CN102250278A - pH-sensitive renewable polymer for water-soluble immobilized cellulase as well as preparation method and application thereof - Google Patents
pH-sensitive renewable polymer for water-soluble immobilized cellulase as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a pH-sensitive renewable polymer for water-soluble immobilized cellulase as well as a preparation method and an application thereof. The pH-sensitive renewable polymer has viscosity average molecular weight of 1.04*10<4>, and is obtained by random copolymerization of methacrylic acid, dimethylamino ethyl methacrylate and butyl methacrylate in a molar ratio of 19:1:1. The pH-sensitive renewable polymer for water-soluble immobilized cellulase is reversibly soluble, is an amphipathic polymer and is soluble in partially acidic and partially basic environments, and can be used as a carrier to prepare water-soluble immobilized cellulase, thereby realizing the recycle of cellulase. In addition, the pH-sensitive renewable polymer can form an aqueous two-phase system together with other environment-sensitive renewable polymers, such as temperature-sensitive or pH-sensitive polymers, thereby realizing the simultaneous performing of enzyme phase transfer catalysis and product separation, and effectively reducing the inhibition of the product, so that the pH-sensitive renewable polymer has broad development and application prospects and is suitable for large-scale popularization and application.
Description
Technical field
The present invention relates to the dissolution invertible polymer technical field, more specifically, relate to the responsive regeneration type of pH technical field of polymer, be meant a kind of responsive regeneration type of pH polymkeric substance that is used for water-soluble immobilized cellulase and preparation method thereof and application especially.
Background technology
Many high polymers are when environmental parameter such as pH, temperature, ionic strength and illumination etc. change, can between precipitation and dissolving, change, these materials just are referred to as the invertible dissolution polymkeric substance, also can be described as solvable-soluble polymkeric substance (soluble-insoluble carriers, S-IS).Just can avoid using separately the resistance to mass transfer of insoluble carrier system enzyme-substrate with this fixing of polymkeric substance enzyme, and the soluble carrier system enzyme uses the unrenewable defective in back.And the invertible dissolution immobilized enzyme also can show bigger avidity to substrate.The various advantages of invertible dissolution polymkeric substance makes it just receive the increasing concern of investigators, uses it for immobilized cellulase and shows promising application.
The poly N-isopropyl acrylamide immobilized cellulase that humans such as Huang Yuewen are temperature sensitive obtains the immobilized cellulase of temperature sensitive property.Allow this immobilized cellulase repeat hydrolyzed carboxymethylcellulo, e (CMC), use the vigor (Mierocrystalline cellulose science and technology, 4 (1996) 25～30) that still can keep after 5 times more than 80%.The enteric coating material Eudragit L-100 immobilized cellulase of a kind of pH sensitivity of humans such as Taniguehi, with 1,3-dimethylamino-propyl-3-ethyl carbodiimide (EDC) is as linking agent, with insoluble Microcrystalline Cellulose is substrate, be hydrolyzed, the storage stability of cellulase be significantly improved (Biotechnology and Bioengineering, 34 (1989) 1092～1097) after the immobilization.Human EudragitL-100 covalent immobilization cellulases such as Yu Zhang, be substrate with insoluble Microcrystalline Cellulose and pretreated rice straw respectively, the residual vigor of immobilized enzyme all remains on more than 50% (Bioresource Technology101 (2010) 3153～3158) of initial enzyme work after 5 circulation hydrolysis.People such as Taniguchi also use enteric coated polymers material HPMC-AS (AS-L) the covalent immobilization cellulase of another kind of pH sensitivity, maize straw with its insoluble hydrolysate, after 9 repeated precipitation-dissolvings, the enzyme of immobilized enzyme is lived and is left about 50% (enzyme activity determination method: hydrolysis CMC 20min) (Biotechnology and Bioengineering, 39 (1992) 287～292).
The pH sensitive polymer kind of being used for fixing cellulase is few at present, therefore necessary more excellent performances, the pH sensitive polymer carrier cheap and easy to get developed.
