全氧冠醚聚硅氧烷毛细管气相色谱固定液的色谱性能和机理研究

本文合成了2种新型聚硅氧烷侧链全氧冠醚(十一烷氧甲基18-冠-6和十一烷氧甲基15-冠-5),并将其涂渍、交联在未经处理的弹性石英毛细管柱上,其柱效较高,使用温度范围较宽,热稳定性和选择性较好.研究了固定液对样品的分离机理.     

芳香族化合物在苯并系列冠醚聚硅氧烷固定液上的保留机理

分离测得了不同结构芳香族化合物在单苯并（ＰＳＯ－Ｂ－３－１５Ｃ５或１８Ｃ６）、双苯并（ＰＳＯ－ＤＢ－３－１５Ｃ５）和双苯并双叔丁基（ＰＳＯ－ＤＴＢ－３－１５Ｃ５）取代的１５Ｃ５聚硅氧烷固定液上的保留指数、相对保留值以及１０组异构体的热力学参数──溶解焓△Ｈｓ,溶解摘△Ｓｓ和自由能△Ｇ;研究探讨了冠醚环上不同苯基取代的固定液结构对芳香族位置异构体保留行为的影响;通过热力学参数对不同冠醚柱子选择性的表征,证明了苯并系列冠醚固定液对芳烃位置异构体的良好选择分离,主要取决于冠醚环腔的高电子云密度所产生的定向力和强诱导力以及分子和冠醚环腔的适应程度,特别是空间位阻效应起了重要作用。     

侧链长短对全氧冠醚聚硅氧烷色谱性能的影响

设计合成了一种新型聚硅氧烷侧链全氧冠醚（丙烷氧甲基１５－冠－５），将其涂渍在示经处理的弹性石英毛细管柱上，其色谱柱具有高柱效，较宽的使用温度范围，高热稳定性和优异的选择性。并且通过与另一种氧烷侧链冠醚固定液涂渍柱的比较，考察了侧链脂肪间隔基的长短对冠醚固定液色谱性能的影响。研究了固定液对样品的分离机理。     

新型侧链聚硅氧烷高分子液晶作毛细管柱气相色谱固定液的研究

 以合成的新型胆甾酯类侧链聚硅氧烷高分子液晶作固定液 ,涂渍在弹性石英毛细管柱上 ,获得了具有较高的柱效和选择性、良好的热稳定性、适于分离多种异构体混合物的毛细管柱。     

Gas chromatographic characteristics and application studies of the stationary phase of CH-B-15-C-5

In this paper, separations of organic compounds, such as, n-alkanes, alcohols, ethyl asters of C(1)-C(8) carboxylic acid, halogen derivatives, position-isomers of the replacement aromatic hydrocarbon, optical isomers of ethyl lactate and isoamyl alcohol, etc. were studied using 4'-cholestenoxycarbonyl-benzo-15-crown-5 liquid crystal crown ether (CH-B-15-C-5) as stationary phase in gas-solid chromatography (GSC), general gas-liquid chromatography (GLC) and crown ether liquid crystal gas-liquid chromatography (CL-GLC). Also, the chromatographic characteristics, such as the chemical stability, thermal stability, selectivity, polarity and operating temperature range, of the CH-B-15-C-5 as stationary phase for GSC, GLC and CL-GLC systems were studied. The results showed that the polarity of this chromatographic column is mean-weak; the chemical and thermal stabilities and the selectivity are good and the operating temperature range is wide. The results of separations of organic compounds are satisfactory.     

The extraction behavior of some dicarbollylcobaltate crown extraction systems

The extraction of cesium, strontium and barium by a nitrobenzene solution of dicarbollylcobaltate in the presence of various crown ethers has been investigated and the influence of the substituent of crown to the extraction possibility has been observed. It has been found, that the addition of DB15C5, DB18C6 and DB21C7 (but not DB24C8 and DCH24C8) increases the distribution ratio of Cs by one order of magnitude. The fivemembered crowns are usually more efficient extractants for strontium than DCH18C6, which is widely used for strontium separation. The distribution ratio of strontium D_Sr decreases in the order 15-crown-5>benzo-15-crown-5>2-hydroxymethyl-15-crown-5>cyclohexyl-15-crown-5 >dibenzo-15-crown-5> nitrobenzo-15-crown-5. The selectivity α(Sr/Ca) decreases in the order 15C5>B15C5>DB15C5>2HM15C5>CH15C5. A selectivity factor α(Sr/Ca)≥1000 can be reached in the presence of 15C5 and B15C5. Six-membered and four-membered crowns extract strontium worse than most of the five-membered crowns. The selectivity factors α(Sr/Ca)≈100 have been reached for six-membered crowns and α(Sr/Ca)<1 has been found for 12C4. The extraction of barium by a nitrobenzene solution of dicarbollylcobaltate in the presence of 15C5 is even more efficient as the extraction of strontium. In that system D_Sr>10⁴ and D_Ba>10⁴ have been found for the extraction of Sr and Ba by a 0.01M nitrobenzene solution of dicarbollylcobaltate (c_B=0.01 mol/l) from 0.1M HNO₃. Maximal values of separation factor α(Ba/Sr) have been found in the system containing DB21C7.     

