环糊精衍生物在荧光分析中的应用进展（上）

本文介绍环糊精衍生物开发概况及目前已或将商品化的环糊精衍生物的合成思路与方法，重点阐述环糊业在荧光分析中增效作用机理和应用，及环糊精母体和衍生物分析特性的不同，较详细地详述了光活性基团修饰性生物对开发和发展远景。     

质谱技术在环糊精衍生物解析中的研究进展

环糊精衍生物仍保留着环糊精的空腔及多羟基结构,并能有效改善与客体分子的结合性能,在分子识别、分离分析、食品、药物等领域得到广泛应用。在这些新型衍生物的表征过程中,质谱技术是一种不可或缺的手段,用于测定新化合物的质荷比。本工作综述了质谱分析在几类环糊精衍生物结构解析中的应用进展,包括环糊精醛衍生物、环糊精醚衍生物、环糊精酯衍生物等。     

新型环糊精衍生物单6-O-苯基胺甲酰基-β-环糊精的合成及其在手性药物毛细管区带电泳拆分中的应用

合成了新型的环糊精衍生物单6-O-苯基胺甲酰基—β-环糊精，并对合成产物进行了表征。以新型环糊精衍生物为手性选择剂，考察了手性选择剂浓度、缓冲液PH值和浓度及有机溶质对8种手性药物对映体的毛细管电泳分离的影响。结果表明：手性选择剂浓度和缓冲液PH值是影响药物对映体分离的重要因素，有机溶质亦对分离有很大影响。单6-O-苯基胺甲酰基—β-环糊精能使所研究的8种手性药物中的5种达基线分离，3种达部分分离。而在同样条件下．β-环糊精仅能使上述药物中的菜心安达部分分离(及。＝0．67)，这说明我们合成的环糊精衍生物手性拆分能力要强于天然环糊精。我们还就单6-O-苯基胺甲酰基-β-环糊精对手性药物可能的拆分机理进行了探讨。     

环糊精衍生物气相色谱手性固定相研究进展

评述近年环糊精衍生物气相色谱手性固定相的研究进展,对环糊精衍生物进行分类并总结了近年来其在GC手性分离上的应用,介绍环糊精衍生物的手性分离机制及纯度问题进展,展望环糊精衍生物作GC手性固定相的应用前景。     

含环糊精膜的制备与应用

本文简要介绍了环糊精的结构和性质,环糊精具有外部亲水,内部疏水的特殊分子构型,在膜内引入环糊精或环糊精衍生物对膜的性能具有很大的影响。综述了环糊精及其衍生物膜在异构体分离、金属离子传递、药物控制释放、药物检测与分析、酯盐水解及其他领域等方面的应用,评述了环糊精在自组装分子管道方面的作用,最后对含环糊精膜的发展方向进行了展望。     

环糊精在手性药物分离分析研究中的应用

环糊精由于自身特殊的手性环境和结构特征,已广泛运用于手性化合物的对映体拆分及分析。对近年来环糊精在各种色谱、质谱及核磁等分析方法中的应用进行了归纳总结,综述了环糊精及其衍生物在手性药物的分离分析方面的研究进展。     

β－环糊精衍生物的合成及对脲酶的抑制作用

β┐环糊精衍生物的合成及对脲酶的抑制作用＊丁志刚任维衡习玲玲罗天顺宋发军（中南民族学院化学系，武汉４３００７４）关键词β－环糊精，衍生物，脲酶，配合物近年来，随着生物医学工程的迅速发展，新型医用级吸附树脂的研制取得了较大进步．其中有关铵离子和尿素的吸...     

环糊精及其衍生物对显色和荧光反应作用的比较研究

比较了α－、β－、γ－环糊精及β－环糊精的离子型衍生物对三种显色反应的作用，结果表明，多数具有增和艇，增的大小与环糊精空胶的几何形状、高低和客体分子的匹配性、环糊精内腔与客体的疏水作用力、环糊精的浓度及离子型衍生物性等因素有关：比较了β－环精及其非离子型衍生物对Ａｌ（Ⅲ）－铁试剂荧光瓜的作用，结果表明：体系的荧光强度均显著增大、选择性明显提高。     