Summary of the invention
Main purpose of the present invention is exactly the problems and shortcomings at above existence, a kind of responsive regeneration type of pH polymkeric substance that is used for water-soluble immobilized cellulase and its production and application is provided, this is used for the responsive regeneration type of the pH reversible polymer dissolving of water-soluble immobilized cellulase, and be amphipathic nature polyalcohol, the inclined to one side alkali of meta-acid all can dissolve, available its prepares water-soluble immobilized cellulase as carrier, thereby realize the recycle of cellulase, in addition, can also and other sensitive polymer, form two waters as temperature sensitive or pH sensitive polymer, realize carrying out the phase-transfer catalysis and the separating simultaneously of product of enzyme, can effectively reduce the restraining effect of product, therefore have very wide development application prospect, be suitable for large-scale promotion application.
To achieve these goals, in a first aspect of the present invention, a kind of responsive regeneration type of pH polymkeric substance that is used for water-soluble immobilized cellulase is provided, has been characterized in, the described viscosity-average molecular weight that is used for the responsive regeneration type of the pH polymkeric substance of water-soluble immobilized cellulase is 1.04 * 10
4Obtained through random copolymerization by methacrylic acid (MAA), dimethylaminoethyl methacrylate (DMAEMA) and butyl methacrylate (BMA), the molar ratio of wherein said methacrylic acid, described dimethylaminoethyl methacrylate and described butyl methacrylate is 19: 1: 1.
In a second aspect of the present invention, a kind of method for preparing the above-mentioned responsive regeneration type of the pH that is used for water-soluble immobilized cellulase polymkeric substance is provided, be characterized in, described methacrylic acid, dimethylaminoethyl methacrylate and described butyl methacrylate are pressed molar ratio to add in the solvent at 19: 1: 1, add initiator again, in the presence of rare gas element, carry out polyreaction and obtain.Brief note is polymer P
MDB
Preferably, described solvent is a deionized water, and described initiator is sodium bisulfite and ammonium persulphate, and described rare gas element is a nitrogen, and the oscillatory reaction under 55 ℃ temperature, condition that rotating speed is 180rpm of described polyreaction realized in 24 hours.
Preferably, described method also comprises following subsequent step: the responsive regeneration type of the pH that the is used for water-soluble immobilized cellulase polymkeric substance that obtains with the described polyreaction of absolute ethanol washing respectively, again it is scattered in the deionized water, add sodium hydroxide, magnetic agitation is fully dissolved, filtration treatment is removed insoluble polymkeric substance, the pH value of the clarifying polymers soln that obtains is adjusted to iso-electric point, the centrifugal precipitation that obtains, vacuum-drying under the room temperature obtains the described pure product that are used for the responsive regeneration type of the pH polymkeric substance of water-soluble immobilized cellulase.
In a third aspect of the present invention, a kind of invertible dissolution immobilized cellulase is provided, be characterized in, adopt above-mentioned be used for the responsive regeneration type polymkeric substance immobilized cellulase of pH of water-soluble immobilized cellulase and obtain.
Preferably, described process for fixation is a linking agent by water-soluble carbodiimide (EDC), adopts the covalent attachment method to realize.
Preferably, described immobilized detailed process is: the described responsive regeneration type of the pH polymkeric substance that is used for water-soluble immobilized cellulase is scattered in deionized water equably, progressively regulate pH to alkalescence and stirring, treat that the described responsive regeneration type of the pH polymkeric substance that is used for water-soluble immobilized cellulase dissolves the back fully and regulates pH to 6.0, add the linking agent water-soluble carbodiimide, activate 10～15min under the room temperature, add cellulase solution then, slowly stir under the room temperature and carry out immobilization, reaction finishes to regulate pH to 3.5～3.6, the centrifugal supernatant liquor that goes obtains precipitation, is described invertible dissolution immobilized cellulase.
In a fourth aspect of the present invention, a kind of pH-is provided thermo-responsive regenerative aqueous two-phase system, be characterized in, comprise thermo-responsive one-tenth gathering compound, and the responsive regeneration type polymkeric substance of the pH that is used for water-soluble immobilized cellulase or the above-mentioned invertible dissolution immobilized cellulase of the preparation of above-mentioned or above-mentioned method.
Preferably, described thermo-responsive one-tenth gathering compound is a polymer P
NBPolymer P
NBIt is a kind of thermo-responsive one-tenth gathering compound, concrete preparation method is referring to the application for a patent for invention of people such as Cao Xuejun application, application number: 200910044915.1, patent name: temperature-sensitive becomes gathering compound, its preparation method and the relevant responsive regenerative aqueous two-phase system of heat-pH, publication number: CN101475666.
