结晶态SO_4~(2-)/ZrO_2-SiO_2超强酸催化剂的制备及性能测定

采用一种沉淀／混合沉淀的方法, 制得了具有类似于分子筛结构的结晶型二元氧化物 Ｚｒ Ｏ２ Ｓｉ Ｏ２． 用１ ｍ ｏｌ／ｄｍ ３ 的硫酸处理该氧化物并在５５０ ℃焙烧, 制得了具有类似于分子筛结构的结晶态超强酸催化剂 Ｓ Ｏ４２－ ／ Ｚｒ Ｏ２  Ｓｉ Ｏ２． 采用 Ｘ Ｒ Ｄ、 Ｉ Ｒ、 Ｔ Ｇ、 Ｓ Ｅ Ｍ 等对催化剂的结构进行了表征, 发现该催化剂的 Ｘ Ｒ Ｄ谱图与 Ｚ Ｓ Ｍ５ 分子筛的 Ｘ Ｒ Ｄ谱图非常类似． 用指示剂法证实了催化剂的超强酸性． 还考察了催化剂对于乙酸／丁醇酯化反应的催化活性．     

对甲烷氧化偶联W—Mn／SiO2催化剂Na2WO4的流失及其影响的考察

用ＸＲＤ，ＦＴ－ＩＲ，ＥＳＲ，Ｈ２－ＴＰＲ和ＴＯＰ等方法，对Ｎａ２ＷＯ４Ｍｎ２Ｏ３／ＳｉＯ２催化剂和其经水煮处理的一系列样品进行一表征。实验发现该催化剂中的结晶态ＮａＷＯ４易于流失，单层分布的Ｎａ２ＷＯ４在苛刻的处理条件下也有可能流失。     

稀土溴化物与甘氨酸配合物标准摩尔生成焓的测定

采用量热法在２９８１５±０１０Ｋ测量了ＲＥＢｒ３·３Ｇｌｙ·３Ｈ２Ｏ（ＲＥ＝Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｙ；Ｇｌｙ为甘氨酸）和甘氨酸在水中的积分溶解热，及ＲＥＢｒ３·ｎＨ２Ｏ（ＲＥ＝Ｌａ、Ｃｅ、Ｐｒ时，ｎ＝７；ＲＥ＝Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｙ时，ｎ＝６）在甘氨酸水溶液中的积分溶解热。用本研究设计的热化学循环求得上述１０种ＲＥＢｒ３·３Ｇｌｙ·３Ｈ２Ｏ配合物的标准摩尔生成焓，并计算出它们的晶格能。     

水面石油污染物的光催化降解

制备了漂浮负载型ＴｉＯ２光催化剂,并用ＸＲＤ,ＢＥＴ,ＴＥＭ和ＳＥＭ等方法进行了表征。研究了这类催化剂对水面石油污染物的光催化降解,实验结果表明,掺杂Ｆｅ＾３＋的ＴｉＯ２光催化剂具有高的光催化活性,经高压汞灯照射８ｈ,水面原油降解７５％。     

纳米尖晶石型Co2MnO4的形成过程及其F-T反应性能

用溶胶凝胶法制备了尖晶石型Ｃｏ２ＭｎＯ４超细粒子，用ＤＴＡＴＧ，ＸＲＤ，ＴＥＭ，ＦＴＩＲ等手段研究了Ｃｏ２ＭｎＯ４超细粒子的形成过程，进而用反应评价结合ＸＲＤ，ＸＰＳ，ＢＥＴ比表面积测试研究了Ｃｏ２ＭｎＯ４催化剂的比表面积和表面结构与其ＦＴ反应性能间的关系．结果表明，Ｃｏ２ＭｎＯ４超细粒子可以在较低温度（２５０～３５０℃）下形成，并具有粒度小，分布均匀等特点．用该法制备的超细粒子Ｃｏ２ＭｎＯ４，其催化活性明显优于相同组成的大颗粒催化剂．     

