CN104759271A - Green synthetic method of macroporous cellulose chromatographic microspheres - Google Patents
Green synthetic method of macroporous cellulose chromatographic microspheres Download PDFInfo
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- CN104759271A CN104759271A CN201510120168.0A CN201510120168A CN104759271A CN 104759271 A CN104759271 A CN 104759271A CN 201510120168 A CN201510120168 A CN 201510120168A CN 104759271 A CN104759271 A CN 104759271A
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Abstract
The invention relates to a green synthetic method of macroporous cellulose microspheres used in bio-separation and belongs to the technical field of materials. The green synthetic method includes following steps: (A) dissolving anhydrous microcrystalline cellulose in an ionic liquid, (B) performing double emulsification to the cellulose solution in an double-oil-phase system; (C) solidifying the cellulose in the ionic liquid with a solidifying agent to form the macroporous cellulose microspheres; and (D) performing crosslinking and modification to the macroporous cellulose microspheres to prepare a cellulose anionic exchange material having a perfusion mass transfer function. The green synthetic method is characterized in that the ionic liquid is used as the solvent of the cellulose so that the green synthetic method is green and environmental-protective and engineering enlargement of the method is simple. The macroporous cellulose microspheres has an individual double-pore structure, so that the perfusion mass transfer function can be achieved during separation. In addition, the macroporous cellulose microspheres is high in adsorption capacity and is especially suitable for quick and high-efficient separation of biological macro molecules.
Description
Technical field
The invention belongs to material invention field, in particular to a kind of preparation method of flash chromatography parting material, particularly a kind of ionic liquid prepares the method for macroporous cellulose microballoon.
Background technology
Liquid chromatography technology is a kind of high efficient separation technology, higher, applied widely at separating substances process intermediate-resolution.For chromatographic technique, chromatograph packing material is its technological core, decides the quality of actual chromatographic isolation effect.In recent years, the fast development of the high-technology fields such as biological medicine, more and more higher to chromatogram separation requirement, traditional chromatograph packing material can not meet the needs of scientific research and industry.Therefore, development of new high efficiency chromatography material, to meet current demand, becomes the research center of gravity of chromatogram worker.
The essential characteristic of liquid chromatogram process is that mobile phase penetrates through Stationary liquid, thus the separating property of liquid chromatogram and the material of chromatograph packing material and space structure (pore size distribution and pattern, granular size, porosity etc.) closely related.Thus can by selecting suitable material and regulating and controlling the raising that suitable space structure realizes chromatographic isolation effect.For the structure of chromatographic material, build perfusion macropore and diffusion hole in chromatograph packing material inside simultaneously, effectively can improve separative efficiency, realize the quick separating of material.This is because perfusion macropore can make mobile phase in the mode of convection current quickly through Stationary liquid, and mass transfer rate improves greatly; And diffusion hole provides more adsorption site, thus effectively improve adsorption capacity.From upper surface analysis, this unique double-pore structure contributes to the lifting of chromatograph packing material separating property, the purifying that it is quick, the stalling characteristic of high power capacity is especially applicable to large biological molecule.Therefore, in chromatograph packing material, build suitable double-pore structure is the effective way improving chromatographic performance.
For bio-separation, another one key factor is that the material of chromatograph packing material is selected.Cellulose is a kind of straight-chain polysaccharide, is widely used as chromatographic stationary phases, biomolecule of purifying.Why cellulose can be widely used, and is because cellulose has plurality of advantages, and comprising to have biocompatibility, be easy to generally ligand modified and suitable porosity thus have high-adsorption-capacity etc. with biomolecule.Although cellulose has above advantage, synthesize and be the Stationary liquid of matrix with cellulose and be not easy, particularly there is the cellulose microsphere of double-pore structure.Its major obstacle factor is that cellulose has flourishing intermolecular hydrogen bonding, thus causes its water insoluble and common organic solvents.Up to the present, only have a small amount of solvent system can dissolving cellulos, the dimethyl sulphoxide solution of such as methyl morpholine oxide, dimethylacetylamide, ammonium fluoride and fused salt hydrate etc., but these solvent overwhelming majority have certain harm for environment, in all these solvents, methyl morpholine oxide is only had to reach industrially scalable in the application of cellulose process.Even but methyl morpholine oxide also exists a lot of defect, as thermal instability, more side reaction and course of dissolution need high temperature etc.Therefore, a kind of new solvent system of cellulose processing industry active demand.
