基于新的整数型分子图论指数M系统探索烷烃核磁共振碳谱(13C NMR)化学位移和CSS规律

系统研究了核磁共振碳谱与化学位移和规律,以及拓扑图论方法在定量结构波谱关系(QSSR)中的应用.本文基于路径长度矢量p=p1,p2,p3,…,pm)组合研究提出了一种新的整数型拓扑图论指数M=(p1+p2)+(p1-p3),并发现它与烷烃¹³C NMR化学位移和有良好线性相关性:回归方程及其统计参数为CSS=+14.329^* M-21.089;n=65,R=0.991,SD=7.684,F=3648.021,U=215381.656,Q=3719.563;交互校验CV结果为:R=0.990,R²(01)=0.981,SD(01)=8.086,F(01)=3288.113,U(01)=214982.172,Q(01)=4119.042.     

An Algebraic Structure of Orthogonal Wavelet Space

In this paper we study the algebraic structure of the space of compactly supported orthonormal wavelets over real numbers. Based on the parameterization of wavelet space, one can define a parameter mapping from the wavelet space of rank 2 (or 2-band, scale factor of 2) and genus gto the (g−1) dimensional real torus (the products of unit circles). By the uniqueness and exactness of factorization, this mapping is well defined and one-to-one. Thus we can equip the rank 2 orthogonal wavelet space with an algebraic structure of the torus. Because of the degenerate phenomenon of the paraunitary matrix, the parameterization map is not onto. However, there exists an onto mapping from the torus to the closure of the wavelet space. And with such mapping, a more complete parameterization is obtained. By utilizing the factorization theory, we present a fast implementation of discrete wavelet transform (DWT). In general, the computational complexity of a rank morthogonal DWT is O(m²g). In this paper we start with a given scaling filter and construct additional (m−1) wavelet filters so that the DWT can be implemented in O(mg). With a fixed scaling filter, the approximation order, the orthogonality, and the smoothness remain unchanged; thus our fast DWT implementation is quite general.     

MSINDO parameterization for third‐row transition metals

The recently developed MSINDO version of the semiempirical SCF MO method SINDO1 has been parameterized for third‐row transition metals Sc to Zn. The set of reference data used for the previous parameterization of SINDO1 has been substantially increased by incorporating results of recent experiments and first‐principles calculations. A comparison of calculated heats of formation, geometries, ionization potentials, and dipole moments with literature values for more than 200 gas phase molecules is presented. The accuracy of the modified MSINDO version achieved for heats of formation and bond lengths has been considerably improved compared to SINDO1. Small clusters of transition metals and metal oxides were included in the parameterization to ensure accurate results for studies of larger systems. The application of the method to small transition metal complexes that were not included in the parameterization shows that the optimized parameters are transferable to other compounds. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 861–887, 2001     

Vicinal Fluorine–Proton Coupling Constants: II. Individual Substituent Effects

The angular dependence and the effect of individual substituents upon the NMR vicinal fluorine–proton couplings3JFHhave been studied using data sets of experimental and calculated couplings. Coupling constants for a series of fluoroethane derivatives, CHXF–CH3and CH2F–CH2X(X= CH3, NH2, OH, and F), were calculated by means of the SCFab initioand semiempirical INDO/FPT methods. The calculated couplings reproduce correctly the main experimental trends in spite of the limitation in the calculation because of lack of electronic correlation and the use of medium size basis set. The individual substituent effects ΔKXiniare described by quadratic expressions on the relative electronegativities of substituents ΔχXi(ΔKXini=k0ni+kniΔχXi+ kniiΔχ2Xi). A selected data set of 58 experimental couplings, ranging from 1.9 to 44.4 Hz, has been collected from the literature. An extended Karplus equation with 16 coefficients that includes the electronegativity substituent effects has been derived from the experimental data set with a root-mean-square deviation of 1.2 Hz.     

Modeling lanthanide complexes: sparkle/AM1 parameters for ytterbium (III)

The Sparkle/AM1 model is extended to ytterbium (III) complexes. Thus, a set of 15 complexes, with various representative ligands, chosen to be representative of all complexes of high crystallographic quality (R-factor <0.05 A) in the Cambridge Crystallographic Database, and which possess oxygen and/or nitrogen as coordinating atoms, was used as the training set. In the validation procedure we added 32 more high quality crystallographic structures. For the 47 complexes, the Sparkle/AM1 unsigned mean error for all interatomic distances between the Yb(III) ion and the ligand atoms of the first sphere of coordination is 0.07 A, similar to present-day ab initio/ECP geometry prediction accuracies, and potentially useful for luminescent complex design while being hundreds of times faster.     

