CN100423831C - Chromatographic fixed-phase for modified glycan substrate, its preparation and use - Google Patents
Chromatographic fixed-phase for modified glycan substrate, its preparation and use Download PDFInfo
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- CN100423831C CN100423831C CNB2006100143585A CN200610014358A CN100423831C CN 100423831 C CN100423831 C CN 100423831C CN B2006100143585 A CNB2006100143585 A CN B2006100143585A CN 200610014358 A CN200610014358 A CN 200610014358A CN 100423831 C CN100423831 C CN 100423831C
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Abstract
A chromatographic fixing phase of modified chitosan matrix used as the filler for the liquid-phase chromatographic separation and solid-phase extraction of flavone compounds is prepared through polymerizing of modified chitosan with cross-linking agent in organic solvent to obtain target polymer. It has high adsorptivity.
Description
Technical field
The present invention relates to chromatogram solid phase and the preparation method and the application of chromatogram solid phase material, particularly a kind of modified glycan substrate, it is the preparation method who is used for the separatory chromatogram solid phase of Chinese medicine constituent flavone compound filler.
Background technology
The flavone compound breed structure is various to be the active ingredient of many Chinese herbal medicines such as ginkgo biloba p.e, and existing separation method is solvent extraction and resin adsorption method, and Comparatively speaking, resin adsorption method is more effective extracting method.The solid-phase media that is used for the separating flavone compounds, normally used alkyl linked silica stationary phase liquid chromatography stuffing C18, and the adsorption capacity of C18 is restricted.
Polysaccharides chiral is fixing to be used for having boundless application prospect aspect chirality Chiral Separation and the preparation.CN200310105270.0 discloses a kind of quick method for preparing the bonded polysaccharide chiral stationary phase, make the bonded polysaccharide chiral stationary phase, can remedy the now commercial similar fixing deficiency of restriction mutually that is subjected to mutually to flow, have solvent selectivity widely.Shitosan (2-amino-2-deoxidation-callose) is by the deacetylated natural polymer that obtains of chitin (2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-callose).Chitin extensively exists in the rudimentary plants such as lower animals such as crab, shrimp and algae, fungi, and content is extremely abundant, is to be only second to cellulosic second largest polysaccharide.A lot of methods are used for shitosan is carried out physical modification or chemical modification, to improve its mechanical strength, chemical stability, hydrophily or biocompatibility.
Summary of the invention
The purpose of this invention is to provide a kind of chromatogram solid phase and preparation method and application of modified glycan substrate.The objective of the invention is to prepare a kind of chromatograph packing material based on natural polymer chitosan, the solid-phase media that can be used for the separating flavone compounds, with normally used alkyl linked silica stationary mutually liquid chromatography stuffing C18 compare, separating effect is similar substantially, but go out peak order difference, the SPE experimental result shows that its adsorption capacity shows that much larger than the C18 filler this material has potential application prospect in the enrichment of flavone compound.
The chromatogram solid phase material of a kind of modified glycan substrate provided by the invention is that shitosan is soluble in water; in the presence of NaOH and sodium borohydride, reacted 3 hours for 40 ℃-90 ℃ with bromopropene; filter; the precipitation that obtains washes with water to neutrality. after the drying; use the ether elution; products therefrom is dissolved in N; in the dinethylformamide; add crosslinking agent, initator reacted 24 hours down in 60 ℃ of nitrogen protections; the polymerizate that obtains is through pulverizing; cross the sieve of 40 μ m, with the product powder sedimentation repeatedly in acetone that obtains, obtain the chromatogram solid phase material that the upper strata fine particle is modified glycan substrate again.
The preparation method of the chromatogram solid phase material of described modified glycan substrate is through following step:
1) shitosan is soluble in water reacted 3 hours for 40 ℃-90 ℃ with bromopropene in the presence of NaOH and sodium borohydride, filtered, and the precipitation that obtains washes with water to neutrality. and after the drying, use the ether elution, get product, its structure is as follows:
2) product is dissolved in N; in the dinethylformamide; add crosslinking agent; initator; reacted 24 hours down in 60 ℃ of nitrogen protections, the polymerizate that obtains is crossed the sieve of 40 μ m through pulverizing; with the product powder sedimentation repeatedly in acetone that obtains, obtain the chromatogram solid phase material that the upper strata fine particle is modified glycan substrate again.
Described shitosan: NaOH: sodium borohydride: the bromopropene mass ratio is 20: 10: 0.5: 28.4.
