甲基锍盐的合成

在四氟硼酸银存在下，分别以硫醚、硫醇、硫酚或过硫醚为原料与碘甲烷反应制备了相应的甲基锍盐。用１ＨＮＭＲ和１３ＣＮＭＲ表征产物的结构并提出了反应的机理。     

Investigation of the behavior of arenediazonium salts with olefins in BmimPF6

The palladium-catalyzed reactions of olefins with arenediazonium salts in ionic liquids were investigated. For methyl acrylate and methyl acrylonitrile, normal Heck cross-coupling products are obtained in good yields. However, highly selective dimerization products are formed in excellent yields for styrenes. The catalyst system can be recycled.     

The discovery of two kinds of ion pairs

The discovery and implications of the existence of two kinds of ion pairs in solutions of carbanion salts is described. Also discussed are the factors controlling tight–loose ion pair equilibrium: the nature of the carbanion and its counterion, temperature, pressure, solvent, and cation‐complexing additives. A few examples are presented of the effect of these ionic species on the mechanisms of anionic polymerization and proton transfer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3655–3667, 2004     

N-alkoxy-pyridinium and N-alkoxy-quinolinium salts as initiators for cationic photopolymerizations

The polymerization of n-butyl vinyl ether (BVE), cyclohexene oxide (CHO) and 3,4-epoxycyclohexyl(methyl)-3′,4′-epoxycyclohexane carboxylate (EEC) was initiated upon UV irradiation (λ_inc > 300 nm) of dichloromethane solutions containing N-ethoxy-2-methylpyridinium ( V ), N-ethoxy-4-phenyl-pyridinium ( VI ) or N-ethoxy-isoquinolinium hexafluorophosphate ( VII ). Whereas the bifunctional EEC was converted into an insoluble gel, BVE and CHO formed polymers of molar mass: M_w = 2 X 10⁴?2 X 10⁵ (PCHO) and M_w ≈ 2 X 10⁴ (PBVE). Protons are formed with a rather high quantum yield [ø(H+) = 0.48 on irradiating VII in dichloromethane; titration with sodium p-nitrophenolate] and it is, therefore, assumed that the polymerization is initiated by photochemically generated protons. © 1992 John Wiley & Sons, Inc.     

Electron-transfer in molecular functional materials

We discuss electron-transfer processes that govern the physics of several materials or systems of interest for advanced applications. The discussion touches upon several topics, ranging from solvatochromism to solvent-induced symmetry breaking, from excitonic to cooperative effects in molecular crystals, from phase transitions to vibrational contributions to the dielectric constant in organic materials, from spectroscopy to molecular transport. In all these diverse systems electron transfer (ET) plays a major role and is discussed with reference to simple models for delocalized charges.     

Condensed rare-earth metal-rich tellurides. Extension of layered Sc6PdTe2-type compounds to yttrium and lutetium analogues and to Y7Te2, the limiting binary member

Six isotypic R₆ZTe₂ phases have been synthesized in Ta at elevated temperatures and characterized by single crystal X-ray refinements for R=Y, Z=Rh, Pd, Ag, Y and for R=Lu, Z=Cu, Ag. All crystallize in the Sc₆PdTe₂-type structure, Pnma, Z=4, a∼21.5 Å, b∼4.1 Å, c∼11.4 Å. The results can be viewed as the replacement of Te3 atoms in the parent isotypic Sc₂Te (or in the hypothetical Y₂Te or Lu₂Te analogues) by the above the Z, the Y example giving the new binary phase Y₇Te₂. The shorter (and stronger) metal-metal bonds concentrate in the region of metal (Z, Y) substitution, as revealed by larger integrated crystal orbital Hamilton population (ICOHP) values derived from linear muffin-tin-orbital (LMTO) calculations. Partial densities-of-states data for Y₇Te₂ reflect a similar behavior. Individual R-R bond distances are seen to deviate appreciably from the more fundamental overlap population measures for each.     

The participation of the anion and alkyl substituent of diaryliodonium salts in photo‐initiated cationic polymerization reactions

The photo‐initiated cationic polymerization (PCP) of epoxides using diaryliodonium salt photoacid generators (PAGs) bearing alkyl groups and anions was investigated. The properties and reactivities of a series of iodonium salts containing various cations and anions were compared in the context of a PCP reaction. The products from the decomposition of the cations of these salts were analyzed using gas chromatography‐mass spectrometry (GC‐MS) spectra. The relationship between the molecular structure of the salts and their reaction mechanism in the PCP reaction was investigated. Based on the results of the investigation, it was concluded that the structures of the cations and anions of theiodonium salts affect the PCP reaction rate, which was controlled by the products from the diaryliodonium salts. As part of an additional investigation, the diaryliodonium salts‐epoxide materials were applied to 254 nm‐photo‐patterning. Copyright © 2006 John Wiley & Sons, Ltd.     

以短链季铵盐/脂肪酸盐为模板合成超微孔二氧化硅

超微孔材料具有1~2 nm的孔径,在分离、催化应用中有望展现出择形催化的能力。 寻找经济、简便的合成超微孔材料的表面活性剂体系是一项有意义的工作。 本研究以短链季铵盐(十烷基三甲基溴化铵,记为C₁₀TAB)和不同链长脂肪酸酸盐混合胶束为模板剂,硅酸钠为硅源,成功制备出高度有序超微孔SiO₂。 通过小角X射线衍射、N₂吸附-脱附、傅里叶变换红外光谱、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术手段对产品的结构和性能进行了表征。 结果表明,合成体系中脂肪酸盐碳链长、加入量、晶化温度等对产物孔道有序性有很大影响。 当选择正辛酸钠(SO)为助表面活性剂,当n(C₁₀TAB):n(Na₂SiO₃):n(SO):n(H₂O)=1:1.5:0.3:800,晶化温度为80 ℃时,可以得到高度有序超微孔SiO₂。 煅烧后样品比表面积为1300 m²/g,孔体积0.49 cm³/g,孔径分布在1.90 nm。     

Electrochemical grafting by reduction of 4-aminoethylbenzenediazonium salt: Application to the immobilization of (bio)molecules

We propose in this study a simple and rapid way to produce stable amino-derivatized conductive surfaces for the subsequent immobilization of (bio)molecules. This was achieved through the use of (4-aminoethyl)benzenediazonium salt (AEBD), which was immobilized on glassy carbon and gold electrodes by its electrochemical reduction. The presence of terminal grafted amino functions was evidenced with XPS by analyzing N1s core level. Besides this conventional surface characterisation, an electrochemical strategy is proposed here to evidence the presence of immobilized amines, in which the chemical reactivity of amines towards 2,4,6-trinitrobenzenesulfonic acid (TNBS) is used. Surface-bound TNBS served as an electrochemical marker and was detected by cyclic voltammetry. Additionally, pre-modified gold electrodes with amino functions can be derivatized with biomolecules such as glutathione (GSH). Glutathione attachment was evidenced by studying the electrochemical behaviour of ferri/ferrocyanide redox before and after its immobilization. The functionalized electrodes were then used for the detection of copper ions in neutral aqueous solutions.     

N-Acyltrifluoromethanesulfonamides as new chemoselective acylating agents for aliphatic and aromatic amines

This work describes advances in the study of the internal condensation of ammonium salts of N-acylsulfonamides. N-Acyltrifluoromethanesulfonamides show considerable advantages over the non fluorinated analogues by virtue of their higher reactivity and acidity. The reaction chemoselectivity has been investigated using a wide range of amines. The sensitivity of the reaction to steric and electronic effects confirms the potential application of these reagents in chemoselective acylation of polyamines.