纳米晶材料SrMgxTi1-xO3的合成与表征

采用硬脂酸法合成纳米晶ＳｒＭｇｘＴｉ１－ｘＯ３（ｘ＝０．１－０．５）材料,用ＤＴＡ,ＴＧ,ＸＲＤ,ＩＲ,ＸＰＳ和ＴＥＭ进行表征,结果表明,粉末粒径ｄ随ＳｒＭｇｘＴｉ１－ｘＯ３中镁含量、烧结温度和烧结时间的改变而变化;烧结所产生的粉末粒度分布均匀,大小适中;Ｍｇ＾２＋部分替ＳｒＴｉＯ３的Ｔｉ＾４＋后,Ｏ的１ｓ光谱随着Ｍｇ＾２＋含量的不同而发生变化。     

阴离子X~-(F~-、Cl~-、Br~-)对中孔分子筛MCM-41合成与性质的影响

在凝胶体系ＮａＸ（Ｆ、Ｃｌ、Ｂｒ）Ｎａ２ＯＡｌ２Ｏ３ＳｉＯ２ＣＴＡＢ（十六烷基三甲基溴化铵）Ｈ２Ｏ中，研究了水热合成中孔ＭＣＭ４１的合成条件。实验证明，在３９８Ｋ下晶化８～１６ｄ，ＮａＸ／ＳｉＯ２介于０．０１～０．０５时，均可合成出ＭＣＭ４１分子筛；ＮａＦ的加入，可以加快ＭＣＭ４１分子筛的晶化速度；ＮａＢｒ的加入，对形成ＭＣＭ４１分子筛有阻碍作用。采用ＸＲＤ、ＳＥＭ、ＴＧＤＴＡ和Ｎ２吸附对合成样品加以表征，证明合成样品具有介孔分子筛特性。     

钙钛矿型（La0.8M0.2）MnO2和（La0.2Sr0.2）（Mn1—xFex）O3的XRD和IR光谱 …

合成了（Ｌａ０．８Ｍ０．２）ＭｎＯ３和（Ｌａ０．８ｓＲ０．２）（ｍＮ１－ｘＦｅｘ）（Ｏ３（Ｘ＝０．１，０．２，０．３，０．４，０．５）两类氧化物，经ＸＲＤ确认为钙钛矿型氧化物，应用ＦＴ－ＩＲ对其进行研究，对主要的红外特征振动υ（Ｍｎ－Ｏ）和δ（Ｏ－Ｍｎ－Ｏ）进行了分析表征。     

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     

1,12－烷基二胺－Na2O－SiO2－Al2O3－H2O系统中ZSM-11沸石的合成及其鉴定

以硅溶胶为硅源，在０．３０１，１２－烷基二胺－ＸＮａ２Ｏ－ＹＡｌ２Ｏ３－ＳｉＯ２－ＺＨ２Ｏ体系中，研究ＺＳＭ－１１沸石于１６０～２００℃之间的水热结晶。用ＸＲＤ鉴定产物，合成纯组ＺＳＭ－１１的反庆物配比是Ｘ＝０．０５；Ｙ＝０－０．０１１；Ｚ＝＝４０。其反应温度为１６０～１８０℃。加入ＺＳＭ－１１晶种或添加ＮａＦ可加快结晶速率，导致ＺＸＳ－１１柱状单晶的生成。该单晶的最大尺寸可达２０×２０×６０μｍ     

在温和条件下巨磁阻材料La0.5Ba0.5MnO3的水热合成与表征

报道了在温和条件下巨磁阻材料Ｌａ０．５Ｂａ０．５ＭｎＯ３的水热合成。系统地研究了原料配比、碱度、时间和温度对产物合成的影响，在最佳合成条件下得到了结晶度较高的纯相，并通过ＸＲＤ，ＤＴＡ－ＴＧ、化学分析及碘量法对产物进行了表征。     

多嵌段共聚物磺酸盐离子导体的合成、结构及导电特性

合成了系列环氧乙烷－（对苯二甲酸乙二酯－ＣＯ－间苯二甲酸乙二酯磺酸钠）多嵌段共聚物（ＥＯＴＭ－ＳＯ_３Ｎａ），用ＮＭＲ、ＷＡＸＤ和ＤＳＣ等方法进行了结构表征。ＥＯＴＭ－ＳＯ_３Ｎａ是一种新型的单阳离子导体，室温电导率可达２．３×１０~（－６）Ｓ·ｃｍ（－１）     

杂原子B—ZSM—35沸石的干法合成,表征及CO＋H2反应性能的研究

首次利用吸附态模板剂在Ｎａ２Ｏ－ＳｉＯ２－Ｂ２Ｏ３－ＤＥＡ干粉体系中合成了杂原子Ｂ－ＳＺＭ－３５沸石，ＸＲＤ，ＳＥＭ，ＩＲ，及ＣＯ加氢反应研究了其物理化学特性。结果表明，Ｂ原子同晶取代Ａｌ原子进入ＺＳＭ－３５沸石骨加。     

1，12－烷基二胺－Na_2O－SiO_2－Al_2O_3－H_2O系统中ZSM

以硅溶胶为硅源．在０．３０１，１２－烷基二胺－ＸＮａ２Ｏ－ＹＡｌ２Ｏ３－ＳｉＯ２－ＺＨ２Ｏ体系中，研究ＺＳＭ—１１沸石于１６０～２００℃区间的水热结晶．用ＸＲＤ鉴定产物．合成纯相ＺＳＭ－１１的反应物配比是Ｘ＝０．０５；Ｙ＝０～０．０１１；Ｚ＝４０．其反应温度为１６０～１８０℃．加入ＺＳＭ－１１晶种或添加ＮａＦ可加快结晶速度，导致ＺＸＳ－１１（ｓｉｌｉｃａｌｉｔｅ－Ⅱ）柱状单晶的生成．该单晶的最大尺寸可达２０×２０×６０μｍ．     

CuZSM-5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量、反应温度、反应时间及ｎ（ＰｈＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响．     

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.     

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.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.