298.15K下Li2B4O7-H2O体系水蒸汽分压及渗透系数的等压测定和离子相互作用模型

在已有研究含硼体系的文献中仅考虑了硼酸根B4O7^-2或B(OH)4^-和H3BO3的存在，而对Li2B4O7-H2O体系具有多种硼物种聚合平衡体系的热力学性质的研究尚未见报道．本文用等压法研究了Li2B4O7-H2O体系于298．15K下浓度由稀到过饱和溶液的平衡气相蒸汽压及渗透系数．考虑了水溶液中多种硼物种的存在，以Pitzer方程为基础，建立了可描述该含硼体系的离子相互作用模型。     

An approach to estimate the energy and strength of the intramolecular hydrogen bond in different conformers of 4‐methylamino‐3‐penten‐2‐one

The molecular structure and intramolecular hydrogen bond energy of 32 conformers of 4‐methylamino‐3‐penten‐2‐one were investigated at MP2 and B3LYP levels of theory using the standard 6–31G** basis set and AIM analyses. Furthermore, calculations for all the possible conformations of 4‐methylamino‐3‐penten‐2‐one in water solution were also carried out at B3LYP/6–31G** level of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the ketoamine conformers of this compound are more stable than the other conformers (i.e., enolimine and ketoimine). This stability is mainly due to the formation of a strong N? H···O intramolecular hydrogen bond, which is assisted by π‐electrons resonance. Hydrogen bond energies for all conformers of 4‐methylamino‐3‐penten‐2‐one were obtained from the related rotamers method. The nature of intramolecular hydrogen bond existing within 4‐methylamino‐3‐penten‐2‐one has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. The results of these calculations support the results which obtained by related rotamers method. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

噁唑硼烷催化芳醛不对称炔基化反应的量化研究

对手性噁唑硼烷催化芳醛不对称炔基化还原反应的机理进行了量子化学半经验方法研究.研究表明,该反应是放热的，炔基转移是反应的控制步骤，炔基转移的过渡态具有扭曲的椅式结构，还原的主要产物是R-手性醇.     

Evaluation of the Coulomb energy in relativistic self-consistent-field theory

 Computational schemes are presented with which to evaluate the electrostatic Coulomb energy in relativistic molecular electronic structure calculations using a basis of four-component Dirac spinor amplitudes. We demonstrate that algorithms may be constructed and implemented which differ only in minor details from those in common use in nonrelativistic quantum chemistry, and that the four-component formalism is neither as complicated nor as expensive as has been suggested recently in the literature. Spherically symmetrical atomic basis sets are presented which indicate that accurate representations of the Coulomb energy may be obtained using modest expansions of the electronic density in a scalar auxiliary basis set of spherical harmonic Gaussian-type functions. Received: 15 April 2002 / Accepted: 15 May 2002 / Published online: 29 July 2002     

Electrophoresis simulations using Chebyshev pseudo-spectral method on a moving mesh

We present the implementation and demonstration of the Chebyshev pseudo-spectral method coupled with an adaptive mesh method for performing fast and highly accurate electrophoresis simulations. The Chebyshev pseudo-spectral method offers higher numerical accuracy than all other finite difference methods and is applicable for simulating all electrophoresis techniques in channels with open or closed boundaries. To improve the computational efficiency, we use a novel moving mesh scheme that clusters the grid points in the regions with poor numerical resolution. We demonstrate the application of the Chebyshev pseudo-spectral method on a moving mesh for simulating nonlinear electrophoretic processes through examples of isotachophoresis (ITP), isoelectric focusing (IEF), and electromigration-dispersion in capillary zone electrophoresis (CZE) at current densities as high as 1000 A/m. We also show the efficacy of our moving mesh method over existing methods that cluster the grid points in the regions with large concentration gradients. We have integrated the adaptive Chebyshev pseudo-spectral method in the open-source SPYCE simulator and verified its implementation with other electrophoresis simulators.     

