Theoretical investigation of isotopic scrambling mechanisms in 2-chloroethyl methyl sulfide

Ab initio and semiempirical molecular orbital calculations have been applied to study the concerted and stepwise isotopic scrambling mechanisms of 2-chloroethyl methyl sulfide in the gas phase and in aqueous solution. The calculations reveal the structural details of the reactants, transition structures, and intermediates involved in this reaction and provide relative energy estimates. The concerted mechanism is found to be competitive with the stepwise mechanism in the gas phase, but the stepwise mechanism is favored in aqueous solution as no true transition structure for the concerted mechanism could be found using the solvation models. A combined approach of evaluating solvation energies with the generalized-Bom-plus-surface-tensions SM _x solvation models of Cramer and Truhlar at ab initio optimized geometries is found to deliver the best agreement with experimentally determined reaction barriers. Together with the recent experimental results of McManus and co-workers, the present study provides insights into the controlling factors involved in the elementary reaction steps of sulfur mustards and a solid foundation for investigations into more complex reactions of related compounds.     

A 31P NMR STUDY OF TERTIARY PHOSPHINE COMPLEXES OF PLATINUM(II) AND PALLADIUM(II)

Complexes of the type NBu ₄ MCl ₃ PR ₃ R=P.Tolyl,Ph,Bu) (M = Pt, Pd) are prepared by the reaction of MCl ₂ or K ₂ [MCl ₄ ] by phosphine ligands. Addition of NBu ₄ Br or NBu ₄ I to these compounds, in dichloromethane results in a redistribution of halogens and formation of all six isomers of the type MBr _{3 ?X}Cl_XPR ₃ X= 0, 1, 2, and 3 which have been identified by ³¹ P- ¹ H NMR spectroscopy. The intensities show that the products are proportional to the statistical distribution.     

The Family of Ferrocene‐Stabilized Silylium Ions: Synthesis, 29Si NMR Characterization,Lewis Acidity,Substituent Scrambling,and Quantum‐Chemical Analyses

The purpose of this systematic experimental and theoretical study is to deeply understand the unique bonding situation in ferrocene‐stabilized silylium ions as a function of the substituents at the silicon atom and to learn about the structure parameters that determine the ²⁹Si NMR chemical shift and electrophilicity of these strong Lewis acids. For this, ten new members of the family of ferrocene‐stabilized silicon cations were prepared by a hydride abstraction reaction from silanes with the trityl cation and characterized by multinuclear ¹H and ²⁹Si NMR spectroscopy. A closer look at the NMR spectra revealed that additional minor sets of signals were not impurities but silylium ions with substitution patterns different from that of the initially formed cation. Careful assignment of these signals furnished experimental proof that sterically less hindered silylium ions are capable of exchanging substituents with unreacted silane precursors. Density functional theory calculations provided mechanistic insight into that substituent transfer in which the migrating group is exchanged between two silicon fragments in a concerted process involving a ferrocene‐bridged intermediate. Moreover, the quantum‐chemical analysis of the ²⁹Si NMR chemical shifts revealed a linear relationship between δ(²⁹Si) values and the Fe???Si distance for subsets of silicon cations. An electron localization function and electron localizability indicator analysis shows a three‐center two‐electron bonding attractor between the iron, silicon, and C′_ipso atoms, clearly distinguishing the silicon cations from the corresponding carbenium ions and boranes. Correlations between ²⁹Si NMR chemical shifts and Lewis acidity, evaluated in terms of fluoride ion affinities, are seen only for subsets of silylium ions, sometimes with non‐intuitive trends, indicating a complicated interplay of steric and electronic effects on the degree of the Fe???Si interaction.     

Dioxygen Activation by Siloxide Complexes of Chromium(II) and Chromium(IV)

The reaction of a tripodal trisilanol with n‐butyllithium and CrCl₂ results in a dinuclear Cr^II complex ( 1 ), which is capable of cleaving O₂ to yield in a unique complex ( 2 ) with an asymmetric diamond core composed of two Cr^IV?O units. Magnetic susceptibility data reveal significant exchange coupling of Cr^II (S=2) in 1 and large zero‐field splitting for Cr^IV (S=1) in 2 owing to strong spin–orbit coupling of the ground state. The Cr^IV?O compound can also be generated using PhIO, and evidence was gathered that although it is the stable product isolated after excessive O₂ treatment, it further activates O₂ to yield an intermediate species that oxidizes THF or Me‐THF. By extensive ¹⁸O labeling studies we were able to show, that in the course of this process ¹⁸O₂ exchanges its label with siloxide O atoms of the ligand via terminal oxido ligands.     

基于图像重组和比特置乱的多图像加密

针对现有多图像加密算法只能同时加密多张同类型同大小的图像,适用范围不广、实用性差等问题,提出一种基于图像重组和比特置乱的多图像加密算法.该算法通过将任意数量、不同大小和不同类型的图像重新组合成新多灰度图,一次完成同时加密,极大提高了加密效率和适用范围.首先,依次提取所有待加密图像像素值重新组合出N张m×n新灰度图,并将其转化成m×n×8N二进制矩阵.然后,采用3D比特置乱方式,对高位页进行行列比特置乱,低位页进行整页比特置乱.最后,进行异或扩散操作,得到密文图像.高低位分开置乱提高了算法的抗噪声能力,最终密文信息熵达到7.999以上,很好地掩盖了明文的统计特性.构造一种新型Logistic与广义三阶Fibonacci级联的混沌系统产生随机序列,增加了初值和控制参数范围,扩大了密钥空间,使其达到8×10^84以上,极大地提高了抗穷举攻击能力.既提高了序列随机性,又同时保留了低维混沌系统的快速性.结合明文哈希值(SHA-256)产生密钥,明文像素值发生微小改变后密文像素值变化率达到0.996以上,极大地提高了的明文敏感性和算法抗选择明文攻击的能力.实验分析表明,提出的多图像加密算法安全性高、实用性强.     

