瓜儿豆胶和刺槐豆胶抑制阿斯巴甜甜感强度的机制探索

目前大分子水溶胶对于味觉物质的影响机制研究主要集中于胶体自身的性质以及胶体结构与味物质的相互作用.本文选择了食品中常用的瓜儿豆胶(GG)和刺槐豆胶(LBG),研究了这两种非离子水溶胶对甜味剂阿斯巴甜(APM)感官甜度的影响,并探索了其中的物理化学机制.感官实验结果表明,高浓度的瓜儿豆胶和刺槐豆胶对阿斯巴甜的甜度有抑制作用,且随着水溶胶浓度的增高,达到高分子临界交叠浓度C*后,抑制作用更明显.基于人工受体模型,利用等温滴定量热(ITC)技术发现,两种水溶胶存在条件下阿斯巴甜与受体模型相互作用的结合常数急剧减小.另外,通过对甜味剂存在下非离子水溶胶的水分分布、扩散性质的考察,发现随水溶胶浓度增加,体系的结合水含量均增多,尤其是水溶胶浓度达到临界交叠浓度(C*)后增多的现象更明显;同时,分子的扩散也受到了阻碍,从而导致阿斯巴甜感官甜度的降低.本研究表明,探索大分子水溶胶对甜味剂分子与受体结合差异性的影响、溶液中水分子的弛豫性质及赋存状态、结合体系的粘度及扩散性质的研究,为理解大分子水溶胶对甜味影响的物理化学机制提供更多的信息.     

水溶液中几种苯衍生物与β-环糊精包合物的热力学研究

β 环糊精 (β Ｃｙｃｌｏｄｅｘｔｒｉｎ ,β ＣＤ)是由 7个葡萄糖残基以α 1 ,4 糖苷键连接而成的环状化合物 ,具有疏水的空腔和亲水的外表面。这种特殊的结构使它可以作为宿主 (主体 )而依疏水作用力、范德华力或氢键包合多种客体分子形成包合物[1～ 3] ,并可增强客体分子对光、热、氧化等的稳定性[4,5] 。有机物质与 β ＣＤ形成包合物后通常会发生光谱等特征的变化 ,因此可用光谱等方法研究包合物的稳定常数[4] ,并进而获得水溶液中包合体系的热力学参数[6 ] 。本文采用紫外分光光度法 ,研究水溶液中几种苯衍生物与β ＣＤ包合物的稳定…     

毛细管电泳法研究环糊精与药物芦丁和氯霉素的相互作用

采用毛细管电泳淌度移动法测定了β-环糊精与芦丁和氯霉素这两种药物的包合常数及包合反应的热力学参数。所用未涂层熔融石英毛细管的规格为内径50 μm,总长37 cm,有效长度30 cm,电泳缓冲液为25 mmol/L硼砂+100 mmol/L硼酸(pH 8.6),并加入不同浓度的β-CD。在25 ℃时测得芦丁和氯霉素与β-CD的包合常数分别为98.5和1204 L/mol。通过测定不同温度下的包合常数,求得包合反应的系列热力学参数。结果表明β-CD与两种药物的包合反应焓熵互补现象明显。采用MM2力场对β-CD与两种药物分子的包合物的稳定构型进行了分子力学模拟,模拟结果与实验结果相符。     

羟丙基-β-环糊精对双苯氟嗪包合作用的热力学研究

The inclusion complexes formation of dipfluzine(DF)with hydroxpropy -β-cyclodextrin(HP-β-CD)in aqueous solution was investigated by the phase-solubility method.With the increase of HP-β-CD concentration in aqueous sloutions,the solubility of DF increased linearly,which showed typical AL-type phase solubility diagram.The molar ratio of the DF-HP-β-CD complex was 1: 1.The effect of temperature on the reaction was studied through thermodynamics.The apparent stability constants of inclusion reation were determined.Thermodynamic parameters during the inclusion process were as follows: △_rH=30.58 kJ·mol~(-1),△_rS=158.8 J·mol~(-1)·K~(-1),△_rG＜0.The complex process was endothermic and spontaneous.With the increase of temperature,the tendency of spontaneous reaction increased.     