Described modification of chitosan: crosslinking agent: the initator mass ratio is 26: 40-100: 0.2.
Described crosslinking agent is: GDMA, trimethoxy propane trimethyl acrylic ester or N, N-methylene-bisacrylamide.
Described initator is an azodiisobutyronitrile.
The chromatogram solid phase material of glycan substrate of the present invention is used for Chinese medicine constituent flavone compound chromatographic isolation and extraction.
Fixedly phase of the present invention can effectively be separated and solid phase extraction filler as the flavone compound liquid chromatogram, and the common ratio that only need regulate flow middle mutually methyl alcohol and water just can satisfy the compartment analysis requirement of sample.The present invention can be used for the solid-phase media of separating flavone compounds, with normally used alkyl linked silica stationary mutually liquid chromatography stuffing C18 compare, its adsorption capacity shows that much larger than the C18 filler this material has potential application prospect in the enrichment of flavone compound.
Description of drawings:
The chromatogram of chromatographic stationary when separating the mixed solution of morin and Quercetin that Fig. 1 the present invention is prepared.
The chromatogram of chromatographic stationary when separating the hydrolysate of ginkgo biloba p.e that Fig. 2 the present invention is prepared.
The specific embodiment
Synthesizing of pi-allyl shitosan: get shitosan 20 grams and be dissolved in the 150mL distilled water, add 10gNaOH and 0.5g sodium borohydride, drip the 20mL bromopropene in the time of 40 ℃, after dripping, in 60 ℃ of reactions 3 hours.Filter, the precipitation that obtains is washed till neutrality with distilled water. and after the drying, use ether in apparatus,Soxhlet's
ElutionThen get product.
The preparation of chromatographic stationary phase: get 2.6g pi-allyl shitosan and be dissolved among the 10mL DMF, add crosslinking agent GDMA (EDMA) 40mmol, initiator A IBN (azodiisobutyronitrile) 20mg reacted 24 hours down in 60 ℃ of nitrogen protections.The bulk polymer that obtains is pulverized, and crosses the sieve of 40 μ m.The powder that obtains in acetone repeatedly sedimentation remove and to obtain the upper strata fine particle, the particle that sedimentation obtains gets final product with the microscopic examination epigranular.The filler that obtains is used methyl alcohol-acetate successively, methyl alcohol in apparatus,Soxhlet's after the elution, vacuum drying.With methyl alcohol is displacement fluid, loads the chromatographic column of 250 * 4.6mm.Note is done the ALCT post.As a comparison, do not add function monomer pi-allyl shitosan, after only handling as stated above with the filler of crosslinking agent preparation, the dress post.Note is done the EDMA post.
The mixed solution of preparation morin and Quercetin carries out the chromatographic isolation experiment.Its chromatographic condition is that UV detector 254nm wavelength detects mobile phase methanol/acetate (90/10-95/5v/v), flow velocity 1.0mL/min, sample size 20 μ L and 100 μ g/mL.Its separating resulting is seen accompanying drawing 1.The chromatogram of chromatographic stationary when separating the mixed solution of morin and Quercetin that Fig. 1 the present invention is prepared, among Fig. 1,1 morin, 2 Quercetins.
Press among the embodiment 1 1) with 2) identical condition prepares material and adorns post, different is,
The methanol solution of the hydrolysate of preparation ginkgo biloba p.e carries out the chromatographic isolation experiment.Its chromatographic condition is that UV detector 254nm wavelength detects, the phase acetonitrile/acetic acid/water (95/3/2v/v) that flows, flow velocity 1.0mL/min, sample size 20 μ L and 100 μ g/mL.Chromatogram is seen shown in Figure 2.The chromatogram of chromatographic stationary when separating the hydrolysate of ginkgo biloba p.e that Fig. 2 the present invention is prepared, among Fig. 2,1 Kaempferol, 2 Isorhamnetins, 3 Quercetins.
Claims (7)
1. the chromatogram solid phase material of a modified glycan substrate, it is characterized in that it is that shitosan is soluble in water, in the presence of NaOH and sodium borohydride, reacted 3 hours for 40 ℃-90 ℃ with bromopropene, filter, the precipitation that obtains washes with water to neutrality, after the drying, uses the ether elution, get product, its structure is as follows:
Products therefrom is dissolved in N; in the dinethylformamide; add crosslinking agent; initator; reaction is 24 hours under 60 ℃ of protection of ammonia, and the polymerizate that obtains is crossed the sieve of 40 μ m through pulverizing; with the product powder sedimentation repeatedly in acetone that obtains, obtain the chromatogram solid phase material that the upper strata fine particle is modified glycan substrate again.
