Restricted rotation about partial C,N double bonds

The restricted rotation about the partial C,N double bond in 2-chloro-6-NR₂-pyran-4-ones is discussed in the light of NMR spectroscopic data and theoretical calculations.Ab initio calculations at the HF/6-31G^* level were carried out using a continuum model to take solvent effects into account. The delocalization of-electron density [described by natural bond orbital analysis (NBO)] was applied to determine the degree of conjugation in the ground state (GS) and in the transition state (TS) for the restricted rotation of the compounds studied. The reason for the different barriers to rotation of the NR₂ substituents (pyrrolidino > dimethylamino > morpholidino > piperidino) at the 2-chloro-pyran-4-one ring appears to be the different steric hindrance of the NR₂ substituents in the GS for the restricted rotation.     

电化学方法研究I3^—和Ti^3＋在铂上的异相催化

用电化学方法研究了Ｉ－３和Ｔｉ３＋在还原铂表面上的电极反应，由此计算出Ｉ－３与Ｔｉ３＋在还原铂表面上的混合催化反应速率（νｍｉｘ）．当混合催化电位（Ｅｍｉｘ）位于极限电流区时，νｍｉｘ对［Ｔｉ３＋］为零级反应，对［Ｉ－３］为一级反应，且正比于电极旋转速率的平方根，Ｈ＋浓度影响不大．由动力学方法研究的结果证实了电化学研究结果的正确性，致使可用电化学方法解释溶液中的异相催化问题     

旋转输液管动力稳定性理论分析北大核心CSCD

基于Lagrange原理和假设模态法建立了旋转输液管的动力学模型.通过降阶升维的方法求解系统的特征值问题,并分析了旋转输液管自由振动特性.得到了不同端部集中质量和转速下,系统特征值随流速升高的演变轨迹.揭示了临界流速随系统参数的变化规律.研究发现,内部流体的流动对旋转输液管动力学特性存在显著影响.在某些参数组合下,系统低阶模态能够形成不同形式的内共振关系.预示了旋转输液管模型蕴含丰富的动力学现象.     

Exact quantum mechanical vibration-rotation kinetic energy operator of four-particle system in various coordinates

The vibration-rotational kinetic energy operators of four-particle system in various coordinates are derived using a new and simple angular momentum method. The operators are respectively suitable for studying the systems described by scattering coordinate, valence coordinate, Radau coordinate, Radau/Jacobi and Jacobi/valence hybrid coordinates and so on. Certain properties of these operators and their possible applications are discussed.     

Scaling properties of ℤ k- 1 actions on the circle

We derive universal scaling properties for ^k–1 actions on the circle whose generators have rotation numbers algebraic of degreek. As fork=2 these properties can be explained for arbitraryk in terms of a renormalization group transformation. It has at least one trivial fixed point corresponding to an action whose generators are pure rotations. The spectrum of the linearized transformation in this fixed point is analyzed completely. The fixed point is hyperbolic with a (k–1)-dimensional unstable manifold. In the casek=2 the known results are therefore recovered.     

Controlled/“Living “Radical Polymerization of(-)-Menthyl Methacrylate

The atom transfer radical polymerization(ARP)of (-)-menthyl methacrylatc((-)-MnMA) mediated by CuCl/bipyridine and ethy1 2-bromopropionate or 1-phenylethyl bromide in THF system has been studied.The dependence of the specific rotation on molecular weight and the CD of Poly((-)-MnMA) thus obatined was investigated.     

透射电镜像转角的测定及应用

论述了完全标定透射电镜像转角所需拍摄的二次曝光电子显微像的数量,推导了由已测的像转角间接计算其它像转角的一般公式,以Philips Cm200电镜为实例,说明了测定像转角的基本步骤,并以实例说明怎样利用像转角,把衍射花样的晶体学信息传递给电子显微像。     

Effect of ether versus ester tethering on Heck cyclizations

Ether tethers allow Heck cyclizations to proceed in high yields. Ester tethers lead to low yields. Styrene trapping experiments indicate that ester reactions form viable organopalladium intermediates that cannot cyclize efficiently.     

Using the diphosphanyl radical as a potential spin label: effect of motion on the EPR spectrum of an R1(R2)P--PR1 radical

The EPR spectrum of the novel radical Mes*(CH3)P--PMes* (Mes*=2,4,6-(tBu)3C6H2) was measured in the temperature range 100-300 K, and was found to be drastically temperature dependent as a result of the large anisotropy of the 31P hyperfine tensors. Below 180 K, a spectrum of the liquid solution is accurately simulated by calculating the spectral modifications due to slow tumbling of the radical. To achieve this simulation, an algorithm was developed by extending the well-known nitroxide slow-motion simulation technique for the coupling of one electron spin to two nuclear spins. An additional dynamic process responsible for the observed line broadening was found to occur between 180 K and room temperature; this broadening is consistent with an exchange between two conformations. The differences between the isotropic 31P couplings associated with the two conformers are shown to be probably due to an internal rotation about the P--P bond.     

First synthesis of enantio-uracil dinucleotide, comparison of physicochemical properties of their enantiomers, and separation by chiral column chromatography

Enantio-uracil dinucleotide 5, which consists of two l-uridylic acids and one pyrophosphate, was synthesized for the first time in our laboratory. Benzolyated l-uridine was prepared by a stereoselective glycosylation of silylated uracil with l-1-O-acetyl-2,3,5-tri-O-benzoylribose (l-ABR 7). After deprotection, l-uridine 9 was converted to P¹,P⁴-di(l-uridine 5′-) tetraphosphate tetrasodium salt (l-UP₄U 5) by treatment of l-UMP morpholidate 10c with triethylammonium pyrophosphate (TEA-PPi 11b). Spectral data of synthesized l-UP₄U 5 are given in the references. All spectral data were identical with those of UP₄U 3 except the specific rotation, which showed a positive value compared to UP₄U 3 having a negative value. Furthermore, the separation by chiral column chromatography was investigated.