硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性,红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升,改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型,吸附等温线服从Langmuir等温线规律,由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载（英文）

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性,红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升,改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型,吸附等温线服从Langmuir等温线规律,由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

有机硅聚合物负载硫、硫、氮三齿配体铂配合物的合成与催化性能

 N,N-双(β-甲硫乙基)γ-(三乙氧硅基)丙胺用气相法二氧化硅固载,再与氯亚铂酸钾作用,合成了三齿型铂配合物-聚γ-[N,N-双(β-甲硫乙基)胺基]丙基倍半硅氧烷铂配合物.研究了该配合物对烯烃与三乙氧基硅烷的硅氢加成反应的催化特性.     

原子层沉积法制备巯丙基硅胶及其对溶液中钯(Ⅱ)离子的吸附行为

采用原子层沉积技术, 在3~5 kPa真空和125~150 ℃ 的反应条件下, 使γ-巯丙基三甲氧基硅烷(MPTMS)、γ-巯丙基三乙氧基硅烷(MPTES)和γ-巯丙基二甲氧基甲基硅烷(MPDMMS)3种巯丙基硅烷试剂气化, 并在三乙胺的催化作用下, 分别将其键合于多孔硅胶表面, 制得贵金属钯(Ⅱ)的高效吸附剂. 分别采用FTIR、¹³C和²⁹Si固体核磁、元素分析、热重分析和氮气吸附-脱附等技术研究了巯基硅胶的键合模式和功能基团键合量. 用分光光度法研究了在pH=3.0条件下水溶液中Pd(Ⅱ)离子在巯基硅胶上的吸附行为. 结果表明, 在MPTMS, MPTES和MPDMMS所修饰的硅胶中, 硅烷试剂的功能基团均以双齿键合结构为主, 表面键合量分别达到2.76, 2.53和2.70 μmol/m². 对Pd(Ⅱ)离子的吸附遵从Langmuir等温吸附方程, 饱和吸附量分别达到5.45, 4.21和4.81 μmol/m², Pd/S的摩尔比分别为1.44, 1.35和1.39. 原子层沉积法制备的巯丙基硅胶基质钯吸附剂的巯基键合密度和对钯(Ⅱ)离子的吸附容量均比传统的有机溶剂介质法高.     

聚γ-(β-氰乙硫基)两基硅氧烷铑配合物的合成与催化硅氢化性能

γ-巯丙基三乙氧基硅烷与丙烯腈加成，得到γ－（β-氰乙硫基）丙基三乙氧基硅烷，后者依次与气相法二氧化硅、三氯化铑作用，合成了聚γ-（β-氰乙硫基）丙基硅氧烷铑配合物，研究了其催化烯烃与三乙氧基硅烷硅氢加成反应的特性。     

PEI/SiO2复合型吸附材料对脲酸吸附特性的研究

通过γ-氯丙基三甲氧基硅烷的偶联, 将聚乙烯亚胺(PEI)偶合接枝在硅胶微粒表面, 制得了对脲酸有强吸附性能的复合型医用吸附材料PEI/SiO₂. 静态吸附实验结果表明, 凭借强烈的氢键相互作用, 硅胶表面的聚胺大分子PEI对脲酸的互变异构体三羟基嘌呤具有很强的吸附能力, 等温吸附满足Freundlich吸附方程, 饱和吸附量可达84.9 mg/g; 介质的pH值对吸附作用有很大的影响, 在中性溶液中(pH＝6～7), 复合吸附材料PEI/SiO₂对脲酸具有强吸附能力, 而在酸性与碱性溶液中吸附能力都较弱; 温度对吸附性能也有影响, 升高温度吸附量增大.     

硅胶负载氨基吡啶的合成及对Ag~+的吸附性能研究

本文以硅胶为载体,通过氯丙基三乙氧基硅烷(CPTS)将2-氨基吡啶负载到硅胶表面,得到硅胶负载氨基吡啶(SG-AP)吸附材料,通过红外光谱、元素分析对其结构进行了表征。研究了SG-AP对Ag+的吸附性能,考察了溶液pH值、接触时间、温度及金属离子初始浓度等因素对吸附性能的影响。结果表明,对Ag+的最佳吸附pH值为6。吸附动力学表明,对Ag+的吸附符合准二级动力学模型,为液膜扩散控制过程。等温吸附表明吸附过程可用Langmuir模型描述,为单分子层吸附。SG-AP对Ag+吸附的热力学参数表明,吸附过程是自发、吸热的过程。     

MCM-41负载硫醚钯配合物的合成及其催化芳基卤化物的羰基化性能

γ-(β-氰乙硫基)丙基三乙氧基硅烷依次用纳米介孔分子筛(MCM-41)固载、与氯化钯反应, 合成了MCM-41负载硫醚钯配合物. 该新型负载钯配合物是芳基卤化物的羰基化反应的有效催化剂, 为各种取代的N-苯基苯甲酰胺、苯甲酸丁酯的合成提供了方便实用的新途径.     

二硫代氨基甲酸键合硅胶对Cu2+吸附性能研究

本文以柱层层析硅胶为原料,用γ-氨丙基三甲氧基硅烷对其表面进行修饰,制得氨基键合硅胶微粒,进而在碱性条件下与二硫化碳反应,合成二硫代氨基甲酸键合硅胶(DTC-SiO2)。以Cu2+为吸附对象,考察DTC-SiO2对金属离子的吸附性能,探讨了溶液pH值、吸附剂用量、初始Cu2+浓度、吸附时间等影响材料吸附效果的因素,并研究了吸附剂对Cu2+的吸附等温线和动力学吸附特性。结果表明,在温度298K下,DTC-SiO2对Cu2+的吸附符合Langmuir等温式,准二级吸附动力学方程能够很好地描述Cu2+在DTC-SiO2上的吸附动力学行为。     

聚γ—（β—氰乙硫基）丙基硅氧烷铂配合物的合成与催化性能

γ－巯丙基三乙氧基硅烷与丙烯腈反应，得到γ－（β－氰乙硫基）丙基三乙氧基硅烷．后者经气相法二氧化硅固载，再与氯亚铂酸钾反应，合成了聚γ－（β－氰乙硫基）丙基硅氧烷铂配合物．研究了该铂配合物对不饱和烃与三乙氧基硅烷的硅氢加成反应的催化特性．     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.