Theory and range of modern semiempirical molecular orbital methods

Semiempirical molecular orbital methods have a long history. They serve to tackle large systems and complicated processes beyond the reach of ab initio or density functional methods. Although their setup is derived from Hartree–Fock theory, the design of approximate energy expressions and the empirical parameters are used to achieve higher accuracy than the underlying ab initio theory. In this way the effect of larger basis sets or correlation can be partially simulated. All widely used semiempirical methods establish their accuracy by error statistics for molecular properties with experimental and high-level ab initio or density functional theory calculations as a reference. Their computational efficiency makes them suitable for the study of biochemical systems and solid materials. The present review presents a variety of applications which demonstrate the need for and success of semiempirical methods.     

The Analytical Parametrization of Fusion Barrier by Using the Skyrme Energy-Density Function Model

Using the skyrme energy density formalism, a pocket formula is introduced for barrier heights and positions of 95 fusion reactions (48 ≤ Z_PZ_T ≤ 1520) with respect to the charge and mass numbers of the interacting nuclei. It is shown that the parameterized values of RB and VB are able to reproduce the corresponding experimental data with good accuracy. Moreover, the absolute errors of our formulas are less than those obtained using the analytical parametrization forms of the fusion barrier based on the proximity versions. The ability of the parameterized forms of the barrier heights and its positions to reproduce the experimental data of the fusion cross section have been analyzed using the Wong model.     

Turbulent statistical characteristics associated to the north wind phenomenon in southern Brazil with application to turbulent diffusion

A parameterization for the transport processes in a shear driven planetary boundary layer (PBL) has been established employing turbulent statistical quantities measured during the north wind phenomenon in southern Brazil. Therefore, observed one-dimensional turbulent energy spectra are compared with a spectral model based on the Kolmogorov arguments. The good agreement obtained from this comparison leads to well defined formulations for the turbulent velocity variance, local decorrelation time scale and eddy diffusivity. Furthermore, for vertical regions in which the wind shear forcing is relevant, the eddy diffusivity derived from the north wind data presents a similar profile to those obtained from the non-extensive statistical mechanics theory. Finally, a validation for the present parameterization has been accomplished, using a Lagrangian stochastic dispersion model. The Prairie Grass data set, which presents high mean wind speed, is simulated. The analysis developed in this study shows that the turbulence parameterization constructed from wind data for north wind flow cases is able to describe the diffusion in a high wind speed, shear-dominated PBL.     

Parameterization of m‐channel orthogonal multifilter banks

A complete parameterization for the m‐channel FIR orthogonal multifilter banks is provided based on the lattice structure of the paraunitary systems. Two forms of complete factorization of the m‐channel FIR orthogonal multifilter banks for symmetric/antisymmetric scaling functions and multiwavelets with the same symmetric center (1 + γ + γ/(m - 1)) for some nonnegative integer γ are obtained. For the case of multiplicity 2 and dilation factor m = 2, the result of the factorization shows that if the scaling function Φ and multiwavelet Ψ are symmetric/antisymmetric about the same symmetric center γ + for some nonnegative integer γ, then one of the components of Φ (respectively Ψ) is symmetric and the other is antisymmetric. Two examples of the construction of symmetric/antisymmetric orthogonal multiwavelets of multiplicity 3 with dilation factor 2 and multiplicity 2 with dilation factor 3 are presented to demonstrate the use of these parameterizations of orthogonal multifilter banks. This revised version was published online in June 2006 with corrections to the Cover Date.     

Mixed implicit/explicit solvation models in quantum mechanical calculations of binding enthalpy for protein–ligand complexes

An approach to quantum mechanical investigation of interactions in protein–ligand complexes has been developed that treats the solvation effect in a mixed scheme combining implicit and explicit solvent models. In this approach, the first solvation shell of the solvent around the solute is modeled with a limited number of hydrogen bonded explicit solvent molecules. The influence of the remaining bulk solvent is treated as a surrounding continuum in the conductor‐like screening model (COSMO). The enthalpy term of the binding free energy for the protein–ligand complexes was calculated using the semiempirical PM3 method implemented in the MOPAC package, applied to a trimmed model of the protein–ligand complex constructed with special rules. The dependence of the accuracy of binding enthalpy calculations on size of the trimmed model and number of optimized parameters was evaluated. Testing of the approach was performed for 12 complexes of different ligands with trypsin, thrombin, and ribonuclease with experimentally known binding enthalpies. The root‐mean‐square deviation (RMSD) of the calculated binding enthalpies from experimental data was found as ～1 kcal/mol over a large range. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006