CN101718041A - Fiber base protein molecularly imprinted polymer aquagel and preparation method thereof - Google Patents
Fiber base protein molecularly imprinted polymer aquagel and preparation method thereof Download PDFInfo
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- CN101718041A CN101718041A CN200910228777A CN200910228777A CN101718041A CN 101718041 A CN101718041 A CN 101718041A CN 200910228777 A CN200910228777 A CN 200910228777A CN 200910228777 A CN200910228777 A CN 200910228777A CN 101718041 A CN101718041 A CN 101718041A
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Abstract
The invention provides fiber base protein molecularly imprinted polymer aquagel and a preparation method thereof. The fiber base protein molecularly imprinted polymer aquagel comprises the following components by weight percent: 1.78-3.96 percent of polypropylene fiber (PP) non-woven cloth, 8.9-21.38 percent of acrylamide, 0.22-2.85 percent of N,N'-methylene-bis-acrylamide, 0.05-1 percent of protein and 71.26-89.06 percent of de-ionized water. The preparation method comprises the following steps of: adding the protein, the acrylamide and the N,N'- methylene-bis-acrylamide based on the component ratio into the de-ionized water to obtain mixed solution A, immersing the polypropylene fiber non-woven cloth into a test tube containing the mixed solution A; performing gamma-ray irradiation on the test tube with the reaction mixture under the condition of radiation dose rate of 0.05-1kGy/h, scraping polyacrylamide gel of fiber surface layers by using nippers and eluting protein template to obtain the fiber base protein molecularly imprinted polymer aquagel.
Description
Technical field
The present invention relates to a kind of manufacture method and molecular imprinting of nonwoven fabric grafting aquogel, be specially a kind of preparation of protein fibre base protein molecule engram polyalcohol hydrogel, belong to functional high polymer material field.
Background technology
The protein molecule engram polymer owing to the potential application foreground in fields such as medical diagnosis, bio-separation and useful for drug delivery become current research focus [cover blue and green, Liu Qiuye, He Xiwen etc. chemical progress .2008,20 (8): 957-968].Because bulky, the easy sex change of protein molecule, space structure are very complicated, the research thinking and the laboratory facilities of protein macromolecule trace all also are in the stage of fumbling.People carry out the research of protein molecule engram more and more with polyalcohol hydrogel in recent years.The swelling that the exquisite structure of aquogel can show under the stimulation of factors such as extraneous pH value, ionic strength, temperature repeatedly changes.With respect to the material of hard, aquogel is more suitable for the trace of protein.
With the acrylamide is that function monomer can prepare selectivity protein molecule engram polymer preferably.Hjerten etc. are monomer with the acrylamide, N, N '-methylene-bisacrylamide is the aquogel that crosslinking agent has synthesized low crosslinking degree, trace hemoglobin, lysozyme, myoglobins etc., the result shows that this gel has very high recognition capability [Hjerten S J, Liao J L to microsphere, Nakazato K, Chromatography, 1997,44:227-234].Guo Tianying etc. as carrier, are diffused in the hole of carrier acrylamide and BHb, then initiated polymerization with the macro porous crosslinking shitosan.Zhi Bei blotting chitosan microballoon has higher binding capacity [Tian-Ying Guo than non-blotting chitosan microballoon and polypropylene amides gel micro-ball to BHb like this, Yong-Qing Xia, Jin Wang.Biomaterials, 2005,26:5737-5745.].
Imprinted sites is mostly at material internal in the imprinted polymer that bulk process obtains, and the template molecule resistance to mass tranfer is big, has seriously reduced the binding capacity and the trace efficient of protein molecule engram polymer, and the time that reaches equilibrium adsorption is also long.The surface molecule print technology helps the mass transfer of template molecule by trace hole and site being based upon table (face) layer of imprinted material, can significantly improve the adsorption rate and the sensitivity of imprinted polymer.The surface grafting engram technology is by at the inorganic or surperficial trace that carries out various molecules of organic carrier, also helps and obtains that form is regular, heat endurance and mechanical strength material preferably.The Chen Lang magnitude is function monomer with the acrylamide, after the polystyrene support surface is modified with " iniferter ", adopts the surface imprinted method of photo-grafting to prepare the molecular blotting polymer microsphere of BHb.The result shows, this trace microballoon to BHb have higher binding capacity and well identification selection [cover blue and green, Liu Qiuye, Li literary friend etc. SCI, 2008,29:64-70].
