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。     

隐丹参酮与环糊精包结物的制备与光谱研究

采用共沉淀法制备了β CD与隐丹参酮(CTan)的固体包结物,并利用差示扫描量热(DSC)、紫外可见光谱法(UV Vis)对包结物进行了表征。利用紫外可见分光光度法测定了包结物的包结常数,β CD和HP β CD对客体的包结能力顺序为HP β CD>β CD,并测定了包结过程在298～317K范围内的热力学参数△G,△H,△S。实验表明,包结是一个放热过程,且是焓控制的过程。包结物抗光解、抗氧化。     

1,4-二甲氧基柱[5]芳烃的合成及其与1,6-己二胺包结常数的测定

合成了1,4-二甲氧基柱[5]芳烃（DMP[5]）,采用核磁滴定方法研究了主体分子DMP[5]与客体分子1,6-己二胺的包结作用。通过摩尔比方法确定了主客体分子间的包结比为1∶1,并利用DynaFit计算了包结常数Ka=49 L/mol。本实验可作为有机化学实验在本科生化学及相关专业开设,有利于学生了解超分子化学前沿知识,激发学习兴趣,培养综合实验能力和科研方法。     

甲基绿的电化学行为及其与环糊精形成超分子体系研究

应用“电流法”研究了甲基绿—环糊精超分子体系 ,测定了甲基绿和 4种环糊精的包结常数 .其包结能力为HP_β_CD >β_CD >SBE_β_CD >CM_β_CD ,包结比为 1 :2 (甲基绿 :环糊精 )但甲基绿与α_CD和γ_CD不能形成超分子体系 .此外 ,本文还探讨了甲基绿的电极反应机理 ,初步表明 ,甲基绿在电极上还原的电子转移数为 4 ,有 2个质子参与反应     

β-环糊精和甾类化合物的分子动力学模拟

运用分子动力学(molecular dynamics, MD)和MM-PBSA (molecular mechanics/Poisson Boltzmann surface area)相结合的方法预测了β-环糊精(cyclodextrin, CD)和甾类客体分子包结模式. 通过重原子均方根偏差(root mean square deviation, RMSD)分析可得, 两种包结模式下客体分子都可以和β-CD形成稳定的包结. 在MD轨迹采样基础上, 采用高效MM-PBSA方法计算了两种包结模式下的包结自由能. 计算结果显示, β-CD和三个甾类客体分子包结的主要驱动力为范德华相互作用, 而溶剂化能和熵变则不利于体系的包结. 进一步分析平均构象和包结自由能发现, 对于波尼松龙, D-up (D-ring up orientation)取向为优势包结模式; 而乙炔雌二醇和雌三醇的优势包结模式均为A-up (A-ring up orientation)取向. 通过比较β-CD和三个客体分子的理论包结自由能, 预测包结稳定性的次序为乙炔雌二醇＞雌三醇＞波尼松龙, 和实验结果相一致.     

葫芦[7]脲的合成及其与甲基橙的超分子行为研究——综合性研究型实验设计

以尿素为原料合成甘脲,再与甲醛反应合成葫芦脲,然后通过红外、紫外、核磁对其进行表征。详细研究了葫芦[7]脲与甲基橙的超分子包结行为。本实验可使学生接触到超分子化学,有利于学生了解有关葫芦脲的合成方法和包结性质,提高综合分析问题和解决问题的能力。     

羟基葫芦[6]脲与孟加拉红包结作用的荧光光谱研究

采用荧光光谱法研究了羟基葫芦[6]脲(HOCB[6])对孟加拉红(TSS)的包结作用,考察了HOCB[6]浓度、缓冲液pH、温度、包结时间、有机溶剂等因素对包结作用的影响,结果表明,体系的荧光强度随着HOCB[6]浓度的升高而增强,呈现显著荧光增敏现象,同时荧光峰位有一定蓝移,Hildebrand-Benesi法计算结果显示HOCB[6]与TSS形成了1∶1的包结配合物,包结反应的热力学参数表明该包结过程为自发放热过程,这可能是主客体分子之间的疏水作用与离子偶极作用所引起的。     

β-环糊精与两性表面活性剂相互作用β

用表面张力法研究了β-环糊精与十一烷基酰胺甲酸钠(C11H23CONHCOONa,SF)两性表面活性剂在不同温度下的包结作用。结果表明:SF的表面张力值(β)及表观临界胶束浓度(cmc)加入β-CD后增加,β-CD浓度越大,γ和cmc增加越多,且SF的cmc与β-CD浓度存在线性关系,随温度的升高,两性表面活性剂的表面张力值降低,意味着它们的表面活性随温度升高而增强。利用表面张力测定了β-CD-SF体系在不同温度下的包结形成常数Ka,进而求得了包结过程的焓变和熵变,结果表明,该过程是焓和熵均有利的过程,进一步说明疏水作用是形成包结物最重要的的作用力之一。     

反式9, 10-二氢-9, 10-二苯基-9, 10-菲二醇包结性能的研究

合成了一种具有螯形结构的反式-9, 10-二氢-9, 10-二苯基-9,10-菲二醇(1)作为主体分子。它能与许多有机小分子化合物, 诸如DMF, DMSO, 吡啶, 哌啶, 喹啉, 异喹啉等形成包结化合物。本文还报道了这些包结化合物的IR, 粉末XRD的表征, 用^1H NMR谱测定了它们的分子摩尔比。DMF包结物的单晶四圆X衍射结果表明主体分子1与客体分子形成的包结物为配位笼状包合物。     

