Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts

We herein report on solution structural studies of Ru^Ⅱ catalysts （3a, 9） composed of achiral bisphosphine ligands （4, 8） and the enantiopure 1,2-diphenylethylenediamine （DPEN）. Complete chiral induction from enantiopure （R,R）-DPEN to achiral bisphosphine ligand 3a was observed in solution, with the complex adopting a single, stable and non-fluxional （even at 70 ℃） configuration. The coordination of the C=O moiety in 4 to the cationic Run center is considered to be of key importance in providing the higher thermodynamic and kinetic rotation barrier for the flexible bisphosphine ligand in the complex. The obtained enantioselectivity （91% enantiomeric excess） and sense of chiral induction in the hydrogenation of acetophenone were found to be solely dependent on the chirality of the 1,2-diamine. Consistent with the hydrogenation product, the （R,R）-DPEN induces a M-conformation （fight-handed） chirality for flexible phosphine ligand 4 in the complex, resulting in a 2,2-configuration about the Ru^Ⅱ center.     

Theoretical study on second hyperpolarizability for cationic pyridine derivatives

The molecular second hyperpolarizabilities γ of cationic 3- or 4-substituted pyridine derivatives have been investigated. The γ values are calculated by an ab initio molecular orbital (MO) method at correlated levels including CCSD(T). The magnitude of γ for the pyridinium cation is shown to be smaller than that of pyridine. It is found that γ for the pyridinium cation changes dramatically with substitution, whereas γ for neutral pyridine does not show such large substituent effects. This remarkable substituent effect on γ of cationic pyridine derivatives is one of the special features of cationic species.     

用长气体靶研究22Na+α共振散射

在日本东京大学CRIB 次级束装置上,用长气体靶开展了22Na+ α共振散射的厚靶实验研究。针对长气体靶实验中的两体运动学重构问题,提出了一套包括构建空间复杂几何关系、计算能量损失以及反应运动学的逐事件分析方法;对22Na+α共振散射的实验数据进行了重构分析,得到了E_c.m. = 4.2 ~ 5.4 MeV 区间22Na( α,α ) 的激发函数,从实验的激发函数中观测到了复合核26Al 5 个较为明显的共振峰。鉴于26Al 共振态的衰变模式比较复杂,本工作发现的26Al新共振态的能级性质有待进一步的理论分析。The 22Na+α resonant scattering is studied via a conventional thick target inverse kinematic method with an extended gas target. A data analysis method is proposed for the two-body reaction kinematic reconstruction, in which the spatial geometry, the reaction kinematics and the energy losses are considered. The experimental data of 22Na+ αresonant scattering have been thus reconstructed, and the excitation function is obtained in the energy interval of Ec.m. =4.2~5.4 MeV. Five resonant states in 26Al are observed in the experimental excitation function. Since several decay modes coexist for the observed 26Al resonant states, multi-channel theoretical analysis is thus needed to reveal their structure and decay features.     

基于毛细管电泳的环介导恒温扩增技术检测方法研究

以大肠杆菌(E.coli)为对象,采用环介导恒温扩增技术(LAMP)对其扩增,在实验室自制的毛细管电泳-诱导荧光平台上建立了LAMP产物的检测新方法。引物F3,B3,FIP,BIP扩增的E.coli LAMP产物大小为240 bp。优化的毛细管电泳条件为:毛细管有效长度/总长度(10 cm/15 cm),筛分介质溶液为0.5%羟乙基纤维素(1 300 K),电场强度(100 V/cm),进样条件(100 V/cm,1.0 s)。毛细管电泳时,DNA长度在100~500 bp范围内与其迁移时间呈线性关系,相关系数为0.996。在相同毛细管电泳条件下对E.coli LAMP产物进行分析,并利用这种线性关系在电泳图中对E.coli LAMP产物与假阳性产物做区分,结果表明,毛细管电泳技术不仅可在15 min内实现LAMP产物及附加产物的快速检测,而且可快速区分LAMP阳性及假阳性实验产物。采用建立的毛细管电泳快速检测LAMP产物的方法,对AB0174 E.coli基因实施了LAMP,结果表明该方法适合DNA LAMP产物的快速检测。     

Characterization of the [Xtilde] 1Σ+ à 3Π and à 1Π electronic states of BBO

The three lowest-lying electronic states, [Xtilde] ¹Σ⁺, à ³II and à ¹II, of the linear BBO molecule have been systematically investigated using ab initio electronic structure theory. The equilibrium structures and physical properties including dipole moments, vibrational frequencies and associated infrared intensities, Renner parameters and energetics for the three states of BBO have been determined employing SCF, CISD, CCSD and CCSD(T) levels of theory and a wide range of basis sets. The ground state of BBO presents a degenerate real bending frequency, while the à ³II and à ¹II states show two distinct real bending frequencies due to the Renner-Teller interaction. The bending motion of the à ¹II state was analysed using the equation-of-motion (EOM)-CCSD and EOM-CC3 techniques in order to avoid possible variational collapse to a lower-lying state. The [Xtilde] ¹Σ⁺-à ³II separation was predicted to be T ₀ = 16.6 kcal mol^?1 (5800 cm^?1, 0.719 eV) at the cc-pVQZ CCSD(T) level of theory. With the cc-pVQZ EOM-CC3 method the [Xtilde] ¹Σ⁺-à ¹II splitting was predicted to be T ₀ = 48.0 kcal mol^?1 (16 800 cm^?1, 2.08 eV), which is in good agreement with the experimental value of T ⁰ = 46.6 kcal mol^?1 (16 300 cm^?1, 2.02 eV). The Renner parameters and averaged harmonic frequencies of the bending mode were determined to be ? = 0.184 and ω₂ = 363 cm^?1 for the à ³II state, and ? = 0.246 and ω₂ = 383cm^?1 for the à ¹II state. The theoretical [Xtilde] ¹Σ⁺ state harmonic B-B stretching frequency ω₃ = 636 cm^?1 is somewhat higher than the experimental estimate of 582 cm^?1 and the predicted à ¹II state harmonic B-B stretching frequency ω₃ = 861 cm^?1 is significantly higher than the experimental estimate of 440 cm^?1     

