CN103752180A - Hydroxypropyl-beta-cyclodextrin chiral composite membrane, and applications thereof - Google Patents
Hydroxypropyl-beta-cyclodextrin chiral composite membrane, and applications thereof Download PDFInfo
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- CN103752180A CN103752180A CN201310680500.XA CN201310680500A CN103752180A CN 103752180 A CN103752180 A CN 103752180A CN 201310680500 A CN201310680500 A CN 201310680500A CN 103752180 A CN103752180 A CN 103752180A
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Abstract
The invention discloses a hydroxypropyl-beta-cyclodextrin chiral composite membrane, and applications thereof. A preparation method of the hydroxypropyl-beta-cyclodextrin chiral composite membrane comprises following steps: a polysulfone membrane is immersed in deionized water for two days, is dried vertically in the air, is immersed in a hydroxypropyl-beta-cyclodextrin solution with a concentration of 0.02g/ml, is dried vertically in the air, and is subjected to interfacial polymerization with a 1,6-hexanedioldiisocyanate solution with a concentration of 0.012g/ml; an obtained product is collected, is washed with deionized water after volatilization of reagents on the surfaces, and is dried in that air so as to obtain a chiral composite membrane; and the chiral composite membrane is delivered into a common dialysis device, and d-p-hydroxyphenylglycine raceme solution is separated by concentration difference, wherein purity of d-p-hydroxyphenylglycine enantiomer in a permeate liquid is more than 55%. The purity of the enantiomer obtained via the preparation is relatively high; cost is low; energy is saved; environment is protected; and the preparation method is convenient for continuous operation and large-scaled industrialized production.
Description
Technical field
The invention belongs to polymeric membrane chiral separation technical field, specifically relate to a kind of HP-β-CD chirality composite membrane.Meanwhile, the invention still further relates to the application of this chirality composite membrane in D-pHPG racemic modification splits.
Background technology
Chiral drug refers in drug molecular structure and introduces after chiral centre, the enantiomter of a pair of mirror image each other obtaining, because the pharmaco-kinetic processes of two enantiomers in chiral drug is different, so in chiral drug two enantiomers often pharmacologically active, metabolic process, metabolic rate and toxicity etc. in vivo there is significant difference, may there is following several situation: in two enantiomers, only have a kind of enantiomer to have pharmacologically active, and another kind of without significant pharmacological action; In two enantiomers, one has activity, and antagonism can occur for another; In two enantiomers, one has activity, and another does not only have activity toxic side effect on the contrary; Two enantiomers have and are equal to or close pharmacologically active, and two enantiomers have close activity sometimes, but still should select single enantiomer from overall balance; Two enantiomers have diverse physiologically active, and for example wherein a kind of enantiomer is appetite inhibitor, and another kind is revitalizer.Owing to before the deficiency of chiral drug understanding having been caused to many bitter lessons, these make people more pay attention to the enantiomer in chiral drug.
The production of chipal compounds generally has asymmetric syntheses and the large approach of chiral resolution two.But the medicine cost obtaining by asymmetric syntheses is at present higher, the superfluous value of enantiomer (e.e.%) is lower, and the overall scope of using is narrower; Chiral resolution technology has again mechanical Split Method, chemical resolution method, molecularly imprinted polymer Split Method, chromatogram Split Method and film Split Method etc., but the advantages such as size of synthesis production, energy-saving and environmental protection, low cost surely belong to chiral polymer film Split Method.
D-pHPG is mainly used in synthetic broad-spectrum antibiotic amoxycillin and cephalosporin analog antibiotic medicine, as Amoxicillin, cefadroxil azoles etc.Because such medicine has the features such as disease resisting effect is good, side effect is little, be therefore widely used.China is large to this type of pharmaceutical requirements amount, and its medical market has a extensive future.D-pHPG has optical activity, and they are left-handed different from dextrorotation, and for medicine and agricultural chemicals is mainly dextrorotation D-pHPG.
So far, there is not yet HP-β-CD composite membrane and the application in D-pHPG racemic modification splits is openly reported.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of chirality composite membrane that HP-β-CD prepares as raw material of take is provided.
The present invention also aims to provide the application of described HP-β-CD chirality composite membrane in D-pHPG racemic modification splits.
Object of the present invention is achieved by the following technical programs.
Except as otherwise noted, percentage of the present invention is mass percent.
A HP-β-CD chirality composite membrane, is characterized in that: with HP-β-CD, soak basement membrane, then carry out obtaining after interfacial polymerization with function groups compound.
