酸盐晶体非线性光学行为的重要因素。     

生物体系中电子转移机理的研究Ⅱ: 分子间电子转移及 电子供、受体间不同基 团的影响

利用自编程序MOPAC-ET中AM1方法,及KT(Koopman'sTheorem)法,研究了二苯负离子体系的分子间电子转移现象,计算了其电子供、受体在不同距离下的V~A~B及它们之间的相关性,另外,还对两苯环间不同介入基团对电子转移的影响做了初步研究,发现不同的介入基团存在着较大的差异。     

Synthesis of linear and starlike polymers from poly(propylene glycol) methacrylate using controlled radical polymerization

The copper‐catalyzed atom transfer radical polymerization (ATRP) of poly(propylene glycol) methacrylate (PPGM) in solution to produce linear and starlike polymers is reported, using methylethyl ketone as the solvent and a temperature of 80 °C. The ATRP system used was efficient for polymerization of the functionalized monomer without protecting hydroxyl end groups of monomer. The polymerizations were consistent with “living” or controlled processes, as revealed by the linear evolution of molecular weight with conversion. Increasing the [M]₀:[I]₀ ratio resulted in increasing molecular weights, whereas the polydispersity indices remained low (M_w/M_n < 1.4) even at high conversion. Decreasing the [CuBr]₀:[I]₀ ratio resulted in lower conversions, slightly larger polydispersities, and decreased molecular weights, likely resulting from a lower initiation efficiency. Polymers were characterized by ¹H and ¹³C NMR; molecular weights of polymers with low degrees of polymerization were estimated by end‐group analysis from ¹³C NMR spectra obtained using distortionless enhancement by polarization transfer and the gated decoupling techniques. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 334–343, 2002     

Atom transfer radical homo‐ and block copolymerization of methyl 1‐bicyclobutanecarboxylate

A non‐olefinic monomer, methyl 1‐bicyclobutanecarboxylate (MBC), was successfully polymerized by the controlled/“living” atom transfer radical polymerization (ATRP) technique, resulting in a well‐defined homopolymer, PMBC, with only cyclobutane ring units in the polymer chain. An AB block copolymer poly(methyl 1‐bicyclobutanecarboxylate)‐b‐polystyrene (PMBC‐b‐PS), having an all‐ring unit segment, was also synthesized with narrow polydispersity and designed number‐average molecular weight in addition to precise end groups. The ¹H NMR spectra, glass‐transition temperature, and thermal stability of PMBC, PMBC‐b‐PS, and PS‐b‐PMBC were investigated. The experimental results showed that the cyclobutane rings in the two block polymers improved their thermal stability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1929–1936, 2002     

Improving the energies of approximate wave functions using the concepts of density functional theory

A simple method, derived from DFT, for improving the energy of a trial density is modified for the case of atoms. It is assumed that errors in the interelectronic repulsion are the only significant ones. The errors in the energies of single‐ζ Slater orbitals for the atoms from He to Ne are reduced an average factor of 21. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001