The structure of liquid methanol revisited: a neutron diffraction experiment at −80 °C and +25 °C

Pulsed neutron diffraction with isotope substitution on the hydroxyl hydrogens (H) is used to study the structure of pure liquid methanol at ?80 °C and +25 °C. Although this liquid has been studied with neutrons several times in the past this is the first time that the composite partial structure factors, XX, XH and HH, are derived from the diffraction data. Here X represents a weighted sum of correlations from carbon (C), oxygen (O), and methyl hydrogen (M) atoms on the methanol molecule. The data are used in an empirical potential structure refinement (EPSR) computer simulation of the liquid at both temperatures. Model distributions of molecules consistent with these data are used to estimate the individual site—site radial distribution functions, the coefficients of the spherical harmonic expansion of the orientational pair correlation function, and the length of possible chains of methanol molecules formed in the liquid. Although the results are qualitatively similar to those of earlier computer simulation studies of this liquid, they do differ in detail from previous work. In particular, although most molecules in the liquid are found as part of chains up to 10 molecules long, the average chain length is only about 2.7 molecules at both temperatures, there are about 1.3 hydrogen bonds per molecule on average, and the chains are highly nonlinear on average.     

Instability of a system and its estimation in terms of the hybrid density functional theory method: a magnetic effective density functional (MEDF) approach

Potential curves and high and low spin energy gaps for radical clusters were calculated by spin polarized molecular orbital methods. Through-space effective exchange integrals (J _ab) and relative energies of spin projected low spin states by post-Hartree-Fock (HF) calculation were reproduced by the hybrid density functional theory (DFT) method. The hybrid parameters that could reproduce post-HF values such as UCCSD(T)'s for each model had close relations with the instabilities of those systems. Information entropy and related chemical indices were used to estimate the magnitude of the instabilities. A magnetic effective density functional (MEDF) scheme for spin clusters was proposed for practical computation of J _ab values in molecular magnetic materials.     

Effects of solute-solvent and solvent-solvent attractive interactions on solute diffusion

A study is reported on the diffusion process of a solute molecule in a Lennard-Jones-like liquid near the triple point by a molecular dynamics simulation. Systematic changes were made to the strength of the solute-solvent or solvent-solvent attractive interaction in order to elucidate its effects on the diffusion coefficient. When the solute-solvent attractive interaction is enhanced, the diffusion coefficient of the solute becomes much smaller than that predicted by the Stokes-Einstein relationship with a stick boundary condition. The generalized friction coefficient on the solute molecule was investigated, and the attractive force between solute and solvent is found to be the main cause for the enhancement of the friction. When the attractive interaction between solvent molecules is weakened, the diffusion coefficient of a solute does not change, whereas that of a solvent does. Compared with the shear viscosity of the solvent, the diffusion coefficient of the solute breaks the Stokes-Einstein relationship, whereas the Stokes-Einstein relationship appears to hold in the case of the solvent molecule.     

Extended Hartree—Fock (EHF) theory of chemical reactions VI: hybrid DFT and post-Hartree—Fock approaches for concerted and non-concerted transition structures of the Diels—Alder reaction

Activation barrier heights for concerted and non-concerted transition structures between butadiene and ethylene have been calculated by the broken-symmetry Hartree-Fock (HF), QCISD(T), and CCSD(T) methods with and without approximate spin projection, and the spin-restricted CASCI, CASSCF UNO MP2 and MR MP2 methods. They also have been calculated by the density functional theory (DFT) and hybrid DFT (HDFT) methods such as B2LYP and B3LYP. The reliability and utility of the HDFT methods have been investigated, and compared with the post-HF and MR MP2 results. The information entropy and related electron correlation indices also have been examined in relation to the polyradical character of the transition structures. Implications of the present results are discussed concerning the applicability of HDFT to large systems.     

毛细管电泳噪声特性分析

为优化毛细管电泳荧光信号检测系统,提高检测灵敏度,以100~1 000碱基对的脱氧核糖核酸作为分离对象,羟乙基纤维素为筛分介质,研究了直流电场下毛细管电泳荧光信号检测系统中的噪声特性.对不同分离电场强度、羟乙基纤维素溶液浓度和分子量、毛细管有效长度以及毛细管内径形状等情况下的噪声特性进行分析.分析得到该检测系统中信噪比最佳的优化参量,即分离电场强度为500~600V/cm、羟乙基纤维素浓度为0.6%~0.7%、羟乙基纤维素分子量为250、圆形内径为50μm以及毛细管有效长度为8cm.