12-钼磷酸-葡聚糖包合物固容体的光致变色

通过DSC曲线,IR光谱,电子光谱和XRD谱分析,发现12-钼磷酸与葡聚糖在水溶液中可形成黄色包合物。以ESR,XPS,IR和电子光谱等手段研究此黄色包合物在紫外光照射下的光致变蓝紫色,是由于其光电子转移反应产物多价态钼(Ⅵ,Ⅴ,Ⅳ)配合物呈蓝紫色,而另一产物带部分羰基葡聚糖为无色所致。由DSC曲线,电子光谱,IR光谱和XRD谱测试结果得知,随着光化反应产物的生成,两者分子间产生包合作用,从而提高光致变色的稳定性。     

Specific inclusion mode of guest compounds in the amylose complex analyzed by solid state NMR spectroscopy

The inclusion compound formation between linear amylose of molecular weight 102500 (AS100) and p-aminobenzoic acid (PA) during the sealed-heating process was investigated by powder X-ray diffractometry, infrared spectroscopy and solid state NMR spectroscopy. Sealed-heating of AS100 and PA at 100 degrees C for 6 h provided an inclusion compound with 6(1)-helix structure, while a 7(1)-helix structure was found when sealed-heating was carried out at 150 degrees C for 1 h. The formation of an inclusion compound was not observed when sealed-heating was performed at 50 degrees C for 6 h. The 7(1)-helix inclusion compound maintained its structure even during storage at high temperature while the 6(1)-helix inclusion compound decomposed and returned to the original V(a)-amylose upon heating to 180 degrees C. Quantitative determination revealed that one PA molecule could be included per one helical turn of AS100 for both 6(1)-helix and 7(1)-helix inclusion compounds. Solid state NMR spectroscopy suggested that PA molecules were included in the amylose helix core in the 7(1)-helix inclusion compound, while in the case of 6(1)-helix inclusion compound, PA molecules were accommodated in the interstices between amylose helices. Moreover, the inclusion compound formation by sealed-heating of AS100 was also observed when using PA analogues as guest compounds. The binding ratio of AS100 and PA analogues varied depending on the size of guest molecules.     

Phase diagrams of urea inclusion compounds

The stearic acid-urea binary system exhibits an unusual phase diagram, which, on the one hand, indicates an incongruently melting inclusion compound and on the other hand a miscibility gap in the liquid phases. The peritectic point lies near the melting point of urea and the unstable congruent melting point of the inclusion compound coincides with the melting point of urea. In addition to the processing of the phase diagram, the pure inclusion compound was prepared and its DSC curve, FTIR spectrum and X-ray diffractogram were recorded.     

Phase Diagrams of Urea Inclusion Compounds 3. Pentadecanoic acid and urea

The phase diagram of the pentadecanoic acid and urea system consists of a combination of a binary system with two incongruently melting compounds and a system with a miscibility gap of the liquid phases. The first compound is a molecular addition compound of 1 molecule of pentadecanoic acid and 4 molecules of urea, which forms three polymorphic modifications. The second compound is a channel inclusion compound, which is known to be in a ratio of 1:12.2. In addition to the thermoanalytical investigations, FTIR spectroscopic and X-ray diffractometric analyses were also conducted for the inclusion compound as well as the stable form of the molecular addition compound. This revised version was published online in July 2006 with corrections to the Cover Date.     

β—环糊精对D／L—酪氨酸对映体的手性识别及超分子包合物的合成

利用圆二色谱研究了β－环糊精（β－ＣＤ）对Ｄ／Ｌ酪氨酸的手性识别行为，制备出了β－ＣＤ与Ｌ－酪氨酸（Ｌ－Ｔｙｒ）的固体超分子化合物，并用元素分析、薄层分析、Ｘ射线粉末衍射及热分析对包合物进行了表征，用荧光光谱法测定了包合物的形成常数．实验结果表明，β－ＣＤ具有选择包结Ｌ－酪氨酸的特性；主客体形成１１的包合物，其组成为Ｌ－Ｔｙｒ／β－ＣＤ·１２Ｈ２Ｏ；稳定常数为５．１３×１０３Ｌ／ｍｏｌ；包合物的热稳定性比主客体皆有改善     

Complexation with diol host compounds. Part 18. Structures and thermal analysis of trans-9,10-dihydroxy-9,10-di-p-tolyl-9,10-dihydroanthracene and its inclusion compounds with acetone,diethyl ether and pyridine

