Solvatochromic Solvent Polarity Measurements In Analytical Chemistry: Synthesiss And Applications Of Et-30

Abstract

The E_T(30) scale of solvent polarity has been shown to be useful in examining many diverse analytical processes. It is based on the charge transfer absorption of 2,6-diphenyl-4-(2,4,6-triphenyl-N-pyridinio)phenolate (referred to as ET-30 in this paper). Unfortunately, use of the E_T(30) scale has been hindered by (a) the lack of a commercial source of the ET-30 dye and (b) the lack of an English language synthetic procedure. Here we discuss recent applications of the E_T(30) scale to analytical techniques, as well as a simplified procedure for the synthesis of ET-30.     

Lignin Chemistry: Biosynthetic Study and Structural Characterisation of Coniferyl Alcohol Oligomers Formed In Vitro in a Micellar Environment

Model coniferyl alcohol lignin (the so‐called dehydrogenative polymerisate, DHP) was produced in water under homogeneous conditions guaranteed by the presence of a micellised cationic surfactant. A complete study of the activity of the enzymatic system peroxidase/H₂O₂ under our reaction conditions was reported and all the reaction products up to the pentamer were characterised by ¹H NMR spectroscopy and ESI mass spectrometry. Our system, and the molecules that have been generated in it, represent a closer mimicry of the natural microenvironment since an enzyme, under micellar conditions, reproduces the cell system better than in buffer alone. On the basis of the oligomers structures a new biosynthetic perspective was proposed that focused attention on a coniferyl alcohol dimeric quinone methide as the key intermediate of the reaction. A formal, strictly alternate sequence of a radical and an ionic step underlines the reaction, thus generating ordered oligolignols structures. Alternatively to other model lignins, our olignols present a lower degree of radical coupling between oligomeric units. This offers a closer biosynthetic situation to the observation of a low rate of radical generation in the cell wall.     

Chemistry of furanidine series ketones

For the first time, oxacyclic ketones and-diketones are reacted with diazoacetic ester in the presence of a Lewis acid. It is found that 2,2, 5, 5-tetramethylfuranid-3-one(I) and 2, 2, 5, 5-tetramethylfuranidine-3, 4-dione (IV) undergo ring enlargement between the third and fourth carbon atoms in the ring, to give, respectively, 4-ethoxycarbonyl-2,2, 6, 6-tetramethyltetrahydropyrone-3 (II) and 4-ethoxycarbonyl-2, 2, 6, 6-tetramethyltetrahydropyran-3, 5-dione (V), with the characteristic properties of ß-ketoesters.For Part III see [17].     

超分子结构化学

超分子 (ｓｕｐｒａｍｏｌｅｃｕｌｅ)通常是指由两种或两种以上分子依靠分子间相互作用结合在一起 ,组装成复杂的、有组织的聚集体 ,并保持一定的完整性 ,使其具有明确的微观结构和宏观特性。由分子到超分子和分子间相互作用的关系 ,正如由原子到分子和共价键的关系一样。　　 1 987年 ,诺贝尔化学奖授予Ｃ .Ｐｅｄｅｒｓｅｎ(佩德森 )、Ｊ Ｍ .Ｌｅｈｎ(莱恩 )和Ｄ .Ｃｒａｍ(克拉姆 )等在超分子化学领域中的奠基工作 :佩德森发现冠醚化合物 ,莱恩发现穴醚化合物并提出超分子概念 ,克拉姆是主客体化学的先驱者[1～ 3] 。此后 ,作为化学的…     

30 years of GEFTA

30 years of GEFTA This revised version was published online in July 2006 with corrections to the Cover Date.     

Electronic Chemistry Conferences: 7 years of CONFCHEM

Between the summer of 1993 and August 2001, members of the ACS Division of Chemical Education's Committee on Computers in Chemical Education (CCCE) managed the online facilities for 17 online conferences. One more conference will occur during fall 2001, and several additional conferences are planned for the future. This article describes the history and the nature of these online conferences, including the advantages and disadvantages of the online format.     