氯诺昔康与中性及电荷型β-环糊精衍生物的包合作用

采用溶解度法研究了不同pH值下氯诺昔康与中性及电荷型β-环糊精衍生物的包合作用．结果表明,氯诺昔康与3种环糊精都形成了1：1的包合物．以包合常数作为包合作用的量度,在酸性和中性条件下包合能力较碱性强,其中磺丁醚-β-环糊精（SBE移CD）在酸性条件下包合常数最大．电荷型伊环糊精除了通常的疏水作用力为主客体间包合驱动力外,还存在额外的静电包合作用力．     

环糊精衍生物在液相有机合成中的应用

综述了环糊精(包括α-环糊精、β-环糊精和y-环糊精)衍生物在液相有机合成中的应用,主要包括其作为人工合成酶、超分子光学手性源、亲偶极体和微通道反应器在氧化、水解、还原、光催化异构化、1,3-偶极环加成等反应中的应用.其中环糊精衍生物作为人工合成酶应用最广,该催化剂中起催化作用的为环糊精衍生物的修饰基团.与环糊精母体相比,修饰基团的引入增加了环糊精分子中官能团的种类和数量,拓展了环糊精在液相有机合成中的应用,并提高了催化反应的催化活性和选择性.     

Use of various β‐cyclodextrin derivatives as chiral selectors for the enantiomeric separation of ofloxacin and its five related substances by capillary electrophoresis

A capillary electrophoretic method for the enantioseparation of ofloxacin and its five related substances (potential impurities, indicated as impurities B–F) was developed using β‐cyclodextrin derivatives as chiral selectors. To our knowledge, there are no previous studies about using capillary electrophoresis for the separation of impurities B–D. Six β‐cyclodextrin derivatives including cationic (piperidine‐ and cyclohexylamine‐), neutral (dimethyl‐ and hydroxypropyl‐), and anionic (carboxymethyl‐ and sulfated‐) β‐cyclodextrin derivatives were tested and operational parameters such as buffer pH and concentration of β‐cyclodextrin derivatives were investigated. The best resolutions were all obtained with anionic β‐cyclodextrin derivatives: ofloxacin, impurities C–F could be best resolved with carboxymethyl‐β‐cyclodextrin at satisfactory resolutions of 8.27, 9.98, 5.92, 8.49 and 6.78, respectively, while for impurity B, a particularly impressive resolution value, up to 21.38, was observed using sulfated‐β‐cyclodextrin. The enhancement of enantioseparation observed for the tested analytes using anionic β‐cyclodextrin derivatives might be due to some favorable interaction between selectors and analytes. Given the fact that the selection of chiral selector depends on the structures of analytes, with the help of structural similarities and differences of the analytes, the structure–separation relationship was further discussed.     

Cyclodextrin dimer derivatives used as stationary phase for capillary gas chromatography

Summary Four cyclodetrin dimer derivatives were synthesized by linking two single cyclodextrin derivatives with difunctional spacer at the primary side of cyclodetrin. The separation properties of these cylodextrin dimer derivatives as CGC stationary phases were investigated and compared with those of the unbridged native cyclodextrin derivative. The results show that two recognition sites and one link spacer of these cyclodextrin dimer derivatives cooperate in separation and affect the separation of disubstituted benzene positional isomers.     

Novel stationary phases for high-performance liquid chromatography analysis of cyclodextrin derivatives

Novel stationary phases were prepared for separation of cyclodextrins and cyclodextrin derivatives by bonding substituted aromatic groups (phenyl and naphthyl) to the silica gel matrix. Both the electron-withdrawing (nitro) and the hydrogen-donor/acceptor (amide or carbamide) substituents of the phenyl group play essential role in the separation of cyclodextrins and cyclodextrin derivatives. On the basis of the comparison of experimental data obtained on different columns the N-(4-nitrophenyl)-carbamide group bonded silica gel stationary phase was selected as the most effective one for analysis of cyclodextrin derivatives. Improved separation potency was observed for hydroxypropylated, methylated and several other cyclodextrin derivatives compared with the previously and presently used stationary phases. Owing to the strong retention of cyclodextrins and its derivatives on the selected column, detection of their decomposition products was easily achieved. Determination of unsubstituted, natural cyclodextrin as an impurity in the cyclodextrin derivatives was implemented. Identification and characterization of cyclodextrin derivatives in industrial products could also be performed.     