Abstract

The structure of the host compound trans-9,10-dihydroxy-9,10-di-p-tolyl-9,10-dihydroanthracene and those of its inclusion compounds with acetone, diethyl ether and pyridine have been elucidated. The non-porous α-phase of the host has a structure in which the molecules are packed in layers parallel to the (100) plane, but exhibit no intermolecular hydrogen bonding. The host:guest stoichiometry of each inclusion compound is 1:2, and the structures are each stabilised by O-H…O or O-H…N hydrogen bonds between host and guest. The thermal decompositions of the acetone and diethyl ether compounds are characterised by single endotherms of the guest-release reaction, but the pyridine inclusion compound has a more complex decomposition, characteristic of similar pyridine inclusion compounds.     

The fluorescence study of the inclusion coordinated compound of beta-cyclodextrin and p-hydroxyphenolacetamide and its analytical applications

The inclusion coordinated compound fluorescence of p-hydroxyphenolacetamide (PHPA) with beta-cyclodextrin was studied and a high sensitive analytical method to determine the content of PHPA was established based on the increased fluorescence intensity of the coordinated compounds in Britton-Robinson buffer solution (pH 7). The wavelength of the excited emission are 282 and 310 nm, respectively. The enhanced coordinated compounds fluorescence intensity is proportional to the concentration of PHPA in the range 0.030-11.0 mg/l. The relative standard deviation (R.S.D.) were within 0.66-4.2%. Correlation coefficient and inclusion binding constant Kf are obtained within 0.9950-0.9996 and 4.67 x 10(2), respectively. Meanwhile, a linear increase of the resonance light scattering (RLS) with the inclusion coordinated compounds concentration was noticed at a synchronous wavelength of 584 nm. The forming reasons of inclusion coordinated compounds were investigated. The 1:1 molar ratio composition of inclusion compound was measured with DTA and elemental analysis. The method is simple, rapid and has a good reproducibility. The method was used for determination of PHPA in an artificial sample with satisfactory results.     

Design and structural extension of a supramolecular inclusion-compound host made by the formation of dimers of isonicotinic acid and thiocyanato coordinating bridges

A new host design for an inclusion compound with a preference for large planar aromatic guest molecules has been proposed. Our host design includes a rectangular cavity made using a long and a short building block based on the concept of supramolecular chemistry. The long building block facilitates the inclusion of large guests, and the short building block prevents the formation of an interpenetrated structure, which is often observed in frameworks with large void spaces. The long building block is made when dimers of 4-pyridinecarboxylic acid (isoH) form through hydrogen bonding between the two carboxylic acid moieties. This isoH dimer can link two transition metal centers using the N atoms at both ends to act as a long building block. For the short building block, the thiocyanato ion was used. This makes a bent bridge between two metal centers to form a 1D double-chain [M(SCN)2]infinity complex. From the self-assembly of isoH, SCN- and Ni2+, a 2D network of [Ni(SCN)2(isoH)2]infinity, in which the 1D [Ni(SCN)2]infinity complexes are linked by the isoH dimers, is built up. The rectangular cavity is formed as a mesh within the 2D network. The crystal of our inclusion compound has a layered structure of 2D networks, and a 1D channel-like cavity penetrating the layered 2D networks is formed where guests may be included. Moreover, our host design has the advantage of easy extension of the host structure. Replacement of isoH with another component and use of three components is possible for making the long building block. In the latter case, a linear spacer having two carboxy groups is inserted into the isoH dimer to form a long building block with a trimer structure. Based on our host design, a series of new inclusion compounds were synthesized. The crystal structures of three compounds were determined by single crystal X-ray diffraction. These were a biphenyl inclusion compound [Ni(SCN)2(isoH)2].1/2C12H10 (the basic case), a 9,10-dichloroanthracene inclusion compound [Ni(SCN)2(acrylH)2].1/2C14H8Cl2, where isoH is replaced with 3-(4-pyridinyl)-2-propenoic acid (acrylH), and a perylene inclusion compound [Ni(SCN)2(isoH)2(fumaricH2)].1/2C20H12, whose long building block is a trimer inserted with fumaric acid (fumaricH2) as a linear spacer.     

