CN101497033B - Anion exchange type macropore crystal glue medium and preparation method thereof - Google Patents
Anion exchange type macropore crystal glue medium and preparation method thereof Download PDFInfo
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- CN101497033B CN101497033B CN2008101638654A CN200810163865A CN101497033B CN 101497033 B CN101497033 B CN 101497033B CN 2008101638654 A CN2008101638654 A CN 2008101638654A CN 200810163865 A CN200810163865 A CN 200810163865A CN 101497033 B CN101497033 B CN 101497033B
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Abstract
The invention provides an anion exchange type macropore crystal-glue medium, which is prepared by fixedly loading groups shown in formulas 1 and 2 on the inner surfaces of pores of a substrate of the crystal-glue medium. The pore size of the anion exchange type macropore crystal-glue medium is between 5 and 300mu m, the porosity is between 50 and 98 percent, and because the amide groups are contained in the pores of the crystal-glue medium, the physical state of the crystal-glue medium is a whole column. The anion exchange type macropore crystal-glue medium has a smaller height equivalent to a theoretical plate, and when the flow rate is between 0.1 and 10cm/min, the height equivalent to a theoretical plate of the crystal-glue bed column is less than 0.2cm. The crystal-glue medium has the advantages that: 1, the monomer material is easily obtained, the process is simple, the cost is low, and the mass production is easily realized; 2, the super large pore is uniform in size, good in connectivity and small in mass transfer resistance, and can be operated in the range of high flow rate; and 3, the direction separation of the target products from complex feed liquid systems such as a fermenting liquor, a culture solution, a cracking solution and the like which contain microbe cells and cell debris at a high flow rate is realized, and the elution is easy and the regeneration is convenient.
Description
(1) technical field
The present invention relates to a kind of anion exchange type macropore crystal glue medium and preparation method thereof.
(2) background technology
Super-macroporous crystal gel medium (cryogel) is the method by the crystallization pore, the chromatography media that solvent freezing and crystallizing and column material polymerisation are obtained simultaneously.Solvent in the preparation process (as water) phase transformation crystallization, the exclusiveness of crystal growth simultaneously make monomer, crosslinking agent be enriched in crystal polymerization on every side and form the bed skeleton.Then form after crystal melted and have tens of super large holes to hundreds of microns, solid phases such as the microbial cell in the material liquid, cell fragment can directly be passed through, and collects centrifugal, filter, several steps such as concentrated and chromatography is one.Resistance to mass tranfer is little, the theoretical cam curve height, the theoretical cam curve of brilliant glue bed remains unchanged in bigger flow velocity mobility scale, bed is also indeformable, therefore can realize under the high flow rate the separation and purification of fermentate, recombinant protein, enzyme, gene therapy with important biomolecule materials such as DNA, antibody, microbial cells, it is rapid to have adsorbing separation, the characteristics that cost is low, the quick isolation and purification that is particularly useful for the biological substance of instability, tolerance difference has broad application prospects at medicine and bio-separation field.
With functional group in the grafting of super-macroporous crystal gel continuous bed is the key and the core of super-macroporous crystal gel functionalization.Patent (ZL 200510060269) discloses super-macroporous crystal gel medium of a kind of embedded submicron particles and preparation method thereof.Journal of Chromatography A, it is that monomer has prepared a kind of anion exchange type crystal gel medium that 1092 (2005) 199-205 disclose with diethyl aminoethyl methacrylate (DEAEMA), but, report as the grafting of amino-ethyl basic group not to other basic groups.In fact, the kind difference of monomer, its solubility property, reactivity have significant difference.Its preparation method is subjected to the influence of monomer concentration, reaction time, solvent, catalyst etc., and the difference of reaction condition also can produce considerable influence to the performance of crystal gel medium simultaneously.Though comparing DEAEMA as dimethylaminoethyl methacrylate structurally only is that aminomethyl is converted to aminoethyl, insoluble in water almost, the preparation method of existing bibliographical information can not directly use.