In a fifth aspect of the present invention, provide the above-mentioned application of the thermo-responsive regenerative aqueous two-phase system of pH-in the separating bio product.
In the present invention: methacrylic acid and butyl methacrylate are commercially available product, and dimethylaminoethyl methacrylate is by N, and N-dimethylethanolamine and methacrylic chloride reaction make.
Beneficial effect of the present invention is specially: the responsive regeneration type of the pH that the is used for water-soluble immobilized cellulase reversible polymer dissolving that designs and synthesizes of the present invention, and be amphipathic nature polyalcohol, the inclined to one side alkali of meta-acid all can dissolve, available its prepares water-soluble immobilized cellulase as carrier, thereby realize the recycle of cellulase, in addition, can also and other environment sensitive regeneration type polymkeric substance, form two waters as temperature sensitive or pH sensitive polymer, realize carrying out the phase-transfer catalysis and the separating simultaneously of product of enzyme, can effectively reduce the restraining effect of product, therefore have very wide development application prospect, be suitable for large-scale promotion application.
Description of drawings
Fig. 1 is the reaction equation of the responsive regeneration type of pH of the present invention polymer manufacture.
Fig. 2 is the reaction equation of invertible dissolution immobilized cellulase preparation of the present invention.
Fig. 3 is responsive regeneration type polymkeric substance of pH and the thermo-responsive regeneration type polymer P that is used for water-soluble immobilized cellulase of the present invention
NBConstitute the phasor of regenerative aqueous two-phase system.
Embodiment
Content for a better understanding of the present invention is described further below in conjunction with specific embodiment.Its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention.
The responsive regeneration type of embodiment 1pH polymer P
MDBPreparation
The deionized water that in the tool plug Erlenmeyer flask of 250mL, adds 120mL, 5.10mL methacrylic acid, 0.53mL dimethylaminoethyl methacrylate and 0.5mL butyl methacrylate add the ammonium persulphate of 0.1235g and the sodium bisulfite (APS-NaHSO of 0.1235g then
3,, filled the nitrogen deoxygenation 10～15 minutes 1.3%w/w) as initiator.Sealed reaction vessel, in 55 ℃, water-bath oscillatory reaction 24 hours (reaction equation is seen Fig. 1) under the 180rpm rotating speed.Reaction finishes, product directly is deposited in the triangular flask bottom, throw out through absolute ethanol washing three times to remove unreacted monomer, it is scattered in a certain amount of deionized water again, adds a certain amount of sodium hydroxide, magnetic agitation makes abundant dissolving, remove by filter insolubles, the clarifying polymers soln that obtains is regulated its pH value to iso-electric point with 3M HCl, and the centrifugal precipitation that obtains is polymer P
MDB, vacuum-drying under the room temperature obtains the pure product of described pH sensitive polymer, and yield is more than 85%, measures polymer P by the Ubbelohde viscometer method
MDBViscosity-average molecular weight be 1.04 * 10
4, record P by weighting method
MDBIso-electric point is pI=3.1.
The preparation of embodiment 2 invertible dissolution immobilized cellulases
Accurately take by weighing the P of 1.00g embodiment 1 preparation
MDBPlace the 40mL deionized water, drip a certain amount of 3M NaOH, magnetic agitation, treat that it dissolves fully after, with being settled to 50ml behind the 3M HCl regulator solution pH to 6.0, gained carrier polymer strength of solution is 2% (w/v); Add 0.3g linking agent EDC, activated carrier P under the room temperature
MDB10～15min; Add cellulase solution 1.11ml (83.25FPU) afterwards, slowly stir under the room temperature and fix 4 hours (reaction equation is seen Fig. 2); When immobilization finishes, with 3M acetic acid regulator solution pH to 3.5～3.6,8000rpm, 4 ℃ of centrifugal 10min remove supernatant liquor and obtain precipitation; (contain 1mol/L NaCl and Ca with the 0.02mol/L acetum
2Cl) the flushing precipitation is three times, promptly gets the invertible dissolution immobilized cellulase, notes by abridging to be polymkeric substance-enzyme complex P
MDB-C is dissolved in the gained precipitation in acetic acid-sodium-acetate buffer of pH5.5, promptly obtains required water-soluble immobilized cellulase, and the immobilized enzyme activity recovery is 63.24%.