喹啉修饰β-环糊精键合胆酸客体的热力学研究

采用微量热滴定、核磁共振和分子模拟等方法研究了三唑基喹啉修饰β-环糊精(1)和羟基喹啉基修饰β-环糊精(2)同胆酸(CA)、脱氧胆酸(DCA)、甘胆酸(GCA)和牛磺胆酸(TCA)的键合行为.二维核磁和分子模拟研究表明胆酸客体分子的尾链和D环部分从大口端进入了环糊精空腔.微量热滴定研究表明两种喹啉基修饰环糊精键合胆酸客体的过程由焓驱动,并且伴随着明显的熵损失,说明主-客体间键合的驱动力主要来自于氢键和范德华相互作用.与天然环糊精相比,喹啉基修饰环糊精对胆酸客体的键合有着更为有利的焓变和更为不利的熵变.     

活性艳红K-2BP与环糊精相互作用的电化学研究

本文研究了活性艳红K-2BP的极谱伏安行为。实验表明:在0.1 mol/L的NaCl(pH 6.9)底液中,活性艳红K-2BP有一稳定、灵敏的还原峰。用线性扫描极谱法考察了活性艳红K-2BP与环糊精的相互作用,测定了活性艳红K-2BP与各种环糊精的包结比和包结常数;对不同类型环糊精的包结能力进行了比较;初步探讨了影响包结能力大小的可能因素。     

氨基化环糊精与氨基酸包络物的电喷雾质谱研究

电喷雾质谱(ESI-MS)作为一种软电离质谱技术,已应用于研究准气相状态下通过各种非共价相互作用所形成的非共价复合物。本研究利用电喷雾飞行时间质谱(ESI-TOF-MS)测定了合成的氨基化环糊精与5种氨基酸所形成的1∶1包络物的结合常数(K),考察了质谱条件及溶液条件对结合常数的影响,通过比较结合常数的大小,探讨了氨基化环糊精与氨基酸在准气相状态下的作用方式。     

哌啶氮氧自由基与环糊精作用的电化学研究

采用循环伏安法测量水溶液中β-环糊精(β-CD)/哌啶氮氧自由基(以2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)为例)体系氧化还原电位及峰值电流,并基于此探讨TEMPO与β-CD之间的包结反应。电化学测量表明,在pH=7.4的磷酸盐缓冲溶液中,以玻碳电极为工作电极,随β-CD浓度增大,β-CD/TEMPO体系的峰电位不断增大,峰电流不断减小。通过电位法测得TEMPO与β-CD的包络比为1∶1,包络常数KS为154L/mol,与电流法测得的包络常数基本吻合。     

β-环糊精修饰的壳聚糖对氯酚吸附的动力学和热力学

制备了β-环糊精(β-CD)修饰的壳聚糖(CS)—β-环糊精-6-壳聚糖(CS-CD), 并用傅里叶变换红外(FT-IR)光谱仪, 扫描电镜(SEM), X 射线衍射(XRD)仪和比表面分析仪(BET)进行了表征. 详细研究了其对2-氯酚(2-CP)、2,4-二氯酚(DCP)和2,4,6-三氯酚(TCP)的吸附行为和机理. 研究表明其吸附较好地满足Langmuir 和Freundlich 吸附模型, β-环糊精的引入能够较大地提高吸附效率, 2-CP、DCP和TCP在CS-CD上吸附的最大吸附量分别为14.51、50.68和74.29 mg·g^-1. 动力学研究表明其吸附速率快, 在1 h内能达到吸附平衡, 并符合假二级动力学模型. 计算出了热力学参数ΔG⁰、ΔH⁰和ΔS⁰的值, ΔG⁰为负值表明吸附剂对氯酚的吸附是一个自发的过程. 电解质和溶液pH值对吸附的影响说明在吸附过程中主要是氯酚与吸附剂之间形成了氢键, 并进一步讨论了可能的吸附机理. 改性吸附剂易重复利用, 重复使用六次后的质量和吸附效率与初次相比分别保持在90%和82%以上, 然而CS的质量有较大的损失, 吸附效率也明显降低.     