Fibrous material has good pliability and mechanical strength, and specific area is big, and mass transfer is apart from weak point, and effectively functional group is many, and rate of adsorption height can be prepared into various shape, and is easy to use.Occurred in recent years at the micromolecular report of fibrous material surface grafting polymerization trace.Wang Bing etc. are template molecule with benzyl glycolylurea and medicine sulphadiazine, prepare the molecular engram hollow fiber separating film on the doughnut matrix.T.Hideaki etc. are monomer with the N-isopropylacrylamide, N, N '-methylene-bisacrylamide are crosslinking agent, by plasma-initiated polymerization on polypropylene non-woven fabric the grafting trace copper ion [Hideaki Tokuyama, Shinji Naohara, Masaru Fujioka.Reactive ﹠amp; Functional Polymers, 2008,68:182-188].The fibre grafting method is more, and major part is grafting chemically, its complex process, and energy resource consumption is big, and necessary initator has certain pollution, is unfavorable for obtaining purified polymer.Compare with traditional grafting method, radiation grafting can be finished chemical method and be difficult to the graft reaction that carries out, and operation is simple, do not need initator, can obtain pure graft copolymer.Can solve the few and mass transfer rate of low, the effective imprinted sites of aquogel intensity and wait problem slowly by carry out protein molecule engram at fiber surface radiation grafting aquogel, thereby obtain the fibrous proteins molecular engram material of high bound and trace efficient, also seldom see the report of this respect at present.
The soft moisture performance of advantages such as this patent is big the polyamide fiber strength of materials, toughness is high, specific area is big and protein molecule imprinting hydrogel combines, cause the polyamide fiber grafted polyacrylamide by the gamma-radiation radiation, the protein molecule imprinting hydrogel material in hole and site is contained on the preparation top layer.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that the gel mechanical strength is low, the rate of adsorption is slow and problem such as reusability difference.
The technical scheme that the present invention solves described raising gel toughness and mechanical strength and reusability technical problem is a kind of fiber base protein molecularly imprinted polymer aquagel of design.
The purpose of this invention is to provide a kind of gamma-radiation radiation and cause the method for preparing fiber base protein molecularly imprinted polymer aquagel.Say that simply the inventive method is: by being total to method of radiating, handle, form free radical, carry out graft reaction with the monomer acrylamide and obtain described fiber base protein molecularly imprinted polymer aquagel with gamma-radiation radiation polypropylene surface.
The invention provides the method that the radiation initiation grafting prepares fiber base protein molecularly imprinted polymer aquagel, the component and the weight percentage of its fiber base protein molecularly imprinted polymer aquagel are as follows:
Polypropylene (PP) fabric nonwoven cloth 1.78%～3.96%
Acrylamide 8.9%～21.38%
N, N '-methylene-bisacrylamide 0.22%～2.85%
Protein 0.05～1%.
Deionized water 71.26%～89.06%
A kind of fiber base protein molecularly imprinted polymer aquagel of the present invention, it is characterized in that described imprinted polymer aquogel is to be grafted on the polypropylene fibre nonwoven fabric, described protein comprises that bovine serum albumin(BSA), cow's serum red eggs are white, ovalbumin or lysozyme, described preparation method adopts gamma-radiation radiation initiation grafting, radiation dose rate is 0.05-1kGy/h, and radiated time is 0.5-30h.
The preparation process of fiber base protein molecularly imprinted polymer aquagel of the present invention is as follows:
A) in deionized water, add protein, acrylamide and N, N '-methylene-bisacrylamide, stirring is fully dissolved it, the mass percent concentration that obtains protein is 0.05～1%, the mass percent concentration of acrylamide is 8.9%～21.38%, N, the mass percent concentration of N '-methylene-bisacrylamide is 0.22%～2.85% mixed solution A, and solution A is poured in the test tube.Take by weighing the polypropylene fibre nonwoven fabric of solution A quality 1.78%～3.96%, it is soaked in the test tube that fills mixed solution A sealing and standing 8h;
B) test tube that reactant mixture will be housed is under the condition of 0.05-1kGy/h in radiation dose rate, carry out the gamma-radiation irradiation, radiated time is 0.5-30h, and the polyacrylamide gel on fiber top layer is scraped off with tweezers, obtains proteinaceous PP fabric nonwoven cloth graft polymers aquogel.
