氧化石墨烯-Ag纳米粒子/聚酰亚胺混合基质膜及其渗透汽化性能

以聚乙二醇(PEG-400)为还原剂,Ag NO3为前驱体,采用浸渍-还原法合成氧化石墨烯-Ag纳米粒子(GO-Ag NP)复合物,再通过共混法制备氧化石墨烯-Ag纳米粒子/聚酰亚胺(GO-Ag NP/PI)混合基质膜,用于苯/环己烷混合物的渗透汽化分离。使用透射电子显微镜、红外吸收光谱、拉曼光谱、热失重以及X射线光电子能谱等分析表征GO-Ag NP复合物、GO-Ag NP/PI混合基质膜的形貌和结构;探讨了Ag掺杂量对GO-Ag NP复合物的结构以及GO-Ag NP/PI混合基质膜的结构和渗透汽化性能的影响。结果发现,Ag+被还原形成Ag NP的同时,GO失去了部分含氧官能团;Ag掺杂破坏了GO的结构,使其无序度增加,但改善了GO-Ag NP复合物在混合基质膜中的分散性,提升了GO-Ag NP/PI混合基质膜的苯/环己烷渗透汽化性能。然而过量的Ag掺杂将使GO片层上产生Ag粒子团聚,从而降低混合基质膜的渗透汽化性能。当Ag掺杂量为15%时,GO-Ag NP/PI混合基质膜渗透汽化性能最佳,渗透通量为1 404 g·m-2·h-1,分离因子可达36.2。     

掺杂Cu的TiO2纳米粒子的制备、表征及其光催化活性

采用Sol-gel法制备了纯的和掺杂不同量Cu的TiO2纳米粒子,并用TG-DTA,XRD,XPS,UV-Vis和荧光光谱对样品进行了表征,考察焙烧温度和Cu含量对TiO2纳米粒子的性质及光催化活性的影响,初步探讨了Cu的掺杂对TiO2相变的作用机制及样品荧光光谱与光催化活性的关系.结果表明,Cu2+的掺杂对TiO2的相变有很大的促进作用,并使其光谱响应范围向可见光区拓展.Cu的掺杂未引起新的荧光现象,但适量Cu的掺杂能够降低TiO2纳米粒子的荧光强度.此外,在光催化降解苯酚的实验中,于500℃处理的掺杂Cu的TiO2纳米粒子的光催化活性较高,与表征结果一致.而掺杂不同量Cu的TiO2的光催化活性顺序与样品荧光光谱强度的顺序相反,即荧光光谱强度越低,其光催化活性越高.     

Ag∶InP/ZnSe纳米晶的合成与生物成像

采用高温热注入法,以P[N(CH_3)_2]_3为磷源合成了具有近红外荧光的Ag∶InP/ZnSe纳米晶.采用紫外-可见-近红外吸收光谱(UV-Vis-NIR)、荧光光谱、透射电子显微镜(TEM)、X射线衍射(XRD)等对产物的结构和光学性质进行了表征,并分析了Ag掺杂浓度和温度对InP纳米晶荧光性能的影响.通过调节Ag掺杂浓度和反应温度,发现当Ag掺杂量为6%,反应温度为200℃时,Ag∶InP纳米晶的发光效率最高.将制备的Ag∶InP的表面包覆ZnSe,粒子的荧光效率从原来的20%提高到45%.将具有近红外荧光的Ag∶InP/ZnSe纳米晶应用于细胞成像,结果表明制备的荧光纳米晶在细胞成像中清晰可见且毒性较低.     

氧化石墨烯-Ag纳米粒子/聚酰亚胺混合基质膜及其渗透汽化性能

以聚乙二醇（PEG-400）为还原剂,AgNO₃为前驱体,采用浸渍-还原法合成氧化石墨烯-Ag纳米粒子（GO-AgNP）复合物,再通过共混法制备氧化石墨烯-Ag纳米粒子/聚酰亚胺（GO-AgNP/PI）混合基质膜,用于苯/环己烷混合物的渗透汽化分离。使用透射电子显微镜、红外吸收光谱、拉曼光谱、热失重以及X射线光电子能谱等分析表征GO-AgNP复合物、GO-AgNP/PI混合基质膜的形貌和结构;探讨了Ag掺杂量对GO-AgNP复合物的结构以及GO-AgNP/PI混合基质膜的结构和渗透汽化性能的影响。结果发现,Ag⁺被还原形成AgNP的同时,GO失去了部分含氧官能团;Ag掺杂破坏了GO的结构,使其无序度增加,但改善了GO-AgNP复合物在混合基质膜中的分散性,提升了GO-AgNP/PI混合基质膜的苯/环己烷渗透汽化性能。然而过量的Ag掺杂将使GO片层上产生Ag粒子团聚,从而降低混合基质膜的渗透汽化性能。当Ag掺杂量为15%时,GO-AgNP/PI混合基质膜渗透汽化性能最佳,渗透通量为1 404 g·m^-2·h^-1,分离因子可达36.2。     