The cellulosic substrate experiment of embodiment 3 water-soluble immobilized cellulase insoluble hydrolysates
Under the concentration of substrate condition of 20g/L, the immobilized cellulase that is dissolved state that adds the 20FPU/g substrate is hydrolyzed to the maize straw of crossing through dilute acid pretreatment, hydrolysis temperature is 50 ℃, pH is 5.0, rotating speed is 120rpm, after hydrolysis in a hour finishes, the centrifugal 5min of 10000rpm removes the intact substrate of unreacted, regulate supernatant liquor pH to 3.5～3.6 with 3M acetic acid, the centrifugal 10min of 8000rpm reclaims immobilized enzyme, it is dissolved in the acetic acid-sodium acetate buffer solution of 0.1M (pH 5.0) being fixed enzyme liquid, measure its enzyme and live, as a circulation.Repeat above-mentioned operating process 5 times.Experimental result shows: after immobilized enzyme recycle 5 times, the enzyme rate of recovery of living still remains on more than 83.1%, and the growing amount of reducing sugar is initial about 72%.
The preparation of the thermo-responsive regenerative aqueous two-phase system of embodiment 4pH-
The polymer P that embodiment 1 is made
MDBWith polymer P
NBPrepare polymer P by phasor shown in Figure 3
MDBWith polymer P
NBConcentration in water reaches when the binodal line is above among Fig. 3, can form two waters.P
MDBWith P
NBConcentration all can be by under spectrophotometer, measuring the absorbancy of the two, and respectively by with the P of concentration known
MDBWith P
NBTry to achieve in the calculating of typical curve.
The recovery of the thermo-responsive regenerative aqueous two-phase system of embodiment 5pH-
Polymer P
MDBRecovery can make its precipitation, polymer P to polymkeric substance iso-electric point 3.1 by the pH value of regulator solution
NBCan its temperature be separated out on 33 ℃ of critical temperatures by attemperation reclaims.P
MDB-P
NBThe rate of recovery of system can obtain by calculating through the precipitation evaporate to dryness of pH-recovery of heat to the ratio that the amount of constant weight adds the amount of polymkeric substance during with preparation.P
MDB-P
NBThe rate of recovery of system can deduct also in the two-phase that residual amount of polymers obtains behind pH-recovery of heat polymkeric substance by the amount that adds polymkeric substance with when preparation.The amount of residual polyalcohol can be tried to achieve concentration by spectrophotometer method, multiply by phase volume or phase weight again and gets.Calculate polymer P by aforesaid method
MDBThe rate of recovery be more than 95%, polymer P
NBThe rate of recovery can reach 98%, aqueous two-phase system can recycle more than 40 times in theory.This regenerative aqueous two-phase system has the potential using value, can be widely used in the extraction separation and the aqueous two-phase system biocatalytic reaction of various biologically active substances, and can keep the active and stable of biomass.
The preparation and the application of the thermo-responsive aqueous two-phase system of pH-of embodiment 6 invertible dissolution immobilized cellulases
Polymkeric substance-enzyme complex P that embodiment 2 is made
MDB-C is mixed with the solution of 5% (w/v) concentration, draws isopyknic P
MDBThe P of-C and 5% (w/v)
NBMix that can to form phase volume ratio after static be 1: 3 aqueous two-phase system.This system can be applicable to phase-transfer-catalyzed reactions, and the polymkeric substance that contains immobilized enzyme is distributed in down mutually with substrate, and the product soluble sugar is distributed in phase, thereby has well solved the problem that product suppresses, and can improve efficiency of pcr product.In containing the aqueous two-phase system of polymkeric substance-enzyme complex, add 1% substrate, 160rpm, after reaction finished under 30 ℃ of conditions, cellulosic percent hydrolysis and the equal conditions aqueous phase catalyzed reaction that places an order was compared and has been improved more than 10%.
The responsive regeneration type of the pH that the present invention designs and synthesizes polymkeric substance, can present the invertible dissolution state along with the change of pH, under the effect of linking agent EDC, carry out cellulase and this polymkeric substance covalently bound, the immobilized enzyme that obtains is the catalytic hydrolysis substrate under solvable state, especially during the insoluble hydrolysate substrate, the enzyme-to-substrate uniform contact can reach hydrolysis result efficiently, soluble state precipitation down reclaims (rate of recovery is up to more than 95%), reach the purpose of recycle, thereby reduced the use cost of cellulase widely.