Specifically by following methods, prepared:
(1) using PS membrane as basement membrane, first by deionized water, soak two days, vertically dry, then put into the 0.02g/mL HP-β-CD aqueous solution and soak 3h, take out and vertically dry;
(2) carry out interfacial polymerization with function groups compound again, polymerization time 10s;
(3) take out the good basement membrane of polymerization, treat surface reagent volatilization, put into 110 ℃ of drying boxes, heat treatment 20min;
(4) film after heat treatment is cleaned by deionized water, obtains required HP-β-CD chirality composite membrane.
Described function groups compound is a kind of in multicomponent isocyanate, polynary acyl chlorides or multi-anhydride, or contains the functional group of plural isocyanates, acyl chlorides or acid anhydrides simultaneously.Because effective body of the crosslinked chiral film of HP-β-CD is HP-β-CD, but in the molecular structure of HP-β-CD, there is a large amount of hydroxyls, therefore, with multicomponent isocyanate, polynary acyl chlorides or polyacid, or contain the functional group of plural isocyanates, acyl chlorides or acid anhydrides as crosslinking agent simultaneously, can reach same chiral separation effect.
Described function groups compound is preferably 0.012g/mL1, hexamethylene-diisocyanate n-heptane solution.
The application of described HP-β-CD chirality composite membrane in D-pHPG racemic modification splits.
Be specially: described HP-β-CD chirality composite membrane is packed in conventional electrodialysis apparatus, under 0～0.5mg/mL concentration difference drives, split the D-pHPG racemic modification aqueous solution.
Compared with prior art, the invention has the advantages that:
1, apply HP-β-CD chirality composite membrane fractionation D-pHPG racemic modification gained enantiomeric purity of the present invention (e.e.%) and can reach more than 55%, can realize the separation of enantiomer higher degree;
2, film splits and to carry out at normal temperatures, undergoing phase transition not, and energy consumption is low;
3, film split process is not added new chemical reagent, environmental protection, and cost is low;
4, film separation is easy to continued operation, easily carries out large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the molecular structural formula of HP-β-CD;
Fig. 2 is that enantiomter sample is crossed film liquid through the detection spectrogram of chiral high performance liquid chromatography.
The specific embodiment
Below in conjunction with drawings and Examples, content of the present invention is described in further detail.But drawings and Examples are not limited to the technical solution.
Embodiment 1
Commodity PS membrane, as basement membrane, soaks two days by deionized water, vertically dries, and puts into 0.02g/mL HP-β-CD solution and soaks 3h, takes out and vertically dries.With 0.012g/mL1, hexamethylene-diisocyanate n-heptane solution carries out interfacial polymerization, polymerization time 10s.Take out PS membrane, treat surface reagent volatilization, put into 110 ℃ of drying boxes, heat treatment 20min.Polysulfone composite membrane is cleaned by deionized water, obtains required HP-β-CD chirality composite membrane.
Application Example 1
The HP-β-CD chirality composite membrane that embodiment 1 is prepared packs in conventional electrodialysis apparatus, under the poor driving of 0.5mg/mL, and the D-pHPG racemic modification solution that fractionation concentration is 0.5mg/mL.
Experimental result shows: utilize HP-β-CD chirality composite membrane of the present invention to split D-pHPG racemic modification, cross the D-pHPG enantiomter sample obtaining after film and show that through high-efficient liquid phase chromatogram its purity is more than 55%.Can realize the separation of enantiomer higher degree; Because splitting, film carries out at normal temperatures, undergoing phase transition not, so energy consumption is low; Because film split process is not added new chemical reagent, so environmental protection, cost is low; Film separation is easy to continued operation, easily carries out large-scale industrial production.
Chiral separation effect as shown in Figure 2.The raw material that chiral film splits is racemic compound, and in racemic compound, left and right enantiomer concentration of revolving equates, if while therefore going resolution of racemates with the film that there is no chiral resolution ability, being reflected in Fig. 2 should be two peaks that area is equal.And we can see that from Fig. 2 the area at two peaks exists obvious difference, therefore illustrate that HP-β-CD chirality cross linking membrane of the present invention has the left and right enantiomer revolving significantly selective.Cross the D-pHPG enantiomter sample obtaining after film and show that through high-efficient liquid phase chromatogram its purity, more than 55%, can realize the separation of high antimer purity.
Embodiment 2
Commodity PS membrane, as basement membrane, soaks two days by deionized water, vertically dries, and puts into 0.02g/mL HP-β-CD solution and soaks 3h, takes out vertical 0.5h.With 0.021g/mL1,3,5-mesitylene formyl chloride n-heptane solution carries out interfacial polymerization, polymerization time 20s.Take out PS membrane, treat surface reagent volatilization, put into 110 ℃ of drying boxes, heat treatment 25min.Polysulfone composite membrane is cleaned by deionized water, obtains required HP-β-CD chirality composite membrane.