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.     

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。     

Macrocycles as components of gas-chromatographic phases

The use of crown compounds (18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5, dibenzo-24-crown-8, 4,13-diaza-18-crown-6,4,13-dibenzyl-diaza-18-crown-6, and cryptand [2.2.2]) as components of stationary phases in the determination of organic compounds by gas chromatography is studied. The polarity, selectivity, efficiency, and working temperature ranges of stationary phases based on crown ethers and cryptand as well as conventional stationary phases for gas chromatography are compared. The influence of the type and number of heteroatoms, the conformational lability of the cavity, and the presence of substituents on the polarity and selectivity of the stationary phases under study is revealed. Preferable types of interactions of stationary phases containing crown compounds with organic compounds of different classes are discussed. It is concluded that phases of the mixed type based on crown ethers are promising for improving the selectivity and efficiency of gas-chromatographic separation     

一种新型主链杯芳冠醚聚硅氧烷毛细管气相色谱固定相(英文)

选用特殊的硅氢加成试剂（ＣＨ３）２ＳｉＨＣｌ，首次合成了一种杯芳冠醚单元位于聚硅氧烷主链的新型毛细管气相色谱固定相（Ｍ－Ｃ［４］Ｃ－５ＰＳＯ）。新型固定相具有很好的热稳定性，并对酚类、硝基及氯取代类芳香族位置异构体有良好的分离。其进一步的应用及分离机理有待于深入研究。     

Open tubular supercritical fluid chromatography of triterpene acids from Dysoxylum pettigrewianum (Meliaceae)

Open tubular supercritical fluid chromatography (SFC) with carben dioxide as the mobile phase has been investigated for the separation of four triterpene acids, two of which were structural isomers. These compounds, isolated from Dysoxylum pettigrewianum (Meliaceae), were chromatographed on three stationary phases with different selectivities. 30%-biphenylmethylpolysiloxane and polyethylene glycol (Carbowax 20M) phases exhibited poor chromatographic selectivity for the compounds. The separation was improved by employing the shape selectivity of a liquid crystalline biphenylcarboxylate ester polysiloxane and utilizing simultaneous temperature and pressure programming. The elution order was explained on the basis of the molecular structures of the triterpene acids, and their interaction with the liquid crystal phase.     

Synthesis and characteristics of [60]fullerene polysiloxane stationary phase for capillary gas chromatography

A new type of fullerene-containing polysiloxane was synthesized by reacting [60]fullerene with azidopropyl polysiloxane directly. The polysiloxanes have been used successfully as stationary phases for capillary gas chromatography. They displayed high column efficiency, wide operational temperature and high thermostability, and exhibited unique selectivity for many organic substances, such as alkanes, alcohols, ketones and aromatic compounds. The stationary phase was especially suitable for separation of high boiling-point compounds like polycyclic aromatic hydrocarbons and phthalic esters, etc. It was also found that some alcoholic or aromatic positional isomers could be well separated on the column. The influence of the fullerene content on the separation was also investigated.     

一种新型主链杯芳冠醚聚硅氧烷毛细管气相色谱固定相(英文):

选用特殊的硅氢加成试剂（ＣＨ３）２ＳｉＨＣｌ,首次合成了一种杯芳冠醚单元位于聚硅氧烷主链的新型毛细管气相色谱固定相（Ｍ－Ｃ［４］Ｃ－５ＰＳＯ）。新型固定相具有很好的热稳定性,并对酚类、硝基及氯取代类芳香族位置异构体有良好的分离。其进一步的应用及分离机理有待于深入研究。     

冠醚修饰型手性固定液的合成及其气相色谱性能的研究

合成了两种含冠醚功能基的手性固定液：（１Ｓ,２Ｓ）－１－对硝基苯基－２－（４＇－西佛碱基苯并１５－冠－５）－丙烷－１,３－烯丙氧基聚硅氧烷和３－甲基－２－（４＇－甲酰胺－苯并１５－冠－５）－丁酸乙酯。用它们涂制的石英毛细管柱呈强极性,色谱性能良好。并探讨了固定液的结构对分离能力的影响。     

From 1D strands to extended molecular assemblies in the binary compounds of dithiooxamide and dithiobiurea with crown ethers

