环糊精包结物的制备与研究方法

环糊精是由6,7,8个葡萄糖基构成的环状化合物,分别叫做α,β,γ-CD。它们具有亲水的外围及疏水的内腔,可与多种物质形成包结物,而改变物质的特性,因而被广泛应用于各行各类,为了更好地研究环糊精包结物,在查阅大量文献的基础上,总结出环糊精包结物的多种制备方法及研究方法。     

极谱法研究大黄酸-环糊精包结物

大黄酸是中药大黄中的有效成份，具有抗菌、止咳和抗肿瘤作用．近年来对大黄酸的研究日渐深入，其应用日趋广泛．由于其水溶性低，且对胃肠有刺激作用，导致生物利用度低，应用受到了限制．环糊精是由葡萄糖基以１，４糖甘键连成的中空筒状化合物，具有疏水的内腔和亲水的外表面，可有效地包结各种客体分子，从而能改变客体分子的状态、稳定性、溶解度等理化特性［１］，文献曾经报道β＿环糊精与药物形成包结物，可提高溶解度［２］及降低对胃的刺激性［３］．近来用电化学方法研究环糊精的报道日渐增多［４，５］．本文用极谱法研究了β＿…     

β—环糊精及其包结物作为气相色谱固定相分离混合物研究

β-环糊精由于其特殊的分子结构,对某些物质具有包结作用,并形成较稳定的复合物,极化能力大大增强,在色谱中具有更大的保留值,气相色谱固定相分离混合物过程中,β-环糊精包结物较β-环糊精具有更强的分离能力。分别对β-环糊精及其包结了某些物质后的β-环糊精作气相色谱固定相,对一系列低佛点有机化合物的分离和保留行为进行研究,比较了β-环糊精包结前后的不同的分离效果,并初步探讨了有关的形成机理和分离机制。     

环糊精包结物包结比的测定

由于环糊精具有“外亲水,内疏水”的独特性质,它可以包结许多物质而形成主客体配合物,从而改变物质的特性,所以被广泛应用于各行各业中,包结物的包结比是决定包络物性质的一个重要参数,在查阅大量文献的基础上,总结出环糊精包结反应过程中测定主客体间的包结比的方法,并对其进行了较详细的介绍。     

环糊精及其包结物的电化学研究及应用

本文概述了近年来环糊精及其包结物的电化学研究及应用，同时介绍了我们实验室开展的关于环糊精电化学研究的一些工作。     

薄层色谱法测定大黄类药物与环糊精的包结常数

以环糊精的水溶液为流动相，聚酰胺薄膜为固定相，用反相薄层色谱法研究了大黄有效成份大黄素、芦荟大黄素与环糊精的包结作用，测定了包结常数，环糊精对大黄类药物有明显的增溶作用，且环糊精与大黄类药物有明显的增溶作用，且环糊精与大黄类药物的包结作用符合熵补偿规律，补偿温度为296．5K；通过熵焓补偿规律得出，大黄类药物与环类精的包结过程中环糊精分子结构发生了较大的变化，同时经历了适中的去溶剂化步骤。     

电化学方法研究环糊精与酮洛芬的包结行为

以电化学方法研究了各种环糊精及其衍生物对酮洛芬电化学行为的影响，测定了酮洛芬与β环糊精，羟丙基β－环糊精和甲基化－β－环糊精的包结常数及其温度对包结作用的影响，并由各包结物的热力学参数解释包结现象。     

β-环糊精与尼古丁的包结配位作用

β 环糊精(β CD)是环状低聚葡萄糖,呈锥形体结构,具有独特的分子包结特性和识别能力,广泛应用于色谱分离、食品、医药等多种行业[1 5]。将卷烟过滤嘴用含β CD的浸渍液处理,可以在使用过程中滤除大部分尼古丁和烟油[6]。为了探索β CD与尼古丁分子的作用机理,本文通过紫外 可见光谱及核磁共振氢谱证实了在中性和碱性缓冲溶液中β CD与尼古丁均具有包结配位作用,并在碱性介质中,采用中和法制备了其超分子固体包结物。1　实验部分1 1　试剂和仪器β 环糊精:(汕头市光华化学厂,生化试剂,重结晶两次,110℃真空干燥12h);尼古丁:(上海第…     

β—环糊精交联聚合物与有机显色剂客体包结反应研究

β－环糊精与环氧氯丙烷交联共聚物是一种具有三维网状结构的聚合树脂，它保留了β－环糊精所原有的与有机疏水基团形成包结物的特性，与一系列含有芳得环的有机显色剂配体（如吡啶偶氮染料，变色酸双偶氮试剂，三苯甲烷类碱性与酸性染料以及杂氧蒽酮类试剂等）均可形成相应的包结配合物，着重研究了有关包结配合物的稳定性及影响稳定性的各种因素，为进一步研究包结物分离富集痕量金属提供必要的理论依据。     

相溶解度法研究芦荟大黄素和环糊精及其衍生物的包结作用

本文用相溶解度法研究了芦荟大黄素与β－环糊精（ＣＤ）衍生物的包结作用,测定了包结物的包结常数,表明β－ＣＤ衍生物对芦蔡大黄素有较好的增溶作用,有应用价值。     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.