侧链携带金刚烷的聚(N-异丙基丙烯酰胺)与环糊精二聚体构筑可控超分子体系

合成了侧链携带金刚烷的温敏性聚合物(Pnipam-Ad)及环糊精二聚体(trans-Azo β-CD Dimer),利用Pnipam-Ad侧链的金刚烷与trans-Azo β-CD Dimer的主客体识别作用构筑了超分子体系.以二维核磁共振谱(2D NMR)、粘度法等手段对Pnipam-Ad与trans-Azo β-CD Dimer之间的主客体包结作用进行了研究,两者之间的缔合受Pnipam-Ad和trans-Azo β-CD Dimer浓度及trans-Azo β-CD Dimer光异构的影响.此外,trans-Azo β-CD Dimer对Pnipam-Ad聚合物链的物理交联作用使两者混合溶液的最低临界溶解温度(LCST)低于纯P(NIPAM)的LCST.     

基于环糊精二聚体与金刚烷修饰的温敏性聚合物的主客体识别构筑超分子水凝胶

利用环糊精二聚体(trans-Stilbene β-CD Dimer)与金刚烷修饰的温敏性聚合物(Pnipam-Ad)的主客体识别作用构筑了超分子水凝胶. 2D NMR 测定结果表明trans-Stilbene β-CD Dimer 和Pnipam-Ad 的主客体相互作用是通过β-CD 空腔和疏水体Ad 形成包结络合物进行的. 环糊精二聚体trans-Stilbene β-CD Dimer 和聚合物Pnipam-Ad 两者之间的缔合程度受trans-Stilbene β-CD Dimer 和Pnipam-Ad 的浓度以及trans-Stilbene β-CD Dimer 光异构的影响. 此外, 由于trans-Stilbene β-CD Dimer 对Pnipam-Ad 聚合物链的物理交联作用使两者混合溶液的最低临界溶解温度(LCST)低于纯聚异丙基丙烯酰胺(Pnipam)的LCST.     

基于环糊精二聚体与紫精聚合物的包结作用制备超分子水凝胶

制备了对苯二甲酸连接的环糊精二聚体(α,α-CD Dimer)及紫精聚合物(VP), 利用α,α-CD Dimer与VP之间的主客体识别作用构筑了一种超分子水凝胶. ¹H NMR测定结果表明α,α-CD Dimer和VP的主客体相互作用是通过α-CD空腔和VP形成包结络合物进行的. 环糊精二聚体α,α-CD Dimer和聚合物VP凝胶体系的构筑受环糊精二聚体类型的影响, 同时该超分子水凝胶对有竞争作用的客体分子表现出响应性, 该超分子水凝胶在竞争性客体分子存在的条件下, 可发生小分子诱导的凝胶与溶胶转化行为. 此外, 该凝胶体系还具有良好的热稳定性.     

环糊精对甲基麻黄碱手性识别的电喷雾质谱研究

利用质谱仪,使用电喷雾离子源,分别研究了以α-环糊精、β-环糊精和产环糊精作为手性拆分剂对手性药物甲基麻黄碱的手性识别效应．实验结果表明,3种环糊精对甲基麻黄碱对映体均有较强的手性识别效应,Rchiral分别为2．43、3．51、4．52．研究了电压的变化对α-环糊精、β-环糊精和γ-环糊精的手性识别的影响,研究发现,在不同的电压下,这3种环糊精对甲基麻黄碱均有手性识别能力．     

Noncovalently-Bound Cyclodextrin Dimers and Related Compounds. (Review)

In the review noncovalently-bound cyclodextrin (CD) dimers, i. e., CD host-guest 2:1 complexes as well as CD self-assembled inclusion oligomers, are briefly characterized, showing methods of their investigations; the properties and possible applications of these species are also described. __________ Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1603–1624, November, 2005.     

Molecular Recognition: Preparation of Polyrotaxan and Tubular Polymer from Cyclodextrin

We found that many α-CDs are threaded on a poly(ethylene glycol) (PEG) chain to form a crystalline complex in high yields, although β-CD did not form complexes with PEG. It was made clear that the relationship between the chain cross-sectional areas of the polymers and the diameters of the cavities of cyclodextrins is very important in the complex formation of polymers and cyclodextrins. Polyrotaxanes were prepared by the reaction of PEG–bisamine (PEGBA), which is PEG with amino groups in both ends, with 2,4-dinitro-1-fluorobenzene. In addition, the molecular tubes, a new family of novel nanostructures, were prepared and characterized. These findings indicate that such template synthesis provides a new approach to construct new nanostrutures, which may have implications for molecular technologies and materials science. © 1997 John Wiley & Sons, Ltd.     

