CN1439454A - Preparation of zeolite modified flyash microbead assembled bodies for having affinity and separation of protein - Google Patents
Preparation of zeolite modified flyash microbead assembled bodies for having affinity and separation of protein Download PDFInfo
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- CN1439454A CN1439454A CN 03115910 CN03115910A CN1439454A CN 1439454 A CN1439454 A CN 1439454A CN 03115910 CN03115910 CN 03115910 CN 03115910 A CN03115910 A CN 03115910A CN 1439454 A CN1439454 A CN 1439454A
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Abstract
A zeolite molecular sieve modified powdered coal ash microbead used for affinity chromatography column to separate protein moleculae is prepared from the zeolite molecular sieve which has rich micrpores and ion exhange performance and the powdered coal ash microbeads which has light weight and high resistance to compression and corrosion through using zeolite molecular sieve to modifying powdered coal ash microbeads by adsorbing and secondary growing, and ion exchanging to fix the transition metal ions to zeolite molecular sieve.
Description
Technical field
The present invention is with the nano zeolite of a series of different topology structures and silica alumina ratio (as dissimilar nano zeolites such as LTA, BEA, FAU, MFI), utilize the method for absorption of nanometer packing engineering method or process diauxic growth to be modified at the fly ash micro-sphere surface, successfully prepare zeolite assembly with spherical morphology.This assembly can pass through cationic exchange, and methods such as electroless plating and surface chemistry grafting are carried out modification, can carry out the separation of functional protein molecule in the complex biological system as a kind of filling carrier of novel affinity chromatography.
Background technology
Protein is the main agent of biological function.Proteomics is important research emphasis after genomics.Being the new ideas by propositions such as Australian scientist Wilkins in 1994, is the new vegetative point of life science.It is the whole proteinic quantitative examination by pair cell on protein level or body genetic expression, with process that discloses life and the mechanism of explaining genetic expression control.One of the research emphasis of proteomics research protein separation; the corresponding significant peptide section that has special site of screening function albumen; set up the technical system of protein group component spectrum, the chain spectrum of protein function and the protein function screening of high-throughput, mass-producing, highly sensitive, high accuracy; in a large number, realize cDNA storehouse, polygene or segmental expression apace; screening has recombinant polypeptide or protein such as the antigen, acceptor, cytokine of market outlook, and is useful for major disease related protein group's research.One of core topic in this field is to set up biological complex sample protein matter group high efficiency separation, mass-producing authenticate technology and novel method.
Zeolite is a kind of porous silico-aluminate, is widely used in fields such as catalysis, absorption, ion-exchange and functional materials.To macromolecular system, because its arctation of zeolitic material, what diffusional resistance was bigger and traditional compares as parting material, and zeolite is restricted in the use range in this field.Development along with isolation technique, because zeolite has the micropore of homogeneous, silicon hydroxyl and ion-exchange performance that the surface is abundant, therefore have unique modifiability energy, zeolite molecular sieve class material has special advantages aspect macromolecular chemistry, material and the biological affinity chromatography isolation technique relating to.
Flyash is the formed solid waste of fine dusts that is given out by the coal-burning power plant, and quantity is very big, deals with improperly to increase flue dust, atmosphere pollution; If enter and can cause the river to silt up in the water system, objectionable impurities wherein also can work the mischief to human body and biology.Therefrom the cenosphere of Ti Quing has unique hollow ball structure and sillico aluminate glass body case, have light weight, characteristics such as withstand voltage, heat-resisting, corrosion-resistant and cheap and easy to get, select it as substrate, zeolite membrane is grown in its surface, the advantage of bound zeolite abundant microporous and ion-exchange performance and cenosphere might obtain new catalytic and parting material.Rely on the light weight of cenosphere, characteristics such as withstand voltage, corrosion-resistant and spheroid thereof to support character, and the specific adsorption of surperficial zeolite layer or ion-exchange performance, and and biomacromolecule high-affinity and high specificity reversible action, can prepare good rigidly, easily functional protein parting material under the suitable higher flow velocity of derivatize.
Summary of the invention
The objective of the invention is to develop the preparation method that a kind of zeolite that is used for the isolated protein molecule is modified the fly ash micro-sphere assembly.The method of technology of the present invention is as follows:
1. utilize the mode of physical and chemical adsorption that multiple nanosized zeolitic material is modified at the fly ash micro-sphere substrate surface.The physical and chemical adsorption assembling mode comprises nanometer engineering methods such as electrostatic adhesion layer laminate, electrophoretic deposition and chemical bonding coupling.Nano zeolite such as LTA (A zeolite), BEA (β zeolite), FAU (Y zeolite), MFI (Silicalite-1, dissimilar nano zeolites such as ZSM-5).