环糊精及其衍生物的超分子晶体结构研究进展

本文对近年来有关环糊精、环糊精衍生物以及它们与各类客体组装成的超分子包合物的晶体结构研究进行的简要概述。     

螯形二羟基主体分子的包结性能与其结构关系的研究

报道了螯形主体分子，反式－9，10－二－1'－萘基－9，10－菲二醇（1）， 能与多种含氮有机化合物，诸如喹啉、异喹啉、哌啶、二环已胺等形成包化合物； 而反式－9，10－二苄基－9，10－菲二醇（2）则不具有包结性能。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，分别为 （1）／喹啉(1:2), (1)/异喹啉(1:2)，（1）／哌啶（1:2）和（1）／二环忆胺 (1:2)。用单晶X射线衍射法测定了（1）与二环忆胺包结物以及（2）的结构，结果 表明前者属正交晶系，空间群为Pnca(标准型Pbca)，晶胞参数: a = 1.6714(3) nm, b = 1.6875(3) nm, c = 1.7224(3) nm, V = 4.858 nm~3, Z = 8，形成了隧 道型配位笼状包合物。后者属三斜晶系，空间群为P1-bar，晶胞参数: a = 0. 8058(2) nm , b = 0.9715 (2) nm, c = 1.4437(3) nm, α = 109.59(3)°, β = 95.96(3)°, γ = 96.03(2)°, V = 1.0471 nm~3, Z = 2, 还比较了(1)和(2) 的结构差异，分析了(1)的结构和包结性能的关系。     

反式-9, 10-二氢-9, 10-二(1-萘基)-9, 10-菲二醇的包合现象 与晶体结构

按文献方法合成了一个螯形主体分子,反式-9,10-二氢-9,10-二(1-萘基)-9,10-菲二醇。研究发现该主体可以和一些含氮杂环化合物形成一定比例的晶体包合物。用X-射线衍射分析二环己胺包合物的晶体结构表明,包合物中主客体之间存在O-H…N氢键相互作用,客体分子包合在主体分子形成的空腔中。     

Spectral and photophysical properties, photo and heat resistance of dipyrrolylmethene borofluoride complex and its hybrid material with polymethylmethacrylate

A hybrid material based on polymethylmethacrylate with immobilized borofluoride dipyrrolylmethene complex. The inclusion of the chromophore in the polymer environment is shown to result in a reduced polarization due to the weakening of the forces of intermolecular interactions. Study of spectral properties, photo and thermal stability showed that inclusion of the complex in the polymer matrix can significantly increase the photo and thermal stability and mechanical strength of the material while preserving the spectral characteristics inherent to the individual compound.     

葫芦脲[7]与核黄素包结物的可能结构和光谱性质

利用密度泛函理论对葫芦脲[7]和核黄素包结物的可能结构进行了理论计算.从5种可能结构分析主客体在包结物中的作用得出:核黄素作为客体分子与主体葫芦脲[7]分子通过不同官能团作用可形成稳定性不同的包结物,其中以核糖醇的羟基插入到葫芦脲[7]分子的腔体与其端羰基氧原子形成较多的氢键最稳定.在理论上证明了此包结反应为一放热反应的实验事实,并进一步说明了包结物分子的相对稳定性受主客体分子的几何畸变能和主客体之间作用能的影响,说明了成键能和稳定性之间的区别.在此基础上利用时间相关的密度泛函理论进行了不同构型包结物的激发态计算并对光谱性质进行了理论预测.比较了包结物中核黄素分子的跃迁轨道的组成变化,分析得出:葫芦脲[7]的包结作用改变了核黄素分子的电子跃迁性质,使其吸收光谱发生红移.并预测出其荧光猝灭的微观机理,此理论计算结果很好地解释了相应的实验现象.     

对叠氮苯甲酸与β-环糊精的包合作用

合成了对叠氮苯甲酸与β-环糊精的包合物，并利用红外、热重、核磁和紫外 等测试方法进行了详细的表征与研究。包合后客体化合物的热稳定性有了明显的提 高，其分解温度提高了+115 ℃；此外还利用紫外光谱的数据计算了包合反应的平 衡常数，为(7933±192)L·mol~(-1)。     

主客体包结法选择分离青花椒挥发油中的化学成分

以1,1,6,6-四苯基-2,4-己二炔-1,6-二醇为主体分子, 可简单、迅速地从青椒挥发油中选择分离出化学成分烯丙基茴香醚, 基于挥发油的用量, 收率为3.78%. IR, ¹H NMR, ¹³C NMR光谱和单晶衍射证实了包结化合物结构, 用气相色谱法评价了选择分离效果, 分离的烯丙基茴香醚气相色谱纯度为94.5%. 同时, 主体分子形成的隧道框架对茴香醛具有识别作用, 形成2∶1(主/客)物质的量比的特殊结构包结物晶体, 它是主客体分子物质的量比为1∶2包结物的超分子异构体.     