环糊精对手性药物伪麻黄碱分子识别的电喷雾飞行时间质谱研究

用电喷雾正交飞行时间质谱仪分别研究了以α－环糊精、β－环糊精和γ－环 糊精作为手性拆分剂对手性药物伪麻黄碱的分子识别效应,同时还分别研究了 Nozzle电的变化对α－环糊精和γ－环糊精的手性识别的影响。在质谱图中能明显 反映出三种手性拆分剂都具备很强的手性识别能力,随Nozzle电压的改变,三种手 性拆分剂双分别具有各自的手性识别特征。     

Structure-Stability Study of Cyclodextrin Complexes with Selected Volatile Hydrocarbon Contaminants of Soils

The association constants for the inclusion compounds of various hydrocarbons (linear alkanes, cycloalkanes, aromatics) with different cyclodextrins (CDs) in aqueous solution have been determined using static headspace gas chromatography (SHSGC). The structure-stability relationship was examined.     

Hartree-Fock and Density Functional Theory Studies on the Molecular Recognition of the Cyclodextrin

Cyclodextrins(CD),cyclicoligomersofa-D-glucoseconnectedthroughglycosidical,4bonds,areseductivemoleculesappealingtoresearchersinpureacademicfieldsandappliedtechnologies'.ModelstudiesonCDinclusioncomplexationofferimportantinsightsintoenZyme-substrateillteractionsZandhenceattractgreatattention.Althoughmanyexperimentalapproachesareavailable,molecularmodelingprovidesanimportantalternativewayinstudyingtheCDchemistry'.Duetotheirlargesize,mosttheoreticalstudiesonCDchosemolecularmechanicsormolecula…     

β—环糊精对D／L—酪氨酸对映体的手性识别及超分子包合物的合成

利用圆二色谱研究了β－环糊精（β－ＣＤ）对Ｄ／Ｌ酪氨酸的手性识别行为，制备出了β－ＣＤ与Ｌ－酪氨酸（Ｌ－Ｔｙｒ）的固体超分子化合物，并用元素分析、薄层分析、Ｘ射线粉末衍射及热分析对包合物进行了表征，用荧光光谱法测定了包合物的形成常数．实验结果表明，β－ＣＤ具有选择包结Ｌ－酪氨酸的特性；主客体形成１１的包合物，其组成为Ｌ－Ｔｙｒ／β－ＣＤ·１２Ｈ２Ｏ；稳定常数为５．１３×１０３Ｌ／ｍｏｌ；包合物的热稳定性比主客体皆有改善     

Differential Complexing by Cyclodextrin Twin-cavity Hosts

The twin-cavity cyclodextrin (1) in which the link is a dithiotrehalosyl unit, and the flexibly-linked dimer (2) were shown to distinguish between the heterocyclic guests 3 and 4 (clofazimine drug) in spite of the guests' small structural difference. Both cyclodextrin dimer hosts form 1:1 complexes with methyl orange and with 3, as shown by double reciprocal plots of UV-absorbance change and host concentration. However with 4, both host molecules formed a 2 : 1 (host : guest) complex . Since both dimer cavities are used to create this effect, it is a new type of selectivity for macrocyclic hosts.     

环糊精葡萄糖基转移酶的固定化及其应用：Ⅲ.固定化环糊精葡萄糖基转…

用固定化环糊精葡萄糖基转移酶催化淀粉环化反应，考察了反应时间，乙醇浓度和淀粉液化程度对环糊精产率的影响。环糊精产率最高达５４％，固定化酶经多次重复使用或长时间连连续操作，酶活力降低较少。     

Redox‐Responsive Hydrogel System Using the Molecular Recognition of β‐Cyclodextrin

Summary: We have successfully constructed a redox‐responsible hydrogel system by combination of β‐cyclodextrin (β‐CD), dodecyl‐modified poly(acrylic acid) [p(AA/C₁₂)], and a redox‐responsive guest, ferrocenecarboxylic acid (FCA). In the reduced state of FCA, the ternary mixture exhibited a gel‐like behavior, whereas, in its oxidized state, the mixture exhibited a sol behavior.

Conceptual illustration for the redox‐responsive hydrogel system.     

