CN103736402B - A kind of sodium alginate chirality cross linking membrane and application thereof - Google Patents
A kind of sodium alginate chirality cross linking membrane and application thereof Download PDFInfo
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- CN103736402B CN103736402B CN201310681096.8A CN201310681096A CN103736402B CN 103736402 B CN103736402 B CN 103736402B CN 201310681096 A CN201310681096 A CN 201310681096A CN 103736402 B CN103736402 B CN 103736402B
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Abstract
The invention discloses a kind of sodium alginate chirality cross linking membrane and application thereof. Take sodium alginate and be dissolved in aqueous acetic acid, ultrasonic aggregated particle molecule, the standing and defoaming of removing; Under room temperature, casting solution is poured on clean smooth glass plate, with scraping hymenotome knifing, dry 4 days; Dry film is immersed in the acetone crosslinking agent that contains glutaraldehyde and hydrochloric acid and is cross-linked; The film being cross-linked is washed to neutrality with a large amount of acetone, ultra-pure water successively, just obtain required chirality cross linking membrane. Cross linking membrane is packed in conventional electrodialysis apparatus, under concentration difference drives, split D, the L-D-pHPG racemic modification aqueous solution, sees through in liquid D-pHPG enantiomeric purity more than 60%. Masking raw material of the present invention is inexpensive, and the single enantiomer purity of acquisition is large compared with high and flux, energy-conserving and environment-protective, cost are low, be easy to continued operation and large-scale industrial production.
Description
Technical field
The invention belongs to chiral polymer membrane separation technique field, specifically relate to a kind of sodium alginate chiralityCross linking membrane. Meanwhile, the invention still further relates to this chirality cross linking membrane at D, L-D-pHPG racemic modificationApplication in fractionation.
Background technology
Chirality is natural a kind of universal phenomenon, is containing a large amount of chiralitys in nature and life entityMolecule. Related to the chirality of compound by natural handedness property, also ask with regard to the chirality that has produced medicineTopic. Chiral drug refers to the medicine being made up of the chipal compounds with pharmacologically active, and drug moleculeThe mirror image of structure and it can not overlap each other, the medicines structure enantiomer of mirror each other. Due to handThe interior medicine dynamics process difference of two enantiomers of property medicine, therefore two of chiral drug kinds of mappingsBody pharmacologically active, metabolic process, metabolic rate and toxicity etc. in vivo often exist conspicuousness poorDifferent, there are following four kinds of situations: (1) only has a kind of enantiomer to have desired pharmacologically active, and anotherA kind of enantiomer does not have pharmacologically active; (2) two kinds of enantiomers wherein one have desired pharmacologically active,And another kind of enantiomer has other malicious secondary pharmacologically actives; (3) the identical but phase not of each enantiomer pharmacologically activeDeng. (4) two kinds of enantiomers have different pharmacologically actives. Due to the deficiency of before chiral drug being familiar withHad many bitter lessons, as " reaction stops " teratogenesis event of the sixties in 20th century, these make peopleRecognize, chiral drug must be noted that the configuration that they are different.
Generally, asymmetric syntheses synthetic by natural origin, chiral source and disappearing outward of the production of chipal compoundsRevolve body and split four large approach. The synthetic scope using at present of chirality is narrower, and the superfluous value of enantiomer (e.e.%)Often lower; Chiral resolution technology has mechanical Split Method, crystallization inoculation Split Method, biological Split Method, changeLearn Split Method, chromatogram Split Method, molecularly imprinted polymer Split Method and film Split Method etc., but be both suitable forLarge-scale production, energy-saving and environmental protection again, low cost surely belong to chiral polymer film Split Method.
Single enantiomer D-pHPG is the raw material of producing antibiotic side chain, and that still synthesizes is rightHydroxyphenylglycine major part is racemic modification, and China is antibiotics production and demand big country,Semi-synthetic cynnematin and semisynthetic penicillin medicine have become development priority and the focus of pharmaceutical industry. CauseThis is to D, and L-D-pHPG chiral resolution tool has very important significance.
So far, there is not yet sodium alginate chirality cross linking membrane and at D, L-D-pHPG racemic modificationThe open report of the application in fractionation.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of with sodium alginate and multi-functionalGroup's compound is the sodium alginate chirality cross linking membrane that raw material prepares.
The present invention also aims to provide described sodium alginate chirality cross linking membrane at D, L-para hydroxybenzene is sweetApplication during propylhomoserin 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 kind of sodium alginate chirality cross linking membrane, is characterized in that: sodium alginate is dissolved in to acetic acid water-solubleDirect plastic film mulch in liquid, dry film makes required chirality cross linking membrane after being cross-linked with function groups compound.