Therefore, exploration will contain the amino-ethyl basic group and be incorporated on the super-macroporous crystal gel medium it is carried out functionalization, and then the super-macroporous crystal gel medium and the solid carrier technology thereof of exploitation anion exchange type, have crucial meaning.
(3) summary of the invention
The object of the invention provides immobilized anion exchange type super-macroporous crystal gel separating medium of a kind of amino-ethyl basic group and preparation method thereof.
The technical solution used in the present invention is:
A kind of anion exchange type macropore crystal glue medium obtains at crystal gel medium matrix pores inner surface by the amino-ethyl basic group is immobilized, and described amino-ethyl basic group is one of following:
Described anion exchange type macropore crystal glue medium aperture is 5～300 μ m, porosity 50～98%, and the crystal gel medium hole contains amide group, and its physical aspect is an integral post.This anion exchange type macropore crystal glue medium has less height equivalent to a theoretical plate, and when flow velocity during at 0.1～10cm/min, the brilliant glue column height equivalent to one theoretical plate (HETP) is less than 0.2cm.
The invention still further relates to the preparation method of described anion exchange type macropore crystal glue medium, described method comprises: the monomer that will contain the amino-ethyl anion exchange groups is under 40～90 ℃, catalyst action, by grafting that amino-ethyl basic group shown in (1) or (2) is immobilized at crystal gel medium matrix pores inner surface, obtain described anion exchange macropore crystal gel medium; Described catalyst is following more than one metal ion solution: Zn
2+, Cu
2+, Ni
+, Ag
+Complex anion is Cl in this solution
-, NO
3 -, SO
4 2-Deng the inert ion that does not participate in reacting.
Described crystal gel medium matrix can prepare by this area conventional method, be specially: the aqueous solution that bed skeleton polymerization single polymerization monomer and crosslinking agent is mixed with gross mass volumetric concentration 20～150g/L, after adding catalyst reactant liquor is placed the cooling system crystallization and carries out polymerisation, heating up then makes crystal melt formation super large hole, obtains described crystal gel medium matrix.Described bed skeleton polymerization single polymerization monomer is generally the polymerisable monomer that contains amino or amide groups, can be one of following or wherein two or more mixtures: acrylamide (AAm), N, N '-DMAA (DMAAm), dimethylaminoethyl methacrylate (DMAEMA); Described catalyst can be the arbitrary proportion mixture of ammonium persulfate (APS) and tetramethylethylenediamine (TEMED), perhaps is triethanolamine; Described crosslinking agent can be N, N '-methylene-bisacrylamide (MBAAm), N, N '-diene propiono ethylenediamine.
The monomer solution that the described monomer that contains the amino-ethyl anion exchange groups is made into 0.01～5M usually earlier carries out graft polymerization reaction with crystal gel medium matrix again, the solvent of described monomer solution is the mixed solvent of water, dimethyl sulfoxide (DMSO) or water and dimethyl sulfoxide (DMSO) volume ratio 1: 0.2～5, or with monomer and sour (as HCl, H
2SO
4, HClO
4Deng) mix behind the protonation stand-by.
The described monomer that contains the amino-ethyl anion exchange groups can be one of following or wherein two or more mixtures: diethyl aminoethyl methacrylate, N, N-diethylaminoethanol acrylate, 3-lignocaine propylene, 4-lignocaine-1-butylene, 4-lignocaine styrene etc.
Described metal ion solution concentration is 0.05～4M.
Concrete, described method is as follows:
(1) diethyl aminoethyl methacrylate is made into the monomer solution of 0.01～0.1M, solvent is the mixed solvent of water, dimethyl sulfoxide (DMSO) or dimethyl sulfoxide (DMSO) and water volume ratio 2～5: 1;
(2) with Zn
2+, Cu
2+, Ni
+, Ag
+In one or more metal ions be made into the aqueous catalyst solution of 0.02～4M;
(3) crystal gel medium matrix is mixed with monomer solution and aqueous catalyst solution, under 40～60 ℃, carried out graft polymerization reaction 1～8 hour, obtain described anion exchange macropore crystal gel medium; Described crystal gel medium matrix, monomer solution and aqueous catalyst solution volume ratio are 1: 1.0～2.0: 1.0～3.0.
