环己烷在Pt/HY-A12O3催化剂上加氢转化反应的研究

采用高压微型反应器，在压力为4．0MPa，温度260℃-350℃、氢油比为500：1、空速1．0h^-1条件下，研究了不同酸性载体HY-Al2O3，负载的铂(Pt)催化剂上环己烷的催化反应规律．结果表明，反应温度和载体酸性是影响催化剂异构化活性、裂化活性的两个重要因素，增加反应温度或提高催化剂酸性都会导致催化剂的异构化活性降低、裂化活性增强．当反应温度为290℃，含15％HY的Pt/HY-Al2O3，催化剂的异构化活性最好，异构化产物的选择性为91．6％，环己烷转化率为71．6％．提高催化剂载体中分子筛含量，有利于环己烷开环反应的发生，从产物的分布可以看出，在Pt/HY-Al2O3，催化剂上环己烷的开环过程是首先异构化为甲基环戊烷继而发生开环反应，反应最终达到平衡状态，致使开环产物中nH：3MP：2MP=1：1：2比值不变，开环机理符合β-断裂的正碳离子机理。     

Cu-Mn-Ce/γ-Al2O3汽车尾气净化催化材料的合成及性能的研究

采用固定床反应装置，模拟汽车尾气的组成成分，以CO氧化和NH3选择还原NO为探针反应，研究了焙烧温度和焙烧时间等因素对复合金属氧化物催化材料Cu-Mn-Ce-O／γ-Al2O3的催化活性的影响，并考察了该催化剂的抗硫化中毒性能。在本研究条件下，焙烧温度在700℃左右，焙烧时间为2．5h时，催化剂对NO-CO体系中CO的氧化率在76％，以上，对NH3-NO体系中的NO的最佳催化还原率在80％以上。催化剂在3．O％S02／空气气氛中强制中毒后，其在NH3-NO气氛中的最佳反应温度．450℃，同样条件下未中毒催化剂的最佳反应温度为350℃左右，并且催化剂中毒后对NO—NH3的最大转化率没有下降，但是对NO-CO体系的反应活性明显下降，说明该催化剂具有良好的高温活性和抗硫中毒性能。     

CsMPVAsMoO/α-Sb2O4杂多化合物对丙烯选择性催化氧化的研究

用组合法合成CsMPVAsMoO(M=Cu、Fe、Ni)系列催化剂，采用FT—IR、H2—TPR方法对催化剂进行了表征；在自制固定床反应器中对丙烯进行选择性氧化，探讨了助剂α—Sb2O4含量，不同活化温度对催化剂催化性能的影响。结果表明，Cu^2 、Fe^3 、Ni^2 的引入，有利于提高丙烯酸的收率；加入助剂极大地增大催化剂活性，降低了反应温度，但丙烯酸的收率有所下降，组成为Cs0.1Cu0.2HzPVAs0．2Mo10Or的催化剂对丙烯具有很好的选择性氧化能力，440℃时，丙烯转化率达86．8％，丙烯酸、丙烯醛、乙酸、丙酮的收率分别可达53．7％、3．2％、10．7％、10．45％；Cs0.1Cu0.2HzPVAs0.2Mo10Or／17％α-Sb2O4，在360℃时，丙烯转化达率89．02％，丙烯酸、丙烯醛、乙酸、丙酮的收率分别可达37．2％、2．2％、18．2％、2．8％。     

石墨炉原子吸收法测定甲壳素中的砷

采用石墨炉原子吸收法直接测定甲壳素中的砷。以HF－HClO4溶解消化试样,用Mg(NO3)2作基体改进剂,灰化温度为1000℃,原子化温度为2300℃。该法相对标准偏差为1．02％,回收率在97．2％－105．8％之间,方法快速、简便,结果准确。     

