A new symmetrically modified α-cyclodextrin tripode: selective metal complexation and fluorescence properties

A new tripodal α-cyclodextrin having three ureido-bipyridyl tethers symmetrically distributed on its upper rim was prepared in one step by the polymer supported ‘phosphine imide’ reaction in a medium yield. As expected, the highly selective complexation properties towards ‘hard’ and ‘soft’ cations were maintained with regards to the URFT-Cd (upper rim fully tethered) family previously investigated. Its Eu^III and Tb^III lanthanide complex fluorescence behaviour clearly indicates that a limited number of tethers allow a better bis-heterocyclic antenna self-organisation around the cation leading to enhanced fluorescence properties.     

环糊精手性微反应器中苯乙烯的不对称环氧化反应

研究了酮与环糊精手性协同催化作用下,用非手性酮与过氧硫酸氢钾(商品名Oxone)原位产生的二氧杂环丙烷实现了对包合在环糊精手性微反应器中苯乙烯的不对称环氧化反应,考察了α-环糊精、β-环糊精、γ-环糊精与不同的酮协同催化反应效果,并对协同催化反应机理进行了探讨.结果表明,β-环糊精和甲基异丁基酮(MIBK)及Oxone原位形成的二氧杂环丙烷具有较好的协同催化作用;MIBK用量、碳酸氢钠用量、反应时间和温度等因素对反应产物的收率和对映体选择性有一定的影响.在优化条件下,环氧苯乙烷的ee值可达46%.     

Design of Supramolecular Cyclodextrin Complex Sensors for Ion and Molecule Recognition in Water

The design and function of novel supramolecular fluoroionophore/cyclodextrin (CyD) complex sensors for ion and molecule recognition in water are reviewed. For the crown ether fluoroionophore/-CyD complex, the dimerization of the fluoroionophore inside the -CyD is found to be selectively promoted by alkali metal ion binding, thereby resulting in metal-ion-selective pyrene dimer emission in water. This supramolecular function is successfully utilized in the design of a podand fluoroionophore/-CyD complex for sensing toxic lead ion in water. The boronic acid fluoroionophore/-CyD complex binds sugars and produces increased fluorescence emission in water. The response mechanism appears to be due to the suppression of the photoinduced electron transfer (PET) from pyrene donor to trigonal phenylboronic acid acceptor. This is a novel emission function provided by the boronic acid fluoroionophore/-CyD complex sensors in water.     

Spectroscopic Study on Interaction of β-Cyclodextrin with Triprolidine Hydrochloride

The complexation of triprolidine hydrochloride （TRP） and β-cyclodextrin （β-CD） in deuterium oxide was investigated by 400 MHz 1^H NMR spectroscopy. The 800 MHz 2D ROESY data revealed that two 1 ：1 and one 2 ： 1 β-CD-TRP inclusion complexes were formed. Both aromatic moieties （p-tolyl and pyridyl ring） has entered into the β-CD cavity, confirming the existence of two different equilibria for 1 ： 1 inclusion complexes in which p-tolyl ring of the guest is more tightly held by the host cavity. The ROE intermolecular interactions provided the plausible structures of these 1 ： 1 and 2 ： 1 stoichiometric inclusion complexes of β-CD-triprolidine hydrochloride in solu- tion.     

两种β－环糊精衍生物手性石英毛细管柱拆分对映体

合成了全戊基化（Ⅰ）和部分戊基化三氟乙酰化（Ⅱ）的两种“环糊精手性固定相。将它们分别与ＯＶ－７混合制备出柱效大于４１００塔片／ｍ，热稳定性可达２１０℃的手性石英毛细管住。对映体拆分结果表明，固定相Ⅰ对醇、二醇、胺、γ－内酯等对映体比Ⅰ有更高的选择性。     

改性环糊精气相色谱手性固定相拆分对映体的选择性及拆分机理的讨论

改性环糊精气相色谱手性固定相拆分对映体的选择性及拆分机理的讨论周昕，万宏，欧庆瑜（中国科学院兰州化学物理研究所兰州７３００００）１前言自１９８８年Ｋｏｎｉｇ￣［１］等人成功地将改性环糊精用于毛细管气相色谱固定相拆分对映体以来，环糊精衍生物以其高选择性...     