不同质子酸掺杂对银/聚苯胺纳米复合材料结构和导电性的影响

利用紫外光作为辅助条件,在反胶束体系中采用一步双原位法合成了硝酸(HNO3)、对甲基苯磺酸(TSA)和5-磺基水杨酸(SSA)掺杂的银/聚苯胺(Ag/PANI)纳米复合材料.通过对复合材料进行红外光谱(FTIR)、紫外光谱(UV-Vis)、扫描电镜(SEM)、X射线衍射(XRD)和导电性能的测试,研究了不同质子酸对Ag/PANI纳米复合材料结构、形貌和导电性能的影响.测试结果表明,3种酸掺杂制备的Ag/PANI纳米复合材料均为聚苯胺包覆银粒子的核-壳结构.不同的质子酸掺杂会对Ag/PANI纳米复合材料的电性能有重要影响.在3种酸掺杂的复合材料中,TSA掺杂的复合材料的电导率最佳,为215.14 S·cm-1.     

La和Cu掺杂对纳米TiO2光生电荷性质的影响及其与光催化活性的关系

采用溶胶-水热法制备了未掺杂的和分别掺杂1%(摩尔浓度)La的、Cu的及La和Cu共掺杂的纳米TiO₂, 并主要利用表面光电压谱(SPS)和光致发光光谱(PL)等技术考察了掺杂对纳米TiO₂表面光生电荷性质的影响, 也探讨了其性质与光催化活性的关系. 结果表明: La的掺杂能够抑制TiO₂相变, 同时其不仅促进TiO₂光生载流子分离, 而且丰富了束缚表面态. 但是Cu的掺杂却与La的作用相反. 这些解释了在光催化氧化降解罗丹明B过程中, La掺杂有利于TiO₂光催化活性的提高, 而Cu掺杂对光催化反应是不利的. 此外, La和Cu共掺杂并没有体现出协同效应.     

Cu掺杂TiO_2薄膜的摩擦学性能

采用溶胶-凝胶法在普通玻璃基底上制备了纯TiO2和Cu掺杂的TiO2(Cu-TiO2)纳米结构薄膜,利用X射线光电子能谱(XPS)、原子力显微镜(AFM)、粉末X射线衍射(XRD)及UMT-3摩擦磨损试验机考察了Cu掺杂量对薄膜组成、结构、表面形貌及摩擦学性能的影响.结果表明,相比于纯TiO2薄膜,Cu掺杂TiO2纳米薄膜平整、均匀,具有较好的耐磨减摩性能.Cu掺杂量的多少直接影响Cu-TiO2薄膜的减摩抗磨性能,当Cu掺杂量为5%(摩尔分数)时,Cu-TiO2膜具有最佳的耐磨寿命和最低的摩擦系数.     

Cu、Ag、Au掺杂BiVO_4可见光催化剂的制备及性能研究

水热法制备了币族金属(Cu、Ag和Au)掺杂的BiVO4可见光催化剂,借助X-射线衍射(XRD)、X-射线光电子能谱(XPS)、紫外-可见漫反射光谱(DRS)和扫描电子显微镜(SEM)对其进行表征.XRD分析显示所有催化剂都呈现单斜结构.XPS结果显示掺杂元素均以其稳定氧化态形式存在与催化剂表面.DRS谱中掺杂样品的吸收边界比纯BiVO4都有不同程度的红移.以甲基橙的可见光催化降解反应为探针,研究了催化剂的可见光催化性能.结果表明,经币族金属掺杂改性的催化剂催化能力比纯BiVO4有所提高.对其掺杂增强催化能力的可能原因进行了分析讨论.     

低熔点YBaCuO超导带材的制备

通过掺杂Ag和PbO的方法降低YBaCuO的区熔温度到945℃以下,从而能够在金属Ag基底上进行区域熔炼,获得有织构的超导带材.掺杂的O bO与YBaCuO反应,生成了BaPbO3.5wt%Ag 10wt%PbO的YBaCuO掺杂区熔样品所得结果较好,厚膜的Jc最大值为442A/cm2.     

溴化银乳剂中Ag2掺杂的位置效应研究

使用微机控制的双注仪,在晶体生长过程的不同时刻,加入一定浓度的二甲基胺硼烷(DMAB),制得了一系列Ag2处于不同掺杂位置的立方体溴化银微晶乳剂.对这些乳剂感光性能的研究表明:1)Ag2掺杂乳剂与未掺杂乳剂相比,感光度有显著提高;2)Ag2掺杂乳剂可同时与常规的硫加金化学增感和光谱增感进行协同增感;3)Ag2掺杂接近微晶表面时乳剂感光度的增幅最大;4)在本实验条件下,掺杂乳剂的灰雾均保持在较低的水平.     

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.