CN102344520B - Two types of pH sensitive regenerated polymers and preparation method thereof, as well as regenerated aqueous two-phase system formed by pH sensitive regenerated polymers and application of regenerated aqueous two-phase system - Google Patents
Two types of pH sensitive regenerated polymers and preparation method thereof, as well as regenerated aqueous two-phase system formed by pH sensitive regenerated polymers and application of regenerated aqueous two-phase system Download PDFInfo
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Abstract
The invention relates to pH sensitive regenerated polymers I and II. In the polymer I, the viscosityaverage molecular weight is 2.93*10<6>g/mol, the isoelectric point is 2.87, the recovery rate is 98.87 percent, the polymer I is randomly copolymerized by compounds shown in formulae (1), (2) and (3), and the molar ratio of feeding is 23:2:1. In the polymer II, the viscosityaverage molecular weight is 3.37*10<5>g/mol, the isoelectric point is 3.91, the recovery rate is 97.18 percent, the polymer I is randomly copolymerized by compounds shown in formulae (1), (2), (3) and (4), and the molar ratio of feeding is 23: 8: 1: 6. The invention also relates to a related preparation method, an aqueous two-phase system formed by the pH sensitive regenerated polymers, as well as an application of the aqueous two-phase system. The two types of polymers are pH sensitive and reversely soluble, the formed regenerated aqueous two-phase system is pH sensitive, and twenty percent of the two types of phase-forming polymers can be efficiently retrieved, so that the use cost is greatly reduced, the retrieving is simple and convenient, and the pH sensitive regenerated polymers provided by the invention is suitable for large-scale popularization and application.
Description
Technical field
The present invention relates to into gathering compound technical field, more specifically, relate to the responsive regenerative technical field of polymer of pH, refer to the responsive regenerative polymkeric substance of two kinds of pH, the regenerative aqueous two-phase system of its preparation method and formation and application especially.
Background technology
Aqueous two-phase system is generally that two kinds of polymkeric substance or a kind of polymkeric substance and a kind of inorganic salt dissolve with suitable concentration in water, form immiscible two-phase water solution system under certain condition, be considered to the extremely promising separation unit operation of one in biological downstream engineering, there is wide prospects for commercial application.The formation of aqueous two-phase system, mainly due to the immiscible property between superpolymer, can be divided into two-phase under certain condition.
Because the two-phase in aqueous two-phase system is all the aqueous solution, in two-phase, moisture all accounts for significant proportion, therefore has stable provide protection to biologically active substance, for biomolecules provides fabulous mild condition.Because biomolecules can be allocated in aqueous two-phase system, overcome the shortcoming that the easy inactivation of biological product in organic solvent extraction and strongly hydrophilic material are insoluble in organic solvent.In addition, it is gentle that two aqueous phases extract two aqueous phase extraction process operational conditions, generally carries out at normal temperatures and pressures; Two aqueous phase extraction processes can direct linear amplification 40000 times, and various operating parameters can scale up and target compound yield does not reduce, particularly favourable for industrial application; Interphase interface tension force between aqueous two-phase system is very little, is significantly less than traditional organic extraction system, and solute distribution process is gentle, is conducive to keeping biological activity, biological substance is not easily damaged, and interphase mass transfer process and equilibrium process quick, energy consumption is little.
Although the tempo of aqueous two-phase system is than very fast at present, the recovery problem forming the polymkeric substance of two aqueous phases more and more comes into one's own.Polymkeric substance can not reclaim the industrial cost by greatly increasing by two aqueous phases, is unfavorable for the popularization of two aqueous phase technology.
Therefore, two aqueous phases researching and developing high-recovery (being greater than 95%) become gathering compound to become this area problem demanding prompt solution.
Summary of the invention
Main purpose of the present invention is exactly with not enough for above Problems existing, the responsive regenerative polymkeric substance of two kinds of pH, the regenerative aqueous two-phase system of its preparation method and formation and application are provided, the responsive invertible dissolution of these two kinds of pH responsive regenerative polymkeric substance pH, the regenerative aqueous two-phase system formed thus is pH susceptibility, twenty percent gathering compound can high efficiente callback, greatly reduce use cost, and reclaim easy, be suitable for large-scale promotion application.