The present invention also provides two kinds of regenerative aqueous two-phase systems and their application, and a kind of is pH sensitive polymer P
MDBWith thermally sensitive polymeric P
NBThe regenerative aqueous two-phase system that forms, another kind is polymkeric substance-enzyme complex P
MDB-C and thermally sensitive polymeric P
NBThe regenerative aqueous two-phase system that forms.But all high efficiente callbacks and recycling of the polymkeric substance that forms two waters greatly reduce use cost, and reclaim easyly, and can keep biomass active and stability.
In sum, the dissolving of the responsive regeneration type of two kinds of pH of the present invention reversible polymer, the regenerative aqueous two-phase system of Xing Chenging is the pH responsive type thus, twenty percent gathering compound can high efficiente callback, greatly reduce use cost, and reclaim easyly, be suitable for large-scale promotion application.
In this specification sheets, the present invention is described with reference to its certain embodiments.But, still can make various modifications and conversion obviously and not deviate from the spirit and scope of the present invention.Therefore, specification sheets and accompanying drawing are regarded in an illustrative, rather than a restrictive.
Claims (10)
1. the responsive regeneration type of a pH polymkeric substance that is used for water-soluble immobilized cellulase is characterized in that, the described viscosity-average molecular weight that is used for the responsive regeneration type of the pH polymkeric substance of water-soluble immobilized cellulase is 1.04 * 10
4Obtained through random copolymerization by methacrylic acid, dimethylaminoethyl methacrylate and butyl methacrylate, the molar ratio of wherein said methacrylic acid, described dimethylaminoethyl methacrylate and described butyl methacrylate is 19: 1: 1.
2. one kind prepares the method that is used for the responsive regeneration type of the pH polymkeric substance of water-soluble immobilized cellulase according to claim 1, it is characterized in that, described methacrylic acid, dimethylaminoethyl methacrylate and described butyl methacrylate are pressed molar ratio to add in the solvent at 19: 1: 1, add initiator again, in the presence of rare gas element, carry out polyreaction and obtain.
3. method according to claim 2, it is characterized in that described solvent is a deionized water, described initiator is sodium bisulfite and ammonium persulphate, described rare gas element is a nitrogen, and the oscillatory reaction under 55 ℃ temperature, condition that rotating speed is 180rpm of described polyreaction realized in 24 hours.
4. method according to claim 2, it is characterized in that, described method also comprises following subsequent step: the responsive regeneration type of the pH that the is used for water-soluble immobilized cellulase polymkeric substance that obtains with the described polyreaction of absolute ethanol washing respectively, again it is scattered in the deionized water, add sodium hydroxide, magnetic agitation is fully dissolved, filtration treatment is removed insoluble polymkeric substance, the pH value of the clarifying polymers soln that obtains is adjusted to iso-electric point, the centrifugal precipitation that obtains, vacuum-drying under the room temperature obtains the described pure product that are used for the responsive regeneration type of the pH polymkeric substance of water-soluble immobilized cellulase.
5. an invertible dissolution immobilized cellulase is characterized in that, adopts the responsive regeneration type polymkeric substance immobilized cellulase of the pH that is used for water-soluble immobilized cellulase according to claim 1 and obtains.
6. invertible dissolution immobilized cellulase according to claim 5 is characterized in that, described immobilization is a linking agent by water-soluble carbodiimide, adopts the covalent attachment method to realize.
7. invertible dissolution immobilized cellulase according to claim 5, it is characterized in that, described immobilized detailed process is: the described responsive regeneration type of the pH polymkeric substance that is used for water-soluble immobilized cellulase is scattered in deionized water equably, progressively regulate pH to alkalescence and stirring, treat that the described responsive regeneration type of the pH polymkeric substance that is used for water-soluble immobilized cellulase dissolves the back fully and regulates pH to 6.0, add the linking agent water-soluble carbodiimide, activate 10～15min under the room temperature, add cellulose enzyme liquid then, slowly stir under the room temperature and fix, reaction finishes to regulate pH to 3.5～3.6, the centrifugal supernatant liquor that goes obtains precipitation, is described invertible dissolution immobilized cellulase.