2. the preparation method of the chromatogram solid phase material of the described modified glycan substrate of claim 1 is characterized in that it is through following step:
1) shitosan is soluble in water reacted 3 hours for 40 ℃-90 ℃ with bromopropene in the presence of NaOH and sodium borohydride, filtered, and the precipitation that obtains washes with water to neutrality, after the drying, uses the ether elution, gets product, and its structure is as follows:
2) product is dissolved in N; in the dinethylformamide; add crosslinking agent; initator; reacted 24 hours down in 60 ℃ of nitrogen protections, the polymerizate that obtains is crossed the sieve of 40 μ m through pulverizing; with the product powder sedimentation repeatedly in acetone that obtains, obtain the chromatogram solid phase material that the upper strata fine particle is modified glycan substrate again.
3. according to the preparation method of the chromatogram solid phase material of the described modified glycan substrate of claim 2, it is characterized in that described shitosan: NaOH: sodium borohydride: the bromopropene mass ratio is 20: 10: 0.5: 28.4.
4. according to the preparation method of the chromatogram solid phase material of the described modified glycan substrate of claim 2, it is characterized in that the 1st) the step products therefrom: crosslinking agent: the initator mass ratio is 26: 40-100: 0.2.
5. according to the preparation method of the chromatogram solid phase material of the described modified glycan substrate of claim 2, it is characterized in that described crosslinking agent is: GDMA, trimethoxy propane trimethyl acrylic ester or N, N-methylene-bisacrylamide.
6. according to the preparation method of the chromatogram solid phase material of the described modified glycan substrate of claim 2, it is characterized in that described initator is an azodiisobutyronitrile.
7. the chromatogram solid phase material of the described modified glycan substrate of claim 1 is used for Chinese medicine constituent flavone compound chromatographic isolation and extraction.
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| CNB2006100143585A CN100423831C (en) | 2006-06-15 | 2006-06-15 | Chromatographic fixed-phase for modified glycan substrate, its preparation and use |
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| CN100423831C true CN100423831C (en) | 2008-10-08 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100434160C (en) * | 2007-03-27 | 2008-11-19 | 河南师范大学 | Method for synthesizing alizarin violet bond silica-gel soid-phase extraction agent |
| CN102101045B (en) * | 2009-12-18 | 2013-01-02 | 中国科学院大连化学物理研究所 | Method for preparing glycosyl fixed phase |
| CN101864046B (en) * | 2010-06-11 | 2012-09-26 | 华南理工大学 | Glucosamine modified poly (ethylene glycol) diacrylate (PEGDA) hydrogel, preparation method and application thereof |
| CN102500275B (en) * | 2011-10-25 | 2013-11-06 | 南通大学 | Segmented glycosyl hyperdispersant and preparation method thereof |
| CN105294932B (en) * | 2015-11-06 | 2018-01-19 | 沈阳药科大学 | A kind of preparation method and its usage of organic polymeric solid phase fiber material |
| CN105797697A (en) * | 2016-05-24 | 2016-07-27 | 夏百庆 | Biocompatible high-purity chromatographic material and preparation method thereof |
| CN107308923B (en) * | 2017-08-03 | 2019-12-10 | 西南大学 | Preparation method of high performance liquid chromatography stationary phase and chromatographic column |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314430A (en) * | 2001-04-26 | 2001-09-26 | 南京大学 | Nanometer microball of chitosan-polyacrylic acid composite and its producing method and use |
| CN1629203A (en) * | 2004-10-21 | 2005-06-22 | 天津大学 | Preparation of temperature-sensitive chitosan-graft-NIPAAm/VL copolymer transgenic carrier |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314430A (en) * | 2001-04-26 | 2001-09-26 | 南京大学 | Nanometer microball of chitosan-polyacrylic acid composite and its producing method and use |
| CN1629203A (en) * | 2004-10-21 | 2005-06-22 | 天津大学 | Preparation of temperature-sensitive chitosan-graft-NIPAAm/VL copolymer transgenic carrier |
Non-Patent Citations (2)
| Title |
|---|
| 二甲胺修饰戊二醛交联壳聚糖树脂的制备及性能. 冯长根，白林山，任启生.离子交换与吸附，第19卷第3期. 2003 |
| 二甲胺修饰戊二醛交联壳聚糖树脂的制备及性能. 冯长根，白林山，任启生.离子交换与吸附，第19卷第3期. 2003 * |
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