The anion exchange type macropore crystal glue medium of method preparation provided by the invention has following characteristic:
1) the crystal gel medium porosity 50～98%, pore diameter range 5～300 μ m.Flow velocity is in 0.2～10cm/min scope, and dielectric structure is constant substantially;
2) in 0.1～10cm/min flow rates, the brilliant glue column height equivalent to one theoretical plate (HETP) is less than 0.2cm;
3) crystal gel medium can be regenerated easily.
Beneficial effect of the present invention is mainly reflected in: 1) monomer material is easy to get, and technology is simple, and cost is low, and large-scale production is easy; 2) the super large pore-size is even, and connective good, resistance to mass tranfer is little, can operate in the high flow rate scope; 3) can realize under the high flow rate from complicated feed liquid such as the zymotic fluid that contains microbial cell, cell fragment etc., nutrient solution, lysate system directly separate targets thing, wash-out is easy, regeneration is convenient, is suitable for the extensive separation and Extraction and the purifying of genetic engineering downstream targets thing, conventional fermentate, biochemical drug etc.
(4) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
With 1.5g DMAAm monomer; 0.3g crosslinking agent N; N '-diene propiono ethylenediamine and 0.5gAGE and 0.15g ethylene glycol diglycidylether mixture aglucon material are dissolved in the 30ml deionized water, after stirring, add 20mg TEMED and 53mg APS rapidly; the gained mixed liquor is packed in the chromatographic column of internal diameter 26mm, long 200mm; after the sealing, but in the constant temperature cooling system of temperature programmed control, drop to-20 ℃ by 0 ℃; constant temperature is 20 hours then, carries out the crystallisation by cooling pore.Be warming up to room temperature, obtain super macroporous continuous bed crystalloid colloid medium matrix, the about 33mL of volume.
(solvent is DMSO: H to the diethyl aminoethyl methacrylate monomer solution of 70ml 0.1M
2O=2: 1, volume ratio) at 70ml 0.02M Zn
2+, Cu
2+The aqueous solution (each 0.01M) (complex ion SO
4 2-) catalytic action carries out glycerol polymerization 6h to aforementioned crystal gel medium matrix for following 60 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 60%, its pore diameter range 10～300 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.12cm in the brilliant glue column; Adsorption capacity 1.6mg BSA/g (wet glue), with 1M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 20 times.
Embodiment 2:
With 1.0g AAm monomer, 0.05g crosslinking agent MBAAm and 0.08g AGE are dissolved in the 10mL deionized water, after stirring, add 7mg TEMED and 15mg APS rapidly, the gained mixed liquor is packed in the glass chromatography column of internal diameter 16mm, long 200mm, after the sealing, but in the constant temperature cooling system of temperature programmed control, carry out crystallisation by cooling pore polymerization.Thermal history is: (A) cooling: drop to-30 ℃ by 0 ℃; (B) heat up: be warming up to-5 ℃; (C) constant temperature: constant temperature 5 hours; (D) cooling: be cooled to-20 ℃ again by-5 ℃; (E) constant temperature: constant temperature 16 hours; (F) heat up: be warming up to room temperature, obtain super macroporous continuous bed crystalloid colloid medium matrix, the about 12mL of volume.
(solvent is DMSO: H to the diethyl aminoethyl methacrylate monomer solution of 30ml 0.1M
2O=5: 1, volume ratio) at 20ml 2M Zn
2+The aqueous solution (complex ion Cl
-) catalytic action carries out glycerol polymerization 5h to aforementioned crystal gel medium matrix for following 40 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 50%, its pore diameter range 5～250 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.1cm in the brilliant glue column; Adsorption capacity 2.2mg BSA/g (wet glue), with 1M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 25 times.