Specifically prepared by following methods:
(1) sodium alginate is placed in to 2wt.% aqueous acetic acid, stirring and dissolving, sea in final solutionThe concentration of mosanom is 5wt.%;
(2) ultrasonic 30min removes aggregated particle molecule, standing and defoaming, obtains casting solution;
(3) under room temperature condition, casting solution is poured on smooth glass plate, with scraping hymenotome knifing, room temperatureDry 4 days;
(4) dry film is cross-linked with function groups compound;
(5) rinse washing to neutral with acetone, water successively again, obtain required sodium alginate chiralityCross linking membrane.
Described function groups compound is polyaldehyde, multicomponent isocyanate, polynary acyl chlorides or multi-anhydrideIn one, or contain the functional group of plural aldehyde, isocyanates, acyl chlorides or acid anhydrides simultaneously.Because effective body of sodium alginate cross-linking chiral film is sodium alginate, but has in the molecular structure of sodium alginateA large amount of hydroxyls, therefore, with polyaldehyde, multicomponent isocyanate, polynary acyl chlorides or multi-anhydride, orContain the functional group of plural aldehyde, isocyanates, acyl chlorides or acid anhydrides as crosslinking agent simultaneously, canReach same chiral separation effect.
Described function groups compound is preferably the acetone soln that contains 5% glutaraldehyde, 0.1% hydrochloric acid.
Described sodium alginate chirality cross linking membrane is at D, during L-D-pHPG racemic modification splits shouldWith.
Be specially: described sodium alginate chirality cross linking membrane is packed in conventional electrodialysis apparatus, 0～0.8mg/mL concentration difference drives the lower D of fractionation, the L-D-pHPG racemic modification aqueous solution.
Compared with prior art, the invention has the advantages that:
1, apply sodium alginate-glutaraldehyde chirality cross linking membrane of the present invention and split D, L-D-pHPGRacemic modification gained enantiomeric purity (e.e.%) can reach more than 60%, can realize compared with high antimerThe separation of purity;
2, in film split process, do not add new chemical reagent, environmental protection, cost are low;
3, to split be to carry out approaching under normal temperature to film, not undergoing phase transition, and energy consumption is low;
4, film separates and is easy to continued operation, easily carries out large-scale industrial production.
Brief description of the drawings
Fig. 1 is the molecular structural formula of sodium alginate;
Fig. 2 is that enantiomter sample is crossed the detection spectrogram of film liquid through chiral high performance liquid chromatography.
Detailed description of the invention:
Below in conjunction with drawings and Examples, content of the present invention is described in further detail. But accompanying drawingBe not limited to the technical solution with embodiment.
Embodiment 1
Commodity sodium alginate is raw material, is dissolved in 2wt.% aqueous acetic acid, and making its concentration is 5wt.%;Stirring and dissolving, ultrasonic 30min remove aggregated particle molecule, standing and defoaming; Under room temperature condition by casting solutionBe poured on smooth glass plate, with scraping hymenotome knifing, drying at room temperature 4 days; By dry film with containing 5% penta 2The acetone crosslinking agent of aldehyde, 0.1% hydrochloric acid is cross-linked; Rinse in washing extremely with a large amount of acetone, water successivelyProperty; Obtain required sodium alginate chirality cross linking membrane.
Application Example 1
The sodium alginate chirality cross linking membrane that embodiment 1 is prepared packs in conventional electrodialysis apparatus,0.8mg/mL concentration difference drives, splits the D that concentration is 0.8mg/mL, L-D-pHPG racemicThe body aqueous solution.
Experimental result shows: utilize sodium alginate chirality cross linking membrane of the present invention to split D, the sweet ammonia of L-para hydroxybenzeneAcid racemic modification, crosses the D-pHPG enantiomter sample obtaining after film through high performance liquid chromatographyFigure shows that its purity, more than 60%, can realize the separation of high antimer purity; To connect because film splitsUnder near ambient temperature, carry out, not undergoing phase transition, therefore energy consumption is low; Because film split process is not added new changeLearn reagent, therefore environmental protection, cost is low; Film separates and 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, disappears outsideRevolve in compound, left and right enantiomer concentration of revolving equates, if therefore with there is no chiral resolution energyWhen the film of power goes resolution of racemates, being reflected in Fig. 2 should be two peaks that area is equal. And weThere is obvious difference in the area that can see two peaks from Fig. 2, therefore alginic acid of the present invention is describedSodium chirality cross linking membrane has significantly selective to the left and right enantiomer revolving. Cross obtain after film to hydroxylPhenylglycine enantiomter sample shows that through high-efficient liquid phase chromatogram its purity is more than 60%, can realizeThe separation of high antimer purity.
