在Ni系ABO3和A2BO4型复合氧化物催化剂上NO吸附性能的研究

合成了具有钙钛石和类钙钛石结构的复合氧化物ＬａＮｉＯ３，Ｌａ０．１Ｓｒ０．９ＮｉＯ３，Ｌａ２ＮｉＯ４和ＬａＳｒＮｉＯ４。考察了它们对ＮＯ的吸附和ＮＯ直接分解反应的催化性能，结合比表面测定，化学分析，ＸＲＤ和ＮＯ－ＴＰＤ对催化剂的表征结果，探讨了该系列复合氧化物对ＮＯ的吸附规律。     

Ni系ABO_3和A_2BO_4型复合氧化物的固态物化性质与NO+CO反应的催化性能

合成了具有钙钛石ＡＢＯ３结构的ＬａＮｉＯ３和Ｌａ０．１Ｓｒ０．９ＮｉＯ３及具有类钙钛石Ａ２ＢＯ４结构的Ｌａ２ＮｉＯ４和ＬａＳｒＮｉＯ４等四个Ｎｉ系复合氧化物催化剂．研究了该系列复合氧化物的晶体结构，缺陷结构，Ｂ位Ｎｉ离子的价态，氧化还原性能及对ＮＯ分子的吸附性能等固态物化性质．考察了它们对ＮＯ＋ＣＯ反应的催化性能，并与ＮＯ直接分解进行了对比研究．探讨了结构因素对Ｎｉ系复合氧化物催化剂的固态物化性质及催化性能的影响．提出了ＮＯ＋ＣＯ反应的反应机理．     

La—Ba—Cu复合氧化物在催化消除NO反应中催化性能的研究

合成了具有钙钛石结构的复合氧化物ＹＢａ２Ｃｕ３Ｏ７、ＬａＢａ２Ｃｕ３Ｏ７、ＬａＢａＣｕ２Ｏ５、Ｌａ２ＢａＣｕ３Ｏ７和Ｌａ４ＢａＣｕ５Ｏ１２。考察了它们对ＮＯ分解和ＮＯ＋ＣＯ反应的催化性能。结合化学分析、ＸＲＤ、ＴＰＤ和ＴＰＲ对催化剂的表征结构，探讨了该系列复合氧化物对ＮＯ分解和ＮＯ＋ＣＯ反应的催化机理。     

钴铝水滑石焙烧产物催化上NO的直接分解

研究了以钴铝水滑石焙烧产物复合钴铝氧化物为催化剂直接分解ＮＯ。当钴铝复合氧化物以还原态存在时,其脉冲催化分解活性在４５０℃时为１００％,相同条件下ＣｕＺＳＭ－５催化剂的活性只有４５％。ＸＲＤ和ＴＰＲ表征表明,焙烧温度不太高的情况下,钴铝复合氧化物中已含有不少的铝酸钴尖晶石,它还原生成高分散态的金属钴,这可能是它分解ＮＯ活性高的原因。     

六铝酸盐SrNiAl11O19—δ催化二氧化碳重整甲烷制合成气反 …

本文通过晶格取代作用，制备了以Ｎｉ为活性组分的六铝酸盐复合氧化物催化剂ＳｒＮｉＡｌ１１Ｏ１９－δ并通过ＸＲＤ，ＸＰＳ，ＴＰＲ等实验技术，对催化剂的结构和性质进行了表征。结果表明，六铝酸盐ＳｒＮｉＡｌ１１Ｏ１９－δ对二氧化碳重整甲烷制合成气反应具有良好的催化活性和稳定性，在７８０℃反应２小时，ＣＨ４和ＣＯ２转化率分别为９５．０％和９３．４％，没有发现活性组分Ｎｉ高温烧结和催化剂失活。     

稀土氧化物上SO2和NO的催化还原 Ⅰ.催化剂的活化特性和机理

以稀土系列氧化物作为ＣＯ还原ＳＯ２和ＮＯ的催化剂,考察了催化剂的活化过程以及催化剂体相结构的变化,发现稀土系列的活化与其水合性能密切相关,而活化之后活性相为相应的稀土氧硫化物,探讨了稀土系列氧化物的活性机理。     

丙烷氨氧化V／Sb系复合氧化物催化剂的研究

考察了不同组成的Ｖ－Ｓｂ－Ｏ系复合氧化物对丙烷氨氧化的催化活性。用ＸＲＤ研究了催化剂的结构，利用程序升温方法研究了催化剂中氧的活动性和表面酸碱性，讨论了催化剂体相和表面结构与催化性能间的关系。结果表明，ＶＳｂＯ４和Ｓｂ２Ｏ４间的协同作用是影响催化活性的重要因素。     

几种稀土卟啉配合物的固相合成及电化学性质研究

在固相条件下合成了４种四（对甲氧基苯基）卟啉稀土（Ｌｎ＝Ｌａ＾３＋,Ｐｒ＾３＋,Ｎｄ＾３＋,Ｄｙ＾３＋）配合物。用元素分析、ＩＣＰ、ＵＶ及ＩＲ光谱进行表征,用循环伏安法研究了它们的电化学性能,实验结果表明,它们的电化学性质相似。在循环伏安图中出现了三对氧化还原峰。第一对为「Ｃ４８Ｈ３６Ｎ４Ｏ４Ｌｎ（Ⅲ）」＾＋／「Ｃ４８Ｈ３６Ｎ４ＯＬｎ（Ⅱ）」,第二为「Ｃ４８Ｈ３６Ｎ４Ｏ４Ｌｎ（Ⅱ）」／「Ｃ４８Ｈ３６Ｎ４Ｏ４Ｌｎ（Ⅰ）」＾－１,第三对为「Ｃ４８Ｈ３６Ｎ４ＯＬｎ（Ⅰ）」＾－／「Ｃ４８Ｈ３６Ｎ４ＯＬｎ」＾２－。     

La(ClO4)3-OCBAAP-H2O体系(30℃)溶度及Ln(OCBAAP)4(ClO4)3·nH2O的合成和表征

测定了三元体系Ｌａ（ＣｌＯ４）３－ＯＣＢＡＡＰ－Ｈ２Ｏ在３０℃时的溶解度．结果表明，该体系有一个新固相（不一致溶解化合物）Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·６Ｈ２Ｏ形成．参考该体系溶度图确定合成条件，合成了系列化合物Ｌｎ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３·ｎＨ２Ｏ（Ｌｎ＝Ｌａ，ｎ＝６；Ｌｎ＝Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ，Ｙｂ，ｎ＝２）．通过化学分析、元素分析、ＴＧ－ＤＴＧ、ＩＲ和密度对化合物进行了表征，计算了Ｌａ（ＯＣＢＡＡＰ）４（ＣｌＯ４）３热分解过程各阶段的表观活化能．     

二氧化碳与环氧丙烷共聚稀土改性羧酸锌催化剂的研究：（Ⅰ）催化剂的？…

用稀土氧化物Ｌｎ２Ｏ３（Ｌｎ：Ｌａ,Ｎｄ,Ｅｕ,Ｈｏ,Ｙｂ,Ｓｍ）对戊二酸锌进行改性,制备出新催化剂。在８０℃,３．０￣３．５ＭＰａ条件下,该催化剂催化二氧化碳与环氧丙烷共聚,反应时间为６．５￣７．０ｈ,催化活性达到３．０￣３．４ｇ ｐｏｌｙｍ．／（ｇｃａｔ．·ｈ）,转化率７０．８％￣７９．７％,共聚物中碳酸酯单元分数４８．４％,产品热分解温度２３８．１℃。     

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.