环糊精的修饰改性及应用研究新进展

简要介绍了环糊精的结构特征及应用,详细综述了:①新型环糊精衍生物的合成;②环糊精超分子纳米材料的制备和应用;③环糊精金属配合物的合成及应用。     

超分子环糊精的研究新进展

随着环糊精衍生物不断被合成、环糊精的性质不断被发现,超分子环糊精的应用也越来越广泛。综述了超分子环糊精在分子识别、分子自组装和模拟生物酶等方面的研究进展,展望了超分子环糊精的发展趋势。     

超分子化学与环糊精

超分子化学是上世纪八十年代末兴起的一门新兴边缘学科,它的发展为各个学科的研究和新技术、新材料的研发开拓了一个崭新的领域。环糊精是超分子化学的重要研究内容之一。本文对环糊精的来源和分子结构特点作了简单介绍,论述了环糊精及其衍生物任超分子化学领域中的地位和作用,显示出超分子化学及环糊精研究和应用的无限潜力。     

新型环糊精衍生物的制备及应用

简要介绍了环糊精化学的产生、发展、性能、应用及结构特征。详细介绍了:新型环糊精衍生物的制备及在医药学中的应用;环糊精超分子作用力的自愈合杂化功能材料的制备及应用;环糊精自组装及主客体识别在分析分离科学中的应用。并对环糊精化学的发展进行了展望。     

蓬勃发展的环糊精化学

简要介绍了环糊精化学的产生、发展、应用及结构特征;重点讨论了:(1)超分子大环主体化合物环糊精的自组装及应用;(2)环糊精自组装在医药学方面的应用;(3)环糊精模拟酶及其选择性识别作用。并对环糊精化学的发展进行了展望。     

超分子化合物及其在色谱分离中的应用

介绍了超分子化学的基本概念;总结了冠醚、环糊精和杯芳烃三代超分子化合物的结构特征及其结构差别;并简述了三代超分子化合物在色谱分离中应用的原理、研究现状和应用前景。     

第二代超分子主体化合物环糊精化学研究的新进展

简要介绍了环糊精化学的产生、发展及应用,重点介绍了:(1)环糊精衍生物的自组装、包合及应用;(2)新型环糊精超分子聚集体的形成及应用;(3)环糊精的包合作用在医药学研究中的应用。并对环糊精化学的发展进行了展望。     

含能化合物的超分子化学研究进展

介绍了以环糊精、碳纳米管、石墨烯、介孔材料为超分子主体的主-客体含能复合物以及共结晶含能材料的最新研究进展,指出了用环糊精制备超分子含能复合物的缺陷,分析了碳纳米管、石墨烯、介孔材料用于制备高能钝感超分子含能复合物及共结晶含能材料的可行性和研究方法,展望了超分子化学方法在含能材料领域的应用前景。附参考文献54篇。     

β-环糊精/氯菊酯包合物制备工艺优化

文章采用超声波法制备了β-环糊精/氯菊酯超分子包合物。采用正交设计研究氯菊酯与β-环糊精的主客体摩尔比、包合温度和包合时间等对包合作用的影响,优选出超声波法制备了β-环糊精/氯菊酯超分子包合物的最佳工艺条件。借助紫外光谱、红外光谱、差热分析证明了超分子包合物的形成。     

基于AB型环糊精主客体相互作用的超分子聚合物的研究进展

对环糊精的羟基进行选择性衍生化,可以调节环糊精分子与客体分子的络合特性。文章综述了各类基于环糊精主客体相互作用的的组装单体,通过自组装可以形成不同拓扑结构的超分子聚合物组装体。     

环糊精包合手性分子的新进展

介绍了环糊精的结构特征及包合性能,环糊精包合手性分子的新进展。重点综述了近几年各类环糊精的包合作用在医药、生命科学及材料科学等领域的新应用,展望了其广阔的前景,期望能在医药学、生命科学及材料科学的应用上更有意义。     

环糊精在医药学应用研究中的新进展

综述了近几年来环糊精与药物分子形成包合物在医药应用上的新进展,即①超声波法合成药用环糊精包合物;②新型药用环糊精包合物的制备;③环糊精及其衍生物对药物的增溶作用。     

Structural background of cyclodextrin-protein interactions

Cyclodextrins are cyclic oligosaccharides with the shape ofa hollow truncated cone. Their exterior is hydrophilic and theircavity is hydrophobic, which gives cyclodextrins the abilityto accommodate hydrophobic molecules/moieties in the cavity.This special molecular arrangement accounts for the varietyof beneficial effects cyclodextrins have on proteins, whichis widely used in pharmacological applications. We have studiedthe interaction between ß-cyclodextrin and four non-carbohydrate-bindingmodel proteins: ubiquitin, chymotrypsin inhibitor 2 (CI2), S6and insulin SerB9Asp by NMR spectroscopy at varying structuraldetail. We demonstrate that the interaction of ß-cyclodextrinand our model proteins takes place at specific sites on theprotein surface, and that solvent accessibility of those sitesis a necessary but not compelling condition for the occurrenceof an interaction. If this behaviour can be generalized, itmight explain the wide range of different effects of cyclodextrinson different proteins: aggregation suppression (if residuesresponsible for aggregation are highly solvent accessible),protection against degradation (if point of attack of a proteaseis sterically ‘masked’ by cyclodextrin), alterationof function (if residues involved in function are ‘masked’by cyclodextrin). The exact effect of cyclodextrins on a givenprotein will always be related to the particular structure ofthis protein. Received May 30, 2003; revised October 27, 2003; accepted October 30, 2003     

Equalizing effect of β‐cyclodextrin on dyeing of polyamide 6,6 woven fabrics with acid dyes