Recently, be found can dissolving cellulos for different kinds of ions liquid (being also referred to as green solvent).2002, first the people such as Rogers found that cellulose can be dissolved in ionic liquid (1-butyl-3-methylimidazolium chloride), and have studied the dissolution characteristics of this ionic liquid.In ensuing a few year, scientific research personnel has carried out more deep research to utilizing 1-butyl-3-methylimidazolium chloride dissolving cellulos, and has successfully prepared several cellulosic material, as fiber, film, gel etc.Compared to other common solvents, 1-butyl-3-methylimidazolium chloride has more advantage, and such as vapour pressure is higher, be easy to recycle, higher heat endurance and simple to operate etc.Based on these advantages, this novel dissolvent has broad application prospects in cellulosic material field.
By the inspiration of cellulose solvent new development, the present invention proposes the new method that the two emulsifying technology of a kind of combination prepares macroporous cellulose microballoon.The macroporous cellulose microballoon excellent performance prepared by the method, is suitable as Stationary Phase for HPLC with separating-purifying biomolecule very much.
Summary of the invention
The object of the invention is to the inherent shortcoming for current cellulose solvent, provide a kind of ionic liquid that utilizes to regenerate the method preparing flash chromatography macroporous cellulose microballoon.The cellulose microsphere utilizing the inventive method to prepare has double-pore structure, comprise perfusion hole and diffusion hole, effectively can improve the mass transfer rate of chromatographic stationary phases and the adsorption capacity to biomolecule, thus effectively improve the separating property of chromatograph packing material, and preparation process environmental protection.
The object of the invention is to be achieved through the following technical solutions.
A green syt new method for bio-separation macroporous cellulose microballoon, specifically comprises the steps:
(1) cellulose is dissolved in ionic liquid, magnetic agitation 10 ~ 20 hours in 80 ~ 120 DEG C of oil baths, forms the colorless viscous solution that percentage by weight is 2 ~ 12 wt%;
(2) by after the 4 ~ 20:5:4 mixing by volume of above-mentioned cellulose solution, cyclohexane and polysorbate60, temperature be 80 ~ 120 DEG C, under stir speed (S.S.) is the condition of 1000 ~ 4000 rpm, emulsification 10 ~ 30 min, formed emulsion (
);
(3) after above-mentioned emulsion process terminates, immediately agitator speed is down to 300 ~ 1000 rpm, adds and be incubated in the transformer oil of 70-100 DEG C and the two oil-based system of sorbester p37, the addition of transformer oil and sorbester p37 be respectively emulsion (
) volume 200 ~ 300% and 10 ~ 20%, continue emulsification 10 ~ 30 min, formed emulsion (
);
(4) by after the 15 ~ 22:1:8 mixing by volume of transformer oil, sorbester p37 and aqueous sodium persulfate solution, temperature be 80 ~ 120 DEG C, stir speed (S.S.) is emulsified 10 ~ 30 min of condition of 700 ~ 1000 rpm, formed emulsion (
);
(5) by emulsion (
) and emulsion (
) after 0.8 ~ 1:1 mixing by volume, be cooled to room temperature, now have precipitation to generate, continue reaction and generate to no longer including new precipitation, react rear collected by filtration, clean with ethanol and distilled water successively, after drying, obtain macroporous cellulose microballoon;
(6) after above-mentioned macroporous cellulose microballoon being mixed by mass volume ratio 0.5 ~ 1:1 with ethylene glycol diglycidylether, it is 30 ~ 70 DEG C in temperature, stir speed (S.S.) is first time cross-linking reaction 30 ~ 60 min under the condition of 150 ~ 300 rpm, add the sodium hydroxide solution that volume is mixed liquor 1.5 ~ 3 times, continue reaction 2 ~ 4 hours under the same conditions, react rear filtration and washed with distilled water, mix with chloropropylene oxide afterwards and carry out second time cross-linking reaction, course of reaction is identical with first time, through filtering after having reacted, washing, drying obtains the macroporous cellulose microballoon be cross-linked,
(7) after above-mentioned crosslinked macroporous cellulose microballoon being mixed by mass volume ratio 0.5 ~ 1:2 with diethyl aminoethanol solution, temperature be 40 ~ 80 DEG C, stir speed (S.S.) be the condition of 120 ~ 200 rpm under reaction 10 ~ 30 min, add the sodium hydroxide solution that volume is mixed liquor 1.5 ~ 3 times afterwards, continue reaction 1 ~ 2 hour under the same conditions, after having reacted, temperature is cooled to room temperature, neutrality is washed with distilled water to after filtration, react 20 ~ 60 min with dilute sulfuric acid again, after filtration, washing, after drying both macroporous cellulose microballoon anion adsorbent.
