CN1210750A - Chiral ligand exchanging and separating membrane and its preparing method - Google Patents
Chiral ligand exchanging and separating membrane and its preparing method Download PDFInfo
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- CN1210750A CN1210750A CN97107670A CN97107670A CN1210750A CN 1210750 A CN1210750 A CN 1210750A CN 97107670 A CN97107670 A CN 97107670A CN 97107670 A CN97107670 A CN 97107670A CN 1210750 A CN1210750 A CN 1210750A
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Abstract
The separating membrane for detachment, concentration and enrichment of antimer has cross-linked multi-hydroxyl polymer as carrier, bonded L- or D-amino acid chiral selector and cooperated metal ion. It can perform effective membrane dialysis detachment, concentration and enrichment of chiral compound, especially of DL-amino acid antimer.
Description
The present invention is chiral ligand exchanging and separating membrane and preparation method thereof.ICL is B01D13/00; BO1D13/04; BO1D53/22.
Film is a kind of energy-efficient parting material, in fields such as desalinization, sewage disposal, gas separation successful Application.Adopt membrane separation technique can realize that mass preparation separates, satisfy industrial needs, but the research of adopting membrane separation technique purification, enrichment or resolving chiral compound but few people set foot in.In nearest minority document, utilize haemocyanin (A.Higuchiet al., J.Membrane Sci., 1994,93,157.), cellulose derivative (E.Yashima et al., J.Appl.Polym.Sci., 1994,54,1087.), polyamide (T.Aoki et al., J.Membrane Sci., 1995,99,117.) etc. the chiral film of preparation is separated some chipal compounds and has been obtained certain effect.These chiral film are that the polymer with chirality is coated with and is stated from some porous membrane support (as polysulfones, polytetrafluoroethylene (PTFE)) and goes up and make.Document has also been reported a kind of with beta-schardinger dextrin-modified polyethylene alcohol film, is used for the pervaporation (A.Yamasaki et al., J.Membrane Sci., 1994,89,111.) of ethanol and aqueous mixtures.
Amino and carboxyl are arranged on the chiral amino acid molecular structure, are good chiral ligands, and when the transition metal ions that has a d track when itself and some combined, particularly bivalent cupric ion and divalent zinc ion formed chiral coordination compound.Under proper condition, the chiral ligand exchange interaction can take place.If chiral amino acid is fixed on the solid dielectric, utilize the ligand exchange effect that takes place between the liquid phase solid phase promptly can realize the separation of chiral ligand in the liquid phase medium.Bibliographical information L-amino acid is bonded on particle silica gel or the macromolecular scaffold, as the fixing phase of liquid phase ligand exchange chromatograph, fractionation amino acid and carboxylic acid enantiomer (Davankov, V A, et al., Adv.Chromtogr., (N.Y.), 1983,22,71; Guebitz, G., etal., J.Liq.Chromatogr., 1981,4,701; Yellow Tian Bao etc., analytical chemistry, 1991,19 (3), 291; 1996,24 (6), 709.).
The purpose of this invention is to provide a kind of novel chiral separation film and preparation method thereof.The chiral film that makes can split effectively, concentrate and the enrichment chipal compounds.
The invention relates to the polyhydroxylated polymer that utilizes crosslinked polyhydroxylated polymer or be dispersed with polyamine compounds and be the film matrix, by containing the bifunctional group compound of expoxy propane structure, L or D-amino acid is bonded to is prepared into chiral film on the polyhydroxylated polymer, the amino acid of bonding is with after metal ion cooperates, have the chiral ligand exchange capacity, realize the separation of chipal compounds.
The polyhydroxylated polymer that the present invention is used, the available dual-functional group compound that contains the expoxy propane structure is directly crosslinked, perhaps before carrying out cross-linking reaction, can add polyamine compounds earlier, and the polyamine compounds consumption is 0～100% of a polyhydroxylated polymer weight.The polyhydroxylated polymer of handling with polyamine compounds has better water repelling property than independent polyhydroxylated polymer, and subsequent processing steps is also more oversimplified.
Polyhydroxylated polymer of the present invention can be water-soluble or organic solvent in, have good filming performance.Can be polyvinyl alcohol, polyallyl alcohol, cellulose and modified cellulose, soluble starch and modified starch.Used polyamine compounds can be molten altogether with polyhydroxylated polymer in solvent for use, and polyamine compounds is scattered in the polyhydroxylated polymer equably.Polyamine compounds can be a diethylene diamine, TEPA, poly-second two support polyamines, polyallylamine.Used crosslinking agent is the ether dissolubility dual-functional group compound that contains propylene oxide group, and crosslinking agent can be an epoxychloropropane, two (glycidyl) glycol ether, three (glycidyl) glycerine ether.Used chiral has the circulus of rigidity, can be L-proline, L-hydroxy-proline or their D-isomers.