Cyclodextrins (CD) are produced from starch by the action of cyclodextrin glycosyltransferase (CGTase) enzyme. Structurally, cyclodextrins consist of 6, 7, or 8 (α, β, and γ cyclodextrins, respectively) D‐glucopyranosyl units connected by α‐(1,4) glycosidic linkages. Having polar and hydrophilic outer sides and hydrophobic cavitation gives cyclodextrins a chance to form inclusion complexes with dyes in hydrophilic mediums. In this research, the equalizing effect of β‐cyclodextrins in dyeing of polyamide 6,6 woven fabrics with 6 different acid dyes were investigated. From the experimental results, it was determined that the β‐cyclodextrin shows a retarding and equalizing effect in dyeings carried out with the dyes that show interaction with β‐CD. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2660–2668, 2007     

Extraction of toluene,o-xylene from heptane and benzyl alcohol from toluene with aqueous cyclodextrins

The separation of aromatic compounds (toluene and o-xylene) from heptane and of benzyl alcohol from toluene with aqueous solutions of cyclodextrins has been experimentally investigated, because cyclodextrins and its derivatives can selectively incorporate several organic compounds, whereas the separation of the aqueous solution of complexed cyclodextrins from the organic feed is simple. Cyclodextrins are not soluble in organic liquids, but cyclodextrin derivatives are highly soluble in water. Hydroxypropyl-β-cyclodextrins with different degrees of substitution and methylated β-cyclodextrin were selected for the extraction of toluene and o-xylene from heptane. Hydroxypropyl-β-cyclodextrin (two different substitution degrees) and hydroxypropyl-α-cyclodextrin were selected for the extraction of benzyl alcohol from toluene. The liquid–liquid distribution experiments were carried out at room temperature. Toluene and o-xylene form 1:1 complexes with different cyclodextrins and heptane can form 1:1 to 1:3 complexes. Benzyl alcohol forms 1:3 complexes with hydroxypropylated cyclodextrins. The models developed describe the experimental data reasonably well, considering the large deviations in the analyses.Aqueous cyclodextrin solutions are not feasible for the separation of aromatic components from aliphatic hydrocarbons, due to low distribution ratios of toluene (0.05) and o-xylene (0.023) between the aqueous and organic phase. With high distribution ratios of benzyl alcohol, between 0.3 and 2.2 depending on the CD concentration (at a solvent-to-feed ratio of 1) and a benzyl alcohol/toluene selectivity of at least 100, aqueous hydroxypropylated cyclodextrin solutions have sufficient potential for extracting benzyl alcohol from toluene.     

Two‐Phase Hydroformylation of Higher Olefins Using Randomly Methylated α‐Cyclodextrin as Mass Transfer Promoter: A Smart Solution for Preserving the Intrinsic Properties of the Rhodium/Trisulfonated Triphenylphosphine Catalytic System

The two‐phase hydroformylation of higher olefins with the rhodium/trisulfonated triphenylphosphine catalytic system in the presence of various chemically modified α‐cyclodextrins has been investigated. These cyclodextrins allowed us to increase greatly the reaction rate and the chemoselectivity of the reaction but, contrary to what has been observed previously with the chemically modified β‐cyclodextrins, the linear to branched aldehydes ratio was not affected by the presence of α‐cyclodextrin derivatives. Indeed, the latter was found to be similar to that obtained without any mass transfer promoter, suggesting that the catalytic species are stable in the presence of α‐cyclodextrin derivatives.     

环糊精及其包合物的研究与应用

介绍了环糊精及其包合物的合成、结构、包合物形成的热力学与动力学等的研究概况，着重叙述了环糊精的包合作用与环糊精的修饰，描绘了环糊精化学的应用与发展前景。     

Sulfobutyl Ether‐β‐Cyclodextrins: Promising Supramolecular Carriers for Aqueous Organometallic Catalysis

The potentialities of sulfobutyl ether‐β‐CDs derivatives as supramolecular carrier in a biphasic Tsuji–Trost reaction catalyzed by a water‐soluble palladium complex of trisulfonated triphenylphosphine have been investigated. The efficiency of these cyclodextrins (CDs) strongly depends on the average molar substitution degree of cyclodextrin and the highest rate enhancements were obtained with cyclodextrins containing about 7 sulfobutyl ether groups. This result was attributed to the absence of a strong interaction between this cyclodextrin and the trisulfonated triphenylphosphine used to dissolve the catalyst in the aqueous phase and to the presence of an extended hydrophobic cavity allowing a better molecular recognition between the substrate and the cyclodextrin. This constitutes the first example of a non‐interacting β‐cyclodextrin/phosphine couple with high catalytic activities.     

High‐Pressure 31P{1H} NMR Studies of RhH(CO)(TPPTS)3 in the Presence of Methylated Cyclodextrins: New Light on Rhodium‐Catalyzed Hydroformylation Reaction Assisted by Cyclodextrins

The effect of methylated cyclodextrins on the RhH(CO)(TPPTS)₃ complex in hydroformylation conditions [50 atm of CO/H₂ (1/1) and 80 °C] has been investigated by high‐pressure ³¹P{¹H} NMR spectroscopy. In the presence of methylated β‐cyclodextrin, the equilibria between the rhodium species lie in favor of phosphine low‐coordinated rhodium species. The formation of a stable inclusion complex between this cyclodextrin and the trisulfonated triphenylphosphine ligand (TPPTS) was found to be the key to understanding the displacement of the equilibria. Indeed, the methylated α‐cyclodextrin which does not interact with the TPPTS and the methylated γ‐cyclodextrin which can weakly bind to the TPPTS have no and a very low effect on the equilibria, respectively. These results explain for the first time why a decrease in the normal to branched aldehydes ratio is always observed when cyclodextrins are used as mass‐transfer agents in aqueous biphasic hydroformylation processes.