Experimental Foundations of Structural Chemistry

本书较全面地汇集结构化学基本数据,应用于物质结构,化学键和结构．性能关联的实际研究,是一本具有手册性的专著。书中系统提供如下数据：原子,自由基,分子和原子簇电离势;元素与化合物的功函数和能带隙;包括范德华分子在内的键能;相变热和单质与化合物晶体的原子化能;各类化合物在不同物态下的键长以及金属,共价,离子和范德华半径的最新数据。还提供了在静态与动态压力下的相变,元素和化合物的状态方程与弹性模量,以及一些纳米晶体材料的特殊性能等丰富资料。     

Structural Chemistry of Magnesium Acetates

Magnesium acetate solvates, Mg(OAc)₂ · nL, and their hydrates were prepared by crystallization of Mg(OAc)₂ · 4H₂O or Mg(OAc)₂ from different solvents (L = MeOH, EtOH, HOAc). Anhydrous Mg(OAc)₂ was obtained by thermal dehydration of the tetrahydrate at 150 °C. X‐ray single crystal diffraction mostly with the use of synchrotron radiation allowed the structure determination of Mg(OAc)₂(H₂O)₃(EtOH) ( I ), Mg(OAc)₂(HOAc)₂(H₂O)₂ ( II ), Mg₃(OAc)₆(MeOH)₆ ( III ), Mg₃(OAc)₆(HOAc)₂(H₂O)₂ · 2HOAc ( IV ), Mg(OAc)₂(HOAc) · 1.8(HOAc) ( V ), Mg(OAc)₂ · H₂O ( VI ), [Mg₃(OAc)₆(EtOH)₂] · 2EtOH ( VII ), and Mg(OAc)₂ ( VIII ). Structural data were discussed in terms of the number of neutral O‐donor ligands per magnesium atom, coordination environment of magnesium atoms, structural functions of acetate groups, and hydrogen bonding systems.     

准晶体的结构化学

介绍准晶体的历史、结构、对称性和性质,介绍Mg32(Al,Zn)49的晶体结构和对称性,同时讨论纳米准晶颗粒的制备方法及其应用。     

Structural Chemistry of Heteroselenometallic Clusters

1INTRoDUCTIoNThechemistryof[MS'j'-(M=Mo,W)anionsandtheirrelatedcompoundshavebeenextensivelyinvestigatedfortheirrelevancetobiologicalsystem,richstruc-turalchemistryandspecialreactivepropertiesaswellaspotentialapplicationinnon-linearopticalmaterials,t1~5iwhereasthatof[MSe'j'-(M=Mo,W)anionsandtheirrelatedcompoundshavereceivedattentiononlyinrecentyears.t6~7)Inl989lMhllerisolatedtwoclustercompounds,namely,cubane-like[OMoSe3Cl-(CuPPh,),j(siandlinear[WSe'(AgPPh,),).t9iAfterthat,lbersstud…     