The diffusion barrier of the present invention's preparation can be used for film infiltration fractionation, enrichment and concentrated chipal compounds effectively, is specially adapted to the amino acid whose chiral resolution of DL-.Also can split carboxylic acid and alkamine enantiomer.
Embodiment 1
Get 2g polyvinyl alcohol (degree of polymerization 1750 ± 50) and 60ml distilled water in the 100ml beaker, soak 2h, be heated to dissolving fully, the glass plate that is poured on level after cold slightly is (on 18 * 18cm), after the air dry, cutting a diameter is 4.5cm, and thickness is the disk of 0.2～0.3mm, puts into 5 parts and contains 6g NaOH and 0.25g NaBH
4The aqueous solution, in the solution of 10 parts of methyl-sulfoxides and 3 parts of epoxychloropropane, at any time stir diaphragm gently, 0.5h take out the back, be reentered into to the 15ml aqueous solution that contains 4g NaOH, add the 10ml epoxychloropropane again, be warming up to 50 ℃ of reaction 3h, get the polyvinyl alcohol diaphragm (A) of crosslinked and band oxygen functional group.Embodiment 2
Get the 1g polyvinyl alcohol, put into 20ml water, be heated to dissolving fully, after cold slightly, add the 1ml diethylene diamine, add water to 30ml, after mixing, be poured on two 9 * 9cm glass plates, after the natural room temperature drying, cut diameter 4.5cm disk, put into the dioxane solution that 50ml contains 20% epoxychloropropane, room temperature reaction 24h is then behind 80 ℃ of reaction 4h, take out drying, get cross-linking polyvinyl alcohol film (B).Embodiment 3
With the film (A) of embodiment 1 preparation, put into concentration and be 20% L-Sodium proline saline solution, behind room temperature reaction 48h, wash with water, immerse again in the 10mM Schweinfurt green, blue L-proline modified polyethylene alcohol chiral film (CM-A).Embodiment 4
Chiral film (CM-A) with embodiment 3 preparations as shown in Figure 1, is installed on the homemade membrane separation device, with distilled water balance 2h, uses the NaAc-HAc-CuAc2 buffer solution balance 2h of pH 4.8 again.In feed well, add 2mmol/L DL-tyrosine (preparation of pH4.8 buffer solution) then, see through and add the pH4.8 buffer solution in the groove, after the room temperature normal pressure permeates certain hour down, the chiral ligand exchange chromatograph analysis is carried out in sampling in seeing through groove, chromatographic column is the chiral ligand exchange chromatograph post, 250 * 5mmI.D., flowing is the NaAc-HAc-CuAc of pH4.1 mutually
2Buffer solution, flow velocity 1.0ml/min, 50 ℃ of column temperatures.Analysis result as shown in Figure 2, enrichment L-tyrosine.Fig. 3 is that best e.e. value reaches 40% through the variation of the excessive e.e. value of amino acid enantiomer in the liquid with the time of seeing through, and promptly L-tyrosine is 70%, and D-tyrosine is 30%.Embodiment 5
Film (B) with embodiment 2 preparations replaces film (A), is undertaken by the step of embodiment 3, gets chiral film (CM-B).Embodiment 6
Chiral film (CM-B) with embodiment 5 preparations replaces (CM-A), is undertaken by the step of embodiment 4, and DL-tryptophan and DL-tyrosine are carried out the film permeability test.Equally in seeing through liquid enrichment the L-isomers, the former can reach 65% at the e.e value, the latter 52%.Figure 4 and 5 are represented respectively through the variation of e.e value in the liquid with the time of seeing through.
Description of drawings:
Fig. 1 is a chiral film separator schematic diagram.A is a feed well among the figure, and B is for seeing through groove, and 1 is injection port, and 2 is sample tap, and 3 is chiral film, and 4 is stirring rod.
Fig. 2 is for seeing through the chiral separation chromatography figure of the tyrosine sample of being got in the groove.
When Fig. 3 separates DL-tyrosine for using chiral film (CM-A), see through the change curve of the e.e value of tyrosine in the liquid with the time of seeing through.
When Fig. 4 separates the DL-tryptophan for using chiral film (CM-B), see through the change curve of the e.e value of tryptophan in the liquid with the time of seeing through.
When Fig. 5 separates DL-tyrosine for using chiral film (CM-B), see through the change curve of the e.e value of tyrosine in the liquid with the time of seeing through.
Claims (6)
1, a kind of enantiomer that is used for splits, concentrate chiral ligand exchanging and separating membrane with enrichment and preparation method thereof, this diffusion barrier is to be loaded with L-amino acid or the amino acid whose crosslinked polyhydroxylated polymer film of D-, at first, the polyamines based compound is scattered in the polyhydroxylated polymer, after the The tape casting film forming, under 10～90 ℃ of conditions, with crosslinking agent and its reaction 1～5h, with the anti-outlet capacity of enhancing polymer film, and be with the epoxide function group, then under 10～30 ℃ of conditions, with L or D-amino acid reaction 20～60h, cooperate with metal ion again, obtain described chiral separation film, it is characterized in that this film has the chiral ligand function of exchange.
