CN105131329A - Preparation method and application of macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with metal ions - Google Patents
Preparation method and application of macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with metal ions Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with metal ions. The preparation method of the membrane comprises the steps that chitosan, polyvinyl alcohol and silica gel are mixed to prepare a chitosan-polyvinyl alcohol membrane; processing and pore forming are performed with a sodium hydroxide solution; the chitosan-polyvinyl alcohol membrane is added in epoxy chloropropane and sodium hydroxide to obtain a macroporous chitosan-polyvinyl alcohol crosslinking membrane of a net structure; the macroporous chitosan-polyvinyl alcohol crosslinking membrane is steeped in a sodium carbonate solution containing iminodiacetic acid; the dried membrane is steeped in a solution containing divalent metal ions, and then the macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with the metal ions is obtained. The macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with the metal ions has the higher mechanical strength and has the efficient affinity adsorption capacity on protein containing histidine; the macroporous chitosan-polyvinyl alcohol crosslinking affinity membrane chelated with the metal ions is applied to separation of protein or enzymes containing the histidine, and the separation method comprises the steps of crude enzyme fluid preparation, specificity affinity adsorption of the membrane on the protein or enzymes containing the histidine, adsorption protein elution and membrane regeneration.
Description
Technical field
The present invention relates to a kind of preparation method and application of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, belong to the preparation of type material, belong to biological chemistry interdisciplinary field.
Background technology
Along with the great achievement that the fast development of the related discipline such as life science and biotechnology, particularly genetically engineered obtain, people can produce required target product in cell, therefore require also more and more higher to the separation and purification of biological product.Affinity chromatography is a kind of protein purification important method, and it has very high selectivity and separation performance with larger carrying capacity.Affinity chromatography group will be made up of affiliation carrier and affinity ligand.Traditional carrier and aglucon expensive, be not suitable for large-scale production.Chitosan comes formerly extensively to be had a large amount of amino and hydroxyl activity functional group and has good film-forming properties, is a kind of good affinity membrane material.
Current chitosan affinity membrane also exists physics, chemical structure is unstable, the shortcoming that physical strength is poor.Directly be used for by the affinity membrane of adsorbing metal ions when being rich in the absorption of histidine protein, because metal ion particle is less, intensive is attached on affinity membrane.Protein belongs to macromole, and film also exists larger sterically hindered during Action of Metal Ions, hinders the application of chitosan in affinity chromatography.
Present method has prepared a kind of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane, by adding polyvinyl alcohol, chitosan and polyvinyl alcohol generation physical-chemical reaction is made to form a kind of superpolymer, increase the physical strength of affinity membrane, utilize epoxy chloropropane as linking agent, make the chitosan polyvinyl alcohol film of chain become reticulated structure, add film physical and chemical stability energy, expand affinity membrane use range under various conditions, as also do not dissolved in acid condition.By connecting different sequestrants and the spacerarms such as iminodiethanoic acid, ciba blue dyestuff or trishydroxymethyl quadrol on affinity membrane, effectively prevent metal ion to reveal, and reduce the space resistance of metal ion and target protein, increase its adsorptive power to albumen, and be conducive to elutriant by target protein from wash-out affinity membrane.
Summary of the invention
The object of the invention is to the defect overcoming prior art, provide a kind of preparation method of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, its affinity membrane prepared has stronger physical strength, and with the film of existing preparation to compared with the protein adsorption ability of histidine mark, its advantage is that it can avoid the loss of metal ion, what reduce between metal ion and target protein is sterically hindered, increase it also can effectively target protein be eluted from film the adsorptive capacity of target protein, played the putamina glycan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions to the adsorptive power of albumen simultaneously, with the synergy of the rejection effect of film itself.The inventive method has a step efficient adsorption albumen, and easy and simple to handle, can reuse, energy consumption is low, has the advantages such as potential industrial applications value.
The present invention is achieved in that
The invention provides a kind of preparation method of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, comprise the following steps: step one: the polyvinyl alcohol 1:(2-3 by volume of concentration to be chitosan and the concentration of 1%-3% be 3%-9%) mix, and add silica gel, 24-30 hour is reacted in 50-60 DEG C of water-bath, reaction mixture pours masking template into, obtains chitosan-polyvinyl alcohol film; Step 2: utilize sodium hydroxide solution to soak chitosan-polyvinyl alcohol film, obtain macropore chitosan-polyvinyl alcohol film that aperture is 5-50nm; Step 3: be added in the mixing solutions of epoxy chloropropane and sodium hydroxide by macropore chitosan-polyvinyl alcohol film, at 50-60 DEG C of temperature, carries out crosslinking reaction, obtains cancellated macropore chitosan-polyvinyl alcohol crosslinked film; Step 4: cancellated macropore chitosan-polyvinyl alcohol film is immersed in the sodium carbonate solution containing iminodiethanoic acid, ciba blue dyestuff or trishydroxymethyl quadrol, react 8-12 hour in 50-60 DEG C of water-bath after, rinse with water, and at room temperature dry; Again the film after drying is immersed in the solution containing divalent-metal ion, carries out chelated metal ions, the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions can be obtained.