8. thermo-responsive regenerative aqueous two-phase system of pH-, it is characterized in that, comprise thermo-responsive one-tenth gathering compound, and the responsive regeneration type polymkeric substance of the pH that is used for water-soluble immobilized cellulase of the arbitrary described method preparation of according to claim 1 or claim 2～4 or according to the arbitrary described invertible dissolution immobilized cellulase of claim 5～7.
9. the thermo-responsive regenerative aqueous two-phase system of pH-according to claim 8 is characterized in that, described thermo-responsive one-tenth gathering compound is a polymer P
NB
10. one kind according to Claim 8 or the application of the thermo-responsive regenerative aqueous two-phase system of 9 pH-in the catalyzed reaction of enzyme.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333283A (en) * | 2013-07-15 | 2013-10-02 | 华东理工大学 | Two pH response regeneration polymers capable of forming slightly alkaline aqueous two-phase system, and preparation method and application of slightly alkaline aqueous two-phase system |
| CN105837741A (en) * | 2016-05-14 | 2016-08-10 | 上海大学 | Oligomeric proline methyl acrylate/dimethyl ammonium ethyl methyl methacrylate copolymer and preparation method thereof |
| CN108359128A (en) * | 2018-03-08 | 2018-08-03 | 华东理工大学 | PH responds regenerative aqueous two-phase system and its application |
| CN112553187A (en) * | 2020-12-10 | 2021-03-26 | 江苏科技大学 | Polymer immobilized xylanase, preparation method and application thereof |
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| CN104474737A (en) * | 2014-12-09 | 2015-04-01 | 常州工程职业技术学院 | Application of affinitive temperature-sensitive polymer to aqueous two-phase system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475666A (en) * | 2009-01-06 | 2009-07-08 | 华东理工大学 | Thermo-sensitive imaging polymer, preparation thereof and related thermal-pH sensitive regenerative aqueous two-phase system |
| CN102010491A (en) * | 2010-11-11 | 2011-04-13 | 常州大学 | Method for preparing methacrylic acid dimethylamino ethyl ester-butyl acrylate copolymer |
-
2011
- 2011-05-26 CN CN 201110138591 patent/CN102250278B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475666A (en) * | 2009-01-06 | 2009-07-08 | 华东理工大学 | Thermo-sensitive imaging polymer, preparation thereof and related thermal-pH sensitive regenerative aqueous two-phase system |
| CN102010491A (en) * | 2010-11-11 | 2011-04-13 | 常州大学 | Method for preparing methacrylic acid dimethylamino ethyl ester-butyl acrylate copolymer |
Non-Patent Citations (2)
| Title |
|---|
| 《高分子学报》 19890228 王玲治，杨守平等 "高分子复合物固定化纤维素酶的研究" 120 , 第1期 * |
| 王玲治，杨守平等: ""高分子复合物固定化纤维素酶的研究"", 《高分子学报》, no. 1, 28 February 1989 (1989-02-28), pages 120 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333283A (en) * | 2013-07-15 | 2013-10-02 | 华东理工大学 | Two pH response regeneration polymers capable of forming slightly alkaline aqueous two-phase system, and preparation method and application of slightly alkaline aqueous two-phase system |
| CN103333283B (en) * | 2013-07-15 | 2015-09-09 | 华东理工大学 | Two kinds of pH that can form meta-alkalescence aqueous two-phase system respond regenerative polymkeric substance and preparation method thereof and application |
| CN105837741A (en) * | 2016-05-14 | 2016-08-10 | 上海大学 | Oligomeric proline methyl acrylate/dimethyl ammonium ethyl methyl methacrylate copolymer and preparation method thereof |
| CN105837741B (en) * | 2016-05-14 | 2018-01-02 | 上海大学 | Oligomerization proline methacrylate/dimethylaminoethyl methacrylate copolymer and preparation method thereof |
| CN108359128A (en) * | 2018-03-08 | 2018-08-03 | 华东理工大学 | PH responds regenerative aqueous two-phase system and its application |
| CN108359128B (en) * | 2018-03-08 | 2020-09-29 | 华东理工大学 | PH response regeneration type two-water-phase system and application thereof |
| CN112553187A (en) * | 2020-12-10 | 2021-03-26 | 江苏科技大学 | Polymer immobilized xylanase, preparation method and application thereof |
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