2. fly ash micro-sphere hydrothermal treatment consists diauxic growth in the aqueous precursor gel of Different Silicon aluminum ratio of modifying of nano zeolite can be in the zeolite membrane of surface growth one deck densification.Fly ash micro-sphere material behind that nano zeolite is modified and the diauxic growth is with certain density transition metal ion vlil, makes transition metal ion by being fixed in the surface of material with zeolite ion-exchange.Transition metal ion such as Co
2+, Zn
2+, Cu
2+, Ni
2+Deng.Diauxic growth treatment process and transition metal ion fixing means are prior aries, and these those skilled in the art all can implement.
3. utilize affinity chromatographic column, adopt above-mentioned type material packing, affine isolated protein molecule, by damping fluid drip washing pillar, can enriching protein molecules.
Molecular sieve of Nano zeolite modify fly ash micro-sphere in electrostatic adhesion layer laminate mode for well, this method technology is simple, controls zeolite-loaded amount easily, and is respond well.
5. the charge capacity of fly ash micro-sphere finishing zeolite molecular sieve of the present invention is 0.5-30%.
6. diauxic growth of the present invention is applicable to how sharp zeolite, comprise LTA (A zeolite), FAU (Y zeolite), MFI (Silicalite-1, ZSM-5) etc.
7. ion-exchange of the present invention institute fixed metal ion is Co
2+, Zn
2+, Cu
2+, Ni
2+Deng transition metal ion.
8. the fixed amount of transition metal ion of the present invention is with assembly and Co
2+, Zn
2+, Cu
2+, Ni
2+Transition metal ion exchanges fully.General transition metal ion strength of solution exchanges secondary and can reach complete switching purpose under 0.3M/L.
9. be that substrate descends production cost with industrial waste extract fly ash micro-sphere, and material property keep good.
10. the fly ash micro-sphere of the zeolite molecular sieve modification that the inventive method is obtained is as the packing material dress post of affinity chromatographic column, pass through balance, can affine isolated protein molecule, be fit to the requirement of micro column high efficiency liquid phase chromatograph technology such as (μ HPLC), and realize the coupling of multiple separate analytical techniques such as microtrabeculae affinity chromatography-μ HPLC-ESI-MS and microtrabeculae affinity chromatography-CE-ESI-MS.
11. dry-packing is easy and simple to handle, respond well during above-mentioned materials dress post.
12. can make packing material obtain repeated regeneration by roasting.
Actual conditions is as follows:
The 1 zeolite decorative material that obtains, is being gone in the homemade affinity chromatographic column with dry-packing fixedly behind the transition metal ion through ion exchange process.
2 utilize nearly neutral buffered soln (2-5 column volume doubly) balance pillar.
3 are added in the top of pillar with the standard protein sample.And, make sample to be separated with the abundant combination of the material in the post through certain hour.
4 elute solns that utilize certain gradient scope drip washing cylinder repeatedly under certain speed, the protein molecular that makes target under appropriate condition, specific being leached out.
5 can make packing material obtain repeated regeneration by roasting.
Traditional affinity chromatography packing material adopts agarose, dextrane gel etc. as supporting body more, not only costs an arm and a leg, easy swelling, and also not high pressure resistant, after surpassing certain limit, column pressure, stops up cylinder very easily because of crimp, influence separation efficiency.After zeolite of the present invention is modified the weighting material of fly ash micro-sphere material as affinity chromatography, owing to not only have unique modifiable outside surface, stable in properties, advantage such as with low cost, the development of various material sieving technologies, the fly ash micro-sphere that can select different size is as modifying substrate, its favorable mechanical physical and chemical stability also can effectively remedy the deficiency of above-mentioned traditional material, can be used as applying filler in microtrabeculae IMAC/CE/ESI-MS and microtrabeculae IMAC/ μ HPLC/ESI-MS coupling technique.It makes things convenient for the character of repeated regeneration and can introduce the characteristics of other function affinity groups simultaneously by technology such as ion-exchanges, will expand the range of application of material in affine separation of this type greatly.The inventive method is simple, convenient, respond well.
