PSEUDOHALOGEN CHEMISTRY. PART IV. HETEROLYTIC ADDITION OF THIOCYANOGEN TO ALKENES

Abstract

Thiocyanogen reacts slowly with alkenes, in the presence of a radical inhibitor in benzene or acetic acid in the dark at 25°, to yield α,β-dithiocyanates, α-isothiocyanates-β-thiocyanates and, in acetic acid, α-acetoxy-β-thiocyanates in varying proportions. The additions to alkyl alkenes are trans-stereospecific, and, in the case of the α-isothiocyanato-β-thiocyanates, non-regiospecific. The additions to aryl alkenes are trans-stereoselective and regiospecific, yielding the Markownikov-orientated α-isothiocyanato-β-thiocyanates. A heterolytic mechanism involving a two-step, kinetically controlled addition, with the formation of a cyano-sulfonium ion intermediate, e.g., 35, in the case of alkyl alkenes and an open carbonium ion, e.g., 36, in the case of aryl alkenes, is suggested. The diothiocyanate: isothiocyanato-thiocyanate ratios are discussed in terms of kinetic and steric control of reaction.     

Synthesis and Molecular Properties of Acceptor‐Substituted Squaraine Dyes

A broad series of more than 20 acceptor‐substituted squaraines was synthesized that feature different acceptor functionalities at the central squaraine four‐membered ring. The influence of these acceptor units on the reactivity of semisquaraine precursors and stability of the respective squaraines were explored. Thereby the dicyanovinyl group was found to be the most versatile acceptor group that enabled various modifications at the donor moiety of the squaraine scaffold, leading to an extended series of dicyanovinyl‐functionalized squaraines. The variation of donor units afforded a set of NIR fluorophores that cover a wavelength region from the visible at about 650 nm far into the NIR up to 920 nm with fluorescence quantum yields between 0.93 and 0.11 and outstanding optical brightness. This excellent optical property is related to a rigid molecular scaffold that is fixed in an all‐cis configuration by the additional dicyanovinyl acceptor unit. The change of the molecular symmetry from C_2h to C_2v upon functionalization of the squaraine core with dicyanovinyl acceptor group has been confirmed in solution by electro‐optical absorption (EOA) spectroscopy, revealing permanent ground‐state dipole moments μ_g in the range between 4.3 and 6.4 D. These dipole moments direct an antiparallel packing of the molecules in the solid state according to single‐crystal X‐ray analyses achieved for four dicyanovinyl‐functionalized squaraines. The structural properties, the EOA results, as well as the band shapes of the optical spectra indicate that these polymethine dyes are cyanine‐type chromophores. It is worth noting that the orientation of the dipole moment vectors is orthogonal to the orientation of the transition dipole moment vectors, which is an uncommon but characteristic feature of this rather novel class of polymethine dyes. With regard to applications of these dyes in organic solar cells, their redox properties were also studied by cyclic voltammetry.     

Limit distribution of the coefficients of polynomials with only unit roots

We consider sequences of random variables whose probability generating functions have only roots on the unit circle, which has only been sporadically studied in the literature. We show that the random variables are asymptotically normally distributed if and only if the fourth central and normalized (by the standard deviation) moment tends to 3, in contrast to the common scenario for polynomials with only real roots for which a central limit theorem holds if and only if the variance is unbounded. We also derive a representation theorem for all possible limit laws and apply our results to many concrete examples in the literature, ranging from combinatorial structures to numerical analysis, and from probability to analysis of algorithms. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46,707–738, 2015     

Valence state parameters of all transition metal atoms in metalloproteins—development of ABEEMσπ fluctuating charge force field

To promote accuracy of the atom‐bond electronegativity equalization method (ABEEMσπ) fluctuating charge polarizable force fields, and extend it to include all transition metal atoms, a new parameter, the reference charge is set up in the expression of the total energy potential function. We select over 700 model molecules most of which model metalloprotein molecules that come from Protein Data Bank. We set reference charges for different apparent valence states of transition metals and calibrate the parameters of reference charges, valence state electronegativities, and valence state hardnesses for ABEEMσπ through linear regression and least square method. These parameters can be used to calculate charge distributions of metalloproteins containing transition metal atoms (Sc‐Zn, Y‐Cd, and Lu‐Hg). Compared the results of ABEEMσπ charge distributions with those obtained by ab initio method, the quite good linear correlations of the two kinds of charge distributions are shown. The reason why the STO‐3G basis set in Mulliken population analysis for the parameter calibration is specially explained in detail. Furthermore, ABEEMσπ method can also quickly and quite accurately calculate dipole moments of molecules. Molecular dynamics optimizations of five metalloproteins as the examples show that their structures obtained by ABEEMσπ fluctuating charge polarizable force field are very close to the structures optimized by the ab initio MP2/6–311G method. This means that the ABEEMσπ/MM can now be applied to molecular dynamics simulations of systems that contain metalloproteins with good accuracy. © 2014 Wiley Periodicals, Inc.     

