Unveiling the relevance of the redox character of nitroaromatic and nitroheteroaromatic compounds as potential medicines

This review discusses the state of the art, challenges, and perspectives in recent applications of nitroaromatics and nitroheteroaromatics, which are redox-bio-activated drugs or leads, in Medicinal Chemistry. It deals mainly with the electrochemical approach toward the electron transfer-based molecular mechanisms of drug action, drug design, estimation and measurement of redox potentials, correlation of physicochemical and pharmacological data, and electrochemical studies of the main representatives of nitro-containing prodrugs, along with approaches to combat their toxicity issues, aiming at a better therapeutic profile. Electrochemical investigation plays essential roles, being strategic in the design and discovery of potential medicines.     

Restriction of Intramolecular Motion(RIM): Investigating AIE Mechanism from Experimental and Theoretical Studies

Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emission(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscience.With the twenty-year development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE effect.In this review,these mechanistic works about RIM are summarized from experimental and theoretical perspectives.Thereinto,the experimental studies are introduced from three parts:external rigidification,structural modification and structural characterization.In the theoretical part,calculations on the low-frequency motion of AIEgens have been performed to prove the RIM mechanism.By virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as restriction of access to conical intersection,suppression of Kasha transition,restriction of access to dark state,etc.It is foreseeable that the RIM mechanism will unify the photophysical theories for both molecules and aggregates,and inspire more progress in aggregate science.     

Electron transfer reactions of nickel(III) and nickel(IV) complexes

This review narrates the electron transfer reactions of various nickel(III) and nickel(IV) complexes reported during the period 1981 until today. The reactions have been categorized mainly with respect to the type of nickel complexes. The reactivity of nickel(III) complexes of macrocycles, 2,2′-bipyridyl and 1,10-phenanthroline, peptides and oxime–imine, and of nickel(IV) complexes derived from oxime–imine, oxime and miscellaneous ligands with various organic and inorganic electron donors have been included. Kinetic and mechanistic features associated with such interactions have been duly analyzed. The relevance of Marcus cross-relation equations in the delineation of the electron transfer paths has also been critically discussed.     

多胺型螯合树脂对重金属离子的吸附研究

研究了含有三乙烯四胺功能基的酚醛树脂（FQ—34）对Cu2 、Ni2 ,Zn2 、Co2 的静态吸附动力学、等温吸附等过程。结果表明，液膜扩散是吸附的主控步骤，可用G．E．Boyd膜扩散方程来描述；等温吸附属单分子层吸附，可用Langmuir等温方程描述。同时，还对吸附机理作了初步探讨。     

Homolytic cyclization of 1,3-propanedithiol to 1,2-dithiolane in the presence of 2,5-dimethyl-2,4-hexadiene

2,2-Diethyl-1,3-propanedithiol undergoes cyclization to 4,4-diethyl-1,2-dithiolane upon interaction with 2,5-dimethyl-2,4-hexadiene in benzene in the presence of azodiisolbutyronitrile. The reaction proceeds according to the radical chain mechanism. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2078–2080, October, 1998.     

Thermal Stability and Degradation Mechanism for Two Main-Chain Liquid Crystal Polyesters a TG-MS Study

The thermal stabilities of two thermotropic liquid crystal polyesters were analysed by means of thermogravimetric analysis (TG), as a function of the chemical structure of the aliphatic spacer between the aromatic-triad mesogenic units. TG was combined with mass spectrometry to confirm that the degradation mechanism previously observed in a Fourier transform infrared study of the degrading polymers follows a β-cis-elimination process. This revised version was published online in July 2006 with corrections to the Cover Date.     

从分子碎片到活性位：分子筛催化材料的原位、共振紫外拉曼光谱研究

在过去的近十年中,各种新型原位表征技术和反应器设计被应用于多相催化过程和催化材料的合成研究中,并获得了许多新认识．特别是最近几年,利用原位、共振拉曼光谱技术对分子筛合成关键物种检测、杂原子分子筛催化活性位的研究取得了一系列进展．这些技术的应用使得从分子水平认识复杂的多孔材料成为可能：从合成初期碎片基元检测、碎片相互连接的关键化学键到预组装类微孔结构;从高度隔离过渡金属中心到配位化学键断裂生成活性中间物种,再到完成催化反应循环．这为设计特定功能和结构的催化材料及高选择性的活性中心奠定了坚实的基础．     

不饱和半夹芯式16e化合物Cp*Ir(S2C2B10H10)与邻、间位取代苯基叠氮的反应性

考虑取代基的位置和电子效应对反应体系的影响, 本文系统地研究了16e化合物Cp^*Ir(S₂C₂B₁₀H₁₀) (1)与邻、间位取代苯基叠氮的反应。研究结果表明：与邻、间位取代苯基叠氮反应均生成苯环邻位碳发生C-H 活化形成C-S 键的金属配合物。这些配合物通过核磁(¹H、¹¹B、¹³C)、红外、质谱、元素分析和单晶结构解析进行了全面地表征。在光照反应结果的基础上, 提出了形成这类产物的自由基机理。     

开放骨架磷酸铝AlPO4-12的晶化过程

以乙二胺为结构导向剂,在200℃加热物质的量组成为nAl₂O₃:nP₂O₅:n_en:nH₂O=1:1:2:226的初始混合物(en=乙二胺),合成了三维开放骨架磷酸铝化合物AlPO₄-12。用X-射线衍射、元素分析、pH测量、液体核磁共振以及电喷雾质谱研究了其晶化过程。依据质谱数据,开发了一个系统枚举在晶化过程中可能生成的小结构单元分子式的方法。研究发现在AlPO₄-12的晶化过程中经历了层状磷酸铝UiO-15和UiO-13中间相,液相中Al物种的浓度极低,在晶化过程中生成的小结构单元中P-OH逐渐增多,乙二胺分子逐渐质子化,在晶化过程中生成了磷酸铝的4元环和6元环。用电喷雾质谱研究晶化过程中的液相可以获得小结构单元的结构和组成信息。     

Investigation of the limitations of saturated fractional factorial experimental designs,with confounding effects for an HPLC ruggedness test

Summary Recently much attention has been directed to the validation of analytical methods. The level of validation will depend on the method application. If a method is developed for general use, for instance by different analysts, instruments or laboratories, then the effect of these changes need evaluation. This is normally referred to as ruggedness testing, where the limitations of the method to changes in the specified conditions are examined.This paper examines the use of Plackett-Burman fractional factorial experiment designs for ruggedness testing in high performance liquid chromatography (HPLC). The ability of these designs to identify confounding effects is applied to the stability indicating analysis of Salbutamol and its major degradation product, AH4045. The results show that confounding effects, proving extremely pertinent to HPLC, can be identified.The assay proved rugged to most tested changes although not to the use of column packing material from different manufacturers.