杯[4]芳烃衍生物气相色谱固定相分离芳烃异构体的热力学/超热力学研究

用热力学／超热力学方法对杯[4]芳烃衍生物气相色谱固定相上芳烃位置异构体的分离进行了研究。考察了一系列芳烃位置异构体在杯芳色谱柱上分离过程的热力学参数及其选择性之间的关系,并对杯[4]芳烃衍生物气相色 谱固定相分离芳烃位置异构体的保留机理进行了探讨。     

含杯[4]芳烃毛细管固定相的制备与色谱性能

杯芳烃是由对位取代的苯酚在邻位通过亚甲基连接起来的环状化合物,由于具有可调节大小的空腔,不仅能络合无机离子,而且还可络合有机分子,在分析分离方面有极好的应用前景［１,２］．杯芳烃已用于气相色谱［３,４］、离子选择性萃取［５,６］、液相色谱［７,８］和...     

两种新型杯（4）芳烃衍生物用作毛细管气相色谱固定相的研究

合成了两种新型的杯（４）芳烃衍生物：５－１′，１′－二甲基十一烯氧基苯基甲基－１１，１７，２３－三－１，１－二甲基乙基－２５，２６，２７，２８－四苄氧基杯（４）芳烃Ｃ（４）ＴＢ）及５－１′，１′－二甲基十一烯氧基苯基甲基－１１，１７，２３－三－１′，１′－二甲基－２５，２６，２７，２８－四乙氧羰甲氧基（Ｃ（４）ＴＥＣＭ）其结构经元素分析ＩＲ，＾１ＨＮＭＲ，ＭＳ的数据证实，分别将其与ＯＶ－１７０１固     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

新型正丁醛杯[4]芳烃醚衍生物的合成

以正丁醛间苯二酚杯[4]芳烃为原料,经酯化、水解、酰氯化后再与9-蒽甲醇反应,合成了蒽单取代的正丁醛间苯二酚型杯[4]芳烃醚衍生物。其结构经1H NMR和IR表征。     

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能;杯[4]芳烃;双杯[4]芳烃;多重氮杂;萃取     

丙醛间苯二酚杯[4]芳烃烷基化衍生物的合成

以间苯二酚和丙醛为原料合成了丙醛杯[4]芳烃(1),1经不同的烷基化反应合成了新的丙醛杯[4]芳烃烷基化衍生物,其结构经1H NMR和IR表征。     

硫杂杯[4]芳烃氧化膦衍生物的合成与晶体结构

合成了部分取代的硫杂杯[4]芳烃氧化膦衍生物, 二(亚甲基二苯基氧化膦)对叔丁基硫杂杯[4]芳烃(化合物1), 培养了化合物的单晶, 用Smart 1000 CCD衍射仪测定了其晶体结构. 结果表明, 1的组成为: C₆₆H₇₀O₆P₂S₄•2CH₃OH, 属三斜晶系, P1空间群, 晶胞参数a＝1.3453(6) nm, b＝1.5289(7) nm, c＝1.7893(9) nm; α＝75.707(9)°, β＝69.131(8)°, γ＝79.734(9)°, Z＝2; V＝3.316(3) nm³, d＝1.215 g/cm³, F(000)＝1288, μ (Mo Kα)＝0.244 mm^－1, R₁＝0.0625, wR₂＝0.1372. 杯芳烃分子采取了锥式构象.     

杯[4]芳烃硫脲基席夫碱衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物与苯基氨基硫脲反应,高产率地合成了含硫脲基席夫碱单元的新型杯[4]芳烃衍生物,其结构经1H NMR,IR和ESI-MS表征。     

四硫脲基杯[4]芳烃衍生物的合成

对叔丁基杯[4]-1,3-二乙酸乙酯与过量的二乙基三胺反应,生成含有游离氨基的杯芳烃酰胺衍物(2),2再与异硫氰酸苯酯反应合成了含4个硫脲基的杯[4]芳烃衍生物,其结构经1H NMR,IR,MS和元素分析表征。     

杯芳烃衍生聚合物用作毛细管气相色谱固定相的研究

合成了两种不同构象的杯芳烃衍生聚合物（杯芳冠醚聚硅氧烷ｃ－ｃ［４］ｃ５－ｐｓｏ和二乙氧基杯［４］芳烃聚硅氧烷ｐ－ｃ［４］－ｐｓｏ），并将其用作毛细管气相色谱固定液，使用温度高达３２０℃，对不同的极性化合物，特别是对酚类异构体有很好的分离能力。同时也研究了分离机理。     

杯芳烃及其衍生物在色谱和毛细管电泳中的应用

杯芳烃是由多个苯酚在2,6位与亚甲基相连形成的大环化合物,具有分子识别功能,是继环糊精和冠醚之后第三代主体分子,它在现代分离科学中有着广泛的应用,本文综述了近年来杯芳烃及其衍生物在色谱和毛细管电泳中的应用进展。     

Environmentally Benign Syntheses of Calixarene Derivatives

New hydroxamic acid derivatives of calixarene have been synthesized by conventional and microwave method.     