荧光光谱法研究盐酸罂粟碱与牛血清白蛋白作用的热力学特征

用荧光光谱法研究了盐酸罂粟碱与牛血清白蛋白(BSA)结合反应的特征，发现盐酸罂粟碱对BSA有较强的荧光猝灭作用，根据荧光猝灭数据和非辐射能量转移机理，由Sterm-Volmer方程和双倒数方程获得了结合反应的结合常数、结合位置和结合过程的基本热力学参数。     

Cyclodextrins as Enhancers of the Aqueous Solubility of the Anthelmintic Drug Mebendazole: Thermodynamic Considerations

Summary.  Inclusion complexes of mebendazole with α-, β-, and γ-cyclodextrins, hydroxylpropyl-β-cyclodextrin (HP-β-CD), and methyl-β-cyclodextrin (Me-β-CD) were investigated employing the Higuchi and Connors solubility method. The solubility of mebendazole increased as a function of cyclodextrin concentration showing an A_L phase diagram indicating the formation of soluble complexes with 1:1 stoichiometry. The Gibbs free energies of transfer of the drug from aqueous solution to the cavity of cyclodextrin are negative and increase negatively with increasing cyclodextrin concentration. The solubility of mebendazole as well as the stability constant of its complex with Me-β-CD are found to be affected by the pH of the medium. The Me-β-CD cavity was found to have a greater affinity for the unionized mebendazole rather than the protonated one. Effects of methanol and temperature on these interactions were also investigated to gain further knowledge on the mechanism of the inclusion process. It was found that the interaction between the drug and the cyclodextrin is weakened as the medium becomes more apolar and the temperature increases. Moreover, the thermodynamic parameters for the binding were derived from the dependence of the stability constants on the temperature (van’t Hoff analysis). The formation of the inclusion complexes between the drug and β-CD or its derivatives was found to be enthalpy controlled, with |ΔH °| > T|ΔS °|. This suggests that hydrophobic and van der Waals interactions as well as solvent reorganization are the main driving forces. Furthermore, the size of the cavity of cyclodextrins plays an important role in the association process. Permanent address: Chemistry Department, Faculty of Science, Mansoura University, Mansoura, Egypt. E-mail: i.shehatta@uaeu.ac.ae Received November 30, 2001. Accepted (revised) December 27, 2001     

Complexation and Sensing Behavior of Dansyl-appended Cyclodextrins and Cyclodextrin Dimers with Bile Salts

The dansyl-modified cyclodextrin derivatives 2 and 3 form complexes with the steroidal bile salts. The selectivity of the monomeric derivative 3 is similar to that of native g -cyclodextrin. All binding constants with 3 are lowered compared to g -cyclodextrin because of the competition for the cavity between the steroids and the dansyl moiety. Cholate ( 4a ) and deoxycholate ( 4b ) form weak complexes, the other bile salts ( 4c - e ) are complexed far more strongly. The difference is attributed to the absence of a 12-hydroxy group in the latter steroids. Data for dimer 2 reveal strongly enhanced binding of 4a and 4b and only slightly stronger complexes with the other steroids. Due to the low binding affinity of 3 for 4a and 4b , this receptor could not be used for their detection by fluorescence spectroscopy. Steroids 4c - e showed a decrease in fluorescence intensity. The detection of all steroids 4a - e was possible using 2 . The fluorescence intensity of the dimer increased or decreased, depending on which steroid was added.     

Determination of the binding constant for the inclusion complex between procaine hydrochloride and beta-cyclodextrin by capillary electrophoresis

The apparent electrophoretic mobilities of procaine hydrochloride (μ_i) in a series of concentration of β-cyclodextrin were measured directly by capillary electrophoresis technology. A new mathematical treatment method is proposed, which based on the fact that the molar ratio of the inclusion complex was 1:1 established by spectrophotometry. Using the proposed method, the binding constant of the inclusion complex of procaine hydrochloride with β-cyclodextrin can be obtained easily. The determination result was in correspondence with those of the spectrophotometric and fluorescence methods.     