To achieve these goals, in a first aspect of the present invention, provide a kind of pH responsive regenerative polymkeric substance I, be characterized in, the viscosity-average molecular weight of described pH responsive regenerative polymkeric substance I is 2.93 × 10
6g/mol, iso-electric point is 2.87, the rate of recovery reaches 98.87%, obtained through random copolymerization by compound shown in compound and formula (3) shown in compound formula (1) Suo Shi, formula (2), shown in wherein said formula (1), shown in compound, described formula (2), shown in compound and described formula (3), the molar ratio of compound is 23: 2: 1, according to
1it is 8.04: 0.58: 0.47 that HNMR measures the actual mol ratio of compound shown in compound and described formula (3) shown in compound, described formula (2) shown in formula (1) described in described pH responsive regenerative polymkeric substance I,
In a second aspect of the present invention, provide a kind of method preparing above-mentioned pH responsive regenerative polymkeric substance I, be characterized in, compound shown in compound and described formula (3) shown in compound described formula (1) Suo Shi, described formula (2) is added in solvent by molar ratio 23: 2: 1, add initiator again, carry out polyreaction in the presence of an inert gas and obtain.Referred to as polymer P
aDB.
Preferably, described solvent to be pH be 7.0 deionized water, described initiator is sodium bisulfite and ammonium persulphate, and described rare gas element is nitrogen, described polyreaction be the condition of 200rpm at temperature, the rotating speed of 55 DEG C under oscillatory reaction within 24 hours, realize.Oscillatory reaction obtains white solid, can carry out abundant drying.
In a third aspect of the present invention, provide a kind of pH responsive regenerative polymkeric substance II, be characterized in, the viscosity-average molecular weight of described pH responsive regenerative polymkeric substance II is 3.37 × 10
5g/mol, iso-electric point is 3.91, the rate of recovery reaches 97.18%, obtained through random copolymerization by compound shown in compound and formula (4) shown in compound shown in compound formula (1) Suo Shi, formula (2), formula (3), shown in wherein said formula (1), shown in compound, described formula (2), shown in compound, described formula (3), the molar ratio of compound shown in compound and described formula (4) is 23: 8: 1: 6, according to
1it is 69.48: 22.35: 2.46 that HNMR measures the actual mol ratio of compound shown in compound and described formula (3) shown in compound, described formula (2) shown in formula (1) described in described pH responsive regenerative polymkeric substance II,
In a fourth aspect of the present invention, provide a kind of method preparing above-mentioned pH responsive regenerative polymkeric substance II, be characterized in, compound shown in compound and described formula (4) shown in compound shown in compound described formula (1) Suo Shi, described formula (2), described formula (3) is added in solvent by molar ratio 23: 8: 1: 6, add initiator again, carry out polyreaction in the presence of an inert gas and obtain.Referred to as polymer P
aDBA.
Preferably, described solvent to be pH be 7.0 deionized water, described initiator is sodium bisulfite and ammonium persulphate, and described rare gas element is nitrogen, described polyreaction be the condition of 200rpm at temperature, the rotating speed of 55 DEG C under oscillatory reaction within 24 hours, realize.Oscillatory reaction obtains white solid, can carry out abundant drying.
In a fifth aspect of the present invention, provide a kind of regenerative aqueous two-phase system, be characterized in, formulated by the responsive regenerative polymkeric substance I of above-mentioned or prepared by above-mentioned method pH and above-mentioned or prepared by above-mentioned method pH responsive regenerative polymkeric substance II.Such as polymer P
aDBand P
aDBAbe dissolved in the sodium hydroxide solution of 150mM with certain proportion, be at room temperature settled into phase.
Two kinds of polymkeric substance of two aqueous phase separation systems that what the present invention designed and synthesized can be used for, are the responsive regenerative polymkeric substance of pH, can both by the recovery regulating the pH value of its solution to reach polymkeric substance, and the rate of recovery is all more than 95%.