Application Example 2
The HP-β-CD chirality composite membrane that embodiment 2 is prepared packs in conventional electrodialysis apparatus, under the poor driving of 0.2mg/mL, and the D-pHPG racemic modification solution that fractionation concentration is 0.2mg/mL.
Experimental result shows: utilize HP-β-CD chirality composite membrane of the present invention to split D-pHPG racemic modification, cross the D-pHPG enantiomter sample obtaining after film and show that through high-efficient liquid phase chromatogram its purity is more than 50%.Can realize the separation of enantiomer higher degree; Because splitting, film carries out at normal temperatures, undergoing phase transition not, so energy consumption is low; Because film split process is not added new chemical reagent, so environmental protection, cost is low; Film separation is easy to continued operation, easily carries out large-scale industrial production.
Claims (5)
1. a HP-β-CD chirality composite membrane, is characterized in that: with HP-β-CD, soak basement membrane, then carry out obtaining after interfacial polymerization with function groups compound.
2. HP-β-CD chirality composite membrane according to claim 1, is characterized in that, specifically by following methods, is prepared:
(1) using PS membrane as basement membrane, first by deionized water, soak two days, vertically dry, then put into the 0.02g/mL HP-β-CD aqueous solution and soak 3h, take out and vertically dry;
(2) carry out interfacial polymerization with function groups compound again, polymerization time 10s;
(3) take out the good basement membrane of polymerization, treat surface reagent volatilization, put into 110 ℃ of drying boxes, heat treatment 20min;
(4) film after heat treatment is cleaned by deionized water, obtains required HP-β-CD chirality composite membrane.
3. HP-β-CD chirality composite membrane according to claim 2, it is characterized in that: described function groups compound is a kind of in multicomponent isocyanate, polynary acyl chlorides or multi-anhydride, or contain the functional group of plural isocyanates, acyl chlorides or acid anhydrides simultaneously.
4. HP-β-CD chirality composite membrane according to claim 3, is characterized in that: described function groups compound is preferably 0.012g/mL1, hexamethylene-diisocyanate n-heptane solution.
5. the application of HP-β-CD chirality composite membrane claimed in claim 1 in D-pHPG racemic modification splits, be specially: described HP-β-CD chirality composite membrane is packed in conventional electrodialysis apparatus, under 0～0.5mg/mL concentration difference drives, split the D-pHPG racemic modification aqueous solution.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104826506A (en) * | 2015-05-18 | 2015-08-12 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN111359455A (en) * | 2020-02-27 | 2020-07-03 | 华中科技大学 | Cyclodextrin modified polyamide thin film composite membrane, preparation and application thereof |
| CN113457468A (en) * | 2021-06-24 | 2021-10-01 | 北京工业大学 | Tannin-hydroxypropyl beta cyclodextrin composite nanofiltration membrane and preparation method thereof |
| CN114100379A (en) * | 2021-11-09 | 2022-03-01 | 天津大学 | Method for preparing high-flux reverse osmosis composite membrane by 4-dimethylaminopyridine-assisted cyclodextrin surface grafting |
Citations (1)
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| CN103357279A (en) * | 2013-07-30 | 2013-10-23 | 云南师范大学 | Teicoplanin chiral conposite membrane and its application in separation of D,L-p-hydroxyphenylglycine racemates |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103357279A (en) * | 2013-07-30 | 2013-10-23 | 云南师范大学 | Teicoplanin chiral conposite membrane and its application in separation of D,L-p-hydroxyphenylglycine racemates |
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| 傅若农等: "环糊精及其衍生物作手性选择剂", 《色谱分析概论》 * |
| 尹国等: "手性异构体拆分方法的研究进展", 《中国药物化学杂志》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104826506A (en) * | 2015-05-18 | 2015-08-12 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN104826506B (en) * | 2015-05-18 | 2017-02-22 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN111359455A (en) * | 2020-02-27 | 2020-07-03 | 华中科技大学 | Cyclodextrin modified polyamide thin film composite membrane, preparation and application thereof |
| CN111359455B (en) * | 2020-02-27 | 2021-05-18 | 华中科技大学 | Cyclodextrin modified polyamide thin film composite membrane, preparation and application thereof |
| CN113457468A (en) * | 2021-06-24 | 2021-10-01 | 北京工业大学 | Tannin-hydroxypropyl beta cyclodextrin composite nanofiltration membrane and preparation method thereof |
| CN114100379A (en) * | 2021-11-09 | 2022-03-01 | 天津大学 | Method for preparing high-flux reverse osmosis composite membrane by 4-dimethylaminopyridine-assisted cyclodextrin surface grafting |
| CN114100379B (en) * | 2021-11-09 | 2023-10-03 | 天津大学 | Method for preparing high-flux reverse osmosis composite membrane by 4-dimethylaminopyridine-assisted cyclodextrin surface grafting |
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