γ-环糊精和波尼松龙的相互作用分子动力学模拟和自由能计算

运用分子动力学（Molecular dynamics,MD）和MM—PBSA（molecular mechanics／Poisson Boltzmann surfaeearea）相结合的方法预测了γ-环糊精（γ-cyclodextrin,γ-CD）和波尼松龙的包结模式．在MD模拟过程中,波尼松龙分别采用A环和D环两种取向从γ-CD大口端进入其空腔．在MD轨迹采样基础上,采用高效MM—PBSA方法计算了两种取向的包结自由能．结果表明,计算包结自由能值和实验包结自由能值非常吻合．进一步分析各个能量项,发现范德华相互作用能为包结的主要驱动力．通过比较两种取向的包结自由能大小,预测D环取向为优势包结模式．     

吲哚类新主体化合物的固相光化学合成及包结性能研究

对苯二甲醛、对甲醛基苯甲酸甲酯和邻硝基苯甲苯醛与吲哚的固相光反应得到５种新产物，其中４种产物具有很好的包结能力。产物１、２、３和４与丙酮、乙酸乙酯、四氯化碳、氯仿分别形成１：１、１：２或２：１包结络合物１ａ，２ａ，３ａ，４ａ和４ｂ。并对包结络合物１ａ，２ａ和３ａ进行了Ｘ射线衍射结构解析。     

Kinetics of Desolvation of Related Organic Inclusion Compounds

Abstract

This study dealt mainly with the structure-reactivity relationship of selected organic inclusion compounds. The crystal structures of the inclusion compounds of three related hosts, 2,2′–bis(2,7–di-tert-butyl-9–hydroxy-9–fluorenyl)biphenyl, 2,2′–bis (2,7–dichloro-9–hydroxy-9–fluoienyl)biphenyl and 2, 2′–bis(2,7-dibromo-9–hydroxy-9–fluorenyl)biphenyl with 1,4–dioxane (Compound 1), 1,3–dioxane (Compound 2) and 1,3–dioxolane (Compound 3) respectively were elucidated, using single crystal X-ray crystallography. It was found that the guests were either located in channels or constricted channels (cavities), formed by the host framework. The kinetics of desolvation of these compounds were studied and their activation energies were compared.     

环状低聚糖──β－环糊精与胆红素包络作用的研究

环状低聚糖──β－环糊精与胆红素包络作用的研究赵晓斌，何炳林（南开大学高分子化学研究所，天津，３０００７１）关键词β－环糊精，胆红素，包络作用，环状低聚糖，包络化合物环糊精（ＣＤｓ）是一类含６、７、８等数目的葡萄糖基单元通过α－１，４－糖苷键联结而成...     

A new approach to the synthesis of N-monosubstituted aniline and its derivatives via β-cyclodextrin host-guest complexes

A novel method for the synthesis of N-monosubstituted aniline and its derivatives β-cyclodextrin(CD)host-guest complexes has been presented.The mild reaction gives the title compounds with high selectivity in good yields of 90-98%.     

Cyclodextrin Inclusion Compounds in Research and Industry

α-, β-, and γ-Cyclodextrins are cyclic oligosaccharides consisting of six, seven, or eight glucose units, which can be obtained on a large scale from starch. They form inclusion compounds with smaller molecules which fit into their 5—8 Å cavity. These (crystalline) complexes are of interest for scientific research as, contrary to the classical clathrates, they exist in aqueous solution and can be used to study the hydrophobic interactions which are so important in biological systems. Cyclodextrins also serve as models both for polymeric starch and, in the form of their polyiodide complexes, for “blue iodine-starch”. As cyclodextrins catalyze several chemical reactions they and their functionalized derivatives provide useful enzyme models. Cyclodextrins can be used to advantage in the production of pharmaceuticals, pesticides, foodstuffs, and toilet articles—the (micro-encapsulated) active and aromatic substances enclosed within them are protected from the effects of light and atmosphere and can be easily handled and stored in powder from. Substances which are not very soluble in water become more soluble in the presence of cyclodextrins—creams and emulsions can be stabilized, and the growth and yield of grain harvests can be increased. Cyclodextrins can be chemically modified for many different purposes; polymerized cyclodextrin or cyclodextrin bound to a polymer carrier have already been employed in gel inclusion and affinity chromatography.     

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.     

The Application of Host-Guest Chemistry from Natural Compounds to Optoelectronics

A host-guest chemistry method for preparing both natural compounds and SHG inclusion crystal has been developed. The function moieties from the herb could be extracted effectively. The SHG crystal values showed that the host and guest compounds aligned as expected.     

聚乙烯醇高聚物保护疏水性氢氧化铁的机理——多核氢氧化铁-聚乙烯醇包合物的形成

实验部分1.试剂和仪器:FeCl_3·6H_2O AR;NaOH AR;PVA(聚乙烯醇)牌号PVA-124日本进口分装.UV分光光度计(日本UV-300);波长488nm激光束(COHERENT,innoVA 70);X射线光电子能谱(XPS)仪(沈阳Np-1型);红外光谱(IR)仪(美国PE-577);电子自旋共振(ESR)仪(西德ER-420). 2.试样制备:A:5%PVA水溶液;B:100ml pH=2的A含0.1克FeCl_3·6H_2O;C,D:100ml pH=7和13的A分别加入0.1克FeCl_3·6H_2O形成的红棕色透明溶液;E:试样D的