C) preparation contain mass percent be 1% lauryl sodium sulfate (SDS) and percent by volume be 10% acetic acid aqueous solution as eluent, wash away protein template, obtain fiber base protein molecularly imprinted polymer aquagel.The preparation of non-imprinted polymer aquogel is identical with fiber base protein molecularly imprinted polymer aquagel with elution process, does not just add protein.
The fiber base protein molecularly imprinted polymer aquagel that the present invention is prepared shows through the protein adsorption test result, and the adsorbance of trace grafting gel is 2.0～5.0 times of non-blot gel adsorbance.
Fiber base protein molecularly imprinted polymer aquagel of the present invention adopts radiation grafted manufacture method, be to have made full use of the strong advantage of radiation grafting ray penetration power, can finish general chemical method and be difficult to the graft reaction that carries out, and simple, convenient easy row, can finish under the room temperature.When radiation grafting, adopted than radiation under the low dose rate, its objective is to make protein when radiation, not be subjected to serious sex change, to satisfy the needs that use.
Preparation method of the present invention is simply simple, and course of reaction is easy to control.Compare with present existing PAHG, characteristics such as fibre grafting trace PAHG has that mechanical strength is big, adsorption rate is fast, reusability is good, gel purity height, convenient use have bright development prospect and purposes widely.
Based on above characteristic, fiber base protein molecularly imprinted polymer aquagel of the present invention can be used for fields such as the purification of recovery, mixed protein of specified protein and detection.
The specific embodiment
Introduce specific embodiments of the invention below, but the present invention is not subjected to the restriction of embodiment.
Embodiment 1. radiation cause PP nonwoven fabric graft acrylamide and prepare bovine serum albumin(BSA) trace aquogel
In deionized water, add bovine serum albumin(BSA), acrylamide and N, N '-methylene-bisacrylamide, stirring is fully dissolved it, the mass percent concentration that obtains bovine serum albumin(BSA) is 0.1%, the mass percent concentration of acrylamide is 8.9%, N, the mass percent concentration of N '-methylene-bisacrylamide is 2.85% mixed solution A, and solution A is poured in the test tube.Take by weighing the polypropylene fibre nonwoven fabric of solution A quality 1.78%, it is soaked in the test tube that fills mixed solution A sealing and standing 8h.With the test tube that reactant mixture is housed is under the condition of 0.05kGy/h in radiation dose rate, carry out the gamma-radiation irradiation, radiated time is 30h, and the polyacrylamide gel on fiber top layer is scraped off with tweezers, obtains proteinaceous PP fabric nonwoven cloth graft polymers aquogel.With containing mass percent is that 1% lauryl sodium sulfate (SDS) and percent by volume are that 10% acetic acid aqueous solution washes away protein template, obtains the polyalcohol hydrogel of fiber base bovine serum albumin(BSA) trace.
Embodiment 2. radiation cause PP nonwoven fabric graft acrylamide and prepare BHb trace aquogel
In deionized water, add BHb, acrylamide and N, N '-methylene-bisacrylamide, stirring is fully dissolved it, the mass percent concentration that obtains BHb is 0.2%, the mass percent concentration of acrylamide is 21.38%, N, the mass percent concentration of N '-methylene-bisacrylamide is 0.22% mixed solution A, and solution A is poured in the test tube.Take by weighing the polypropylene fibre nonwoven fabric of solution A quality 2%, it is soaked in the test tube that fills mixed solution A sealing and standing 8h.With the test tube that reactant mixture is housed is under the condition of 0.1kGy/h in radiation dose rate, carry out the gamma-radiation irradiation, radiated time is 10h, and the polyacrylamide gel on fiber top layer is scraped off with tweezers, obtains proteinaceous PP fabric nonwoven cloth graft polymers aquogel.With containing mass percent is that 1% lauryl sodium sulfate (SDS) and percent by volume are that 10% acetic acid aqueous solution washes away protein template, obtains the polyalcohol hydrogel of fiber base BHb trace.
