硫化镉/二氧化硅复合材料的合成

结合亲核取代反应与硅氧烷水解和硅羟基缩合反应,制备了羧酸镉/二氧化硅复合材料。通过硫化反应,实现了立方结构和六方结构硫化镉纳米粒子在复合材料中的原位制备。复合材料中硫化镉纳米粒子的发射峰位在617 nm,属于红色荧光(三元色之一)。硫化镉/二氧化硅复合材料在光学器件方面具有潜在的应用前景。     

水溶性CdSe/CdS核壳纳米粒子制备的影响因素及其对CdSe/CdS光谱特性的影响

以半胱氨酸镉配合物为前体, 在水溶液中合成CdSe纳米粒子, 以CdS对其表面进行修饰, 得到具有核壳结构的CdSe/CdS 纳米粒子. 采用XRD, TEM表征其结构及形貌; 以荧光光谱研究了时间、pH值、壳量、壳前体加入方式、稳定剂用量等因素对CdSe/CdS光谱特性的影响.     

溶剂热法制备MWNTs/CdS复合材料

分别以醋酸镉和硫脲为原料,二乙三胺和去离子水为混合溶剂,采用溶剂热技术制备了MwNTs/CdS复合材料,并用TEM、XRD、FT-IR及UV-vis等技术对材料的结构、形貌和性质进行表征.研究结果表明:硫化镉纳米粒子附着在多壁碳纳米管表面,且无团聚现象.     

CdS/TiO2复合纳米粒子的光学性质

在Brij35/正己醇/环己烷/水构成的反相微乳体系中，分别合成了CdS、TiO2纳米粒子和TiO2包覆CdS（CdS/TiO2）的复合纳米粒子.测定了它们的紫外-可见吸收和荧光光谱.结果表明， CdS/TiO2复合纳米粒子在可见光区的吸收比相应的两组分的吸收之和更强.纳米CdS和纳米TiO2均有较强的荧光.而且在相同浓度时纳米TiO2的荧光比纳米CdS的荧光更强.但在CdS/TiO2复合纳米粒子中，TiO2的荧光被淬灭，而CdS的荧光稍有降低.     

溶胶凝胶法制备CdS/SiO2量子点玻璃的研究

通过溶胶凝胶转变过程制备了硫化镉／二氧化硅量子点复合玻璃材料（硫化镉在复合材料中的最大掺杂质量比可达到30％）；并针对两种催化剂对复合体系的不同影响对这一类体系的物理化学性质进行了较为系统的研究．复合体系的溶胶凝胶转变点可通过对复合溶胶粘度随时间变化的观测而确定．TEM法与低频Raman散射法的测定表明实验制备的样品中CdS颗粒基本为nm级的球形粒子。其CdS颗粒粒径随CdS含量增加而增大。随CdS／SiO2量子点玻璃材料中CdS颗粒粒径的减小，其吸收光谱中的吸收边界与常规尺寸颗粒的吸收光谱边界相比有明显的蓝移，体现出显著的量子效应．适宜的热处理过程对复合材料中CdS颗粒粒径的减小和量子效应的增强起着有利的作用．     

CoFe2O4/CdS纳米复合物的制备、表征及其声催化降解有机染料污染物

在低温(200℃)下采用一步水热分解CoFe2O4纳米粒子表面的镉二硫代氨基甲酸酯配合物制备了磁性CoFe2O4/CdS纳米复合物,运用X射线衍射、红外光谱、扫描电镜、X射线能量散射谱、紫外-可见光谱、透射电镜(TEM)、N2吸附-脱附、X射线光电子能谱和振动样品磁强计对所制样品进行了表征.TEM结果表明,CoFe2O4/CdS纳米复合物由几乎均一的约20nm球形纳米粒子组成.光吸收谱显示该样品的带隙为2.24 eV,很适合用于声/光催化降解有机污染物.在紫外光照射下评价了CoFe2O4/CdS纳米复合物的声催化H2O2辅助降解甲基蓝、罗丹明B和甲基橙反应活性.结果表明,该纳米复合物对这3种染料均表现出很好的声催化活性(5-9 min内完全降解).另外,比较实验结果表明,CoFe2O4/CdS纳米复合物是一个比纯CdS更高效的声催化剂.因此,纳米复合是一种非常好的提高CdS声催化活性的手段.该CoFe2O4/CdS纳米复合物表现出的磁性使其很容易从反应混合物中分离出来而重复使用.     

纳米CdS/聚乙烯咔唑(PVK)复合材料制备与表征

采用反相微乳法在庚烷/琥珀酸二异辛酯磺酸钠(AOT)/水体系中成功制备出纳米CdS/聚乙烯咔唑(PVK)复合材料。通过紫外-可见光谱(UV-Vis)、X射线衍射(XRD)、透射电子显微镜(TEM)、荧光光谱(PL)对复合材料进行了结构表征和形貌观察。结果表明,UV-Vis光谱吸收峰在325 nm和360 nm,表现出纳米粒子明显的量子尺寸效应;TEM照片显示纳米CdS粒径分布较窄,均匀分散在PVK中。XRD分析表明,CdS纳米颗粒已经形成。PL结果显示:产物的荧光发射光谱峰波长在375 nm和520 nm。     

核壳结构CdS/CuS纳米复合材料的制备及光催化性能

以乙酸镉、 2-巯基苯并噻唑、 硫化钠和氯化铜为原料, 依次利用液相热分解与离子吸附法, 改变CdS晶化时间及含量, 制备了4种CdS/CuS纳米复合材料. 研究结果表明: CdS/CuS纳米复合材料呈类球形核壳结构, 改变CdS晶化时间可以控制CdS/CuS纳米复合材料粒径大小; CdS的晶化时间为10 min, CdS与CuS摩尔比为4∶1的纳米复合材料光催化活性最佳, 25 min内对RhB和MB的降解效率均达到99%.     

用HRS技术研究CdS/Cd纳米粒子的二阶光学非线性

用新发展的超瑞利散射（HRS）技术（一种非相干的方法）研究了表面富镉的CdS纳米粒子的二阶非线性光学性质。结果表明每个纳米粒子的二次非线性极化率β值在10^-26esu量级,这是目前报导的具有最大β值的溶液物种之列。探讨了CdS纳米粒子产生二阶非线性的机制。认为纳米粒子大的比表面及表面缺陷结构对CdS纳米粒子的二阶光学非线性有很大影响。另外,双光子吸收诱导的共振增强作用亦可能贡献CdS纳米粒子的HRS信号,这种双光子共振吸收被其双光子荧光谱所证实。     

聚丙烯酸丁酯接枝的纳米SiO2对聚甲醛的改性

采用原子转移自由基聚合法(ATRP)在纳米SiO2粒子表面接枝聚丙烯酸丁酯(PBA)制备了纳米复合粒子SiO2-g-PBA,并以此对聚甲醛(POM)进行改性. 通过红外光谱、热失重分析、透射电子显微镜及扫描电子显微镜等分析技术进行了表征. 结果,SiO2-g-PBA在POM中分散均匀,使POM/SiO2-g-PBA复合材料的缺口冲击强度明显高于POM及POM/ SiO2复合材料. 当SiO2-g-PBA纳米复合粒子的质量分数为2%时,POM/SiO2-g-PBA复合材料的冲击强度达71.2 kJ/m2,较纯POM提高了7倍多,同时拉伸强度也有一定的提高,达到68.1 MPa.     

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.