2, preparation method according to claim 1, it is characterized in that the polyhydroxylated polymer filming performance is good, be easy to other functional group of covalent bonding, this polymer is polyvinyl alcohol, polyallyl alcohol, cellulose and modified cellulose, soluble starch and modified starch preferably.
3, preparation method according to claim 1 is characterized in that having adopted polyamine compounds, and it is with 0～100% of polyhydroxylated polymer weight the most, preferably diethylenetriamine, TEPA, poly-second two support polyamines, polyallylamine.
4, preparation method according to claim 1, its feature used crosslinking agent be the bifunctional group compound that contains propylene oxide group, preferably epoxychloropropane, two (glycidyl) glycol ether, three (glycidyl) glycerine ether.
5, preparation method according to claim 1 is characterized in that with the chiral amino acid molecule preferably having L-proline, L-hydroxyproline, D-proline or the D-hydroxyproline of rigid structure as the chirality chooser.
6, preparation method according to claim 1 is characterized in that used divalent transition metal ion is bivalent cupric ion, divalent zinc ion, divalence cadmium ion, is preferably bivalent cupric ion.
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| CN97107670A CN1210750A (en) | 1997-09-08 | 1997-09-08 | Chiral ligand exchanging and separating membrane and its preparing method |
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Cited By (7)
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| EP2223964A1 (en) * | 2009-02-27 | 2010-09-01 | General Electric Company | Membranes comprising amino acid mobile carriers |
| EP2223963A1 (en) * | 2009-02-27 | 2010-09-01 | General Electric Company | Membranes comprising amino acid mobile carriers |
| CN102179185A (en) * | 2011-03-29 | 2011-09-14 | 北京化工大学 | Method for preparing chiral separation solid film |
| CN103736402A (en) * | 2013-12-13 | 2014-04-23 | 云南师范大学 | Sodium alginate chiral cross-linked membrane and applications thereof |
| CN104975376A (en) * | 2015-06-12 | 2015-10-14 | 国家纳米科学中心 | Chiral nanometer fiber and its preparation method and use |
| CN111229189A (en) * | 2018-11-29 | 2020-06-05 | 天津大学 | Self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material and preparation method and application thereof |
| CN111621541A (en) * | 2019-02-27 | 2020-09-04 | 上海艾美晶生物科技有限公司 | Method for resolving optical isomers using electrodialysis techniques |
-
1997
- 1997-09-08 CN CN97107670A patent/CN1210750A/en active Pending
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| CN105289333A (en) * | 2009-02-27 | 2016-02-03 | 通用电气公司 | Membranes comprising amino acid mobile carriers |
| EP2223963A1 (en) * | 2009-02-27 | 2010-09-01 | General Electric Company | Membranes comprising amino acid mobile carriers |
| JP2010202872A (en) * | 2009-02-27 | 2010-09-16 | General Electric Co <Ge> | Membrane comprising amino acid mobile carrier |
| JP2010202870A (en) * | 2009-02-27 | 2010-09-16 | General Electric Co <Ge> | Membrane comprising amino acid mobile carrier |
| CN101954247A (en) * | 2009-02-27 | 2011-01-26 | 通用电气公司 | The film that comprises the amino acid movable carrier |
| CN101954249A (en) * | 2009-02-27 | 2011-01-26 | 通用电气公司 | The film that comprises the amino acid movable carrier |
| EP2223964A1 (en) * | 2009-02-27 | 2010-09-01 | General Electric Company | Membranes comprising amino acid mobile carriers |
| US8382883B2 (en) | 2009-02-27 | 2013-02-26 | General Electric Company | Membranes comprising amino acid mobile carriers |
| CN102179185A (en) * | 2011-03-29 | 2011-09-14 | 北京化工大学 | Method for preparing chiral separation solid film |
| CN103736402A (en) * | 2013-12-13 | 2014-04-23 | 云南师范大学 | Sodium alginate chiral cross-linked membrane and applications thereof |
| CN103736402B (en) * | 2013-12-13 | 2016-05-25 | 云南师范大学 | A kind of sodium alginate chirality cross linking membrane and application thereof |
| CN104975376A (en) * | 2015-06-12 | 2015-10-14 | 国家纳米科学中心 | Chiral nanometer fiber and its preparation method and use |
| CN111229189A (en) * | 2018-11-29 | 2020-06-05 | 天津大学 | Self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material and preparation method and application thereof |
| CN111229189B (en) * | 2018-11-29 | 2022-02-08 | 天津大学 | Self-assembly type amino acid derivative functionalized magnetic-carbon nanotube composite material and preparation method and application thereof |
| CN111621541A (en) * | 2019-02-27 | 2020-09-04 | 上海艾美晶生物科技有限公司 | Method for resolving optical isomers using electrodialysis techniques |
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