In a sixth aspect of the present invention, provide above-mentioned regenerative aqueous two-phase system and distributing the application in microbiotic.
Preferably, described microbiotic be erythromycin, Spiramycin Base or Ledermycin.
In a seventh aspect of the present invention, provide and a kind ofly adopt above-mentioned regenerative aqueous two-phase system to distribute antibiotic method, be characterized in, described microbiotic is added in described regenerative aqueous two-phase system, mix rear leaving standstill and be divided into upper and lower phase, described microbiotic on described mutually or described lower mutually in enrichment.So in upper phase still in lower phase, can by adjustment above-mentioned two aqueous phases in polymer P
aDBand P
aDBAconcentration ratio, the pH of phase system, in phase system, the kind of salt ion and concentration regulate and control the distribution of microbiotic in aqueous two-phase system.
In the present invention: shown in formula (1), shown in compound, formula (2), shown in compound, formula (3), compound shown in compound and formula (4) is commercially available product.
Beneficial effect of the present invention is specially: the two kinds of polymkeric substance that can be used for two aqueous phase separation systems designed and synthesized of the present invention: polymkeric substance I and polymkeric substance II, be the responsive regenerative polymkeric substance of pH, the responsive invertible dissolution of pH, the regenerative aqueous two-phase system formed thus is pH susceptibility, twenty percent gathering compound can by the high efficiente callback regulating the pH value of its solution to reach polymkeric substance, the rate of recovery is all up to more than 95%, therefore recovery two can be regulated to become gathering compound by pH value, greatly reduce aqueous two-phase system isolating biological products or carry out the use cost of phase transition biocatalytic reaction, reclaimer operation is easy, be suitable for large-scale promotion application.
Accompanying drawing explanation
Fig. 1 is the phasor that the responsive regenerative polymkeric substance of pH of the present invention I and pH responsive regenerative polymkeric substance II forms 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 object is only better understand content of the present invention but not limit the scope of the invention.
The responsive regenerative polymer P of embodiment 1 pH
aDBpreparation
The deionized water that 120ml pH is 7.0 is added in the tool plug Erlenmeyer flask of 250ml, 5ml vinylformic acid, 1ml dimethylaminoethyl methacrylate, 0.5ml butyl methacrylate (mol ratio is 23: 2: 1), add initiator sodium bisulfite, each 0.1235g of ammonium persulphate, shake up and make it dissolve.Pass into nitrogen 10 ~ 15min, to ensure only having rare gas element in triangular flask.With the mouth of self-styled band sealing Erlenmeyer flask, and be placed in the shaking bath of 55 DEG C, vibrate under 200rpm rotating speed 24h.After reaction terminates, the white gummy solid bottom triangular flask is taken out, with ethanol, acetone cleaning, be put in vacuum drying oven drying.The white solid of dry gained is polymer P of the present invention
aDB.According to
1hNMR measures polymer P
aDBin three kinds of actual mol ratios of monomer be 8.04: 0.58: 0.47, by Ubbelohde viscometer method measure polymer P
aDBviscosity-average molecular weight be 2.93 × 10
6g/mol, according to example 3, method records polymer P
aDBiso-electric point is 2.87.
The responsive regenerative polymer P of embodiment 2 pH
aDBApreparation
The deionized water that 120ml pH is 7.0 is added in the tool plug Erlenmeyer flask of 250ml, add 5ml vinylformic acid, 4ml dimethylaminoethyl methacrylate, 0.5ml butyl methacrylate, 1.284ml vinylcarbinol (mol ratio is 23: 8: 1: 6), add initiator sodium bisulfite, each 0.1235g of ammonium persulphate, shake up and make it dissolve.Pass into nitrogen 10 ~ 15min, to ensure only having rare gas element in triangular flask.With the mouth of self-styled band sealing Erlenmeyer flask, and be placed in the shaking bath of 55 DEG C, vibrate under 200rpm rotating speed 24h.After reaction terminates, the white gummy solid bottom triangular flask is taken out, with ethanol, acetone cleaning, be put in vacuum drying oven drying.The white solid of dry gained is polymer P of the present invention
aDBA.According to
1hNMR measures polymer P
aDBAin above-mentioned first three to plant monomer actual mol ratio be 69.48: 22.35: 2.46, by Ubbelohde viscometer method mensuration polymer P
aDBAviscosity-average molecular weight be 3.37 × 10
5g/mol, according to example 3, method records polymer P
aDBAiso-electric point is 3.91.
