环瑚精作为超分子结构的构筑单元

对环糊精的来源和分子结构特点作了简要介绍,论述了环糊精及其衍生物在超分子化学领域中的地位。理论研究上,环糊精是研究弱相互作用的模型分子化合物,化学工业中环糊精及其衍生物具有广泛用途,显示出环糊精化学研究和应用的无限潜力。     

超分散剂的分子结构设计

超分散剂是一类新型的聚合物分散助剂，其分子结构上含有溶剂化链与锚固基团两个部分，这两部分的性能和功用均不相同。在进行超分散剂产品开发时，必须根据分散体系的理化性质，就溶剂化链的单元结构，链长及锚固基团的种类，数量等进行合理的设计。     

环糊精和环糊精包合物

环糊精是由6个或6个以上D－吡喃葡萄糖单元通过α－1，4成键形成的环状低聚糖，其分子具有较大的非极性柱状内腔供尺寸足够小的各种客体嵌入，形成包合物。介绍了环糊精对各种有机，无机和金属有机客体的包合，讨论了主客体双方的尺寸和性质对包合物的结构的影响，着重比较了环糊精和不同客体间的相互作用及形成包合物的稳定性。     

β-环糊精与苄基甲基酮超分子包合物

研究了β-环糊精与苄基甲基酮主、客体分子的包合反应.通过红外、热重-差热、X-射线衍射、核磁共振及元素分析方法确定了包合物的形成与组成.包合物明显改变了主、客体的晶相、光谱及热学性质.核磁共振及元素分析结果表明：β-环糊精与苄基甲基酮形成了包合比（主、客体的物质的量之比）为2：1的包合物,苄基甲基酮的苄基及甲基分别嵌入了两个β-环糊精的空腔.     

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。     

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。     

滑石粉对聚甲醛超分子结构及性能的影响

滑石粉作为聚甲醛(POM)的成核剂和填充料使用已为人们所接受。聚合物借助各种晶胞形成结晶,可结晶性聚合物熔体在冷却时,结晶作用从各个晶核铺开,并形成由诸多晶粒构成的球晶。结晶聚合物材料的抗冲强度主要取决于球晶的大小及分布。已有人注意到     

Threading Cyclodextrins in Chloroform: A [2]Pseudorotaxane

The unusual self-assembly in chloroform of a novel cyclodextrin-based [2]pseudorotaxane, composed of heptakis-2,6-di-O-methyl-3-O-acetyl-β-cyclodextrin and a viologen-containing linear component, is reported.     

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。     

Supramolecular Materials from Inorganic Building Blocks

Inorganic materials of nanometric dimensions and controllable morphologies are now widely available permitting their use as building blocks in supramolecular structures. Incorporation of inorganic blocks into hybrid structures can yield unique materials that have no naturally occurring or organic synthetic analogues. In this short review, we describe the construction and functions of supramolecular materials prepared using inorganic building blocks, with emphasis on material-like components. Examples described in this review are categorized as (i) inorganic structures within organic assemblies (silica-supported Langmuir monolayers, organic–inorganic lipid bilayer vesicles etc.), (ii) organic components in inorganic nanospaces (mesoporous materials including biocomponents such as peptides and proteins), (iii) organic/inorganic nanohybrid blends (nanorod-liquid crystal blends and surfactant-guided gold nanostructures), and (iv) hierarchic structures (layer-by-layer assemblies of mesoporlous carbons and capsules).     

环糊精二聚体与金刚烷修饰聚丙烯酰胺的主客体相互作用

合成了环糊精二聚体(trans-Azoβ-CD Dimer)及侧链含金刚烷(Ad)的聚丙烯酰胺(PAM-Ad),利用trans-Azoβ-CD Dimer与PAM-Ad侧链的Ad基团的主客体识别作用构筑了一类超分子体系。2D NMR测定结果表明,trans-Azoβ-CD Dimer和PAM-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-Azoβ-CD Dimer和聚合物PAM-Ad两者之间的缔合程度受trans-Azoβ-CD Dimer和PAM-Ad的浓度、温度、盐浓度以及trans-Azoβ-CD Dimer光异构的影响。     

pH sensitive supramolecular vesicles from cyclodextrin graft copolymer and benzimidazole ended block copolymer as dual drug carriers

Supramolecular assemblies from chitosan-graft-β-cyclodextrin (CS-g-CD) and benzimidazole ended poly(ethylene glycol)-block-poly(ε-caprolactone) (PEG-b-PCL-BM) were formed based on the inclusion complexation between β-cyclodextrin and benzimidazole. The supra-amphiphiles self-assembled into complex vesicles with PCL/β-CD as the hydrophobic membrane, hydrophilic PEG and CS as the corona. The hydrophobic membrane and aqueous lumen of vesicles exhibited efficient entrapment both for hydrophobic curcumin (CUR) and hydrophilic doxorubicin (DOX). The drug loading of vesicles was more than 20.2% and 38.4% for CUR and DOX, respectively. Decreasing pH to acidic condition or increasing temperature, more controllable and rapid release of two drugs was observed. Cytotoxicity assays revealed that dual drug-loaded vesicles retained high cell proliferation inhibition efficiency than free drugs.GRAPHICAL ABSTRACT     

