钴镁铁水滑石的合成、表征及衍生复合氧化物酸碱催化活性研究

以Co(NO3)2.6(H2O)、Mg(NO3)2.6(H2O)和Fe(NO3)3.9(H2O)为原料,以NaOH和Na2CO3为沉淀剂采用低过饱和共沉淀法合成了CoMgFe系列的碳酸根水滑石,通过XRD,IR,TG-DTA,等手段对样品进行测试和表征,X-衍射结果显示,其M2 /M3 投料物质的量比为2-4得到的水滑石为理想构型。经焙烧后,发现其复合氧化物对乙醇催化脱水、脱氢反应有一定的活性。     

t-ZrO2/α-Al2O3超细晶复合粉体的低温燃烧合成

以Al(NO3)3*9H2O、ZrO(NO3)2*2H2O和Y(NO3)3*6H2O为原料,采用低温燃烧合成(LCS)法制备了多种不同ZrO2/Al2O3比的复合粉体,对其物相和形貌进行了表征.实验结果表明,采用LCS法在400℃合成的t-ZrO2/α-Al2O3复合粉体晶粒超细,其结晶程度随ZrO2/Al2O3比的增加逐渐降低,晶粒大小也随ZrO2/Al2O3比的变化而有规律地变化.     

四元轻稀土硝酸盐水溶液体系{H2O+La(NO3)3+Pr(NO3)3+Nd(NO3)3}的热力学研究

在298.15 K条件下, 利用等压法研究了四元轻稀土硝酸盐水溶液{H2O La(NO3)3 Pr(NO3)3 Nd(NO3)3}及其3个二元亚系{H2O La(NO3)3}, {H2O Pr(NO3)3}和{H2O Nd(NO3)3}的热力学性质. 以NaCl或CaCl2水溶液为参考溶液, 测定了不同水活度条件下该四元溶液的渗透系数及各溶质组元的活度系数. 实验结果表明, 上述四元系与其3个二元亚系之间存在简单共性, 在实验误差允许范围之内(|Δ|≤0.0010), 该四元系符合偏理想溶液模型.     

FTIR-ATR原位观测Mg(NO3)2气溶胶的潮解和风化过程

利用FTIR-ATR(傅里叶变换红外-衰减全反射)原位光谱技术在分子水平上研究了ZnSe基底上Mg(NO3)2气溶胶颗粒的潮解和风化过程.根据FTIR-ATR光谱的演变可知,Mg(NO3)2气溶胶在潮解过程中经历了复杂的相变:相对湿度(relative humidity,RH)接近3%时,Mg(NO3)2气溶胶颗粒为无定型水合物;稍微升高相对湿度,无定型颗粒转化为Mg(NO3)2·nH2O(n≤5)晶体,并且在其表面逐渐形成热力学稳定的Mg(NO3)2·6H2O晶体;相对湿度达到Mg(NO3)2·6H2O的饱和点(53%RH)时,Mg(NO3)2·6H2O开始溶解,同时,内核Mg(NO3)2·nH2O(n≤5)晶体在其表面持续转化为Mg(NO3)2·6H2O晶体,导致固态气溶胶颗粒全部潮解时的相对湿度延迟到76%.风化过程中,Mg(NO3)2液滴随相对湿度的降低逐渐失水进入过饱和区域;相对湿度降至5%以下时,形成无定形颗粒.在过饱和Mg(NO3)2液滴的FFIR-ATR光谱中,NO-3对称伸缩振动(v1-NO3-)的吸收强度明显增加,是溶剂共享离子对,甚至接触离子对持续形成的结果.     

Al-Y共掺杂对ZnO纳米棒形成及光催化活性的影响

以Zn(NO3)2·6H2O,Al(NO3)3·9H2O,Y(NO3)3·6H2O和Na OH为原料,采用溶液法制备了Al-Y共掺杂Zn O光催化剂(Al-Y/Zn O),并用X射线衍射(XRD)、扫描电镜(SEM)考察了Al,Y共掺杂对Zn O纳米棒形成及形貌的影响。结果表明,Al-Y共掺杂对Zn O晶粒大小基本没有影响,但会严重抑制Zn O纳米棒的生成,促使碱式硝酸锌(Zn5(OH)8(NO3)2·2H2O)的生成。以甲基橙(MO)为模型污染物考察了Al-Y共掺杂对Zn O纳米棒光催化活性的影响。结果发现,适量的Al-Y共掺杂会显著提高Zn O纳米棒的光催化活性。     