LaCaMnO3催化剂活性相的结构和形成机理的研究

利用ＴＧ，ＤＴＡ，ＸＲＤ和ＸＰＳ方法研究了Ｌａ０．２Ｃａ０．８ＭｎＯ３催化剂的结构和形成机理。样品用Ｌａ，Ｃａ，Ｍｎ混合硝酸盐制备。随着焙烧温度的升高发生的一系列的固相反应，发现氨氧化催化剂催化活性与生成的ＣａＭｎＯ３含量成正比。在９００℃制备的含有ＣａＭｎＯ３，Ｌａ０．５７５Ｃａ０．４２５ＭｎＯ３，Ｍｎ２Ｏ３和Ｌａ２Ｏ３的混合物是氨氧化最佳催化剂，活性相是ＣａＭｎＯ３，并具有大量的氧空穴。     

结晶态SO^2—4／ZrO—SiO2超强酸催化剂的制备及性能测定

采用一种沉淀／混合沉淀的方法,制得了具有类似于分子筛结构的结晶二元二氧化物ＺｒＯ２－ＳｉＯ２。用１ｍｏｌ／ｄｍ＾３的硫酸处理经物并在５５０℃焙烧,制得了具有类似于分子筛结构的结晶态超强酸催化剂ＳＯ＾２－４／ＺｒＯ２－ＳｉＯ２。采用ＸＲＤ,ＩＲ,ＴＧ,ＳＥＭ等对催化剂的结构进行了表征,发现该催化剂的ＸＲＤ谱图与ＺＳＭ－５分子筛的ＸＲＤ谱图非常类似,用指示剂法证实了催化剂的超强酸性。还考察了催化剂对于     

Ce2O—TiO2／SiO2的制备及除氟性能研究

以ＳｉＯ２为基质，ＣｅＯ２ＴｉＯ２为包覆物质，采用溶胶凝胶法制备ＣｅＯ２ＴｉＯ２／ＳｉＯ２表面复合物，并对所制复合物进行除氟测试。用扫描电镜（ＳＥＭ）观察表面形貌，讨论实验环境、试剂用量等因素对ＣｅＯ２ＴｉＯ２／ＳｉＯ２制备及除氟性能的影响，结果表明：ｎＴｉ（ＯＣ４Ｈ９）４／ｎＣｅＣｌ３·７Ｈ２Ｏ＝１、ｎＣＨ３ＣＯＯＨ／ｎＴｉ（ＯＣ４Ｈ９）４＝４５、ｎＣ３Ｈ８Ｏ３／ｎＴｉ（Ｏ４Ｈ９）４＝０３、ＲＨ＝９５％，热处理温度１１０℃时，所制ＣｅＯ２ＴｉＯ２／ＳｉＯ２对Ｆ－的吸附容量（ｑ）为２１４ｍｇ／ｇ，去除率（Ｅ）为８５６％。     

在（TPA）2O—Na2O—SiO2—H2O体系中MFI型硅沸石的结晶行为（Ⅱ）

以白炭黑和硅溶胶为硅源，在（ＴＰＡ）２Ｏ－Ｎａ２Ｏ－ＳｉＯ２－Ｈ２Ｏ体系６０℃下合成了高结晶度纯相硅沸石，由ＳＥＭ没得其晶粒尺寸为０．２μｍ和０．４５μｍ用ＸＲＤ线宽法是的为０．０２μｍ，一１８０℃时合成的硅沸石样品相比，低温合成的细晶粒硅沸石已上备内米级的若干特性，其正己烷吸附量反常增大；ＸＲＤ、ＦＴＩＲ、＾２９ＳｉＭＡＳ ＮＭＲ和ＴＧ／ＤＴＧ／ＤＴＡ的研究证明，其结构破坏温度和单斜／正交对称性     

TiO2负载非晶态合金NiB催化剂的制备、表征及HDS动力学研究

用等体积浸渍－还原法制备了负载型的ＮｉＢ／ＴｉＯ２（Ｂ／Ｎｉ＝５：１摩尔比）非晶态合金,并在相同条件下制备了ＮｉＢ／Ａｌ２Ｏ３（Ｂ／Ｎｉ＝５：１摩尔比）与之对照。用ＸＲＤ,ＳＥＭ和ＴＥＭ等表征方法比较了样品的非晶性质,在脉冲反色谱装置上以噻吩的ＨＤＳ反应为探针测定了ＮｉＢ／ＴｉＯ２、ＮｉＢ／Ａｌ２Ｏ３的反应活性,进行了动力学研究。结果证明,ＮｉＢ／ＴｉＯ２的低温活性远高于ＮｉＢ／Ａｌ２Ｏ３,其原因     

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.