Further, described chitosan is dissolved in aqueous acid, and described polyvinyl alcohol is soluble in water.
Further, described divalent-metal ion is cupric ion, nickel ion or cobalt ion.
Further, the concentration of described divalent-metal ion is 0.05-0.1mol/L.
Further, the described solution containing divalent-metal ion is CuCl
2solution or NiCl
2solution or CoCl
2solution.
The present invention also provides a kind of application of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, and the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of described chelated metal ions is for the abstraction and purification of the albumen or enzyme that are rich in Histidine.
Further, the step that the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of described chelated metal ions carries out abstraction and purification to the albumen or enzyme that are rich in Histidine is as follows: step one: the preparation of mixed enzyme solution, gets the crude protein mixed solution being rich in histidine protein matter or crude enzyme liquid that concentration is 0.2-1mg/ml; Step 2: protein adsorption, get above-mentioned mixed enzyme solution 5mL, add the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane 0.1g of chelated metal ions respectively, regulate pH4-8 and ionic concn 0.1-0.5mol/L, at temperature 4-25 DEG C to being rich in histidine protein or enzyme spcificity absorption 1-5 hour; Step 3: target protein or enzyme wash-out, get the affinity membrane of adsorbed target albumen in step 2, utilizing volume for 2-10ml concentration is 0.05-0.1mol/L imidazoles wash-out affinity membrane, utilize dialysis process to be separated with imidazoles small-molecule substance by protein macromolecule, obtain the target protein or the enzyme that are rich in Histidine; Step book four: the renaturation of film, be the EDTA solution of 0.1-0.2mol/L in 5ml concentration by the affinity membrane in step 3, temperature is 25-30 DEG C, soak 2-3h, with deionized water rinsing 2-10 time, drying at room temperature, again chelated metal ions, adsorbed target albumen, carries out multi-pass operations repeatedly, realizes the recycle of film.
The present invention has following beneficial effect:
The preparation method of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions provided by the invention, the affinity membrane prepared by above-mentioned steps has stronger physical strength, and has efficient affine adsorptive power to the protein containing Histidine.With the film of existing preparation to compared with the protein adsorption ability of histidine mark, its advantage is that it can avoid the loss of metal ion, what reduce between metal ion and target protein is sterically hindered, increase it also can effectively target protein be eluted from film the adsorptive capacity of target protein, putamina glycan-polyvinyl alcohol crosslinked the affinity membrane simultaneously having played chelated metal ions to the adsorptive power of albumen, with the synergy of the rejection effect of film itself.The inventive method has a step efficient adsorption albumen, and easy and simple to handle, can reuse, energy consumption is low, has the advantages such as potential industrial applications value.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, other embodiments all that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belong to the scope of protection of the invention.
The embodiment of the present invention provides a kind of preparation method of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, comprises the following steps:
Step one: the polyvinyl alcohol 1:(2-3 by volume of concentration to be chitosan and the concentration of 1%-3% be 3%-9%) mix, and add 200-300 order silica gel 2.5%-7.5% simultaneously, mix, 24-30 hour is reacted in 50-60 DEG C of water-bath, reaction mixture pours masking template into, obtains chitosan-polyvinyl alcohol film.Wherein, described concentration is that the chitosan of 1%-3% is dissolved in the acetic acid aqueous solution of 2-5%, and described concentration is that the polyvinyl alcohol of 3%-9% is soluble in water.In this preferred embodiment, arbitrary ratio of chitosan and polyvinyl alcohol 1:2 to 3:8 by volume mixes.
Step 2: utilize the sodium hydroxide solution of 1-3mol/L to soak chitosan-polyvinyl alcohol film, soak time is 1-3 hour, and obtain macropore chitosan-polyvinyl alcohol film that aperture is 5-50nm, the permeability rate of film is 1-50ml (cm
2min).