In technique scheme, cellulose described in step (1) is microcrystalline cellulose, general fibre element powder and be rich in cellulosic plant powder etc.
In technique scheme, step (1) described ionic liquid is can the ionic liquid of dissolving cellulos, comprises the dialkylimidazolium class of various routine or functionalization, N-alkyl pyridine class, quaternary amines chloro salt, carboxylic acids and alkyl phosphate salt.
In technique scheme, step (2) described emulsion (
) be O/W type.
In technique scheme, step (3) described emulsion (
) be O/W/O type.
The present invention compared with prior art, has the following advantages:
(1) solvent used in the present invention is ionic liquid, and be a class green solvent, good to cellulosic solubility property, heat endurance is high, is easy to operation and reclaims, environmentally safe;
(2) product macroporous cellulose microballoon of the present invention has perfusion macropore and diffusion micropore two kinds of pore passage structures, can effectively improve mass transfer rate and keep higher column capacity;
(3) improve active porosity diffusion coefficient, mass tranfer coefficient and adsorption capacity, higher dynamic bind carrying capacity had to protein and other, column efficiency and mechanical strength high, be suitable as very much the Stationary liquid of fast liquid chromatography;
The preparation condition of macroporous cellulose microballoon of the present invention is gentle, and raw material is easy to get, easy and simple to handle, is easy to large-scale industrial and produces.
Accompanying drawing explanation
Accompanying drawing 1 is the stereoscan photograph of the invention process example 1 product;
Accompanying drawing 2 is graph of pore diameter distribution of the invention process example 1 product;
Accompanying drawing 3 is that the invention process example 1 product is as the graph of a relation of post pressure during chromatography column packings with flow velocity;
Accompanying drawing 4 is that the invention process example 1 product is to the adsorption isothermal curve of BSA;
Accompanying drawing 5 is that the invention process example 1 product is to the curve of adsorption kinetics of BSA;
Accompanying drawing 6 is breakthrough curves of the invention process example 1 product BSA adsorption;
Dynamically/balance carrying capacity that accompanying drawing 7 is the invention process example 1 products when being chromatography column packings is than the relation with flow velocity.