Structural properties of a series of photochromic fluorinated indolylfulgides

Fluorinated indolyl­fulgides are a class of photochromic organic compounds that meet many of the requirements for use as optical memory media and optical switches. The X‐ray crystal structures of a series of five photochromic fluorinated indolyl­fulgides have been determined, namely (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,2‐tri­fluoro­ethyl­idene]‐4‐(1‐methyl­ethyl­idene)­dihydrofuran‐2,5‐dione (tri­fluoro­methyl­iso­propyl­idene­indolyl­fulgide), C₁₉H₁₆F₃NO₃, (I), (3Z)‐3‐[1‐(1,2‐dimethyl‐1H‐indol‐3‐yl)‐2,2,3,3,3‐penta­fluoro­propyl­idene]‐4‐(1‐methyl­ethyl­idene)­dihydrofuran‐2,5‐dione (penta­fluoro­ethyl­iso­propyl­idene­indolyl­fulgide), C₂₀H₁₆F₅NO₃, (II), (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,3,3,4,4,4‐hepta­fluoro­butyl­idene]‐4‐(1‐methyl­ethyl­idene)­dihydrofuran‐2,5‐dione (hepta­fluoro­propyl­iso­propyl­idene­indolyl­fulgide), C₂₁H₁₆F₇NO₃, (III), (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,2‐tri­fluoro­ethyl­idene]‐4‐(tri­cyclo­[3.3.1.1^3,7]­decyl­idene­)dihydrofuran‐2,5‐dione (tri­fluoro­methyl­adamantyl­idene­indolyl­fulgide), C₂₆H₂₄F₃NO₃, (IV), and (3Z)‐3‐[1‐(1,2‐di­methyl‐1H‐indol‐3‐yl)‐2,2,3,3,4,4,4‐hepta­fluoro­butyl­idene]‐4‐(tri­cyclo­[3.3.1.1^3,7]­decyl­idene­)dihydrofuran‐2,5‐dione (hepta­fluoro­propyl­adamantylidenein­dolyl­fulgide), C₂₈H₂₄F₇NO₃, (V). The photochromic property of fulgides is based on the photochemically allowed electrocyclic ring closure of a hexatriene system to form a cyclo­hexa­diene. For each fulgide examined, the bond lengths within the hexatriene system alternate between short and long, as expected. Comparing the structures of the five fulgides with each other demonstrates no significant difference in bond lengths, bond angles or dihedral angles within the hexatriene systems. The distance between the bond‐forming C atoms at each end of the hexatriene system does vary. Correlations of structural properties with optical properties are addressed.     

Dinitrogen fixation and activation after 30 years: a puzzle still unsolved

The most relevant literature in the field of dinitrogen activation/fixation promoted by early transition metals is critically reviewed in the occasion of the 30th anniversary of its discovery. Our contribution to this research is also reviewed.     

Structural diversity in a series of alkyl-substituted cesium aryloxides

A family of cesium aryloxides [Cs(OAr)](n) were synthesized and structurally characterized from the reaction of 1:1 or 1:excess stoichiometry of Cs(0) and the appropriate alkyl-substituted phenol: 2-alkylphenol [alkyl = methyl (H-oMP), isopropyl (H-oPP), and tert-butyl (H-oBP)] and 2,6-dialkylphenol [alkyl = methyl (H-DMP), isopropyl (H-DIP), tert-butyl (H-DBP), and phenyl (H-DPhP)]. The products were structurally identified as [Cs(oMP)(H-oMP)(2)](n) (1), [Cs(5)(oPP)(5)](n) (2), [Cs(4)(oBP)(4)(H-oBP)(6)](n) (3x, shown), [Cs(3)(DMP)(3)](n) (4), [Cs(2)(DIP)(2)](n) (5), [Cs(DIP)(H-DIP)](n) (5x), and [Cs(DPhP)](n) (7). Compounds 1-7 were found to adopt complex polymeric structures employing π interactions from the neighboring pendant phenoxide ligands. The solution behavior of these compounds was studied using solution (133)Cs NMR spectroscopy, and for each compound, a single (133)Cs NMR resonance was observed, with chemical shift values found to be strongly solvent-dependent. This implies that monomeric cesium salt species involving solvent interactions exist in solution.     

梦萦魂牵--《化学通报》复刊30年

哲学家和物理学家都喜欢研究和讨论“时间” ,时间之矢告诉人们光阴冉冉不复返 ,矢者失也。然而人们却总想回忆 ,寻找那些美好的或沮丧的过去 ,是安慰或自娱吧。我一直相信生活总是向前的 ,社会总是进步的 ,就和宇宙不停地膨胀一样。《化学通报》复刊已经 3 0年了 ,既然是复刊 ,必然先有停刊。历史总是把破坏和重建放在一起考虑的 ,才能找出规律。人们都说 2 0世纪是自然科学大发达的时代 ,然而 2 0世纪又是人类社会灾难最多的时代。正因如此 ,才促使科学多极化地、多样性地发展起来 ,从欧洲到美洲到亚洲 ,一点点 ,慢慢地扩散开来 ,也许 ,真…