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1.
研究了以环糊精为主体,左氧氟沙星为客体的配位反应,用紫外-可见吸收光谱法,分子荧光光度法,差热分析法,X-衍射法等方法对超分子配合物进行了表征,并对超分子配合物的形成进行了初步讨论,实验结果表明:β-环糊精与左氧氟沙星分子形成物质的量比为1∶1的超分子配合物.通过β-环糊精超分子配合物的形成,进一步研究了左氧氟沙星与DNA的作用机理,发现它们之间主要作用力是疏水作用.  相似文献   

2.
研究了诺氟沙星与β-环糊精(简称β-CD)及其两种衍生物羟丙基-β-环糊精(简称Hp-β-CD)、甲基-β-环糊精(简称Me-β-CD)形成的超分子体系.利用荧光光谱法测定了超分子体系的包结常数和包结比,及其热力学参数.诺氟沙星与3种环糊精均形成1∶1稳定的包合物,诺氟沙星与β-CD、Me-β-CD及Hp-β-CD作用...  相似文献   

3.
光谱法研究环糊精与艾地苯醌的超分子作用   总被引:1,自引:1,他引:0  
用荧光光谱法研究了药物艾地苯醌与β-环糊精在溶液中的超分子复合作用,发现在加入β-环糊精后其荧光强度显著增强;Benesi-Hildebrand曲线显示在溶液中它们之间以1∶1的方式结合,包合常数K为412mol/L;紫外滴定实验显示出艾地苯醌的去质子化常数在加入β-CD后与本身的pKa基本一致,说明超分子复合物中艾地苯醌分子中的—OH基团存在于环糊精空腔外面。核磁测试显示在加入β-CD后艾地苯醌的C-11的化学位移向高场移动,而C-11上的氢位移则向低场移动,表明芳环上的甲氧基进入了环糊精的空腔。  相似文献   

4.
紫外光谱法研究β-环糊精与卵磷脂的包结作用   总被引:8,自引:0,他引:8  
不同摩尔配比的β-环糊精/卵磷脂的甲醇-水溶液的紫外吸收光谱和固体包结化合物的元素分析结果表明,约2分子的β-环糊精和1分子的卵磷脂依据范德华作用力和疏水作用力等发生包结作用,生成了稳定的包结化合物。  相似文献   

5.
α-环糊精包合物中环己烷构象平衡的PM3研究   总被引:1,自引:0,他引:1  
用PM3分子轨道方法研究了α-环糊精的包合作用对怀烷构象平衡的影响。发现α-环糊精的包合作用可以改变环己烷的构象平衡。计算结果表明,虽然环己烷的椅式构象比船式构象稳定18.5kJ·mol^-1,但在α-环糊精的包合物中,船式环己烷包合物比椅式环己烷包合物稳定4.4kJ·mol^-1。因此,超分子体系中客体分子的构象平衡不能简单地从其游离态的构象平衡外推得到,而应该考虑在超分子体系中分子间相互作用对  相似文献   

6.
紫外光谱法研究环糊精/精噁唑禾草灵超分子复合体   总被引:1,自引:0,他引:1  
采用紫外光谱法研究了β-环糊精(β-CD)、羟丙基-β-环糊精(HP-β-CD)和部分甲基化β-环糊精(RAMEB)与精噁唑禾草灵(FE-p)间的超分子作用。在体积比为1:4的乙醇水溶剂中,在298.15~318.15K的温度范围内,3种环糊精均能与FE-p形成稳定的1:1型的超分子复合体,其结合常数值大小依次是KRAMEB〉KHP-βCD〉KβCD,且随着温度的升高而降低。经过计算,热力学参数AG,△H和△S均为负值,说明结合反应是放热反应且能自发进行,焓变是形成超分子复合体的主要驱动力,符合熵焓补偿效应。  相似文献   

7.
研究了β-环糊精(β-CD)及其衍生物甲基-β-环糊精(M-β-CD)、羟丙基-β-环糊精(HP-β-CD)对水杨酸甲酯(MS)双重荧光光谱的影响,并将其与MS在不同溶剂中的荧光光谱进行对比.结果表明.MS的双重荧光与所处微环境的氢键性质密切相关,β-CD取代基的大小会导致空腔口处的极性和空间位阻不同,相应改变了分子间氢键相互作用.当MS分子进入β-CDs空腔时会引起其基态互变异构体之间平衡的移动.从而导致光谱的变化.包合物稳定常数测定表明.三种β-CDs对MS包合能力的大小为M-β-CD>HP-β-CD>β-CD.  相似文献   

8.
以甲基橙为探针,用紫外光谱法研究了β-环糊精与不同神经递质分子(多巴胺、去甲基肾上腺素、肾上腺素和异丙基肾上腺素)的作用,并通过竞争包结法测定了β环糊精和不同神经递质分子形成包结物的包结常数,证实了疏水作用和氢键对包结物的形成起重要作用。  相似文献   