用极谱法研究酸性大红GR与环糊精超分子体系

本文用线性扫描二阶导数极谱法研究了酸性大红与各种环糊精的超分子体系;测定了它们的包结常数和包结比,比较了它们的包结能力,初步探讨了影响包结能力大小的可能因素。     

Denitrosation of N-Nitrososulfonamide as Chemical Probe for Determination of Binding Constants to Cyclodextrins

The influence of β-CD concentration on the acid hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) has been studied in the presence and absence of different alcohol concentrations. The rate of the denitrosation reaction in bulk water decrease as the β-CD concentration increases due to MNTS complexation in the CD cavity and the reaction taking place exclusively outside the cyclodextrin. Changes in this inhibition due to the presence of β-CD allow us to obtain the binding constants of different alcohols to the cyclodextrin. These binding constants are in very good agreement with those determined in the bibliography by other methods.     

A study of the interaction between enantiomers of zolmitriptan and hydroxypropyl-beta-cyclodextrin by capillary electrophoresis

The enantioresolution of zolmitriptan was performed using cyclodextrin (CD)-modified capillary zone electrophoresis (CZE) with hydroxypropyl-β-CD (HP-β-CD) as the chiral selector. The influence of experimental conditions on the enantioseparation of zolmitriptan, such as pH, temperature, applied voltage, and concentrations of running electrolyte and CD, was systematically investigated, obtaining a baseline separation of two enantiomers by the use of a 25 mM sodium dihydrogen phosphate (SDPH) running electrolyte (pH 2.4) containing 30 mM HP-β-CD at 15 °C. Binding constants for each enantiomer–HP-β-CD pair at different temperatures, as well as thermodynamic parameters for binding, were calculated. A nonlinear van’t Hoff plot was obtained, indicating that the thermodynamic parameters of complexation were temperature-dependent for zolmitriptan enantiomers. The significant contribution of the enthalpy difference to the Gibbs free energy change suggested a stereomeric barrier mechanism for chiral recognition. Figure Resolution of zolmitriptan enantiomers was achieved by using CD-modified CZE Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

环糊精及其衍生物在环境污染物治理中的应用

环糊精是由不同的D-吡喃葡萄糖单元环状排列而成的圆锥状中空桶形分子,其独特的外亲水内疏水结构决定了其特殊的性能。目前环糊精及其衍生物在药剂学中的应用最为广泛,而在环境污染物治理方面的报道较少。本文介绍了环糊精主-客体包合作用影响因素、环糊精衍生物的合成方法,综述了近年来环糊精及其衍生物在污染水、土壤及大气治理中的研究进展,表明其在环境污染治理方面有较好的应用前景,并提出了其在环境污染物治理中未来的研究方向。     

Thermodynamics of the Dissociation of Carbonic Acid in Mixed Solvent.4. The System of NaHCO_3-Na_2CO_3-NaCl-Ethanol-Water

Theeffectofethanol-watermixtureontheseconddissociationconstantofcarbonicacidwasofinterestnotonlyforbiologistsbutalsoforchefestsandchemicalengineers,becauseitmayprovideusefulinformationinregardtotheidentificationofthenatureofthesesolute-solventinteractionpatternsinbinarysolventsystem"'.ThispaperreportStheseconddissociationconstantsofcarbonicacid,K,,atfivetemperaturesfrom278.15to318.15Kin5,15,25mass%ethanol-water"dxedsolventsdeterminedfrompreciseelnfmeasurementsincell(A)withoutliquidjunction:Pt…     

环糊精超分子组装体的研究进展

环糊精是由若干个D-吡喃葡萄糖单元通过α-1,4-糖苷键连接而成的环状低聚糖,具有一个亲水性的外表面和一个疏水性的空腔。利用主客体相互作用,环糊精及其衍生物能够选择性地与大小匹配的疏水性客体分子形成各种超分子包合物。本文概述了环糊精的结构与性质,并介绍了近年来国内外以环糊精为基础的纳米粒子、水凝胶等超分子组装体的设计原理、作用机制、刺激响应及应用特点,并对环糊精超分子组装体的前景进行了展望。