以N2O为氧化剂, Fe-P-O催化剂气相催化氧化苯制苯酚的研究

考察了应用N2O为氧化剂，FePO4、FePO4／SiO2、Fe0．5Al0.5PO4为催化剂气相催化氧化苯制苯酚的反应。在450℃下，FePO4催化剂上苯的转化率为2％，苯酚的选择性为85%；FePO4／SiO2(5％)催化剂上苯的转化率约为7％，苯酚的选择性为89％．Fe0．5Al0.5PO4催化剂可以使反应温度降低约100℃，350℃下反应苯的转化率为3．5％，苯酚的选择性为60％．分析表明，四面体结构的FeO4在该催化反应中具有重要的作用。     

钆及双稀土元素掺杂TiO2可见光催化降解罗丹明B的研究

以钛酸丁酯为前驱体，采用溶胶一凝胶法制备了钆及双稀土元素共掺杂纳米TiO2光催化剂，研究了自制催化剂在可见光下对有机染料罗丹明B催化降解反应的活性。稀土掺杂后的TiO2在可见光下催化活性比纯的TiO2有显著的提高。当Gd^3＋与TiO2的摩尔比为1．5％，催化剂经过500℃焙烧，对罗丹明B的降解率达到99．5％；Gd^3＋：La^3＋：TiO2的摩尔比为O．5：0．5：100，焙烧温度为600℃，降解率高达99．9％，比双元素掺杂的结果更好。     

助剂α-Sb2O4对杂多化合物催化剂选择氧化异丁烷的影响

采用组合法制备了具有Keggin结构的杂多化合物催化剂，采用FTIR、UV-VIS-DR、H2-TPR、BET、TG-DTA和SEM对合成的催化剂的结构和性质进行了研究．探讨了催化剂中助剂α-Sb2O4含量对异丁烷选择性催化氧化的影响．并考察了反应温度对催化剂的催化性能影响．实验表明，助剂含量为8．3％，在C4H10／O2／N2／H2O=1／2．6／6／1，GHSV为910h^-1，温度为380℃的条件下，甲基丙烯酸的收率可达10．4％，选择性为44．3％．     

氢部分选择性催化还原NO反应研究

在低钯含量活性非均布Pd/Al2O3催化剂上，实现了富氧条件下，氢部分选择性催化还原NO过程，低温、富氧条件下NO的转化率高达80％－100％。NO直接分解实验表明，600℃，NO分解转化率在无氧时为17．3％，有0．5％氧存在时接近于0。氢非选择性还原NO条件下，100℃以下，NO转化率为100％。根据实验结果及文献，推测了氢部分选择性还原NO过程中可能存在的反应，不同的反应温度下，NO脱除反应有所不同。在115℃以下，NO还原产物为NH3；115℃－155℃，NO还原产物为NH3、N2O和N2；155℃以上，NO还原产物中无NH3存在。NO还原反应与氢氧反应是平行的竞争反应。     

La2O3：Sm发光粉的合成与发光性质的研究

以La2O3和Sm2O3为原料，用碳酸盐沉淀法制备了La2O3:Sm^3 发光粉，并分别用XRD，SEM和发光光谱及寿命进行了表征，La2O3晶相的形成温度为800℃，其发光强度随温度升高而增强，La2O3基质中Sm^3 的最佳掺杂浓度为1．5％（摩尔分数）。     

掺铬铝酸钇红色颜料的合成、结构和性能表征

研究了高温固相合成制备掺铬铝酸钇红色颜料的方法，着重考察了灼烧温度（1000-1400℃）、灼烧时间（1-2h）、主要原料配比（Al／Y：1：0．5—1：1．5，Cr2O3％：0．3％-5％）等实验条件对产物结构和色泽的影响。XRD等方法对样品进行的相态分析表明，主相为铝酸钇石榴石相；运用反射光谱对红色颜料的色泽进行了反射峰位和相关强度的表征。当Y2O3：Al2O3摩尔比为1：1，掺杂3％的Cr2O3作显色剂，在少量矿化剂存在时，在1300℃下灼烧1 h，得到了色坐标为x=0．577，Y=0．401的红色陶瓷颜料。     

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.