Step 3: be added in the mixing solutions of epoxy chloropropane and sodium hydroxide by macropore chitosan-polyvinyl alcohol film, at 50-60 DEG C of temperature, carries out crosslinking reaction 2-3 hour, obtains cancellated macropore chitosan-polyvinyl alcohol crosslinked film; Wherein, the content of epoxy chloropropane is 10%-20%.By may-O-H association ,-C-H ,-C-O-, R-NO be contained in the known chitosan-polyvinyl alcohol film of infrared spectra
2with the functional group such as-C-N-, after crosslinked by epoxy chloropropane ,-O-H-freely associates to-O-H and changes ， – c h bond and to diminish R-NO
2,-C-N key dies down.Make single chitosan-polyvinyl alcohol become reticulated structure, stability increases, and makes its physical strength higher.
Step 4: cancellated macropore chitosan-polyvinyl alcohol film is immersed in the sodium carbonate solution containing iminodiethanoic acid, ciba blue dyestuff or trishydroxymethyl quadrol, react 8-12 hour in 50-60 DEG C of water-bath after, rinse with water, and at room temperature dry; Again the film after drying is immersed in the solution containing divalent-metal ion, continues 2-3 hour, carry out chelated metal ions, the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions can be obtained.Described divalent-metal ion is cupric ion, nickel ion or cobalt ion, and the concentration of described divalent-metal ion is 0.05-0.1mol/L, and in this preferred embodiment, the described solution containing divalent-metal ion is CuCl
2solution or NiCl
2solution or CoCl
2solution.
Further, in step 4, the concentration of sodium carbonate is 1-3mol/L, and the concentration of iminodiethanoic acid and ciba blue dyestuff is 0.1-1mol/L; Or the concentration of sodium carbonate is 1-3mol/L, the content of trishydroxymethyl quadrol is 5%-10%.
Macropore chitosan-polyvinyl alcohol crosslinked affinity membrane connects iminodiethanoic acid, chelated copper ion, and the schematic construction of the protein of purifying histidine mark is as follows:
Concrete experimental group of the present invention is as follows:
The present invention also provides a kind of application of macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, macropore chitosan-polyvinyl alcohol crosslinked the affinity membrane of chelated metal ions prepared by preparation method of the present invention can be used for protein or enzyme that abstraction and purification is rich in Histidine, and its main process is:
(1) preparation of protein solution or crude enzyme liquid
Get the crude protein mixed solution being rich in histidine protein matter that concentration is 0.2-1mg/ml or crude enzyme liquid (as the restructuring pfu crude enzyme liquid of the bovine serum albumin (BSA) of concentration 0.2-1mg/ml or concentration to be Recombinant SHMT (SHMT) crude enzyme liquid of 0.5-1.3mg/ml or concentration be 0.4-0.8mg/ml or 0.2-1.5mol/L hydantoin enzyme or 0.2-1mol/L immunoglobulin (Ig) or 0.2-1mol/L recombinant penicillin acylase, being not limited to listed crude enzyme liquid).
BSA surface is containing 17 histidine residues, and cupric ion can interact with the histidine residues being exposed to BSA surface, and cupric ion has 6 haptos, and wherein 3 points are combined with IDA, and other 3 points can be combined with BSA.Restructuring SHMT, the thick enzyme of restructuring pfu, recombinant penicillin acylase are all containing histidine mark.N,O-Diacetylmuramidase is the single peptide chain be made up of 18 kinds of 129 amino-acid residues.It is rich in basic aminoacids, and having 4 pairs of disulfide linkage to maintain enzyme configuration, is a kind of basic protein, and its N holds as Methionin, and C end is leucine.Hydantoin enzyme is a metalloid dependent enzyme, active centre mainly in conjunction with divalent cation ion, by activity necessary; Immunoglobulin (Ig) and immunoglobulin G (IgG), immunoglobulin A (IgA), immunoglobulin M (IgM), immunoglobulin D (IgD) and immunoglobulin E (IgE).
(2) protein adsorption
Get each 5ml of mixed enzyme solution in (1), add the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane 0.1-1g of chelated metal ions respectively, regulate pH=4-8, temperature is 4-25 DEG C, and ionic concn is 0.1-0.5mol/L, absorption 1-5 hour.
(3) albumen wash-out
Get the affinity membrane of adsorbed target albumen in (2), utilize volume for 2-10ml, concentration is 0.05-0.1mol/L imidazoles wash-out affinity membrane, utilizes dialysis process to be separated with imidazoles small-molecule substance by protein macromolecule, obtains the target protein or the enzyme that are rich in Histidine;
(4) renaturation of film
Be the EDTA solution of 0.1-0.2mol/L in 5ml concentration by the affinity membrane in (3), temperature is 25-30 DEG C, soaks 2-3h.With deionized water rinsing 2-10 time, drying at room temperature, again chelated metal ions, adsorbed target albumen, carries out multi-pass operations repeatedly, realizes the recycle of film.