9.
采用紫外光谱法研究了β-环糊精(β-CD)、羟丙基-β-环糊精(HP-β-CD)和部分甲基化β-环糊精(RAMEB)与精(口恶)唑禾草灵(FE-p)间的超分子作用.在体积比为1:4的乙醇-水溶剂中,在298.15~318.15K的温度范围内,3种环糊精均能与FE-p形成稳定的1:1型的超分子复合体,其结合常数值大小依次是KRAMEB>KHP-β-CD>KβCD,且随着温度的升高而降低.经过计算,热力学参数△G,△H和△S均为负值,说明结合反应是放热反应且能自发进行,焓变是形成超分子复合体的主要驱动力,符合熵焓补偿效应.  相似文献   

10.
β-环糊精(cyclodcxtrin)与环氧氯丙烷(Epichlorohydrin)一个系列的共聚物获得,~1HNMR以D_2O或DMSO-d_6为溶剂的测定,其谱峰被归属.共聚合反应机理为以羟基和环氧基为活性中心的亲核取代.当环氧氯丙烷:β-环糊精=n≤3时,聚合物分子链呈现以β-环糊精母体为中心的线状或低枝化状链结构;当n≥5时,分子链出现交联网络结构.n越大(n≤12),分子量越急剧增加,其交联度也越大.  相似文献   

11.
环糊精包结物的形成及光谱表征   总被引:13,自引:0,他引:13  
环糊精包结物的制备、结构、性质和应用研究一直是环糊精化学的重要内容。本文对近年来关于环糊精的形成条件、制备方法、包结类型、检测手段和表征方法进行了较详细的综述 ,希望对环糊精应用研究工作的进行起到积极的、科学的指导作用。  相似文献   

12.
Cyclodextrin-based aggregates and characterization by microscopy   总被引:2,自引:0,他引:2  
Cyclodextrin-based aggregates have been widely investigated with microscopies such as STM, AFM, SEM, TEM, and fluorescent microscopy to obtain the direct morphology and structure of samples. In the present review, we discuss various types of cyclodextrin aggregates, that is, native and modified cyclodextrins, inclusion complexes and their aggregates of cyclodextrins, cyclodextrin rotaxanes and polyrotaxanes, cyclodextrin nanotubes and their secondary assembly, and other high-order aggregates of cyclodextrins. Especially, we focus on the use of microscopy to characterize above aggregates. The application of modern microscopy tools promotes the investigation on cyclodextrins.  相似文献   

13.
Solutions of alpha, beta, and gamma cyclodextrin have been shown to enhance the chemiluminescence of the reaction between hydrogen peroxide and 10,10'-dimethyl-9,9'biacridinium nitrate. A 20-fold increase in chemiluminescence intensity is observed in 10-2 M beta cyclodextrin. The enhancement is attributed to an increase in the excitation efficiency and the rate of the reaction through the inclusion of a reaction intermediate in the cyclodextrin cavity.  相似文献   

14.
The reactivity of Chlorpyrifos‐Methyl ( 1 ) toward hydroxyl ion and the α‐nucleophile, perhydroxyl ion was investigated in aqueous basic media. The hydrolysis of 1 was studied at 25 °C in water containing 10% ACN or 7% 1,4‐dioxane at NaOH concentrations between 0.01 and 0.6 M ; the second‐order rate constant is 1.88 × 10?2 M ?1 s?1 in 10% ACN and 1.70 × 10?2 M ?1 s?1 in 7% 1,4‐dioxane. The reaction with H2O2 was studied in a pH range from 9.14 to 12.40 in 7% 1,4‐dioxane/H2O; the second‐order rate constant for the reaction of HOO? ion is 7.9 M ?1 s?1 whereas neutral H2O2 does not compete as nucleophile. In all cases quantitative formation of 3,5,6‐trichloro‐2‐pyridinol ( 3 ) was observed indicating an SN2(P) pathway. The hydrolysis reaction is inhibited by α‐, β‐, and γ‐cyclodextrin showing saturation kinetics; the greater inhibition is produced by γ‐cyclodextrin. The reaction with hydrogen peroxide is weakly inhibited by α‐ and β‐cyclodextrin (β‐CD), whereas γ‐cyclodextrin produces a greater inhibition and saturation kinetics. The kinetic data obtained in the presence of β‐ or γ‐cyclodextrin for the reaction with hydroxyl or perhydroxyl ion indicate that the main reaction pathway for the cyclodextrin‐mediated reaction is the reaction of HO? or HOO? ion with the substrate complexed with the anion of the cyclodextrin. The inhibition is attributed to the inclusion of the substrate with the reaction center far from the ionized secondary OH groups of the cyclodextrin and protected from external attack of the nucleophile. Sucrose also inhibits the hydrolysis reaction but the effect is independent of its concentration. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