Description of drawings Fig. 1, Fig. 2 are the sem photograph of fly ash micro-sphere.Select the size of microballon not wait by a micron from several microns to hundreds of.Fig. 3 has been the fly ash micro-sphere finishing sem photograph of LTA nano zeolite.Fig. 4 has been the fly ash micro-sphere finishing sem photograph of FAU nano zeolite.Fig. 5 has been the fly ash micro-sphere finishing sem photograph of MFI nano zeolite.Fig. 6 has been the fly ash micro-sphere finishing sem photograph of BETA nano zeolite.Fig. 7 and Fig. 8 are that MFI nano zeolite modification fly ash micro-sphere is 28 Na in the mole proportioning
2O: 1.5 Al
2O
3: 100 SiO
2: 4000 H
2The sem photograph of the fly ash micro-sphere that later MFI (ZSM-5 zeolite) zeolite of 180 ℃ of diauxic growth 12h is modified in the presoma of O.Fig. 9 is that MFI nano zeolite modification fly ash micro-sphere is 28 Na in the mole proportioning
2O: 1.5 Al
2O
3: 100 SiO
2: 4000 H
2The sem photograph of the fly ash micro-sphere that later MFI (ZSM-5 zeolite) zeolite of 180 ℃ of diauxic growth 24h is modified in the presoma of O.Figure 10 is that MFI nano zeolite modification fly ash micro-sphere is 28 Na in the mole proportioning
2O: 1.5 Al
2O
3: 100SiO
2: 4000 H
2The sem photograph of the fly ash micro-sphere that later MFI (ZSM-5 zeolite) zeolite of 180 ℃ of diauxic growth 36h is modified in the presoma of O.Figure 11 is the XRD figure spectrum of the fly ash micro-sphere of the later MFI of raw material powder fly ash micro-bead and diauxic growth (ZSM-5 zeolite) zeolite modification.(A) raw material powder coal ash and be 28 Na in the mole proportioning
2O: 1.5 Al
2O
3: 100 SiO
2: 4000 H
2180 ℃ of growth (B) 12h and (B) 24h respectively in the presoma of O.Figure 12 and Figure 13 are that LTA nano zeolite modification fly ash micro-sphere is 40 Na in the mole proportioning
2O: Al
2O
3: 3SiO
2: 600 H
2The sem photograph of the fly ash micro-sphere that later LTA (A zeolite) zeolite of 80 ℃ of diauxic growth 9h is modified in the presoma of O.Figure 14 is that LTA nano zeolite modification fly ash micro-sphere is 40 Na in the mole proportioning
2O: Al
2O
3: 3SiO
2: 400 H
2The sem photograph of the fly ash micro-sphere that the later A Zeolites Zeolites of 80 ℃ of diauxic growth 12h is modified in the presoma of O.Figure 15 Zn
2+ZSM-5 after the ion-exchange (growth 12h) zeolite is modified fly ash micro-sphere and is separated two kinds of proteic elution curves.Display-object albumen chicken egg white and bovine serum albumin flow out successively corresponding to the imidazoles leacheate of different concns, and peak 1 is a chicken egg white, and peak 2 is a bovine serum albumin.Two kinds of different protein moleculars are different with the affinity interaction power of pillar as can be seen.Utilize the powder coal ash glass-microballons of ZSM-5 zeolite modified protein can be reached affine isolating purpose by the specificity affinity interaction as sorbent material.
Example below the embodiment is to the preparation of zeolite decorative material provided by the present invention and further specifying of carrying out that the affinity chromatography sepn process done.Example 1-4 prepares nanometer Silicalite-1 zeolite: with the TPAOH solution of 1M and TEOS according to mol ratio (TPA)
2O: SiO
2: EtOH: H
2O=1: 5.5: 22: 90 mixed, stir under the room temperature and wore out in 1 day, be put in 100 ℃ of oil baths then and refluxed three days.Preparation nanometer LTA and FAU zeolite: LTA and FAU zeolite are respectively according to 2.46 (TMA)
2O: 0.43 Na
2O: Al
2O
3: 3.40 SiO
2: 370 H
2O: 13.6 EtOH and 2.46 (TMA)
2O: 0.032 Na
2O: Al
2O
3: 3.40 SiO
2: 370 H
2O: the mole proportioning of 13.6 EtOH is dissolved in calculated amount aluminium foil and TEOS respectively in an amount of TMAOH, the NaOH solution, mixes then and stirs aging one day.LTA and FAU zeolite precursor body refluxed respectively in 100 ℃ of oil baths three days and seven days then.Preparation nanometer BEA zeolite: the calculated amount aluminium foil is dissolved in an amount of TEAOH aqueous solution, is added in the mixture of homodisperse white carbon black and TEAOH solution, stir, become glue sial (SiO
2/ Al
2O
3) mol ratio is respectively 60, and TEAOH/SiO