Embodiment 3. radiation cause PP nonwoven fabric graft acrylamide and prepare ovalbumin trace aquogel
In deionized water, add ovalbumin, acrylamide and N, N '-methylene-bisacrylamide, stirring is fully dissolved it, the mass percent concentration that obtains ovalbumin is 1%, the mass percent concentration of acrylamide is 10%, N, the mass percent concentration of N '-methylene-bisacrylamide is 1% mixed solution A, and solution A is poured in the test tube.Take by weighing the polypropylene fibre nonwoven fabric of solution A quality 2%, it is soaked in the test tube that fills mixed solution A sealing and standing 8h.With the test tube that reactant mixture is housed is under the condition of 0.05kGy/h in radiation dose rate, carry out the gamma-radiation irradiation, radiated time is 10h, and the polyacrylamide gel on fiber top layer is scraped off with tweezers, obtains proteinaceous PP fabric nonwoven cloth graft polymers aquogel.With containing mass percent is that 1% lauryl sodium sulfate (SDS) and percent by volume are that 10% acetic acid aqueous solution washes away protein template, obtains the polyalcohol hydrogel of fiber base ovalbumin trace.
Embodiment 4. radiation cause PP nonwoven fabric graft acrylamide and prepare lysozyme trace aquogel
In deionized water, add lysozyme, acrylamide and N, N '-methylene-bisacrylamide, stirring is fully dissolved it, the mass percent concentration that obtains lysozyme is 0.5%, the mass percent concentration of acrylamide is 15%, N, the mass percent concentration of N '-methylene-bisacrylamide is 0.5% mixed solution A, and solution A is poured in the test tube.Take by weighing the polypropylene fibre nonwoven fabric of solution A quality 3%, it is soaked in the test tube that fills mixed solution A sealing and standing 8h.With the test tube that reactant mixture is housed is under the condition of 1kGy/h in radiation dose rate, carry out the gamma-radiation irradiation, radiated time is 5h, and the polyacrylamide gel on fiber top layer is scraped off with tweezers, obtains proteinaceous PP fabric nonwoven cloth graft polymers aquogel.With containing mass percent is that 1% lauryl sodium sulfate (SDS) and percent by volume are that 10% acetic acid aqueous solution washes away protein template, obtains the polyalcohol hydrogel of fiber base lysozyme trace.
Claims (4)
1. fiber base protein molecularly imprinted polymer aquagel is characterized in that component and weight percentage are as follows:
Polypropylene (PP) fabric nonwoven cloth 1.78%～3.96%
Acrylamide 8.9%～21.38%
N, N '-methylene-bisacrylamide 0.22%～2.85%
Protein 0.05～1%
Deionized water 71.26%～89.06%
2. the preparation method of a fiber base protein molecularly imprinted polymer aquagel may further comprise the steps:
A) in deionized water, add protein, acrylamide and N, N '-methylene-bisacrylamide, stirring is fully dissolved it, the mass percent concentration that obtains protein is 0.05～1%, the mass percent concentration of acrylamide is 8.9%～21.38%, N, the mass percent concentration of N '-methylene-bisacrylamide is 0.22%～2.85% mixed solution A, and solution A is poured in the test tube.Take by weighing the polypropylene fibre nonwoven fabric of solution A quality 1.78%～3.96%, it is soaked in the test tube that fills mixed solution A sealing and standing 8h;
B) test tube that reactant mixture will be housed is under the condition of 0.05-1kGy/h in radiation dose rate, carry out the gamma-radiation irradiation, radiated time is 0.5-30h, and the polyacrylamide gel on fiber top layer is scraped off with tweezers, obtains proteinaceous PP fabric nonwoven cloth graft polymers aquogel;
C) preparation contain mass percent be 1% lauryl sodium sulfate (SDS) and percent by volume be 10% acetic acid aqueous solution as eluent, wash away protein template, obtain fiber base protein molecularly imprinted polymer aquagel.The preparation of non-imprinted polymer aquogel is identical with fiber base protein molecularly imprinted polymer aquagel with elution process, does not just add protein;
3. fiber base protein molecularly imprinted polymer aquagel as claimed in claim 1 is characterized in that described protein comprises that bovine serum albumin(BSA), cow's serum red eggs are white, ovalbumin or lysozyme.