Antibacterial,antioxidant and anthelmintic studies of inclusion complexes of some 4-arylidenamino-5-phenyl-4H-1,2,4-triazole-3-thiols

A series of 4-arylidenamino-5-phenyl-4H-1,2,4-triazole-3-thiols have been synthesised and their inclusion complexes have been prepared with β-cyclodextrin. The compounds and their inclusion complexes have been characterised by studying their physical and spectral properties. The thermodynamic stability constant and free energy of activation have been determined to know the stability of inclusion complexes. Finally, the compounds and their inclusion complexes are screened for antibacterial, antioxidant and anthelmintic activities. It is found that inclusion complexes of the newly synthesised compounds have appreciable stability and inclusion complex formation increases the antibacterial, antioxidant and anthelmintic activities significantly as compared to naked compound.     

Study on the inclusion compound of β-cyclodextrin with (η5-cyclopentadienyl)tricarbonylmanganese(0)

The supramolecular inclusion compound of β-cyclodextrin (β-CD, host) with (η5-cyclopentadienyl)tricarbonylmanganese [MnCp(CO)3, guest] was obtained in a crystalline state. The host-guest compound is thermally stable and do not liberate the guest on heating at 100$ in vacuum. It was characteried by elemental analysis,1H NMR, differential scanning thermal (DSC) analysis and TLC. Continueous variation plot by NMR method shows that β-CD formed 1:1 inclusion compound with MnCp(CO)3. On the basis of 1H NMR spectra and the model building with Corey Pauling Koltum (CPK) models, the most probable inclusion mode is proposed.     

Inclusion Compound Formation of Amylose by Sealed-Heating with Salicylic Acid Analogues

The inclusion compounds of linear amylose and salicylic acid analogues preparedby sealed-heating were evaluated by using powder X-ray diffraction and infraredspectroscopy. Sealed-heating of amylose and either salicylamide or benzoic acidinduced the amylose structural change from the 6₁- to the 7₁-helix structure, while sealed-heating with o-toluic acid, o-chlorobenzoic acid and o-nitrobenzoic acid induced the change from the 6₁- to the 8₁-helix structure. In contrast to theresults in the salicylic acid system, the amylose helix type of sealed-heated samplewas not varied by the load of the guest compound, but was fixed only by the guestspecies. No change of the helical structure of amylose depending on the amylose molecular weight was observed. From the comparison of inclusion compound formation among different guest systems, it was found that the higher vapor pressure at 100 °C of the guest resulted in faster inclusion compound formation. The vapor pressure of the guest compound would be an important factor affecting the progress of inclusion compound formation.     

Determination of 20(S)-protopanaxadiol in rat plasma by LC-MS/MS and its application to the pharmacokinetic study: A comparative study of its solution and two oral formulations

A high-performance liquid chromatography — tandem mass spectrometry method was used in a comparative pharmacokinetic study on 20(S)-protopanaxadiol in its solution, pharmacosomes and hydroxy-propyl-β-cyclodextrin inclusion compound. The calibration linearity range was 2.5–5000 ng/mL and the limit of quantification was 2.5 ng/mL. The intra- and inter-assay coefficients of variation were less than 7% and the recoveries were 67.4, 63.3 and 69.6% at 5, 250 and 4500 ng/mL. In contrast to 20(S)-protopanaxadiol solution, its pharmacosomes and hydroxypropyl-β-cyclodextrin inclusion compound improved the oral bioavailability to different extent and meanwhile were much safer in clinical use.     

对磺酸基杯[6]芳烃与葛根素相互作用的荧光光谱研究

采用荧光光谱法研究了在pH=6、不同温度(25、35和45℃)下对磺酸基杯[6]芳烃(SCX6)与葛根素的包合作用;并利用最小二乘法进行非线性拟合,计算出不同温度下的包合常数,初步验证了SCX6与葛根素的包合模式.结果表明,固定葛根素的浓度、逐渐增加对磺酸基杯[6]芳烃的浓度,葛根素荧光强度有规律地降低,表明SCX6和葛根素形成主-客体包合物.在不同温度下,葛根素与SCX6的包合比均为1∶1;且其包合过程可自发进行,温度越高,包合越易发生.