Embodiment 3:
With 0.5g DMAEMA monomer, 0.1g crosslinking agent MBAAm and 0.15g aglucon material ethylene glycol diglycidylether are dissolved in the 20ml deionized water, after stirring, add 18mgTEMED and 25mg APS rapidly, the gained mixed liquor is packed in the glass chromatography column of internal diameter 16mm, long 200mm, after the sealing, but in the constant temperature cooling system of temperature programmed control, cool to-25 ℃, carry out the crystallisation by cooling pore.Then, thawing obtains super macroporous continuous bed crystalloid colloid matrix, the about 22mL of volume.
The diethyl aminoethyl methacrylate aqueous solution of 25ml 0.1M, 30min is stirred in 25ml 0.1M HCl reaction, then with aforementioned crystal gel medium matrix at 50ml 4M Ni
2+, Cu
2+The aqueous solution (the complex ion NO of (mol ratio 1: 5)
3 -) catalytic action carries out graft polymerization reaction 3h for following 40 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 90%, its pore diameter range 50～300 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.15cm in the brilliant glue column; Adsorption capacity 1.2mg BSA/g (wet glue), with 2M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 20 times.
Embodiment 4:
With 2g AAm monomer, 0.2g crosslinking agent MBAAm and 0.09g aglucon materials A GE are dissolved in the 40ml deionized water, after stirring, add 20mg TEMED and 15mg APS rapidly, the gained mixed liquor is packed in the glass chromatography column of internal diameter 26mm, long 200mm, after the sealing, but in the constant temperature cooling system of temperature programmed control, cool to-25 ℃; Carry out the crystallisation by cooling pore.Then, at room temperature melt crystal, obtain super macroporous continuous bed crystalloid colloid medium matrix, the about 43mL of volume.
The diethyl aminoethyl methacrylate aqueous solution of 50ml 0.01M, 30min is stirred in 50ml 0.01M HCl reaction, then with aforementioned crystal gel medium matrix at 50ml 2M Cu
2+The aqueous solution (complex ion NO
3 -) catalytic action carries out graft polymerization reaction 1h for following 90 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 98%, its pore diameter range 50～300 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.15cm in the brilliant glue column; Adsorption capacity 1.1mg BSA/g (wet glue), with 2M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 28 times.
Embodiment 5:
With 1.0g DMAEMA monomer, 0.5g crosslinking agent MBAAm and 0.3g aglucon material ethylene glycol diglycidylether are dissolved in the 15ml deionized water, after stirring, add 30mgTEMED and 30mg APS rapidly, the gained mixed liquor is packed in the glass chromatography column of internal diameter 10mm, long 200mm, after the sealing, but in the constant temperature cooling system of temperature programmed control, cool to-23 ℃, carry out the crystallisation by cooling pore.Then, at room temperature melt crystal, obtain super macroporous continuous bed crystalloid colloid medium matrix, the about 17mL of volume.
The diethyl aminoethyl methacrylate of 50ml 0.1M, 30min is stirred in 50ml 0.1M HCl reaction, then with aforementioned crystal gel medium matrix at 50ml 0.05M Cu
2+, Ag
+The aqueous solution (mol ratio 3: 1) (complex ion NO
3 -) catalytic action carries out graft polymerization reaction 8h for following 60 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 92%, its pore diameter range 5～300 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.16cm in the brilliant glue column; Adsorption capacity 1.2mg BSA/g (wet glue), with 2M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 18 times.
Embodiment 6:
With 0.6g DMAEMA monomer, 0.2g crosslinking agent MBAAm and 0.15g aglucon material ethylene glycol diglycidylether are dissolved in the 25ml deionized water, after stirring, add 20mgTEMED and 30mg APS rapidly, the gained mixed liquor is packed in the glass chromatography column of internal diameter 16mm, long 200mm, after the sealing, but in the constant temperature cooling system of temperature programmed control, cool to-22 ℃, carry out the crystallisation by cooling pore.Then, thawing obtains super macroporous continuous bed crystalloid colloid matrix, the about 27mL of volume.