氨基酸、多肽的环糊精化学

本文着重介绍了氨基酸、多肽－环糊精连接物的合成,分子识别和自组装,对环糊精及其衍生物与氨基酸、多肽的包合行为,异构体识别和仿酶合成作了简要概述。     

环糊精醛及其衍生物的合成与性能研究进展

综述了环糊精醛及其衍生物的合成、分子识别作用和模拟酶催化方面的最新研究进展.     

Molecular Dynamic Study for Chiral Discrimination of a -Phenylethylamine by Modified Cyclodextrin in Gas Chromatography

A molecular dynamic method in conjunction with a statistic test has been utilized to model chiral recognition of a -phenylethylamine on heptakis (2,6-di-O-butyl-3-O-butyryl)-b -cyclodextrin in gas chromatography. The modelling data correlated with the chromatographic elution order, and indicated that the preferred site of a -phenylethylamine is the interior of cavity.     

Macromolecular Recognition by Polymer‐Carrying Cyclodextrins: Interaction of a Polymer Bearing Cyclodextrin Moieties with Poly(acrylamide)s Bearing Aromatic Side Chains

Summary: The interaction of a polymer bearing β‐cyclodextrin moieties (β‐CD polymer) with poly(acrylamide)s bearing aromatic side chains was investigated by viscometry to study the effect of collectivity (i.e., interactions at multi‐sites) in macromolecular recognition. The formation of inclusion complexes at multi‐sites caused a large difference in the size of interpolymer aggregates, even though the difference in association constants for complexation of native β‐CD with guest moieties was not very much large.

Conceptual illustration for interpolymer aggregates of β‐CD polymer with poly(acrylamide)s bearing naphthyl groups substituted on the (a) 1‐ and (b) 2‐positions (see Scheme 1 ).     

Use of Quantum Chemical Methods to Study Cyclodextrin Chemistry

Studies of cyclodextrin chemistry by quantum chemical methods are briefly surveyed. Emphases are put on what types of quantum chemical methods can be used for cyclodextrin chemistry, how to use quantum chemical methods to find the global minimum, to study the structures, binding energies, driving forces for cyclodextrin complexes, as well as chemical reactions occurring inside cyclodextrin cavities. Problems associated with the application of quantum chemical methods in cyclodextrin chemistry are also discussed.     

Fluorescence Properties of Porphyrin Dimers Incorporating an Anhydride Linker

IntroductionOligomeric porphyrins play a number of criticalbiological roles in many processes, such as energytransfer and electron transfer, molecular binding, mul-tielectron redox catalysis and light harvest[1,2]. Amongthe arrays of covalently linked por…     

Synthesis and Supramolecular Studies of Chiral Boronated Platinum(II) Complexes: Insights into the Molecular Recognition of Carboranes by β‐Cyclodextrin

The synthesis and characterisation of a novel isomeric family of closo‐carborane‐containing Pt^II complexes ((R/S)‐( 1 – 4 )?2 NO₃) are reported. Related complexes ( 5 ?NO₃ and 6 ?NO₃) that contain the 7,8‐nido‐carborane cluster were obtained from the selective deboronation of the 1,2‐closo‐carborane analogues. The corresponding water‐soluble supramolecular 1:1 host–guest β‐cyclodextrin (β‐CD) adducts ((R/S)‐( 1 – 4 ) ? β‐CD?2 NO₃) were also prepared and fully characterised. HR‐ESI‐MS experiments confirmed the presence of the host–guest adducts, and 2D‐¹H{¹¹B} ROESY NMR studies showed that the boron clusters enter the β‐CD from the side of the wider annulus. Isothermal titration calorimetry (ITC) experiments revealed enthalpically driven 1:1 and higher‐order supramolecular interactions between β‐CD and (R/S)‐( 1 – 4 )?2 NO₃ in aqueous solution. A comparison of the predominate 1:1 binding mode established that the affinity of β‐CD for the guest molecule is mainly influenced by the pyridyl ring substitution pattern and chirality of the host, whilst the nature of the closo‐carborane isomer also plays some role, with the most favourable structural features for β‐CD binding being the presence of the 4‐pyridyl ring, 1,12‐closo‐carborane, and an S configuration. The results reported here represent the first comprehensive calorimetric study of the supramolecular interactions between closo‐carborane compounds and β‐CD, and it provides fascinating insights into the structural features influencing the thermodynamics of this phenomenon.