Detailed description of the invention
For a better understanding of the present invention, below in conjunction with embodiment and accompanying drawing, the present invention is further explained.But it should be noted that, embodiment is only for being further expalined the present invention, and the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Take the anhydrous microcrystalline cellulose of 10 g and be dissolved in 133 mL ionic liquid chlorination 1-butyl-3-methylimidazole salt, magnetic agitation 13 hours in 90 DEG C of oil baths, obtains water white transparency and the cellulose solution of thickness.Measure after the above-mentioned cellulose solution of 20 mL mixes with 20 mL cyclohexanes and 0.8 mL Tween 80 and pour thermostatic mixer into, at emulsified 10 min of condition of temperature 100 DEG C, stir speed (S.S.) 2000 rpm, obtain emulsion (
).Subsequently, stir speed (S.S.) is down to rapidly 800 rpm, adds the 80 mL transformer oil and 3.6 mL sorbester p37s that are incubated to 100 DEG C, continue emulsification 10 min, obtain emulsion (
).In addition, after 100 mL transformer oil, 4.5 mL sorbester p37s and 40 mL aqueous sodium persulfate solutions (0.2 mol/L) are mixed, temperature be 100 DEG C, stir speed (S.S.) is emulsified 10 min of condition of 800 rpm, obtain emulsion (
).By emulsion (
) and emulsion (
) be cooled to room temperature after mixing, now there is precipitation to generate, continue reaction and generate to no longer including new precipitation, react rear collected by filtration, clean with ethanol and distilled water successively, after drying, obtain macroporous cellulose microballoon.After the macroporous cellulose microballoon obtained by 10 g mixes with 10 mL ethylene glycol diglycidylethers, temperature be 40 DEG C, stir speed (S.S.) be the condition of 200 rpm under first time cross-linking reaction 40 min, add the 3.0 mol/L sodium hydroxide solutions of 20 mL, continue reaction 2.5 hours under the same conditions, react rear filtration and washed with distilled water, add 10 mL chloropropylene oxides afterwards and carry out second time cross-linking reaction, course of reaction is identical with first time, after react through filtering, washing, drying obtains the macroporous cellulose microballoon that is cross-linked.After the macroporous cellulose microballoon be cross-linked by 10 g mixes with the 2.0 mol/L diethyl aminoethanol solution of 20mL, temperature be 60 DEG C, stir speed (S.S.) reacts 10 min under being the condition of 160 rpm, add the 3.5 mol/L sodium hydroxide solutions of 20 mL afterwards, continue reaction 1 hour under the same conditions, after having reacted, temperature is cooled to room temperature, neutrality is washed with distilled water to after filtration, again with sulfuric acid reaction 30 min of 1 mol/L, finally by after filtration, washing, drying both macroporous cellulose microballoon anion adsorbent.
Embodiment 2
Take 10 g general fibre element powder and be dissolved in 130 mL ionic liquid 1-ethyl-3-methylimidazole acetate, magnetic agitation 15 hours in 100 DEG C of oil baths, obtains water white transparency and the cellulose solution of thickness.Measure after the above-mentioned cellulose solution of 20 mL mixes with 20 mL cyclohexanes and 0.8 mL Tween 80 and pour thermostatic mixer into, at emulsified 10 min of condition of temperature 100 DEG C, stir speed (S.S.) 2000 rpm, obtain emulsion (
).Subsequently, stir speed (S.S.) is down to rapidly 800 rpm, adds the 80 mL transformer oil and 3.6 mL sorbester p37s that are incubated to 100 DEG C, continue emulsification 10 min, obtain emulsion (
).In addition, after 100 mL transformer oil, 4.5 mL sorbester p37s and 40 mL aqueous sodium persulfate solutions (0.2 mol/L) are mixed, temperature be 100 DEG C, stir speed (S.S.) is emulsified 10 min of condition of 800 rpm, obtain emulsion (
).By emulsion (
) and emulsion (
) be cooled to room temperature after mixing, now there is precipitation to generate, continue reaction and generate to no longer including new precipitation, react rear collected by filtration, clean with ethanol and distilled water successively, after drying, obtain macroporous cellulose microballoon.After the macroporous cellulose microballoon obtained by 10 g mixes with 10 mL ethylene glycol diglycidylethers, temperature be 40 DEG C, stir speed (S.S.) be the condition of 200 rpm under first time cross-linking reaction 40 min, add the 3.0 mol/L sodium hydroxide solutions of 20 mL, continue reaction 2.5 hours under the same conditions, react rear filtration and washed with distilled water, add 10 mL chloropropylene oxides afterwards and carry out second time cross-linking reaction, course of reaction is identical with first time, after react through filtering, washing, drying obtains the macroporous cellulose microballoon that is cross-linked.After the macroporous cellulose microballoon be cross-linked by 10 g mixes with the 2.0 mol/L diethyl aminoethanol solution of 20mL, temperature be 60 DEG C, stir speed (S.S.) reacts 10 min under being the condition of 160 rpm, add the 3.5 mol/L sodium hydroxide solutions of 20 mL afterwards, continue reaction 1 hour under the same conditions, after having reacted, temperature is cooled to room temperature, neutrality is washed with distilled water to after filtration, again with sulfuric acid reaction 30 min of 1 mol/L, finally by after filtration, washing, drying both macroporous cellulose microballoon anion adsorbent.