The hydrogen-bonding networks for seven new binary compounds of dithiooxamide, (NH2CS)2 (dtox) and dithiobiurea (NH2CSNH)2 (dtur) with crown ethers, 18-crown-6 (18C6), 15-crown-5 (15C5), 12-crown-4 (12C4), cis-syn-cis-(DCHA), and cis-anti-cis-(DCHB) isomers of dicyclohexyl-18 -crown-6 are discussed. (15C5.dtox), (18C6.dtur) and (DCHB.dtur) afford one-dimensional hydrogen-bonded polymeric arrays where the components alternate. In (DCHA.2dtox) and (DCHB.2dtox) the similar hydrogen-bonded chains are further interlinked via dtox molecules to generate layered motifs. In (15C5.2dtur) the dtur molecules are self-assembled into layers via N-H...S hydrogen bonds. 15C5 spacers link adjacent layers into a three-dimensional network. In (12C4.dtur) the dtur molecules are arranged in chains. These chains alternate with the crown molecules attached to them through N-H...O hydrogen bonds in such a way that each 12C4 appears to be linked with four dtur molecules and vice versa thus providing a three-dimensional grid.     

聚硅氧烷键合离子液体的合成及色谱性能

提出了一种基于聚硅氧烷键合离子液体(PSOIL)的气相色谱固定相的方法, 即首先合成γ-氯丙基聚硅氧烷, 然后通过氯丙基与甲基咪唑的反应合成了聚硅氧烷负载的离子液体, 并对其色谱性能及分离选择性进行了评价.     

冠醚共缩聚物的合成与性能（Ⅱ）

采用２，６－二羟甲基苯酚类化合物分别与单苯并冠醚（Ｂ１５ＣＳ、Ｂ１８Ｃ６）和Ｍ苯并冠醚（２Ｂ１８Ｃ６、２Ｂ２４Ｃ８、２Ｂ３０Ｃ１０）在酸催化下缩聚，合成了两个系列冠醚共缩聚物．这些聚合物Ｍ＝１２００—４５００，可溶于氯仿等溶剂，萃取性能和络合选择性均有所提高．作为树脂使用，动态吸附容量为０．０５—０．１５ｍｍｏｌ／ｇ，并有较好的色谱特性．     

双苯甲酰胺冠醚固定相的合成及毛细管柱气相色谱性能的研究

合成了一种新型的双苯甲酰胺冠醚固定相:(1S,2S)-1-(对苯甲酰胺基)苯基-2-苯甲酰胺基-16-冠-5,其结构经红外光谱、核磁共振、质谱及元素分析数据证实。考察了这种固定相的柱效、热稳定性、极性及选择性等色谱特性。该类固定相对极性位置异构体分离效果良好。由于冠醚上引入苯甲酰胺取代基,因而对苯胺类及不经衍生化的碱性化合物能特殊选择性地分离。     

The nitrogen position effect on the selectivity of diazacrown ethers to metal ion

In this paper, the nitrogen position isomers of diaza-18-crown-6, diaza-15-crown-5, diaza-12-crown-4, and their complexes with Na⁺ ion are studied by the density functional theory. Their stable structures are identified by geometry optimization without strict for their geometry. The binding capability that reflects the selectivity of these diazacrown ethers to metallic ions is estimated by the binding energy. The position effects of nitrogen on the stability of these complexes are also investigated by the explicit natural bond orbital and atoms-in-molecule analysis. It is found that different nitrogen position in crown ring will result in different relative energy. To those diazacrown ethers under consideration, the calculation results show that 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane, 1,4-diaza-7,10,13-trioxacyclopentadecane, and 1,7-diaza-4,10-dioxacyclododecane exhibit higher metal binding selectivity than their corresponding nitrogen position isomers, respectively. Clearly, the position of nitrogen plays an important role in the selectivity of diazacrown ethers to metal ions in the system involved. This work will be help for the material design of ionic recognition and other related fields.     

溶胶-凝胶法制备羟基苯并冠醚固定相用于毛细管气相色谱(英文)

 用溶胶 凝胶 (sol gel)技术制备了羟基 苯并冠醚毛细管气相色谱固定相 ,并测定了它的色谱性能。结果表明该柱具有柱效高 ( >30 0 0 /m)、热稳定性好 ( 330℃ )和去活能力强的优点。与溶胶 凝胶羟基硅油柱相比 ,该柱具有良好的选择性。一些芳香族位置异构体如二甲苯、二氯苯、硝基甲苯和硝基氯苯在溶胶 凝胶羟基 苯并冠醚柱上得到了很好的分离。该柱具有很高的柱容量 ,一些不能在冠醚聚硅氧烷上分离的小分子化合物 ,如小分子醇、酯、酮、短链脂肪酸和挥发性的胺 ,在溶胶 凝胶冠醚柱上有很好的分离。