Specific embodiment is as follows:
The result of above-mentioned experiment shows, macropore chitosan-polyvinyl alcohol crosslinked the affinity membrane of preparation connects iminodiethanoic acid (IDA), ciba blue dyestuff (Cibacronblue3GA), trishydroxymethyl quadrol (TED) can chelated metal ions effectively, avoids the loss of metal ion.There is larger adsorptive capacity to the albumen of histidine mark, in the separation of protein, there is larger application prospect.
In sum, the preparation method of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions provided by the invention, the affinity membrane prepared by above-mentioned steps has stronger physical strength, and with the film of existing preparation to compared with the protein adsorption ability of histidine mark, its advantage is that it can avoid the loss of metal ion, what reduce between metal ion and target protein is sterically hindered, increase it also can effectively target protein be eluted from film the adsorptive capacity of target protein, played the synergy of affinity membrane to the rejection effect of the adsorptive power of albumen and film itself simultaneously.The inventive method has a step efficient adsorption albumen, and easy and simple to handle, can reuse, energy consumption is low, has the advantages such as potential industrial applications value.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a preparation method for the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions, is characterized in that, comprise the following steps:
Step one: the polyvinyl alcohol 1:(2-3 by volume of concentration to be chitosan and the concentration of 1%-3% be 3%-9%) mix, and add silica gel, in 50-60 DEG C of water-bath, react 24-30 hour, reaction mixture pours masking template into, obtains chitosan-polyvinyl alcohol film;
Step 2: utilize sodium hydroxide solution to soak chitosan-polyvinyl alcohol film, obtain macropore chitosan-polyvinyl alcohol film that aperture is 5-50nm;
Step 3: be added in the mixing solutions of epoxy chloropropane and sodium hydroxide by macropore chitosan-polyvinyl alcohol film, at 50-60 DEG C of temperature, carries out crosslinking reaction, obtains cancellated macropore chitosan-polyvinyl alcohol crosslinked film;
Step 4: cancellated macropore chitosan-polyvinyl alcohol film is immersed in the sodium carbonate solution containing iminodiethanoic acid, ciba blue dyestuff or trishydroxymethyl quadrol, react 8-12 hour in 50-60 DEG C of water-bath after, rinse with water, and at room temperature dry; Again the film after drying is immersed in the solution containing divalent-metal ion, carries out chelated metal ions, the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions can be obtained.
2. the preparation method of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions as claimed in claim 1, it is characterized in that: described chitosan is dissolved in acetic acid aqueous solution, described polyvinyl alcohol is soluble in water.
3. the preparation method of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions as claimed in claim 1, is characterized in that: described divalent-metal ion is cupric ion, nickel ion or cobalt ion.
4. the preparation method of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of the chelated metal ions as described in claim 1 or 3, is characterized in that: the concentration of described divalent-metal ion is 0.05-0.1mol/L.
5. the preparation method of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of the chelated metal ions as described in claim 1 or 3, is characterized in that: the described solution containing divalent-metal ion is CuCl
2solution or NiCl
2solution or CoCl
2solution.
6. an application for the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions as claimed in claim 1, is characterized in that: the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of described chelated metal ions is for the abstraction and purification of the albumen or enzyme that are rich in Histidine.
7. the application of the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of chelated metal ions as claimed in claim 6, is characterized in that: the step that the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane of described chelated metal ions carries out abstraction and purification to the albumen or enzyme that are rich in Histidine is as follows:
Step one: the preparation of mixed enzyme solution, gets the crude protein mixed solution being rich in histidine protein matter or crude enzyme liquid that concentration is 0.2-1mg/ml;
Step 2: protein adsorption, get above-mentioned mixed enzyme solution 5mL, add the macropore chitosan-polyvinyl alcohol crosslinked affinity membrane 0.1g of chelated metal ions respectively, regulate pH4-8 and ionic concn 0.1-0.5mol/L, at temperature 4-25 DEG C to being rich in histidine protein or enzyme spcificity absorption 1-5 hour;
Step 3: target protein or enzyme wash-out, get the affinity membrane of adsorbed target albumen in step 2, utilizing volume for 2-10ml concentration is 0.05-0.1mol/L imidazoles wash-out affinity membrane, utilize dialysis process to be separated with imidazoles small-molecule substance by protein macromolecule, obtain the target protein or the enzyme that are rich in Histidine;
Step book four: the renaturation of film, be the EDTA solution of 0.1-0.2mol/L in 5ml concentration by the affinity membrane in step 3, temperature is 25-30 DEG C, soak 2-3h, with deionized water rinsing 2-10 time, drying at room temperature, again chelated metal ions, adsorbed target albumen, carries out multi-pass operations repeatedly, realizes the recycle of film.
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