15.
The inclusion complexes of p‐sulfonated calix[4, 6] arene and β‐cyclodextrin with dopamine were studied by fluorescence spectrometry in aqueous media. It was found that the fluorescence intensity of dopamine regularly decreased upon the addition of p‐sulfonated calix[4, 6] arene, on the contrary, it increased upon the addition of β‐cyclodextrin. 1H NMR spectra were applied to verify the formation of the complexes. According to the experimental results, 1:1 stoichiometry for the complexes was established and their association constants at 25°C were calculated by applying a deduced equation. Judging from the magnitude of their inclusion constants, the p‐sulfonated calix[4, 6] arene showed better inclusion capability than β‐cyclodextrin. The probable interaction mechanisms are proposed.  相似文献   

16.
The study of the hydrogen/deuterium exchange reactions of the C(2)‐proton for different carbene precursors has been carried out in the absence and presence of β‐cyclodextrin in D2O at 25°C. Formation of the inclusion complexes of imidazolium salts with the native β‐cyclodextrin and the β‐dimethylcyclodextrin is demonstrated by 1D and 2D 1H NMR, ESI/HRMS and a molecular modelling study. Formation of the inclusion complexes of imidazolium salts with the native β‐cyclodextrin and the β‐dimethylcyclodextrin is a simple and efficient method to modify the acidity of the imidazolium H(2) and to modify its environment. Encapsulation of 1,3‐disubstituted imidazolium chloride by β‐cyclodextrins results in the inhibition of the H(2)/D exchange in the complex. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

17.
In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: AuxHySz clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of AuxHySz (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of AuxHySz clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na+, (M+H)Na+, AuMNa+, (M2−S)Na+, and M2Na+ are determined, and also in cationized forms with K+. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM2 and Au2M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of AuxMw where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.  相似文献   

18.
β-环糊精与二苯硫脲、二苯脲包结作用的紫外光谱研究   总被引:1,自引:0,他引:1  
采用紫外光谱法研究β-环糊精与二苯硫脲、二苯脲的包结作用,运用摩尔比法和直线拟合法(Hildebrand-Benesi法)确定了包结物形成的化学计量比,计算了主客体在不同温度下的包结稳定常数Ks,从而得到包结过程的热力学数据△H,△S.结果表明:β-环糊精与二苯硫脲、二苯脲均形成2∶1型的包结物,由于相邻的2个β-环糊精空腔间的协同作用,包结稳定常数Ks较1∶1型包结物大.包结过程是焓驱动的,主客体间的范德华作用力和偶极-偶极相互作用力是包结过程的主要驱动力.  相似文献   

19.
Interactions between niflumic acid and native and hydroxypropylated α‐ and β‐cyclodextrins (CDs) were investigated by 1H NMR, UV‐vis spectroscopy, densimetry, and calorimetry at pH = 7.4 (phosphate buffer) and T = 298.15 K. Thermodynamic parameters of 1:1 complex formation were calculated and discussed in terms of influence of cavity size and availability of hydroxypropyl substituents on the complex stability. The 1H NMR data indicated the inclusion of niflumic acid into macrocyclic cavity of all CDs under study. It was found that both phenyl and pyridine rings of niflumic acid molecule can be included in the cyclodextrin cavity. The co‐existence of two different kinds of 1:1 inclusion complexes in the solution was suggested. In spite of the fact that binding of niflumic acid with α‐cyclodextrin is more enthalpically favorable, stability of the inclusion complexes is very low due to the enthalpy–entropy compensation effect. Complex formation of β‐CDs with niflumic acid is characterized by the higher enthalpy and entropy changes caused by more intense dehydration. Introduction of hydroxypropyl groups in the cyclodextrin molecule was found to promote the binding with niflumic acid. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

20.
A series of nitrophenyl β‐cyclodextrin derivatives: mono[6‐deoxy‐6‐(4‐nitrobenzamido)]‐per‐ O‐methyl‐β‐cyclodextrin (R1? Ph? NO2), mono[6‐deoxy‐6‐(3‐nitrobenzamido)]‐per‐O‐methyl‐β‐cyclodextrin (R2? Ph? NO2) and heptakis[6‐deoxy‐6‐(4‐nitrobenzamido)‐2,3‐di‐O‐methyl]‐β‐cyclodextrin [R3? (Ph? NO2)7] were synthesized. Purity and composition of the obtained substances were checked. Electroreduction of nitro groups of the new synthesized compounds was investigated on mercury electrode using cyclic voltammetry and chronocoulometry. The parameters of the reduction processes of ? NO2 groups of the investigated compounds were found not to be comparable to the reduction of nitrobenzene under the same experimental conditions. Moreover, the electroreduction of nitro groups in these nitrophenyl derivatives was dependent on pH, the type of the studied compound, and slightly on the solvent composition. All the reactants were strongly adsorbed on mercury electrode. In the case of R3? (Ph? NO2)7, its seven nitro groups were reduced practically at the same potential, and no radical anion formation was observed. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

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