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Preparation Of Gas Chromatographic Chiral Columns With β-Cyclodextrins As Stationary Phases And Studies On Their Chromatographic Properties

Posted on:2003-01-28Degree:MasterType:Thesis
Country:ChinaCandidate:A H DengFull Text:PDF
GTID:2121360092460086Subject:Analytical Chemistry
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Cyclodextrin(CD) is a kind of polymer formed by over 6 D-(+)-glucose molecules linking by α 1,4-glucoside bond. The most commonly used of them are α, β and γ-CD respectively formed by six, seven and eight glucose molecules with five chiral carbon atoms each. The shape of CD can be presented as a truncated cone. The inner diameter of b-CD cone is 0.65nm and the extra is 1.53nm. The hydroxyl groups of C(6) (the sixth carbon atoms of glucose unit and the same as follows) are located on the smaller opening of the cone with counterclockwise direction, while the hydroxyl groups of C(2) and C(3) are located on the larger opening of the cone with reverse direction. The inner cone is hydrophobic with only C-H and C-O bonds, while the edge of the cone is hydrophilic with many hydroxyl groups. Moreover, the inner cone has the characteristic of Lewis basis with high electron density because of the lone-pair electrons of oxygen atoms stretching towards it and can form inclusive compounds with varied compounds. The special structure of CD is very important to separate and analyze enantiomers, which has become the most important mainbody of super-molecular chemistry and greatly improved the developments of bioscience and pharmaceutical chemistry. Over 50 kinds of chiral stationary phases (CSPs) have been prepared with CDs and its derivatives as gas chromatographic(GC) stationary phases and hundreds of enantiomers have been separated since CDs and its derivatives were utilized to separate enantiomers in 1978. At present, more and more novel CD chiral stationary phases are being gradually synthesized and extensively applied for separating enantiomers by High Performance Liquid Chromatography (HPLC) and Capillary Electrophoresis (CE).Gas Chromatographic capillary columns with CD and its derivatives as stationary phases are often prepared by using CD and its derivatives dissolved in polysiloxanes of middle polarity (e.g.OV-1701) for their high melting points make them difficult to be used as GC stationary phase coatings.However, another approach is to prepare CD derivatives having lower melting points coated on capillary columns to separate enantiomers without using diluents. In this paper, the 1,2-diaminoethanl-β-CD with the intermediate of monootysol β-CD has been synthesized. Then it was coated on poly (vinyl alcohol), a new β-CD polymer has been got and then was coated on 101 supporter washed by HCl, By this method we prepared the gas chromatographic stationary phase for packed column. The chromatographic property of the stationary phase was also studied by investigating the retention behavior and separations of a series of compounds. We found that the polymer has good separation of some compounds, especially of some positional isomers and enantiomers. The retention mechanism of the β-CD polymer was also discussed. Respectively, glutamic acid (GLU) derivatized β-CD (β-CD-Glu) has been synthesized with epoxy chloropropane as the intermediate, a water-insoluble yellow liquid was got after the acetylating of the (β-CD-Glu) by using acetic anhydride, which was used as a novel gas chromatographic CSP; A water-soluble β-CD polymer cross-linked with epoxy chloropropane has been synthesized, and the derivatives of β-CD polymer were synthesized by its alkylating and acetylating. The different β-CD derivatives were coated on silica capillary columns by dynamic method, the chromatographic properties and retention behaviors of the fused silica capillary columns were studied, the results showed that the β-CD derivatives had good stereoselectivity and separation results to some compounds, especially to various positional isomers and enantiomers. All showed that the chiral chromatographic columns coated by the β-CD derivatives had excellent properties and very good value and excellent prospects o...
Keywords/Search Tags:Cyclodextrin Gas Chromatography Chiral stationary phase
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