系列单取代烷氧基-2-羟丙基-β-环糊精的合成与表征

以环氧氯丙烷和脂肪醇为原料, 通过相转移催化法合成了乙基、正丙基、正丁基和正戊基缩水甘油醚(1～4), 并利用所合成的缩水甘油醚和β-环糊精为原料, 分别在弱碱水溶液(1.5%)和强碱水溶液(30%)中制备并用硅胶柱分离出单2位取代的乙氧基、丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(1a～4a)和单6位取代的丙氧基、丁氧基和戊氧基-2-羟丙基-β-环糊精(2b～4b), 利用薄层色谱、红外光谱、差热扫描量热分析、质谱和核磁共振等手段对所合成的产品进行了表征.     

Enatiomeric analysis of simendan by CE with beta-CD as chiral selector compared with CMPA-HPLC

The chiral separation of simendan enantiomers using capillary electrophoresis was studied with beta-cyclodextrin (beta-CD) as chiral selector. The influences of the concentration and pH of borate buffer solution, beta-CD concentration and methanol content in the background electrolyte were investigated. These factors were compared with those in an HPLC with beta-CD as chiral mobile phase additive (CMPA-HPLC). The quantification properties of the developed CE method were examined. A baseline separation of simendan enantiomers was achieved in the background electrolyte of 20 mmol/L borate buffer (pH 11.0) containing 12 mmol/L beta-CD-methanol (50:50 in volume ratio). The CE method is comparable with CMPA-HPLC in chiral resolution, although the optimal pH in CE (11.0) is much higher than that (6.0) in CMPA-HPLC. This chiral CE method is applicable to the quantitative ananlysis and enantiomeric excess value determination of L-simendan.     

Some Pharmaceutical Properties of a New Branched Cyclodextrin, 6-O-α-(4-O- α-D-Glucuronyl)-D-glucosylβ-cyclodextrin

Some physicochemical and biological properties of a new branched cyclodextrin, 6-O--(4-O--d-glucuronyl)-d-glucosyl--cyclodextrin GUG--CyD) were investigated. Further, theinteraction of GUG--CyD with several drugs was studied by the solubility and spectroscopic methods, and compared with those of parent -CyD and 6-O--maltosyl--CyD(₂--CyD).The hemolytic activity of GUG--CyD on rabbit erythrocytes was lower than those of -CyD and ₂--CyD. GUG--CyD and ₂--CyD showed negligible cytotoxicity on Caco-2 cells up to at least 0.1 M. The inclusion ability of GUG--CyD to neutral and acidic drugs was comparable to or slightly smaller than those of -CyD and ₂--CyD, probably because of a steric hindrance of the branched sugar. On the other hand, GUG--CyD showed greater affinity for the basic drugs, compared with -CyD and ₂--CyD, owing to the electrostatic interaction of its carboxylate anion with positive charge of basic drugs. Thus GUG--CyD may be useful as a safe solubilizing agent particularly for basic drugs.     

甲基丙烯酸N,N-二甲氨基乙酯与丙烯酰β-环糊精共聚水凝胶的合成及其性能研究

用不同的方法合成了两种结构不同的丙烯酰 β 环糊精酯 (β CD 3 A和 β CD 6 A) ,以此为单体与甲基丙烯酸N ,N 二甲氨基乙酯 (DMAEMA)通过氧化还原自由基引发聚合 ,合成出两类含 β 环糊精结构单元的新型水凝胶 .用核磁共振 ,红外光谱及元素分析对两种单体及共聚物的结构和组成进行了表征 .溶胀实验结果表明 ,两类水凝胶均具有较好的pH、温度及离子强度敏感性 ,且因其交联网络结构不同 ,其溶胀性能有所差异