2Mol ratio is 0.6, moves into to have in the teflon-lined stainless steel cauldron static crystallization certain hour under the 413K autogenous pressure.The nano zeolite glue that all obtain all with 4 times of distilled water dilutings to reduce its viscosity and pH value, high speed centrifugation (16 then, 000rpm) separate, and washing, then a part of product being dispersed into solid content in deionized water, to be about the colloidal solution of 1wt% standby, and adjust pH value about 10 with weak ammonia.It is that 0.2% polycation electrolyte PDDA solution and 0.1% polyanion electrolyte PSS modify and be with corresponding positive charge that example 5-8 puts into concentration with garbled fly ash micro-sphere successively according to the order of PDDA/PSS/PDDA, with the ammonia soln washing of 0.01M 4 times.Get then in right amount and adsorb zeolite seed crystal in above-mentioned four kinds of zeolite glues, filter then, drying obtains the flyash microballoon that nanometer Silicalite-1, FAU, LTA and BEA adsorb respectively.Example 9-11 is respectively with Al
2(SO
1)
318H
2O and Na
2SiO
39H
2O is dissolved in the proper amount of deionized water, mixes then, stirs at 30% silicon sol that adds aequum, and the mole proportioning of gained precursor mixture is 28 Na
2O: 1.5 Al
2O
3: 100 SiO
2: 4000 H
2O.0.4gSilicalite-1 coal fly ash hollow micro bead that nano zeolite is modified and the presoma clear solution of 10ml are sealed in 180 ℃ of reaction 12h, 24h and 36h down.All product distilled water washs, dry then, product is the fly ash micro-sphere that the ZSM-5 zeolite is modified.Example 12-14 repeats above-mentioned experimental procedure, and the diauxic growth temperature is adjusted into 100 ℃, 120 ℃ and 160 ℃ of reaction 36h, the fly ash micro-sphere that product is modified for the ZSM-5 zeolite respectively.Example 15-17 adjusts the presoma silica alumina ratio and is respectively 25,60,200, and reacting the 24h product down at 180 ℃ is the fly ash micro-sphere that the ZSM-5 zeolite is modified.Example 18-21 preparation mole proportioning is 40 Na
2O: Al
2O
3: 3SiO
2: 600 H
2The presoma of O, coal fly ash hollow micro bead that the 0.4gLTA nano zeolite is modified and the presoma of 6ml react 6h, 9h, 12h and 15h down at 80 ℃, and product is the fly ash micro-sphere that the A zeolite is modified.Example 22-24 repeats above-mentioned experimental procedure, and the diauxic growth temperature is adjusted into 60 ℃, 90 ℃ and 110 ℃ of reaction 9h, the fly ash micro-sphere that product is modified for the LTA zeolite respectively.Example 25-27 preparation mole proportioning is 24 Na
2O: Al
2O
3: 10SiO
2: 1600 H
2The presoma of O, coal fly ash hollow micro bead that the 0.4gFAU nano zeolite is modified and the presoma of 6ml react 3h, 5h, 10h and 12h down at 90 ℃, and product is the fly ash micro-sphere that Y zeolite is modified.Example 28-30 repeats above-mentioned experimental procedure, and the diauxic growth temperature is adjusted into 80 ℃ and 100 ℃ of reaction 5h, the fly ash micro-sphere that product is modified for the FAU zeolite respectively.Example 31 with the material of growth 12h preparation among the example 9-11 550 ℃ of following roastings, at 90 ℃ 0.3Zn (NO
3)
2Stir 30min in the solution, with Zn
2+Exchange on the framework of molecular sieve in the matrix, repeatedly wash, promptly obtain required affinity chromatography separator column after drying at 80 ℃ and fill filler through deionized water.Example 32-34 repeats above-mentioned experimental procedure, and exchange ion uses Co respectively
2+, Cu
2+, and Ni
2+, obtain required affinity chromatography separator column and fill filler.Example 35 installs to the filler dry method of example 31 preparations in the homemade affine separator column, column internal diameter 15mm, and bed height is about 10mm, adds equalizing and buffering solution (Tris-HCl solution, pH7.0) the balance pillar of 4 times of column volumes respectively.Bovine serum albumin and the pure proteic standardized solution of ovum gallinaceum (China Shun biotechnology company limited provides by Shanghai) of preparing 2mg/ml respectively mixed with 1: 1; get 0.5ml mixed protein sample solution and join the separator column top; after treating that protein solution flows through cylinder; leave standstill about 20min, make the target protein molecule with fixed configuration metal ions Zn in the weighting material
2+Fully combination, the repetitive scrubbing cylinder is continued with the equalizing and buffering solution of 3 times of column volumes in the back.The imidazoles solution gradient wash-out of target protein by a series of different concns that will fixedly be adsorbed at last in the column filling comes out, and collects and flows out component, utilizes UV to detect proteic characteristic absorbance signal at the 280nm wavelength, and draws the working curve of effluent.
