光谱法研究水团簇结构对AlCl3溶液与血清白蛋白作用的影响

研究了冷冻-解冻处理对A1CI₃溶液团簇结构和AICl₃与血清白蛋白相互作用的影响。测定了AICl₃溶液冷冻-解冻处理前后电导率的变化,发现AICI₃溶液经冷冻处理后,电导率有明显增加。采用紫外分光光度法和荧光光谱法对冷冻前后AICI₃溶液与血清白蛋白相互作用的研究表明,A1C1₃溶液经冷冻-解冻处理后,与血清白蛋白的相互作用变弱,配位诱导作用降低,静态猝灭作用变小,这种相互作用变弱的效应是由于水的分子团簇结构变化引起的。     

Configuration interaction study on low-lying states of AlCl molecule

High-level ab initio calculations of the Λ–S states for aluminum monoiodide(Al Cl) molecule are performed by utilizing the explicitly correlated multireference configuration interaction(MRCI-F12) method. The Davidson correction and scalar relativistic correction are investigated in the calculations. Based on the calculation by the MRCI-F12 method, the spin–orbit coupling(SOC) effect is investigated with the state-interacting technique. The adiabatic potential energy curves(PECs) of the 13 Λ–S states and 24 Ω states are calculated. The spectroscopic constants of bound states are determined,which are in accordance with the results of the available experimental and theoretical studies. Finally, the transition properties of 0~+(2)–X0~+, 1(1)–X0~+, and 1(2)–X0~+ transitions are predicted, including the transition dipole moments(TDMs),Franck–Condon factors(FCFs), and the spontaneous radiative lifetimes.     

对甲氧基苯胺与丙烯腈的催化加成

对甲氧基-N,N-二氰乙基苯胺是一种重要的有机中间体,可由对甲氧基苯胺与丙烯腈在酸的催化下发生加成反应而得。然而芳胺与丙烯腈发生的加成反应较难进行,采用HAc,FeC l3,CuC l2,Cu2C l2,ZnC l2,蒙脱土,Cu(Ac)2·3H2O作催化剂得到的主要为单氰乙基物[1-4]。赵莹[5-10]报道了用A     

Preparation of glycerol plasticized chitosan films using AlCl3·6H2O as the solvent: optical,crystalline, mechanical and barrier properties

Chitosan films plasticized with the complex of AlCl₃·6H₂O and glycerol were prepared by using AlCl₃·6H₂O as the solvent. The effect of AlCl₃·6H₂O and glycerol complex with Chitosan was studied by SEM, XRD, TGA, and tensile testing. The complex would increase the water resistance and destroy the crystals of chitosan film. The TGA results proved that the chitosan film plasticized with the complex showed higher thermal stability at the temperature below 200?°C than pure chitosan film. With the addition of the complex of AlCl₃·6H₂O and glycerol, the tensile strength of chitosan film decreased and the elongation at break increased.     

Epoxy ether cleaving reactions catalyzed by supporting Lewis acidic ionic liquid

Lewis acidic ionic liquids were used to catalyze the reaction of epoxypropane with POCl₃.Considering the lower cost and catalytic activities,we concluded that[Et₃NH]Cl/AlCl₃ was the most attractive ionic liquid from an economical point of view.But it would be easily inactivated because of sensitive to water and air.Moreover,it could not be reused easily because of difficulty recovery in the reaction.However,supporting[Et₃NH]Cl/AlCl₃ catalyst could resolve above problems.Supporting[Et₃NH]Cl/ AlCl₃ catalyst could be separated by filter easily and reused 5 times in 98%yield.Furthermore,the catalyst was applicable to other epoxy ether cleaving reactions.     

Me2(CH2Cl)SiCN和Me3SiCN在醛的不对称氰化反应中的比较研究

研究考察了在手性（salen）AlCl-叶立德络合物（R,R）-1/2a作为催化剂和异丙醚作为溶剂的条件下,两种不同硅氰化试剂[Me₂（CH₂Cl）SiCN和Me₃SiCN（TMSCN）]在对醛的不对称氰化中的应用情况.一系列不同取代的芳香醛均可分别与这两种试剂发生反应,以高到优秀的产率和对映选择性得到目标产物.脂肪醛的反应产物的对映选择性最高只能达到中等.对比研究发现,Me₂（CH₂Cl）SiCN在醛的硅氰化反应中显示出了明显高于TMSCN的反应活性,但是产物的对映选择性大体相当.     

石墨烯吸附Al2Cl6分子的第一性原理与Monte Carlo研究

采用第一性原理与蒙特卡罗方法研究Al₂Cl₆气体分子在石墨烯表面的吸附性能与光电性质，结果表明：(1)石墨烯对Al₂Cl₆气体分子具有较强的物理吸附作用，两个Al原子的连线与石墨烯平面近乎平行且两个Al原子处于紧靠顶位的桥位位置时最稳定；(2)温度升高不利于Al₂Cl₆气体分子吸附并存在阶跃式降低，气体逸度增加有利于吸附并存在阶跃式升高，Al₂Cl₆气体分子插入石墨/双层石墨烯/多层石墨烯宜将温度维持在AlCl₃沸点附近，并增加气体的压力；(3)Al₂Cl₆的吸附对石墨烯的电子结构进行了调控，但没有明显改变石墨烯费米能级附近的态密度以及“赝能隙”;(4)Al₂Cl₆的吸附对体系光学参数的影响十分明显，静态介电常数提高近5倍，使体系屏蔽效应有较大增强，在长波波段的吸收性能、反射性能及光电导也有了明显提升.     

Synthesis and Evaluation of Ruthenium 2‐Alkyl‐6‐mercaptophenolate Catalysts for Olefin Metathesis

A series of ruthenium carbene catalysts containing 2‐sulfidophenolate bidentate ligand with an ortho‐substituent next to the oxygen atom were synthesized. The molecular structure of ruthenium carbene complex containing 2‐isopropyl‐6‐sulfidophenolate ligand was confirmed through single crystal X‐ray diffraction. An oxygen atom can be found in the opposite position of the N‐heterocyclic carbene (NHC) based on the steric hindrance and strong trans‐effects of the NHC ligand. The ruthenium carbene catalyst can catalyze ring‐opening metathesis polymerization (ROMP) reaction of norbornene with high activity and Z‐selectivity and cross metathesis (CM) reactions of terminal alkenes with (Z)‐but‐2‐ene‐1,4‐diol to give Z‐olefin products (Z/E ratios, 70:30–89:11) in low yields (13%–38%). When AlCl₃ was added into the CM reactions, yields (51%–88%) were considerably improved and process becomes highly selective for E‐olefin products (E/Z ratios, 79:21–96:4). Similar to other ruthenium carbene catalysts, these new complexes can tolerate different functional groups.     

Cp2ZrCl2-catalyzed hydroalumination of norbornene derivatives withi-Bu2AlCl

Cp₂ZrCl₂-catalyzed (Cp = ⁵-C₅H₅) hydroalumination of substituted norbornenes withi-Bu₂AlCl was conducted, yielding higher cycloalkylhaloalanes with high yields.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2791–2798, December, 1992.     

Facile synthesis of indene and fluorene derivatives through AlCl3‐catalyzed cyclization of in situ formed iminium ions

A simple AlCl₃‐catalyzed condensation/cyclization cascade process between aldehydes and sulfonamide is reported, in which two new bonds and one five‐membered ring are simultaneously formed with water as the byproduct. This method provides a rapid access to indenamine and 9‐aminofluorene derivatives. Additionally, these products can be transformed into corresponding indanones and fluorenones under the developed conditions.