Image Encryption Scheme with Compressed Sensing Based on a New Six-Dimensional Non-Degenerate Discrete Hyperchaotic System and Plaintext-Related Scrambling

Digital images can be large in size and contain sensitive information that needs protection. Compression using compressed sensing performs well, but the measurement matrix directly affects the signal compression and reconstruction performance. The good cryptographic characteristics of chaotic systems mean that using one to construct the measurement matrix has obvious advantages. However, existing low-dimensional chaotic systems have low complexity and generate sequences with poor randomness. Hence, a new six-dimensional non-degenerate discrete hyperchaotic system with six positive Lyapunov exponents is proposed in this paper. Using this chaotic system to design the measurement matrix can improve the performance of image compression and reconstruction. Because image encryption using compressed sensing cannot resist known- and chosen-plaintext attacks, the chaotic system proposed in this paper is introduced into the compressed sensing encryption framework. A scrambling algorithm and two-way diffusion algorithm for the plaintext are used to encrypt the measured value matrix. The security of the encryption system is further improved by generating the SHA-256 value of the original image to calculate the initial conditions of the chaotic map. A simulation and performance analysis shows that the proposed image compression-encryption scheme has high compression and reconstruction performance and the ability to resist known- and chosen-plaintext attacks.     

Modeling sequence scrambling and related phenomena in mixed-model production lines

In this paper we examine the various effects that workstations and rework loops with identical parallel processors and stochastic processing times have on the performance of a mixed-model production line. Of particular interest are issues related to sequence scrambling. In many production systems (especially those operating on just-in-time or in-line vehicle sequencing principles), the sequence of orders is selected carefully to optimize line efficiency while taking into account various line balancing and product spacing constraints. However, this sequence is often altered due to stochastic factors during production. This leads to significant economic consequences, due to either the degraded performance of the production line, or the added cost of restoring the sequence (via the use of systems such as mix banks or automated storage and retrieval systems). We develop analytical formulas to quantify both the extent of sequence scrambling caused by a station of the production line, and the effects of this scrambling on downstream performance. We also develop a detailed Markov chain model to analyze related issues regarding line stoppages and throughput. We demonstrate the usefulness of our methods on a range of illustrative numerical examples, and discuss the implications from a managerial point of view.     

A theoretical characterization of the structure formation enthalpy,and fluzional behaviour of B2H6 and AlBH6

Summary A comprehensive study of the binary association complexes B₂H₆ and AlBH₆ has been performed by ab initio molecular orbital theory. Reliable formation enthalpies can be computed only be extended basis sets and a reasonably complete account of correlation. The greater stability towards neutral dissociation of AlBH₆ with respect to B₂H₆ obtained at the Hartree-Fock level employing the 6-21G^* basis set ( 10 kcal/mol) is reduced to only 2 kcal/mol when the basis set is sufficiently saturated and correlation energy properly included. The value of the activation energy for hydrogen scrambling in AlBH₆ is much less sensitive to the method used, although correlation still plays a significant rôle reducing the potential energy barrier from 11.4 to 7.7 kcal/mol.     

基于HVS的小波域信息隐藏方法

为了提高信息隐藏的不可感知性和鲁棒性,结合人眼视觉系统(HVS)的相关知识,提出了一种新的小波域信息隐藏算法。将载体图像的中等亮度区域设为不可用区域,不在该区域隐藏信息,同时选择在载体图像小波变换的高频系数细节子图隐藏信息,并优先选择在对角高频系数细节子图中隐藏。计算局部子块的方差值作为隐藏信息的嵌入系数,并通过计算高频子图的噪声敏感模型ωθ(i,j)决定隐藏信息的位置。充分考虑了人眼的各种视觉掩蔽效应,使得隐藏信息后的结果图像相比隐藏之前没有出现明显的降质。实验结果表明该方法能够有效提高信息隐藏的不可知性,达到了很好的隐藏效果,同时能够有效地抗击噪声、裁剪和压缩等攻击影响,具有很好的鲁棒性,在信息安全领域有较好的应用前景。     

Highly Enantioselective Synthesis of 1,2,3‐Substituted Cyclopropanes by Using α‐Iodo‐ and α‐Chloromethylzinc Carbenoids

Herein, we report the enantio‐ and diastereoselective formation of trans‐iodo‐ and trans‐chlorocyclopropanes from α‐iodo‐ and α‐chlorozinc carbenoids by using a dioxaborolane‐derived chiral ligand. The synthetically useful iodocyclopropane building blocks were derivatized by an electrophilic trapping of the corresponding cyclopropyl lithium species or a Negishi coupling to give access to a variety of enantioenriched 1,2,3‐substituted cyclopropanes. The synthetic utility of this method was demonstrated by the formal synthesis of an HIV‐1 protease inhibitor. In addition, the related stereoselective bromocyclopropanation was also investigated. New insights about the relative electrophilicity of haloiodomethylzinc carbenoids are also presented.