1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉的合成及锌离子探针的研究

设计合成了1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-苯基-2-吡唑啉(4), 测试了其紫外光谱和荧光光谱, 研究了其对锌离子的选择性识别作用. 结果表明, 化合物4作为锌离子荧光探针, 受常见离子的干扰较小, 对于锌离子有着较高的选择性和较低的检出限.     

有机化合物的光物理研究——Ⅻ.水杨醛缩对-(N,N-二甲氨基)苯胺的荧光光谱

通过对水杨醛缩对-(N,N-二甲氨基)苯胺在不同溶剂中的荧光光谱的研究,发现在不同浓度的溶液中存在3个发光体,它们是激发态中间体(EI),激基复合物(EX)和激发态的二聚体(ED),研究了该化合物在溶液中的性质,发现该化合物在溶液中的基本存在形式不是单分子而是二聚体,通过研究溶剂的性质对发光体的影响,所得到的结论是溶剂的极性越小,越有利于二聚体的形成,根据荧光光谱和动力学数据提出了三种发光组份的形成过程和发光机理     

锌酞菁-紫精-二茂铁三元化合物分子内光致电子转移及光电转换性能的研究

本文合成了锌酞菁、紫精与二茂铁经共价键相连接的两亲性新的三元化合物,测定了它的吸收光谱、荧光光谱、荧光寿命和瞬态吸收及其衰减,并与二元化合物锌酞菁-紫精进行了比较,结果表明:在DMF和表面活性剂溶液中三元化合物都发生了有效的分子内光致电子转移反应,给出了稳定的电荷转移离子对,其寿命长达100μs以上,表明存在着一个两步电子转移过程,用LB膜技术成功地组装了三元化合物的分子,并检测到明显的光电效应。     

5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌配合物的合成表征

设计合成了5种未见文献报道的5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌金属配合物,并用IR,UV-Vis,1H NMR,元素分析以及XPS对其组成和结构进行了表征,研究了这10种酰胺基系列卟啉化合物的拉曼光谱和荧光光谱的变化.结果显示链长对荧光和拉曼光谱没有明显影响,其取代基效应基本相同,配体的荧光强度强于锌配合物的荧光强度.在拉曼光谱中,由于卟啉分子平面的对称性由D2h变为D4h群及其锌离子d轨道的电子效应,卟啉配体和锌配合物之间的拉曼光谱有很大差别.     

3,6-二(蒽醌-2-乙烯基)-N-乙基咔唑的合成及光谱性质研究

利用N-乙基咔唑和2-甲基蒽醌合成了一种A-π-D-π-A分子内电荷转移型化合物3,6-二(蒽醌-2-乙烯基)-N-乙基咔唑,并对该化合物的光化学和光物理行为进行了研究。荧光光谱表明,该化合物的发光行为对溶剂的极性非常敏感,随着溶剂极性的增大,其荧光最大发射峰有明显红移,并在强极性溶剂乙腈中出现了双荧光现象。该化合物的激发态和基态的偶极矩差值△μ为3.014D,发生了从给体(咔唑基)的N原子到分子两端受体(蒽醌)的羰基的分子内电荷转移。     

1-乙酰基-3-(2-羟基-4,6-二甲氧基苯基)-5-芳基-2-吡唑啉的合成及Cu2+荧光探针行为

设计合成了6个1-乙酰基-3-(2-羟基-4,6二甲氧基苯基)-5-芳基-2-吡唑啉化合物4a～4f.测试了它们的紫外光谱和荧光光谱,研究了其对铜离子的选择性识别作用.结果表明,化合物4f作为铜离子荧光探针,受常见离子干扰较小,对于铜离子有着较高的选择性和较低的检出限.     

1,5-二芳基-3-(2-羟基-4,6-二甲氧基苯基)-2-吡唑啉的合成及铜离子荧光探针行为

设计合成了4个1,5-二芳基-3-(2-羟基-4,6-二甲氧基苯基)-2-吡唑啉化合物(4a～4d).其结构由IR,1HNMR,MS和元素分析确认.通过紫外光谱和荧光光谱研究了化合物对铜离子的选择性识别作用,结果发现,化合物4a～4d均可以选择性地识别铜离子,作为铜离子荧光探针,受常见离子干扰较小,选择性较高.     

二{2-{2-{9-乙基-6-[2-(8-羟基喹啉-2-基)乙烯基]咔唑-3-基}乙烯}-8-羟基喹啉}锌配合物的合成与荧光光谱特性

合成了新的N-乙基咔唑衍生物: 3,6-二[2-(8-羟基喹啉基)乙烯基]咔唑(4)及其锌配合物(5); 化合物4经质谱、红外光谱、核磁共振氢谱、元素分析表征其结构, 并测定了它的荧光光谱. 结果显示: 化合物4的荧光发射为蓝绿色光(500 nm), 其发射光谱随着溶剂极性的增大荧光光谱向长波方向移动(即发生红移); 同时, 考察了化合物5的荧光性质, 其荧光发光峰值为600 nm, 与2-甲基-8-羟基喹啉锌相比, 发生了明显的红移.     

1,3-二苯基-5-吡唑啉酮三种异构体的结构及其发光性能

本文以1,3-二苯基-5-吡唑啉酮(DPP)为研究对象,采用不同溶剂对其进行重结晶,得到了3种不同颜色和不同构型的异构体。通过XRD粉末衍射、IR、1H NMR等确定了3种异构体的组成和结构,通过荧光光谱研究了它们的发光行为。结果表明这类化合物具有聚集诱导发光性能和光异构化性能,而且溶剂对产物的构型及发光性能均有明显的影响。此外,将该化合物与无规聚苯乙烯复合制备的薄膜也具有很好的荧光性能,在防伪领域具有潜在的应用。     

水杨醛-4-甲氧基苯甲酰腙识别锌离子的研究

设计合成了荧光传感分子水杨醛-4-甲氧基苯甲酰腙(SAMB),通过IR、1HNMR和元素分析确证了其结构,利用紫外-可见吸收光谱和荧光光谱考察了其对不同阳离子的识别作用。结果表明,SAMB的荧光发射对锌离子表现出高选择性响应,且形成1∶1型配合物。乙醇中锌离子的加入导致SAMB的荧光增强328倍,而其他过渡金属离子只引起SAMB的荧光的略微增强。初步探讨了受体分子与锌离子的结合模式与荧光增强机理。     

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.