Chiral separation of cathinone derivatives using β‐cyclodextrin‐assisted capillary electrophoresis–Comparison of four different β‐cyclodextrin derivatives used as chiral selectors

In the past decade, more than 100 different cathinone derivatives slopped over entire Europe due to their enormous popularity. Generally, these novel psychoactive substances are easily available via the internet. This fact leads to various social problems, since cathinones are substances with consciousness‐changing effects and are mainly misused for recreational matters by their consumers. Cathinones possess a chiral center including two enantiomeric forms with potentially different pharmacological behavior. This fact makes analytical method development regarding their chiral separation indispensable. In this study, a chiral capillary zone electrophoresis method for the enantioseparation of 61 cathinone and pyrovalerone derivatives was developed by means of four different β‐cyclodextrin derivatives. As chiral selectors, native β‐cyclodextrin as well as three of its derivatives namely acetyl‐β‐cyclodextrin, 2‐hydroxypropyl‐β‐cyclodextrin, and carboxymethyl‐β‐cyclodextrin were used. The cathinone and pyrovalerone derivatives were either purchased in internet stores or seized by police. As a result, overall 58 of 61 studied substances were partially or baseline separated by at least one of the four chiral selectors using 10 mM of β‐cyclodextrin derivative in a 10 mM sodium phosphate buffer (pH 2.5). Furthermore, the method was found to be suitable for simultaneous enantioseparations, for enantiomeric purity checks and to differentiate between positional isomers. Moreover, an intra‐ and an interday validation was performed successfully for each chiral selector to prove the robustness of the method.     

环糊精衍生物在金属催化有机合成中的应用

综述了环糊精(包括α-环糊精,β-环糊精和γ-环糊精)衍生物在金属催化有机合成中的应用,主要包括其作为金属离子配体、金属纳米粒子稳定剂和反相相转移催化剂在氧化、水解、还原、偶联等金属催化反应中的应用.其中环糊精衍生物作为金属离子配体应用最广,由于环糊精部分与底物形成包结络合物,拉近了底物和具有催化活性的金属离子的距离,并固定了底物的反应部位,往往可以显著提高催化反应的反应速率,增强反应的区域选择性和对映选择性.     

Modified gamma-cyclodextrins and their rocuronium complexes

A series of per-6-substituted cyclodextrin derivatives was synthesized as synthetic host molecules for rocuronium, a steroidal muscle relaxant. By forming host-guest complexes with rocuronium, these cyclodextrin derivatives reverse the muscle relaxation induced by rocuronium in vitro and in vivo. The isothermal microcalorimetry data are consistent with the biological data supporting the encapsulation mechanism of action. Binary and biphasic complexes are reported with NMR experiments clearly showing free and bound rocuronium. [structure: see text]     

环糊精及其衍生物在毛细管电泳手性拆分中的应用

对环糊精衍生物进行分类,总结了近几年来环糊精衍生物在毛细管电泳手性拆分中的应用。     

Phosphocontaining Cyclodextrins as a New Class of Supramolecular Structures

Principal peculiarities of the use of phosphocontaining cyclodextrins as a new class of supramolecular structures are discussed. For the first time cyclodextrin perphosphite has been obtained and isolated in an individual state by the treatment of g -cyclodextrin with triazolide neopentylenephosphorous acid. Cyclodextrin perphosphite exhibited an unusual transphosphorylation under reaction with some chlorophosphites. The inclusion of adamantane into the cyclodextrin cavity results in slowing this reaction down. Some water-soluble cyclodextrin derivatives displayed high activity as phase transfer catalysts in biphase catalysis.     

Comparison of Different Di‐tert‐butyldimethyl‐Silylated Cyclodextrins as Chiral Stationary Phases in Capillary Gas Chromatography

Separation factors and thermodynamic data for the separation of various chiral analytes on different di‐O‐tert‐butyldimethyl‐silylated cyclodextrin derivatives are collected and described. Modifying the substitution pattern of the tert‐butyldimethylsilyl group in position 2 and 3 or changing from β‐ to γ‐cyclodextrin significantly affects the separation properties of the cyclodextrin derivatives.