Embodiment 2
Commodity sodium alginate is raw material, is dissolved in 2wt.% aqueous acetic acid, and making its concentration is 5wt.%;Stirring and dissolving, ultrasonic 30min remove aggregated particle molecule, standing and defoaming; Under room temperature condition by casting solutionBe poured on smooth glass plate, with scraping hymenotome knifing, drying at room temperature 4 days; By dry film with containing 6.7%1, hexamethylene-diisocyanate n-heptane solution is cross-linked; Use successively a large amount of heptane, acetone, Shui ChongBe washed till neutrality; Obtain required sodium alginate chirality cross linking membrane.
Application Example 2
The sodium alginate chirality cross linking membrane that embodiment 2 is prepared packs in conventional electrodialysis apparatus,0.4mg/mL concentration difference drives, splits the D that concentration is 0.4mg/mL, L-D-pHPG racemicThe body aqueous solution.
Experimental result shows: utilize sodium alginate chirality cross linking membrane of the present invention to split D, the sweet ammonia of L-para hydroxybenzeneAcid racemic modification, crosses the D-pHPG enantiomter sample obtaining after film through high performance liquid chromatographyFigure shows that its purity, more than 55%, can realize compared with the separation of high antimer purity; Due to film split beApproach under normal temperature and carry out, not undergoing phase transition, therefore energy consumption is low; Because film split process is not added newChemical reagent, therefore environmental protection, cost is low; Film separates and is easy to continued operation, easily carries out large-scale industry rawProduce.
Claims (2)
1. a sodium alginate chirality cross linking membrane, is characterized in that, is prepared by following methods:
(1) sodium alginate is placed in to 2wt.% aqueous acetic acid, stirring and dissolving, sea in final solutionThe concentration of mosanom is 5wt.%;
(2) ultrasonic 30min removes aggregated particle molecule, standing and defoaming, obtains casting solution;
(3) under room temperature condition, casting solution is poured on smooth glass plate, with scraping hymenotome knifing, room temperatureDry 4 days;
(4) dry film is cross-linked with function groups compound, and described function groups compound is for containingThe acetone soln of 5% glutaraldehyde, 0.1% hydrochloric acid;
(5) rinse washing to neutral with acetone, water successively again, obtain required sodium alginate chiralityCross linking membrane.
Described in claim 1 sodium alginate chirality cross linking membrane at D, L-D-pHPG racemicApplication during body splits, is specially: pack described sodium alginate chirality cross linking membrane into conventional electrodialysis apparatusIn, under driving, 0～0.8mg/mL concentration difference splits D, and L-D-pHPG racemic modification is water-solubleLiquid.
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| CN201310681096.8A CN103736402B (en) | 2013-12-13 | 2013-12-13 | A kind of sodium alginate chirality cross linking membrane and application thereof |
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| CN201310681096.8A CN103736402B (en) | 2013-12-13 | 2013-12-13 | A kind of sodium alginate chirality cross linking membrane and application thereof |
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| CN103736402B true CN103736402B (en) | 2016-05-25 |
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| CN104749237B (en) * | 2015-03-27 | 2017-05-10 | 常州大学 | Selective recognition of sodium alginate modified glassy carbon electrodes to tyrosine enantiomers |
| CN105330875B (en) * | 2015-11-23 | 2019-01-29 | 青岛大学 | A kind of cross-linking modified sodium alginate and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210750A (en) * | 1997-09-08 | 1999-03-17 | 中国科学院成都有机化学研究所 | Chiral ligand exchanging and separating membrane and its preparing method |
| US6654635B1 (en) * | 1998-02-25 | 2003-11-25 | Hisamitsu Pharmaceutical Co., Inc. | Iontophoresis device |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210750A (en) * | 1997-09-08 | 1999-03-17 | 中国科学院成都有机化学研究所 | Chiral ligand exchanging and separating membrane and its preparing method |
| US6654635B1 (en) * | 1998-02-25 | 2003-11-25 | Hisamitsu Pharmaceutical Co., Inc. | Iontophoresis device |
Non-Patent Citations (2)
| Title |
|---|
| "Optical resolution of α-amino acids through enantioselective polymeric membranes based on polysaccharides";Jang Hoon Kim et al.;《Journal of Membrane Science》;20030301;第273-283页 * |
| "分子印迹膜分离手性氨基酸研究";赵艳艳;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090415;第18-19页 * |
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