On the automatic restricted-step rational-function-optimization method

The rational function optimization algorithm is one of the widely used methods to search stationary points on surfaces. However, one of the drawbacks of this method is the step reduction procedure to deal with the overstepping problem. We present and comment on a method such that the step obtained from the solution of the rational function equations possesses the desired correct length. The analysis and discussion of the method is mainly centered on the location and optimization of transition states. Received: 18 June 1998 / Accepted: 17 September 1998 / Published online: 23 November 1998     

Overlapping spectra resolution using non-negative matrix factorization

Non-negative matrix factorization (NMF), with the constraints of non-negativity, has been recently proposed for multi-variate data analysis. Because it allows only additive, not subtractive, combinations of the original data, NMF is capable of producing region or parts-based representation of objects. It has been used for image analysis and text processing. Unlike PCA, the resolutions of NMF are non-negative and can be easily interpreted and understood directly. Due to multiple solutions, the original algorithm of NMF [D.D. Lee, H.S. Seung, Nature 401 (1999) 788] is not suitable for resolving chemical mixed signals. In reality, NMF has never been applied to resolving chemical mixed signals. It must be modified according to the characteristics of the chemical signals, such as smoothness of spectra, unimodality of chromatograms, sparseness of mass spectra, etc. We have used the modified NMF algorithm to narrow the feasible solution region for resolving chemical signals, and found that it could produce reasonable and acceptable results for certain experimental errors, especially for overlapping chromatograms and sparse mass spectra. Simulated two-dimensional (2-D) data and real GUJINGGONG alcohol liquor GC-MS data have been resolved soundly by NMF technique. Butyl caproate and its isomeric compound (butyric acid, hexyl ester) have been identified from the overlapping spectra. The result of NMF is preferable to that of Heuristic evolving latent projections (HELP). It shows that NMF is a promising chemometric resolution method for complex samples.     

N-Alkyl cysteine-assisted thioesterification of peptides

A new method for the preparation of peptide thioester by the post-solid phase peptide synthesis (SPPS) approach was developed. A series of N-alkyl cysteine derivatives were prepared and used as the C-terminus residue of the peptides prepared by the Fmoc SPPS. The synthetic peptides released from resin by TFA were readily converted to the peptide thioester in aqueous 3-mercaptopropionic acid (MPA) without significant side reactions.     

Method to determine quadruple points of a two-component system containing a simple hydrate phase and behavior of the system near these points

A method for determining quadruple points of a two-component system containing a simple hydrate phase is proposed. This method utilizes the quasi-static change of the system along three-phase equilibrium lines and was proved to be able to determine the quadruple points as accurately as the conventional method. By using this method, even though some preparation is necessary, a quadruple point can be determined in just a single experimental run. The behavior of the system near the quadruple points was also examined experimentally, for both the quasi-static and the irreversible change cases. At the quadruple points, the temperature and pressure of the system were kept constant for a while, as at the triple point of water. In both cases, the representative point of the state of the system passed through the quadruple point on a p–T diagram.     

H, C NMR spectral and single crystal structural studies of toxaphene congeners. Quantum chemical calculations for preferred conformers of 2,5-endo,6-exo,8,9,9,10,10-octachloro-2-bornene and their DFT/GIAO C chemical shifts

The ¹H and ¹³C NMR chemical shifts for six toxaphene congeners: 2-exo,3-endo,6-exo,8,9,10-hexachloro- (1), 2-exo,3-endo,5-exo,9,9,10,10-heptachloro- (2), 2-exo,3-endo,6-exo,8,9,10,10-heptachloro- (3), 2-exo,3-endo,5-exo,6-endo,8,9,10-heptachloro- (4), 2-exo,3-endo,5-exo,6-endo,8,9,9,10-octachlorobornane (5) and 2,5-endo,6-exo,8,9,9,10,10-octachloro-2-bornene (6) are reported. Their chemical shift assignments have been obtained by means of Pulsed Field Gradient (PFG) Double Quantum Filtered (DQF) ¹H,¹H correlation spectroscopy (COSY), PFG ¹H,¹³C Heteronuclear Multiple Quantum Coherence (HMQC) and PFG ¹H,¹³C Heteronuclear Multiple Bond Correlation (HMBC) experiments. A single crystal X-ray structural analysis was made for compounds 1, 3, 4 and 6. The prevalences of two octachlorobornene rotamers (6a,6b) were elucidated by ab initio MO method and single point DFT/GIAO calculations for ¹³C chemical shifts. Theoretical calculations proved that the single crystal structure of 6 corresponds its most stable conformer in solution.