Preparation of β-Cyclodextrin-Dextran Polymers and their Use as Supramolecular Carrier Systems for Naproxen

Summary Dextran, previously activated by periodate oxidation, was grafted with mono-6-amino-6-deoxy-β-cyclodextrin, mono-6-ethylenediamino-6-deoxy-β-cyclodextrin, and mono-6-butylenediamino-6-deoxy-β-cyclodextrin by reductive alkylation in the presence of NaBH₄. The polymers were able to form inclusion complexes with Naproxen, increasing the solubility of the drug by 2.2-2.6 folds. The β-cyclodextrin-grafted dextrans were used as macromolecular carriers for Naproxen, improving the “in vivo” anti-inflammatory activity of the drug.     

Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins: How to Design the Water‐Soluble Phenylphosphane to Avoid Interaction with Cyclodextrin

The ability of cyclodextrin to interact with meta‐trisulfonated triphenylphosphane derivatives bearing one or two methyl (or methoxy) groups on the aromatic ring has been investigated by NMR and UV‐vis spectroscopy. In the case of native β‐cyclodextrin (β‐CD), the presence of one methyl or methoxy group in the ortho‐position on each aromatic ring is necessary to hamper the formation of an inclusion complex between the β‐CD and meta‐trisulfonated triphenylphosphane derivatives. In the case of methylated β‐CD, the formation of an inclusion complex is only observed when the meta‐trisulfonated triphenylphosphane contains a methyl group in the para‐position. The poor affinity of methylated β‐CD towards modified trisulfonated triphenylphosphanes was attributed to the steric hindrance generated by the methyl groups on the CD secondary face. The absence or presence of an interaction between phosphanes and methylated β‐CD was also confirmed by catalytic experiments. Thus, the phosphanes that do not interact with the methylated CD were the most efficient mass‐transfer promoters in an aqueous biphasic palladium‐catalyzed Tsuji–Trost reaction.     

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。     

Supramolecular Zn(II)-Dipicolylamine-Azobenzene-Aminocyclodextrin-ATP Complex: Design and ATP Recognition in Water

Cyclodextrins (CyDs) are water-soluble host molecules possessing a nanosized hydrophobic cavity. In the realm of molecular recognition, this cavity is used not only as a recognition site but also as a reaction medium, where a hydrophobic sensor recognizes a guest molecule. Based on the latter concept, we have designed a novel supramolecular sensing system composed of Zn(II)-dipicolylamine metal complex-based azobenzene (1-Zn) and 3A-amino-3A-deoxy-(2AS,3AS)-γ-cyclodextrin (3-NH₂-γ-CyD) for sensing adenosine-5′-triphosphate (ATP). 1-Zn showed redshifts in the UV-Vis spectra and induced circular dichroism (ICD) only when both ATP and 3-NH₂-γ-CyD were present. Calculations of equilibrium constants indicated that the amino group of 3-NH₂-γ-CyD was involved in the formation of supramolecular 1-Zn/3-NH₂-γ-CyD/ATP. The Job plot of the ICD spectral response revealed that the stoichiometry of 1-Zn/3-NH₂-γ-CyD/ATP was 2:1:1. The pH effect was examined and 1-Zn/3-NH₂-γ-CyD/ATP was most stable in the neutral condition. The NOESY spectrum suggested the localization of 1-Zn in the 3-NH₂-γ-CyD cavity. Based on the obtained results, the metal coordination interaction of 1-Zn and the electrostatic interaction of 3-NH₂-γ-CyD were found to take place for ATP recognition. The “reaction medium approach” enabled us to develop a supramolecular sensing system that undergoes multi-point interactions in water. This study is the first step in the design of a selective sensing system based on a good understanding of supramolecular structures.     

Multivalent Protein Assembly Using Monovalent Self-Assembling Building Blocks

Discotic molecules, which self-assemble in water into columnar supramolecular polymers, emerged as an alternative platform for the organization of proteins. Here, a monovalent discotic decorated with one single biotin was synthesized to study the self-assembling multivalency of this system in regard to streptavidin. Next to tetravalent streptavidin, monovalent streptavidin was used to study the protein assembly along the supramolecular polymer in detail without the interference of cross-linking. Upon self-assembly of the monovalent biotinylated discotics, multivalent proteins can be assembled along the supramolecular polymer. The concentration of discotics, which influences the length of the final polymers at the same time dictates the amount of assembled proteins.