不同Mn源对Li1+xMn2-xO4尖晶石正极材料的电化学性能的影响

以Li2CO3为Mn源,采用醇水混合溶剂分散与中温固相反应法考察了Mn(NO3)2@6H2O,Mn(MeCO2)2@4H2O,MnCO3,化学MnO2(CMD)和电解MnO2(EMD)等不同Mn前驱物对制备Li1+xMn2-xO4尖晶石正极材料的电化学性能的影响,并采用XRD,BET,TEM等手段对材料进行了表征.结果表明,由不同Mn前驱物制备的正极材料均呈尖晶石结构,其容量大小和循环性能(依Mn源为顺序)为EMD＞Mn(NO3)2@6H2O＞MnCO3＞Mn(MeCO)2@4H2O＞CMD.材料呈立方晶体,比表面积(依Mn源为顺序)为CMD＞MnCO3＞Mn(NO3)2@6H2OMn(MeCO2)2@4H2O＞EMD,正好与容量及稳定性顺序相反.采用本文的制备方法时,EMD和Mn(NO3)2@6H2O都是较好的Mn前驱物,Mn(MeCO2)2@4H2O和MnCO3也可以做Mn源,但焙烧时需要富氧气氛,CMD不适宜作Mn前驱物.     

反相微乳液介质中Nd2(CO3)3·8H2 O的可控合成

以十六烷基三甲基溴化铵(CTAB)/正丁醇/正辛烷/硝酸钕[Nd(NO3)3]溶液(碳酸钠溶液)所组成的反相微乳液为反应介质, 采用微乳液溶剂热法合成了Nd2(CO3)3·8H2O, 并考察了水/核比([H2O]/[CTAB])和Nd(NO3)3的浓度对其形貌和尺寸的影响. 利用X射线衍射(XRD)、 热分析(DSC-TGA)、 扫描电子显微镜(SEM)和透射电子显微镜(TEM)等对Nd2(CO3)3·8H2O的晶型、 形貌及尺寸进行了表征, 并提出了不同形貌Nd2(CO3)3·8H2O形成的可能机理. 结果表明, 随着水/核比的增大, Nd2(CO3)3·8H2O的形貌从多面体变成鱼尾状, 再变成针状; 随着Nd(NO3)3浓度的增大, 针状Nd2(CO3)3·8H2O的尺寸逐渐减小.     

铕(Ⅲ)牛磺酸席夫碱配合物的合成、表征及其与DNA的作用模式

合成了3种铕(Ⅲ)与牛磺酸缩水杨醛席夫碱配合物[(Eu(Tsal)L(NO3)] ·2H2O(Tsal :席夫碱配体,L1:1,10-邻菲咯啉,L2:2-氨基吡啶,L3:2,2′-联吡啶),并对其进行了结构表征;采用荧光光谱法和粘度法研究了配合物与小牛胸腺DNA的相互作用模式.实验结果表明,3种配合物对DNA均有不同强度的插入作用,其插入能力在一定范围内与配合物的浓度正相关,且与配合物分子适宜的平面性有关,3种配合物对DNA插入能力顺序为:[Eu(Tsal)L1(NO3)]·2H2O＞[Eu (Tsal)L3(NO3)]·2H2O＞[Eu(Tsal)L2(NO3)]·2H2O.     

4-(3H)-喹唑酮Co(Ⅱ)、Ag(Ⅰ)配合物的合成、晶体结构、荧光和抗癌活性

以4(3H)-喹唑酮、Co(NO3)2·6H2O、Ag NO3为原料,在相同物料比、溶剂和常温条件下,合成了配合物[Co(L)2·(H2O)2·(NO3)2](1)和[Ag(L)2·(NO3)](2)(L=4-(3H)-喹唑酮)。对其进行了X-射线单晶衍射表征和热重分析。X-射线单晶衍射分析表明,它们都属于三斜晶系,但1是六配位,2是三配位的。还测定了2的固体荧光和抗癌活性。配合物2的最大发射波长比配体红移了27 nm,其对NCI(人非小细胞肺癌细胞)有较好的抗癌作用。     

Cu-Ni-Mg-Al-CO_3四元水滑石的合成及结构分析

以Cu(NO3)2 ·3H2 O,Ni(NO3)2 ·6H2 O,Mg(NO3)2 ·6H2 O和Al(NO3)3·9H2 O为原料,以NaOH和Na2 CO3为沉淀剂,采用成核/晶化隔离法合成了Cu Ni Mg Al CO3四元水滑石,通过XRD,FT IR,TG DTA,ICP等手段对样品进行测试和表征,并且对水滑石结构的层板和层间阴离子相互作用进行分析和讨论.结果表明,控制Cu2 +离子与其它二价金属离子的配比,可制备晶体结构规整的M(II)4 M(III)2 (OH)12 CO3·4H2 O型水滑石;Cu2 +离子的引入导致了明显的Jahn Teller效应;且随Mg2 +量的增加,使得这种效应更加显著,另一方面Mg2 +量的增加有利于Cu Ni Mg Al CO3四元水滑石晶体在a方向上生长,增强其热稳定性     

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.