Lewis酸性Mg(Ⅱ)在有机合成中的应用

综述了Lewis酸性的Mg(Ⅱ)及其配合物在有机官能团转化和碳-碳键形成反应中的应用.较强的Lewis酸性、较强的亲氧性和较高的配位数对Mg2+独特的催化反应活性起着关键的作用.     

Lewis酸性Mg(II)在有机合成中的应用

综述了Lewis酸性的Mg(II)及其配合物在有机官能团转化和碳—碳键形成反应中的应用 .较强的Lewis酸性、较强的亲氧性和较高的配位数对Mg2 + 独特的催化反应活性起着关键的作用 .     

氯代苄基葡萄糖在芳香碳苷立体选择性合成中的应用

Hosomi等人曾报道了1-α-氯代-2,3,4,6-四-O-苄基-D-吡喃葡萄糖(1)与烯丙基硅醚反应主要得到α异构体占优势的烯丙基碳苷。我们研究了化合物1在Lewis酸存在下和芳香醚反应,结果发现,产物都是β构型的芳香碳苷。这与Schmidt等人和Williams等     

TS-1分子筛Lewis酸性的理论研究

应用密度泛函理论和量子力学与分子力学联合的ONIOM2方法对含Ti的MFI分子筛(TS-1)中Ti4+离子在三种不同骨架落位上所表现的Lewis酸性进行了理论研究. 利用碱性探针分子(CO, NH3, 乙腈和吡啶)在骨架Ti活性中心的吸附作用,对吸附络合物的几何结构和吸附能进行了计算,并通过自然键轨道(NBO)分析考察了吸附络合物的电子结构. 结果表明,骨架Ti在T12位表现出明显的Lewis酸性,对NH3分子有较强的吸附作用. NBO分析表明,骨架Ti活性中心的Lewis酸性是由于 Ti - O 键的空σ反键轨道接受碱性探针分子提供的孤对电子;NH3分子吸附导致Ti4+离子由近正四面体中心对称变为五配位的三角双锥对称.     

新型Br?nsted酸性离子液体催化二氧化碳与环氧化合物偶联反应

设计合成了一系列由碳链长度可调节的Br?nsted酸中心阳离子及Lewis碱中心阴离子构成的酸性离子液体,,并应用于二氧化碳与环氧化合物的偶联反应合成环碳酸酯。考察了离子液体结构以及温度、压力和催化剂用量等参数的影响。结果表明,具有长碳链的离子液体表现出高催化活性及可重复使用性能。离子液体的酸性影响催化活性。     

新型Br?nsted酸性离子液体催化二氧化碳与环氧化合物偶联反应

设计合成了一系列由碳链长度可调节的Br?nsted酸中心阳离子及Lewis碱中心阴离子构成的酸性离子液体,,并应用于二氧化碳与环氧化合物的偶联反应合成环碳酸酯。考察了离子液体结构以及温度、压力和催化剂用量等参数的影响。结果表明,具有长碳链的离子液体表现出高催化活性及可重复使用性能。离子液体的酸性影响催化活性。     

轨道去除方法及其应用

介绍了能对正碳离子及硼烷化合物中的电子离域现象作定量研究和分析的轨道去除方法 .一般的分子轨道方法能得到电子离域体系的波函数 ,而轨道去除方法则能得到电子离域效应被湮灭之后的假想定域体系的波函数 .通过对两者的对比分析 ,可定量而又清晰地了解分子内的电子离域是如何影响分子结构、能量及其他分子性质的 .具体讨论了正碳离子中烷基的超共轭现象和三卤化硼的Lewis酸性 .结果表明 ,轨道去除方法可非常有效地解释一些传统的化学问题     

新型Brnsted酸性离子液体催化二氧化碳与环氧化合物偶联反应（英文）

设计合成了一系列由碳链长度可调节的Brnsted酸中心阳离子及Lewis碱中心阴离子构成的酸性离子液体,,并应用于二氧化碳与环氧化合物的偶联反应合成环碳酸酯.考察了离子液体结构以及温度、压力和催化剂用量等参数的影响.结果表明,具有长碳链的离子液体表现出高催化活性及可重复使用性能.离子液体的酸性影响催化活性.     

基质Lewis酸性调控及其催化轻烃裂化反应性能（英文）

催化剂分子筛和基质的合理匹配是提高石脑油催化裂化制低碳烯烃产量的最有效路径之一,但是基质表面Lewis酸性对裂化反应的影响尚未明确。本研究通过硼和锌改性γ-Al₂O₃和锡改性KIT-6介孔氧化硅材料调变表面的Lewis酸,研究基质及其与ZSM-5分子筛配合使用时催化正庚烷和1-己烯裂化制低碳烯烃的性能。采用XRD、TEM、N₂物理吸附-脱附以及NH₃-TPD等方法探讨了改性γ-Al₂O₃和KIT-6的结构性质和表面酸性质。结果表明,B可以降低γ-Al₂O₃的表面Lewis酸性(酸量和酸强度),而Zn可以增强其表面酸性;此外,Sn可以提高有序介孔KIT-6表面Lewis酸性。催化裂化反应结果表明,当基质单独使用时,随基质表面Lewis酸性增强,轻烃反应活化能降低且转化率升高;当基质与ZSM-5配合使用时,基质在上分子筛在下的双床层排布方式对应的转化率最高,且随基质Lewis酸性增强,轻烃转化率升高,但Lewis酸性...     