The N of 20ml 0.1M, the N-diethylaminoethanol acrylate aqueous solution, 40min is stirred in 20ml 0.1M HCl reaction, then with aforementioned crystal gel medium matrix at 40ml 0.05M Cu
2+The aqueous solution (complex ion SO
4 2-) catalytic action carries out graft polymerization reaction 6h for following 50 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 95%, its pore diameter range 5～300 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.15cm in the brilliant glue column; Adsorption capacity 1.2mg BSA/g (wet glue), with 2M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 18 times.
Embodiment 7:
With 0.6g DMAEMA monomer, 0.15g crosslinking agent MBAAm and 0.15g aglucon material ethylene glycol diglycidylether are dissolved in the 15ml deionized water, after stirring, add 10mgTEMED and 20mg APS rapidly, the gained mixed liquor is packed in the glass chromatography column of internal diameter 16mm, long 200mm, after the sealing, but in the constant temperature cooling system of temperature programmed control, cool to-30 ℃, carry out the crystallisation by cooling pore.Then, thawing obtains super macroporous continuous bed crystalloid colloid matrix, the about 16mL of volume.
The N of 30ml 0.1M, (solvent is DMSO: H to N-lignocaine propylene solution
2O=5: 1, volume ratio) with aforementioned crystal gel medium matrix at 30ml 0.1M Cu
2+The aqueous solution (complex ion Cl
-) catalytic action carries out graft polymerization reaction 8h for following 40 ℃, obtains the anion exchange type crystal gel medium of immobilized amino functional group.Its porosity 98%, its pore diameter range 5～300 μ m; Flow velocity is in 0.1～10cm/min scope, and the structure of medium is constant, height equivalent to one theoretical plate (HETP) 0.15cm in the brilliant glue column; Adsorption capacity 1.1mg BSA/g (wet glue), with 2M NaCl and the regeneration of 0.2M ammoniacal liquor, reusable more than 28 times.
Claims (1)
1. the preparation method of an anion exchange type macropore crystal glue medium is characterized in that described method is as follows:
(1) diethyl aminoethyl methacrylate is made into the monomer solution of 0.01～0.1M, solvent is the mixed solvent of water, dimethyl sulfoxide (DMSO) or dimethyl sulfoxide (DMSO) and water volume ratio 2～5: 1;
(2) with Zn
2+, Cu
2+, Ag
+In one or more metal ions be made into the aqueous catalyst solution of 0.02～4M;
(3) crystal gel medium matrix is mixed with monomer solution and aqueous catalyst solution, under 40～60 ℃, carried out graft polymerization reaction 1～8 hour, obtain described anion exchange type macropore crystal glue medium; Described crystal gel medium matrix, monomer solution and aqueous catalyst solution volume ratio are 1: 1.0～3.0: 1.0～3.0.
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| CN103252218B (en) * | 2013-04-26 | 2015-08-05 | 浙江工业大学 | Hybrid overall crystal gel medium and preparation method thereof |
| CN108217814A (en) * | 2018-02-12 | 2018-06-29 | 浙江工业大学 | A kind of method using brilliant glue adsorption treatment on sewage |
| CN115850792B (en) * | 2022-09-30 | 2024-01-30 | 北京石油化工学院 | Preparation method of high-loading anion exchange chromatography medium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085797A (en) * | 2007-06-29 | 2007-12-12 | 浙江工业大学 | Cryogel adsorption chromatography separation method for adenosine triphosphate |
| CN101085798A (en) * | 2007-06-29 | 2007-12-12 | 浙江工业大学 | Cryogel adsorption chromatography separation method for cytidine triphosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085797A (en) * | 2007-06-29 | 2007-12-12 | 浙江工业大学 | Cryogel adsorption chromatography separation method for adenosine triphosphate |
| CN101085798A (en) * | 2007-06-29 | 2007-12-12 | 浙江工业大学 | Cryogel adsorption chromatography separation method for cytidine triphosphate |
Non-Patent Citations (1)
| Title |
|---|
| Junxian Yun, et al..One-step isolation of adenosine triphosphate from crude fermentation broth of Saccharomyces cerevisiae by anion-exchange chromatography using supermacroporous cryogel.《J. Chromatogr. B》.2007,第860卷(第1期),57-62. * |
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