一种高准确率的交通监控视频车辆检测算法

针对高速视频监控的车辆识别易受几何变换影响且准确度不高的问题,提出了高效的阴影去除和车辆分类两种视频处理算法来提高车辆识别性能。利用阴影区域前景和背景的对比度参数进行有效的阴影去除;利用Hu不变矩表征车辆,从而克服了几何变换的影响。对比试验结果证明,本算法具有较高的阴影检测性能和极佳的车辆分类性能,明显优于其他同类型算法。     

Rotational and rovibrational transitions in the a 1Δ2 and b 1Σ+0+ states of sulfur monoxide radical

ABSTRACT

Sulfur monoxide radical has widely been detected in outer space using ground-state spectroscopy. The a ¹Δ₂ and b ¹Σ⁺₀₊ states of this radical have low excitation energies, and they possibly exist in outer space. In this work, the potential energy curves and dipole moment functions of the two states were evaluated using the complete active space self- consistent field method, followed by the valence internally contracted multireference configuration interaction approach. The transition line positions, oscillator strengths, band transition dipole matrix elements, Einstein A coefficients, and Franck–Condon factors of all transitions were calculated for lower vibrational levels at rotational angular momentum quantum number J up to 150. The transition line positions calculated in this study are in good agreement with the experimental results. The rovibrational transition became noticeably weak at Δυ > 5. Comparing the results of a ¹Δ₂ and b ¹Σ⁺₀₊ states reported in this paper with the previous values, we conclude that these results are the most accurate and complete to date.     

Electrodynamics of Magnetoelectric Media and Magnetoelectric Fields

The relationship between magnetoelectricity and electromagnetism is a subject of a strong interest and numerous discussions in microwave and optical wave physics and material sciences. The definition of the energy and momentum of the electromagnetic (EM) field in a magnetoelectric (ME) medium is not a trivial problem. The question of whether electromagnetism and magnetoelectricity can coexist without an extension of Maxwell's theory arises when the effects of EM energy propagation are studied and the group velocity of the waves in an ME medium is considered. The energy balance equation reveals unusual topological structure of fields in ME materials. Together with certain constraints on the constitutive parameters of a medium, definite constraints on the local field structure should be imposed. Analyzing the EM phenomena inside an ME material, the question “what kind of the near fields arising from a sample of such a material can be measured?” should be answered. The visualization of the ME states requires an experimental technique that is based on an effective coupling to the violation of spatial as well as temporal inversion symmetry. To observe the ME energy in a subwavelength region, it is necessary to assume the existence of first-principle near fields—the ME fields. These are non-Maxwellian near fields with specific properties of violation of spatial and temporal inversion symmetry. A particular interest to the ME fields arises in studies of metamaterials with “artificial-atoms” ME elements.     

考虑塑性变形发展程度系数的RC梁开裂弯矩改进计算公式

针对RC梁开裂荷载计算方法尚未统一的现状,首先,结合18根RC梁试验数据对比了已有的6种RC梁开裂弯矩计算公式,发现开裂弯矩理论计算值与试验值的偏差大小和混凝土强度有关;然后,通过提出塑性变形发展程度系数k,推导新的RC梁开裂弯矩计算公式,并进一步基于k值和塑性影响系数计算值γ_k进行改进;最后,选取12根RC试验梁验证改进公式的准确性,证明改进公式的计算值与试验值吻合更好且偏于安全。     

铁磁性过渡离子掺杂对纤锌矿相硫化锌电子结构的影响

通过第一性原理计算,优化了铁磁性过渡离子掺杂的纤锌矿相硫化锌Fm0.125Zn0.875S(Fm=Fe、Co、Ni)的几何结构,计算了其电子结构,分析了其半金属性及其微观机制。结果表明:对不同的铁磁性杂质离子,Fm0.125Zn0.875S在费米面处的自旋极化率均为-100%,具有半金属性,是潜在的优质自旋注入材料。Fm0.125Zn0.875S具有较宽的自旋带隙,从而具有较高的居里温度和广泛的应用前景。Fe0.125Zn0.875S、Co0.125Zn0.875S和Ni0.125Zn0.875S的2×2×1超胞的磁矩分别为3.96μB、2.90μB和2.00μB,主要来自于铁磁性过渡离子Fe、Co和Ni离子。这3种离子的电子结构分别为eg2↑eg1↓t2g3↑,eg2↑eg2↓t2g3↑和eg2↑eg2↓t2g3↑t2g1↓。