氟离子亲合能——定量标度Lewis酸性强度的方法

评述了Lewis酸碱电子理论及氟离子亲合能的概念,指出了可以通过离子回旋共振实验方法和量子化学理论方法获得氟离子亲合能数值以定量确定Lewis酸性强度,并介绍了表示Lewis酸性强度的PF-标度。     

Modification of high spin coordination polymers of the groups VII and VIII 3d-elements with pivalic bridges

Methods for the synthesis of high spin polynuclear and high dimension structures of manganese(II), iron(II), cobalt(II) and nickel(II) pivalates with exchange interactions of different types are considered.     

有序介孔有机金属 Pd(II) 的制备及其催化水介质中的 Suzuki 反应

 以有机金属 Pd 硅烷和乙基桥联硅烷为混合硅源, 在表面活性剂作用下进行共缩聚反应, 制备了有序介孔有机金属 Pd(II) 催化剂 Pd(II)-PMO(Et). 采用傅里叶变换红外光谱、核磁共振谱、X 射线衍射、透射电子显微镜和 N2 吸附脱附等手段对催化剂进行了表征. 结果表明, 与后嫁接法相比, 共聚法制得的催化剂活性位分散均匀, 孔道不易堵塞, 同时乙基修饰的孔壁增强了催化剂表面疏水性, 有利于反应物在孔道内的扩散和吸附. 在水介质 Suzuki 反应中, Pd(II)-PMO(Et) 的催化活性与均相催化剂 Pd(PPh3)2Cl2 的相当, 且可重复使用.     

Subtractive differential pulse anodic stripping voltammetry at a stationary mercury-coated glassy carbon electrode

The application of subtractive mode differential pulse anodic stripping voltammetry (SDPASV) at a stationary mercury-coated glassy carbon electrode for the analysis of labile Zn(II), Cd(II), Pb(II) and Cu(II) is described. It is shown that the method has an improved sensitivity to Cu(II) owing to elimination of high background currents normally encountered in normal mode DPASV at the TFME. The sensitivity limits of the present method to Cd(II) and Cu(II) is estimated to be 0.025 and 0.067 ppb respectively, when a 2 min deposition time is used. It is suggested that the high sensitivity of the method coupled to the relative simplicity of the stationary electrodes could make the method useful in environmental and natural water studies.     

Rational ligand design for metal ion recognition. Synthesis of a N-benzylated N2S3-donor macrocycle for enhanced silver(I) discrimination

Four previously documented ligand design strategies for achieving Ag(I) discrimination have been applied to the design of a new N-benzylated N2S3-donor macrocycle; the latter shows high selectivity for Ag(I) over Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) in log K and bulk membrane transport studies.     

Stripping voltammetric detection of mercury(II) based on a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) films modified glassy carbon electrode

This work reports a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) (MPMBT) films at the surface of glassy carbon electrode (GCE) for the electrochemical detection of Hg(II). The Hg(II)-imprinted MPMBT/GCE exhibits larger binding to functionalized capacity, faster binding kinetics and higher selectivity to template Hg(II) due to their high ratio of surface-imprinted sites, larger surface-to-volume ratios, the complete removal of Hg(II) templates and larger affinity to Hg(II). The square wave anodic stripping voltammetry (SW ASV) response of the Hg(II)-imprinted MPMBT/GCE to Hg(II) is ca. 3.0 and 5.9 times larger than that at the direct imprinted poly(2-mercaptobenzothiazole) modified GCE and non-imprinted MPMBT/GCE sensor, respectively; and the detection limit for Hg(II) is 0.1 nM (which is well below the guideline value given by the World Health Organization). Excellent wide linear range (1.0–160.0 nM) and good repeatability (relative standard deviation of 2.5%) were obtained for Hg(II). The interference experiments showed that mercury signal was not interfered in the presence of Pb(II), Cd(II), Zn(II), Cu(II) and Ag(I), respectively. These values, particularly the high sensitivity and excellent selectivity compared favorably with previously reported methods in the area of electrochemical Hg(II) detection, demonstrate the feasibility of using the prepared Hg(II)-imprinted MPMBT/GCE for efficient determination of Hg(II) in aqueous environmental samples.     