Embodiment 3
Take 15 g wheat stalk powder and be dissolved in 150 mL ionic liquid chlorination 1-butyl-3-methylimidazole salt, magnetic agitation 20 hours in 100 DEG C of oil baths, obtains water white transparency after filtration and the cellulose solution of thickness.Measure after the above-mentioned cellulose solution of 20 mL mixes with 20 mL cyclohexanes and 0.8 mL Tween 80 and pour thermostatic mixer into, at emulsified 10 min of condition of temperature 100 DEG C, stir speed (S.S.) 2000 rpm, obtain emulsion (
).Subsequently, stir speed (S.S.) is down to rapidly 800 rpm, adds the 80 mL transformer oil and 3.6 mL sorbester p37s that are incubated to 100 DEG C, continue emulsification 10 min, obtain emulsion (
).In addition, after 100 mL transformer oil, 4.5 mL sorbester p37s and 40 mL aqueous sodium persulfate solutions (0.2 mol/L) are mixed, temperature be 100 DEG C, stir speed (S.S.) is emulsified 10 min of condition of 800 rpm, obtain emulsion (
).By emulsion (
) and emulsion (
) be cooled to room temperature after mixing, now there is precipitation to generate, continue reaction and generate to no longer including new precipitation, react rear collected by filtration, clean with ethanol and distilled water successively, after drying, obtain macroporous cellulose microballoon.After the macroporous cellulose microballoon obtained by 10 g mixes with 10 mL ethylene glycol diglycidylethers, temperature be 40 DEG C, stir speed (S.S.) be the condition of 200 rpm under first time cross-linking reaction 40 min, add the 3.0 mol/L sodium hydroxide solutions of 20 mL, continue reaction 2.5 hours under the same conditions, react rear filtration and washed with distilled water, add 10 mL chloropropylene oxides afterwards and carry out second time cross-linking reaction, course of reaction is identical with first time, after react through filtering, washing, drying obtains the macroporous cellulose microballoon that is cross-linked.After the macroporous cellulose microballoon be cross-linked by 10 g mixes with the 2.0 mol/L diethyl aminoethanol solution of 20mL, temperature be 60 DEG C, stir speed (S.S.) reacts 10 min under being the condition of 160 rpm, add the 3.5 mol/L sodium hydroxide solutions of 20 mL afterwards, continue reaction 1 hour under the same conditions, after having reacted, temperature is cooled to room temperature, neutrality is washed with distilled water to after filtration, again with sulfuric acid reaction 30 min of 1 mol/L, finally by after filtration, washing, drying both macroporous cellulose microballoon anion adsorbent.
Claims (5)
1. a bio-separation green syt new method for macroporous cellulose microballoon, is characterized in that comprising the steps:
(1) cellulose is dissolved in ionic liquid, magnetic agitation 10 ~ 20 hours in 80 ~ 120 DEG C of oil baths, forms the colorless viscous solution that percentage by weight is 2 ~ 12 wt%;
(2) by after the 4 ~ 20:5:4 mixing by volume of above-mentioned cellulose solution, cyclohexane and polysorbate60, temperature be 80 ~ 120 DEG C, under stir speed (S.S.) is the condition of 1000 ~ 4000 rpm, emulsification 10 ~ 30 min, formed emulsion (
);
(3) after above-mentioned emulsion process terminates, immediately agitator speed is down to 300 ~ 1000 rpm, adds and be incubated in the transformer oil of 70-100 DEG C and sorbester p37 oil-based system, the addition of transformer oil and sorbester p37 be respectively emulsion (
) volume 200 ~ 300% and 10 ~ 20%, continue emulsification 10 ~ 30 min, formed emulsion (
);
(4) by after the 15 ~ 22:1:8 mixing by volume of transformer oil, sorbester p37 and aqueous sodium persulfate solution, temperature be 80 ~ 120 DEG C, stir speed (S.S.) is emulsified 10 ~ 30 min of condition of 700 ~ 1000 rpm, formed emulsion (
);
(5) by emulsion (
) and emulsion (
) after 0.8 ~ 1:1 mixing by volume, be cooled to room temperature, now have precipitation to generate, continue reaction and generate to no longer including new precipitation, react rear collected by filtration, clean with ethanol and distilled water successively, after drying, obtain macroporous cellulose microballoon;
