计算机辅助13CNMR谱解析——Ⅱ:取代烯烃13C化学位移预测

本工作基于经验参数加和规则预测烯烃类化合物¹³C化学位移,并已计算机程序化。此程序不仅能预测小分子烯烃结构的¹³C化学位移,而且对长链聚烯烃结构的化学位移计算也能得到较满意的结果。对于线型与支化结构,程序采用不同的处理方法,使计算值与实际观察值误差在2ppm左右。在计算环烯类化合物化学位移时,由于分子成环效应等影响,其计算值低于观测值。本程序用FORTRAN Ⅳ和编译BASIC两种语言编写,可在PDP11/23、PDP11/24和IBMPC/XT等机上运行。     

Van Der Waals heterogeneous layer‐layer carbon nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on graphene and graphane sheets

Noncovalent interactions involving aromatic rings, such as π···π stacking, CH···π are very essential for supramolecular carbon nanostructures. Graphite is a typical homogenous carbon matter based on π···π stacking of graphene sheets. Even in systems not involving aromatic groups, the stability of diamondoid dimer and layer‐layer graphane dimer originates from C − H···H − C noncovalent interaction. In this article, the structures and properties of novel heterogeneous layer‐layer carbon‐nanostructures involving π···H‐C‐C‐H···π···H‐C‐C‐H stacking based on [n ]‐graphane and [n ]‐graphene and their derivatives are theoretically investigated for n = 16–54 using dispersion corrected density functional theory B3LYP‐D3 method. Energy decomposition analysis shows that dispersion interaction is the most important for the stabilization of both double‐ and multi‐layer‐layer [n ]‐graphane@graphene. Binding energy between graphane and graphene sheets shows that there is a distinct additive nature of CH···π interaction. For comparison and simplicity, the concept of H‐H bond energy equivalent number of carbon atoms (noted as NHEQ), is used to describe the strength of these noncovalent interactions. The NHEQ of the graphene dimers, graphane dimers, and double‐layered graphane@graphene are 103, 143, and 110, indicating that the strength of C‐H···π interaction is close to that of π···π and much stronger than that of C‐H···H‐C in large size systems. Additionally, frontier molecular orbital, electron density difference and visualized noncovalent interaction regions are discussed for deeply understanding the nature of the C‐H···π stacking interaction in construction of heterogeneous layer‐layer graphane@graphene structures. We hope that the present study would be helpful for creations of new functional supramolecular materials based on graphane and graphene carbon nano‐structures. © 2017 Wiley Periodicals, Inc.     

水溶液中八种氨基酸与尿素的焓相互作用

用LKB-2277精密微热量计测定了298.15K时甘氨酸、L-丙氨酸、L-丝氨酸、L-脯氨酸、L-羟脯氨酸、L-蛋氨酸、L-苏氨酸和L-缬氨酸分别与尿素在水溶液中的混合过程焓变,根据McMillan-Mayer理论关联得到各组焓作用系数,并运用基团贡献法探讨了不同氨基酸与尿素分子的相互作用机制。结果表明,氨基酸的两性离子部分及α-碳上的非极性脂肪侧基、极性的羟基侧基和五元吡咯环侧基等对焓对作用系数具有不同的贡献。     

A Modified Potential Method for Electrons Scattering Total Cross Section Calculations on Several Molecules at 30 ～ 5000 eV: CF4, CCl4, CFCl3, CF2Cl2, and CF3Cl

A complex optical model potential modified by the concept of bonded atom, which takes into consideration the overlapping effect of electron clouds between two atoms in a molecule, is employed to calculate the total cross sections (TCSs) for electrons scattering from several molecules (CF4, CCl4, CFCl3, CF2 Cl2, and CF3 Cl) over an incident energy range 30 ～ 5000 eV using the additivity rule model at Hartree-Fock level. The quantitative TCSs are compared with those obtained by experiments and other theories wherever available, and good agreement is obtained above 100 eV.It is shown that the modified potential can successfully calculate the TCSs of electron-molecule scattering over a wide energy range, especially at lower energies.     

Determination of binary systems based on light elements by the ratio of the Compton and Rayleigh scattering intensities

A generalization of the Compton method for determining elements with a low atomic number Z from 1 (H) to 9 (F) by the ratio of the intensities of incoherent (Compton) and coherent (Rayleigh) scattering is proposed. The generalization takes into account not only the dependence of this ratio on the effective atomic number of the scatterer material but also the momentum transfer variable x = . The new method is based on the application of calibration function of obtained by measuring scattering spectra at two values of x₁= 0.831 Å⁻¹ and x₂= 1.297 Å⁻¹ with a WDXRF spectrometer. The elemental atomic numbers and their concentrations of binary compounds with unknown compositions are determined by the solution of a system of linear equations. Coefficients of the equations are calculated from the measured ratios for the test sample and the regularization solution for the corresponding calibration. The experiments have been carried out for standard samples of single-component, binary and triple stoichiometric compounds based on H, Li, Be, B, C, O and F. The identification of these elements was found to be possible in the absence of a relationship between the positions of scattering peaks and the composition of the sample, and a qualitative and quantitative analysis of the composition of the material was carried out as part of the solution of a single inverse problem.     

Benson group additivity values of phosphines and phosphine oxides: Fast and accurate computational thermochemistry of organophosphorus species

Composite quantum chemical methods W1X-1 and CBS-QB3 are used to calculate the gas phase standard enthalpy of formation, entropy, and heat capacity of 38 phosphines and phosphine oxides for which reliable experimental thermochemical information is limited or simply nonexistent. For alkyl phosphines and phosphine oxides, the W1X-1, and CBS-QB3 results are mutually consistent and in excellent agreement with available G3X values and empirical data. In the case of aryl-substituted species, different computational methods show more variation, with G3X enthalpies being furthest from experimental values. The calculated thermochemical data are subsequently used to determine Benson group additivity contributions for 24 Benson groups and group pairs involving phosphorus, thereby allowing fast and accurate estimations of thermochemical data of many organophosphorus compounds of any complexity. Such data are indispensable, for example, in chemical process design or estimating potential hazards of new chemical compounds. © 2018 Wiley Periodicals, Inc.     

Spectra of 2, 5- and 3, 4-Dichlorobromobenzene Molecules in Ultraviolet

Vibrational analyses have been presented for the absorption bands of 2, 5- and 3, 4-dichlorobromobenzene molecules photographed in the regions 2925 - 2690 A and 2900 - 2580 A respectively. The following constants have been determined:

The 0.0 band shifts have been explaine on the basis of simple additivity rule.     

Cochran's statistical theorem for outer inverses of matrices and matrix quadratic forms

We extend the matrix version of Cochran's statistical theorem to outer inverses of a matrix. As applications, we investigate the Wishartness and independence of matrix quadratic forms for Kronecker product covariance structures.