Preconcentration of copper on ion-selective imprinted polymer microbeads

Molecular recognition-based separation techniques have received much attention in various fields because of their high selectivity for target molecules. Molecular imprinting has been recognized as a promising technique for the preparation of such systems. In this study, we have prepared a novel molecular imprinted adsorbent to remove heavy metal ions with high selectivity. The Cu(II)-imprinted poly(ethylene glycol dimethacrylate–methacryloylamidohistidine/Cu(II)) (poly(EGDMA–MAH/Cu(II))) microbeads with an average size of 150–200 μm were prepared by dispersion polymerization. These Cu(II) imprinted microbeads were used in the adsorption–desorption of copper(II) ions from metal solutions. Adsorption equilibria was achieved in about 1 h. The maximum adsorption of Cu(II) ions onto imprinted microbeads was about 48 mg/g. The pH significantly affected the adsorption capacity of imprinted microbeads. The observed adsorption order under competitive conditions was Cu(II) > Zn(II) > Ni(II) > Co(II) in mass basis. The imprinted microbeads can be easily regenerated by 0.1 M EDTA solution with higher effectiveness. The imprinted microbeads showed excellent selectivity for the target molecule (i.e. Cu(II) ions due to molecular geometry). These features make imprinted microbeads very good candidate for selective removal of Cu(II) ions at high adsorption capacity. Detection limit was increased at least 1000-folds with the preconcentration approach using the imprinted microbeads. The method was also applied to certified reference and seawater samples.     

Synthesis and properties of a chelating resin containing triazolethiol groups

A macroreticular poly(acrylic acid)-based resin with triazolethiol as the functional group has been synthesized. The stability of the resin in acidic media and the behaviour in sorption and desorption of various metal ions have been investigated and compared with those of the acylthiosemicarbazide resin which is an intermediate in synthesis of the triazolethiol resin. Both resins show high affinity for copper(II) silver, cadmium and mercury(II), and high selectivity for silver and mercury(II) at low pH (1–2), and even at pH 7 if EDTA is present. The triazolethiol resin sorbs metal ions faster than the acylthiosemicarbazide resin does and sorbs mercury(II) from high concentrations of acids and neutral salt solutions. This resin has been applied to the concentration of silver and mercury(II) from sea-water samples by column operation.     

A chelating polymer resin: synthesis,characterization, adsorption and desorption performance for removal of Hg(II) from aqueous solution

A chloromethylated polystyrene-N-methyl thiourea chelating resin (DMTUR) was successfully prepared by the reaction of chloromethylated polystyrene beads (PS-Cl) with N-methyl thiourea (DMTU). The DMTUR exhibited a high selective adsorption toward Hg(II) in the mixture of different metal ions containing Cu(II), Hg(II), Cd(II), Pb(II), Cr(III) and Ni(II), and the adsorption capacity of Hg(II) approached a maximum with a value of 347 mg/g at pH = 4.0. Moreover, the batch kinetic study showed that the adsorption behavior of Hg(II) presented as a pseudo-second-order manner. And the adsorption isotherms fitted well with Langmuir model, and the maximum uptake of Hg(II) could reach to be 476 mg g^?1 at 35 °C. The thermodynamics study ensured the adsorption process essentially as favorable and endothermic. Finally, an eluent of 4 M HNO₃ solution could completely remove the adsorbed Hg(II) and the adsorption capacity allowed a high level at least five cycles. As aforementioned appealing properties, the DMTUR with simple technology, high adsorption capacity, significant selectivity and good regenerability may have a potential application in industrial scale as a treatment of enriched Hg(II) in wastewater.     

High adsorptive γ-AlOOH(boehmite)@SiO2/Fe3O4 porous magnetic microspheres for detection of toxic metal ions in drinking water

γ-AlOOH(boehmite)@SiO(2)/Fe(3)O(4) porous magnetic microspheres with high adsorption capacity toward heavy metal ions were found to be useful for the simultaneous and selective electrochemical detection of five metal ions, such as ultratrace zinc(II), cadmium(II), lead(II), copper(II), and mercury(II), in drinking water.     

含亚硫酸乙烯酯和碳酸乙烯酯功能基树脂的合成及其对贵金属离子的选择吸附性

制备了高功能基转化率的孪二羟基树脂,由此合成了含亚硫酸乙烯酯功能基(2.30毫摩尔/克树脂)和碳酸乙烯酯功能基(2.57毫摩尔/克树脂)的树脂4和5。在酸度范围内树脂4选择吸附Pt(Ⅱ),两者对Au(Ⅲ) 有高选择吸附性,而很少吸附共存的Pd(Ⅱ)、Pt(Ⅳ)及铁、钴、镍、铜、锰、锌、铅、镉等二价金属离子。树脂4对金的吸附容量为126(毫克 Au(Ⅲ)/克树脂),分配系数Kd为824(毫升/克),一次洗脱率达85％。树脂5的吸附容量为46.0(毫克 Au(Ⅲ)/克树脂),Kd为84.1(毫升/克)。两种树脂吸附Au(Ⅲ)的速率T_(1/2)分别为1、0.8小时.