(6) after above-mentioned macroporous cellulose microballoon being mixed by mass volume ratio 0.5 ~ 1:1 with ethylene glycol diglycidylether, it is 40 DEG C in temperature, stir speed (S.S.) is first time cross-linking reaction 30 ~ 60 min under the condition of 150 ~ 300 rpm, add the sodium hydroxide solution that volume is mixed liquor 1.5 ~ 3 times, continue reaction 2 ~ 4 hours under the same conditions, react rear filtration and washed with distilled water, mix with chloropropylene oxide afterwards and carry out second time cross-linking reaction, course of reaction is identical with first time, through filtering after having reacted, washing, drying obtains the macroporous cellulose microballoon be cross-linked,
(7) after above-mentioned crosslinked macroporous cellulose microballoon being mixed by mass volume ratio 0.5 ~ 1:2 with diethyl aminoethanol solution, temperature be 60 DEG C, stir speed (S.S.) be the condition of 120 ~ 200 rpm under reaction 10 ~ 30 min, add the sodium hydroxide solution that volume is mixed liquor 1.5 ~ 3 times afterwards, continue reaction 1 ~ 2 hour under the same conditions, after having reacted, temperature is cooled to room temperature, neutrality is washed with distilled water to after filtration, react 20 ~ 60 min with dilute sulfuric acid again, after filtration, washing, after drying both macroporous cellulose microballoon anion adsorbent.
2. the green syt new method of bio-separation macroporous cellulose microballoon according to claim 1, is characterized in that described cellulose is microcrystalline cellulose, general fibre element powder and any one or the multiple mixture that are rich in cellulosic plant powder.
3. the green syt new method of bio-separation macroporous cellulose microballoon according to claim 1, is characterized in that step (1) described ionic liquid is the dialkylimidazolium class of various routine or functionalization, N-alkyl pyridine class, quaternary amines chloro salt or carboxylic acids and alkyl phosphate salt.
4. the green syt new method of bio-separation macroporous cellulose microballoon according to claim 1, it is characterized in that emulsion that the described emulsion process of step (2) formed (
) be O/W type.
5. the green syt new method of bio-separation macroporous cellulose microballoon according to claim 1, it is characterized in that emulsion that the described emulsion process of step (3) formed (
) be O/W/O type.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732740A (en) * | 2019-03-25 | 2020-10-02 | 四川大学 | Novel preparation method of super-macroporous cellulose microspheres |
| CN113908813A (en) * | 2021-10-22 | 2022-01-11 | 浙江大学衢州研究院 | Cellulose derivative-silicon-based hybrid microsphere and preparation method thereof |
| CN115608329A (en) * | 2022-09-22 | 2023-01-17 | 四川大学 | Novel preparation method of through hierarchical porous polysaccharide microspheres |
-
2015
- 2015-03-19 CN CN201510120168.0A patent/CN104759271A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| KAI-FENG DU: ""Preparation and characterization of novel macroporous cellulose beads regenerated from ionic liquid for fast chromatography"", 《JOURNAL OF CHROMATOGRAPHY A》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111732740A (en) * | 2019-03-25 | 2020-10-02 | 四川大学 | Novel preparation method of super-macroporous cellulose microspheres |
| CN113908813A (en) * | 2021-10-22 | 2022-01-11 | 浙江大学衢州研究院 | Cellulose derivative-silicon-based hybrid microsphere and preparation method thereof |
| CN115608329A (en) * | 2022-09-22 | 2023-01-17 | 四川大学 | Novel preparation method of through hierarchical porous polysaccharide microspheres |
| CN115608329B (en) * | 2022-09-22 | 2024-01-26 | 四川大学 | New preparation method of polysaccharide microsphere penetrating through multistage holes |
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Application publication date: 20150708 |