Full four‐component relativistic calculations of the one‐bond 77Se–13C spin‐spin coupling constants in the series of selenium heterocycles and their parent open‐chain selenides

Four‐component relativistic calculations of ⁷⁷Se–¹³C spin–spin coupling constants have been performed in the series of selenium heterocycles and their parent open‐chain selenides. It has been found that relativistic effects play an essential role in the selenium–carbon coupling mechanism and could result in a contribution of as much as 15–25% of the total values of the one‐bond selenium–carbon spin‐spin coupling constants. In the overall contribution of the relativistic effects to the total values of ¹J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin‐orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second‐order polarization propagator approach (CC2) with the four‐component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of ¹J(Se,C). Solvent effects in the values of ¹J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2–78.4) are next to negligible decreasing negative ¹J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of ⁷⁷Se–¹³C spin‐spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1–0.2‐Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd.     

Jordan operator algebras revisited

Jordan operator algebras are norm‐closed spaces of operators on a Hilbert space with for all . In two recent papers by the authors and Neal, a theory for these spaces was developed. It was shown there that much of the theory of associative operator algebras, in particular, surprisingly much of the associative theory from several recent papers of the first author and coauthors, generalizes to Jordan operator algebras. In the present paper we complete this task, giving several results which generalize the associative case in these papers, relating to unitizations, real positivity, hereditary subalgebras, and a couple of other topics. We also solve one of the three open problems stated at the end of our earlier joint paper on Jordan operator algebras.     

材料表征方法理论与实践课程的改革与建设*

通过与超星专业慕课制作团队合作搭建网络教学平台,将线上慕课教学与线下实验教学相结合,对材料表征方法理论与实践课程进行了全方位的改革。与传统实验教学相比,改革后的课程不仅能够激发学生的学习兴趣,实现时间空间的相对自由,还可以完善考核机制,提升教学质量,从而为高校化学研究生实验课程的改革提供一定的借鉴意义。     

On the Lipschitz equivalence of self‐affine sets

Recently Lipschitz equivalence of self‐similar sets on has been studied extensively in the literature. However for self‐affine sets the problem is more awkward and there are very few results. In this paper, we introduce a w‐Lipschitz equivalence by repacing the Euclidean norm with a pseudo‐norm w. Under the open set condition, we prove that any two totally disconnected integral self‐affine sets with a common matrix are w‐Lipschitz equivalent if and only if their digit sets have equal cardinality. The main methods used are the technique of pseudo‐norm and Gromov hyperbolic graph theory on iterated function systems.     

一种新的磁共振图像处理流水线的设计与实现

磁共振图像的重建、后处理及可视化是磁共振成像（MRI）系统的重要组成部分.本文开发了一个新的用于磁共振图像重建、后处理及可视化的开源框架YAP（Yet Another Pipeline），利用此框架可以方便地构建图像处理流水线.与现有的一些其他开源框架相比，本文开发的框架具有如下特点：（1）采用基于接口的设计，可使用基于接口的插件对流水线的功能进行扩展；（2）允许用户使用编写脚本的方式构建图像处理流水线，编辑与修改流水线都很方便；（3）支持带有分支结构的流水线，便于流水线的构建与调试.目前，该框架已经在商用系统中获得了应用.     

Direct Proof of Determinant Representation for Scalar Products of the XXZ Gaudin Model with Generic Non-Diagonal Boundary Terms

After constructing the Bethe state of the XXZ Gaudin model with generic non-diagonal boundary terms,we analyze the properties of this state and obtain the determinant representations of the scalar products for this XXZ Gaudin model.     

Reactions of cyclochlorotriphosphazatriene with 2-mercaptoethanol. Calorimetric and spectroscopic investigations of the derived products

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N₃P₃Cl₆ (1) with 2-mercaptoethanol, 2-HS-CH₂-CH₂-OH (2), in (1:1, 1:2 and 1:3) mole ratios, in excess of NaH, in THF and diethylether solutions yield a total of 6 novel products: one mono spiro, N₃P₃Cl₄[O-CH₂-CH₂-S] (3); one mono-substituted open chain, N₃P₃Cl₅[S-CH₂-CH₂-OH] (4); one dispiro, N₃P₃Cl₂[O-CH₂-CH₂-S]₂ (5); one tri-substituted open chain, N₃P₃Cl₃[S-CH₂-CH₂-OH]₃ (6); one tris-spiro, N₃P₃[O-CH₂-CH₂-S]₃ (7) and one disubstituted open chain, N₃P₃Cl₄[S-CH₂-CH₂-OH]₂ (8) derivatives. The spiro products (3, 5 and 7) are formed as the major products in this system and all of the synthesized compounds are found to be stable at room temperature. The structures of the derived compounds were elucidated by elemental analysis, TLC-MS, ³¹P and ¹H NMR spectral data. For evaluation of melting behavior of derivatives (6) and (7), thermal transition peaks and their corresponding enthalpies were determined via DSC technique.     

An assessment of pure,hybrid, meta,and hybrid‐meta GGA density functional theory methods for open‐shell systems: The case of the nonheme iron enzyme 8R–LOX

The performance of a range density functional theory functionals combined in a quantum mechanical (QM)/molecular mechanical (MM) approach was investigated in their ability to reliably provide geometries, electronic distributions, and relative energies of a multicentered open‐shell mechanistic intermediate in the mechanism 8R–Lipoxygenase. With the use of large QM/MM active site chemical models, the smallest average differences in geometries between the catalytically relevant quartet and sextet complexes were obtained with the B3LYP^* functional. Moreover, in the case of the relative energies between ⁴II and ⁶II , the use of the B3LYP^* functional provided a difference of 0.0 kcal mol^–1. However, B3LYP^± and B3LYP also predicted differences in energies of less than 1 kcal mol^–1. In the case of describing the electronic distribution (i.e., spin density), the B3LYP^*, B3LYP, or M06‐L functionals appeared to be the most suitable. Overall, the results obtained suggest that for systems with multiple centers having unpaired electrons, the B3LYP^* appears most well rounded to provide reliable geometries, electronic structures, and relative energies. © 2012 Wiley Periodicals, Inc.     

Quantum McKay Correspondence for Disc Invariants of Toric Calabi–Yau 3-orbifolds

We announce a result on quantum McK ay correspondence for disc invariants of outer legs in toric Calabi–Yau 3-orbifolds, and illustrate our method in a special example [C3/Z5(1, 1, 3)].