Claims (9)
1. preparation method that the zeolite molecular sieve that is used for affine isolated protein is modified the fly ash micro-sphere assembly, it is characterized in that: (1) evenly modifies in the fly ash micro-sphere surface nano zeolite by physical and chemical adsorption, pass through diauxic growth then, organic formwork agent is removed in roasting; (2) with the material of above-mentioned preparation by ion-exchange, transition metal ion is fixed in the molecular sieve, make the zeolite molecular sieve modifying spherical material that is suitable for the affinity chromatography column packed; (3) above-mentioned sphere material is packed in the chromatographic column, makes the affinity chromatographic column of protein separation.
2, the preparation method who is used for the zeolite molecular sieve modification fly ash micro-sphere assembly of affine isolated protein according to claim 1 is characterized in that it is the method for electrostatic adhesion layer laminate that nano zeolite is modified the physical and chemical adsorption method of fly ash micro-sphere.
3, the preparation method who is used for the zeolite molecular sieve modification fly ash micro-sphere assembly of affine isolated protein according to claim 1 is characterized in that the charge capacity of fly ash micro-sphere finishing zeolite molecular sieve is 0.5-30%.
4, the preparation method who is used for the zeolite molecular sieve modification fly ash micro-sphere assembly of affine isolated protein according to claim 1 is characterized in that fly ash micro-sphere finishing zeolite molecular sieve kind is LTA, BEA, FAU or MFI zeolite.
5, the preparation method who is used for the zeolite molecular sieve modification fly ash micro-sphere assembly of affine isolated protein according to claim 1 is characterized in that ion-exchange institute fixed metal ion is Co
2+, Zn
2+, Cu
2+, Ni
2+Transition metal ion.
6, the preparation method who is used for the zeolite molecular sieve modification fly ash micro-sphere assembly of affine isolated protein according to claim 1, the fixed amount that it is characterized in that transition metal ion is with assembly and Co
2+, Zn
2+, Cu
2+, Ni
2+Transition metal ion exchanges fully.
7, the zeolite molecular sieve that the is used for affine isolated protein according to claim 1 preparation method that modifies the fly ash micro-sphere assembly is characterized in that zeolite molecular sieve assembly after the ion-exchange is as the affinity chromatography column material.
8, the preparation method who is used for the zeolite molecular sieve modification fly ash micro-sphere assembly of affine isolated protein according to claim 1, it is characterized in that adorning post is to fill the dress post with the dry method zeolite molecular sieve assembly.
9, the zeolite molecular sieve that the is used for affine isolated protein according to claim 1 preparation method that modifies the fly ash micro-sphere assembly is characterized in that can making by roasting the zeolite molecular sieve repeated regeneration of the assembling of filling.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391590C (en) * | 2006-09-07 | 2008-06-04 | 上海交通大学 | Method for preparing composite assembled object of magnetic ferriferous oxide/ molecular sieve of Nano zeolite |
| CN105531020A (en) * | 2013-05-07 | 2016-04-27 | 陶氏环球技术有限责任公司 | Vacuum-assisted process for preparing an ion-exchanged zeolite membrane |
| CN109453805A (en) * | 2018-11-26 | 2019-03-12 | 上海绿强新材料有限公司 | A kind of oxidation catalyst and its method for handling hydrometallurgy raffinate waste water |
-
2003
- 2003-03-20 CN CNB031159109A patent/CN1181911C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391590C (en) * | 2006-09-07 | 2008-06-04 | 上海交通大学 | Method for preparing composite assembled object of magnetic ferriferous oxide/ molecular sieve of Nano zeolite |
| CN105531020A (en) * | 2013-05-07 | 2016-04-27 | 陶氏环球技术有限责任公司 | Vacuum-assisted process for preparing an ion-exchanged zeolite membrane |
| CN109453805A (en) * | 2018-11-26 | 2019-03-12 | 上海绿强新材料有限公司 | A kind of oxidation catalyst and its method for handling hydrometallurgy raffinate waste water |
| CN109453805B (en) * | 2018-11-26 | 2021-07-16 | 上海绿强新材料有限公司 | Oxidation catalyst and method for treating hydrometallurgy raffinate wastewater by using same |
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