4. fiber base protein molecularly imprinted polymer aquagel as claimed in claim 1 is characterized in that described imprinted polymer aquogel is grafted on the polypropylene fibre nonwoven fabric.The grafting weight gaining rate of described aquogel is between 10%～200%.Grafting weight gaining rate G (%)=[(W
g-W
0)/W
0] * 100%, W
0Quality for nonwoven fabric before the grafting; W
gQuality for nonwoven fabric after the grafting.
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Cited By (10)
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| CN102086592A (en) * | 2010-12-07 | 2011-06-08 | 天津工业大学 | Polymeric hydrogel grafted on fibers by calcium ion crosslinking and preparation method thereof |
| CN102294231A (en) * | 2011-05-06 | 2011-12-28 | 中山大学 | Molecularly imprinted fiber material and preparation method thereof |
| CN102619089A (en) * | 2012-01-16 | 2012-08-01 | 天津工业大学 | Preparation method of fiber carrier-based western blotting calcium alginate hybrid gel membrane |
| CN103304833A (en) * | 2013-04-23 | 2013-09-18 | 天津工业大学 | Preparation method of molecular imprinted polymer membrane by means of grafting rejection |
| CN103319831A (en) * | 2013-07-15 | 2013-09-25 | 天津工业大学 | Pectin/acrylamide semi-interpenetrating hydrogel material |
| CN104297043A (en) * | 2014-09-29 | 2015-01-21 | 宁波大学 | Method for extracting pyrethroid pesticide residues in complex samples by film |
| CN104804116B (en) * | 2014-01-23 | 2017-09-15 | 中国科学院化学研究所 | A kind of preparation method of hydrogel/composite for base fabric film |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102086592A (en) * | 2010-12-07 | 2011-06-08 | 天津工业大学 | Polymeric hydrogel grafted on fibers by calcium ion crosslinking and preparation method thereof |
| CN102086592B (en) * | 2010-12-07 | 2012-10-17 | 天津工业大学 | Polymeric hydrogel grafted on fibers by calcium ion crosslinking and preparation method thereof |
| CN102294231A (en) * | 2011-05-06 | 2011-12-28 | 中山大学 | Molecularly imprinted fiber material and preparation method thereof |
| CN102294231B (en) * | 2011-05-06 | 2013-04-24 | 中山大学 | Molecularly imprinted fiber material and preparation method thereof |
| CN102619089A (en) * | 2012-01-16 | 2012-08-01 | 天津工业大学 | Preparation method of fiber carrier-based western blotting calcium alginate hybrid gel membrane |
| CN103304833A (en) * | 2013-04-23 | 2013-09-18 | 天津工业大学 | Preparation method of molecular imprinted polymer membrane by means of grafting rejection |
| CN103319831A (en) * | 2013-07-15 | 2013-09-25 | 天津工业大学 | Pectin/acrylamide semi-interpenetrating hydrogel material |
| CN104804116B (en) * | 2014-01-23 | 2017-09-15 | 中国科学院化学研究所 | A kind of preparation method of hydrogel/composite for base fabric film |
| CN104297043A (en) * | 2014-09-29 | 2015-01-21 | 宁波大学 | Method for extracting pyrethroid pesticide residues in complex samples by film |
| CN104297043B (en) * | 2014-09-29 | 2017-07-04 | 宁波大学 | The membrane extraction method of pyrethroid pesticide is remained in a kind of complex sample |
| CN107473459A (en) * | 2017-10-13 | 2017-12-15 | 重庆华亚家私有限公司 | A kind of method of timber processing waste water processing |
| CN113372608A (en) * | 2021-05-18 | 2021-09-10 | 暨南大学 | PNIPAAm (AM)/DA composite imprinted gel and preparation method and application thereof |
| CN113512225A (en) * | 2021-06-16 | 2021-10-19 | 上海大学 | High critical solution temperature type temperature sensitive hydrogel film and preparation method thereof |
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