杯芳烃衍生物在分析化学中的应用

杯芳烃衍生物是以杯芳烃为“分子平台”，经过不同的衍生化而得。根据杯芳烃的空腔大小，构象及其衍生官能团与客体分子间的适应程度，杯芳烃衍生物可实现对金属离子及有机分子的选择性识别。本文介绍了芳烃衍生物在分析化学领域，包括萃取分离，液膜分离，色谱分析及光分析中的应用情况。     

新型杯[4]芳烃气相色谱固定相的研究

合成了上缘特丁基脱去的杯[4]芳烃25，27-二丁氧基-26，28-二（ω-十一碳烯氧基）杯[4]芳烃（p-H-C[4]B)及其相应的聚硅氧烷化高分子（PSO-p-H-C[4]B)，以有上缘用N，N-二乙基氨甲基取代的杯[4]芳烃5，11，17，23-四（N，N-二乙基氨甲基）-25，26，27，28-四（ω-十一碳烯氧基）杯[4]芳烃（p-DEAM-C[4]U），并首次将它们用作毛细管柱气相色谱固定液，涂制成色谱柱，考察了这些杯[4]芳烃色谱柱的性能。结果表明，研制的杯[4]芳烃柱对芳香位置异构体均有良好的分离能力。     

Preparation and study of two polysiloxanes with pendant hand-basket type calixarene stationary phases for capillary gas chromatography

In this study two novel pendant hand-basket type calixarene gas chromatography stationary phases were prepared by hydrosilylation of ω-undecenyloxymethyl dimethyl calix[4]-15C5 and ω-undecenyloxymethyl dimethyl calix[4]-18C6 with dichloromethane followed by condensation reaction with silanol-terminated polydimethylsiloxane. Important stationary phase properties of these two novel stationary phases such as column efficiency, polarity, and selectivity were examined and compared with those of ω-undecyloxymethyl-18-crown-6, 2,3-benzo-9-propyloxymethyl-15-crown-5 and 2,3-benzo-11-propyloxymethyl-18-crown-6. Excellent thermostability from 60 to 330°C with onset bleeding temperatures at 308°C have been found. The mechanism of specific selectivity for position isomers based on the calix[4]crown ether ring, the molecular size of the solute and its shape are discussed.     

Characterizations for Vinylimidazolium Based Ionic Liquid Polymer Stationary Phases for Capillary Gas Chromatography

Six polyvinylimidazolium based ionic liquids were prepared for use as stationary phases for gas chromatography. The influences of the attached side-chains (hexyl-, octyl- and phenylpropyl-) on the vinylimidazolium cations and of different counter ions (bromide, hexafluorophosphate, bis-trifluoromethanesulfonlyimide, and bis-trifluoroethanesulfonylimide) were studied. Linear solubility parameter experiments were conducted to characterize the specific interactions of these stationary phases. Some of the polymerized ionic liquid stationary phases exhibited unique structural selectivity. m-, and p-xylenes could be distinguished. The preparation of the polymerized ionic liquid column is simple and reliable. This work provides detailed information for designing polymerized ionic liquids, and shows that these materials have great potential extending the range of options for stationary phases in gas chromatography.     

Silica-bonded Calixarenes in Chromatography: Enantioseparations on Molecular Basket Phases for Rapid Chiral LC

Abstract

The synthesis of a new type of chiral stationary phase, prepared from triethoxysilyl derivatives of calixarenes, and by the chemical immobilisation of these chiral molecular baskets to 3μm silica particles, is reported. Specifically, a silica-bonded calix[4]arene, funcrionalised at the lower rim with L-(-)-ephedrine, is prepared and packed into a short LC column for rapid chiral separations. Using reversed phase conditions and high flow rate, such new phases based on funcrionalised calixarenes are applicable to chiral aromatic and non-aromatic solutes and are capable of resolving the enantiomers of R(-) and S(+)-1-phenyl-2,2,2-trifluoroethanol in less than 45 seconds.     

Studies on Properties of p-Nitrophenylazo Calixarene Derivatives

Organiccompoundswithsecond ordernonlinearoptical(NLO)propertieshavevariouspotentialinthedevelopmentofmaterialsforapplicationssuchasfrequencydoublingandop ticalswitching .1,2 TraditionalorganicNLOmaterialsareor ganicmoleculesthatcontainelectron donatingandelectron acceptinggroupsconnectedviaaconjugatedπsystem ,i.e .,socalledD π Astructure .Generally ,thesecond ordernon linearhyperpolarizability βofamoleculeincreaseswithin creasinglengthoftheconjugatedπsystemandincreasingstrengthofthedono…     

杯芳烃衍生物在主-客体识别荧光分析中的应用及进展

综述了近年来杯芳烃衍生物在主一客体识别荧光分析中的研究与应用进展，主要从杯芳烃母体官能化作主体分子和杯芳烃与冠醚、环糊精及卟啉构成偶联物作主体分子两方面进行了评述，并对今后工作进行了展望。引用文献62篇。