Embodiment 3 polymer P
aDBand polymer P
aDBArecovery experiment
First the weight of empty centrifuge tube sleeve pipe is weighed.In centrifuge tube sleeve pipe, add the polymers soln of 1.25% (w/w), drip 0.3mol/L HCl and regulate pH, until there is solid to separate out, solution turned cloudy.Continue to drip HCl until precipitation is separated out completely, sedimentation, supernatant liquor becomes clarification.Measure solution ph now, be iso-electric point.Centrifuge tube sleeve pipe is put into the centrifugal 30min of supercentrifuge, revolution is 10000rpm.After centrifugal, supernatant liquor is outwelled, put into vacuum drying oven and be dried to constant weight.The dry weight terminating mensuration centrifuge tube sleeve pipe is again just the quality of the polymkeric substance reclaimed with difference before.After measured, polymer P
aDBAiso-electric point be 3.91, the rate of recovery reaches 97.18%, and polymer P
aDBiso-electric point be 2.87, the rate of recovery reaches 98.87%.
The preparation of the responsive regenerative aqueous two-phase system of embodiment 4 pH
Respectively by 1g by the obtained polymer P of embodiment 1 and 2
aDBwith polymer P
aDBAbe dissolved in the sodium hydroxide solution of 20ml 150mM, configure the P of 5% respectively
aDBsolution and 5% P
aDBAsolution.Respectively getting the above-mentioned solution of 1ml is mixed in the graduated centrifuge tube of 2ml, vibration mixing, at room temperature static 5h, aqueous two-phase system.By polymer P
aDBwith polymer P
aDBAprepare by the concentration shown in Fig. 1, polymer P
aDBwith polymer P
aDBAwhen concentration to reach in Fig. 1 more than binodal line in water, two aqueous phases can be formed.Fig. 1 is made up of binodal line and anchor line (string), and on binodal line, point ' ● ' is measured by cloud point method, namely first by certain density polymer P
aDBwith polymer P
aDBAsolution composition two-phase system, adds a certain amount of solvent and makes it clarify, and concentration is now exactly the point on binodal line.On anchor line (string), point ' ■ ' is the concentration gained by measuring two kinds of polymkeric substance mutually up and down respectively.Polymer P
aDBAconcentration in two-phase is by measuring 415nm place P
aDBAabsorbancy after 2% (w/w) potassium permanganate oxidation, by the P with concentration known
aDBAtry to achieve in the calculating of the typical curve at 415nm place after 2% (w/w) potassium permanganate oxidation.And P
aDBconcentration in two-phase by measuring in 200nm place mutually or the absorbancy of lower phase mixed solution, by the P with concentration known
aDBAtypical curve at 200nm place and the P calculated
aDBAconcentration tries to achieve P in calculating
aDBin the absorbancy at 200nm place, then by the P with concentration known
aDBtry to achieve in the calculating of the typical curve at 200nm place.
The distribution experiment of embodiment 5 erythromycin in the responsive regenerative aqueous two-phase system of pH
Add 6mg erythromycin and certain density salt ion in the responsive regenerative aqueous two-phase system of pH of the 2ml obtained in embodiment 4, dissolve vibration mixing, be settled into phase.Upper and lower Xiang Gequ 200 μ l solution, adds 3ml ethanol respectively and polymkeric substance is separated out, centrifugal, measures the erythromycin concentration in supernatant liquor according to known method, and the ratio of the concentration of phase erythromycin is erythromycin at the responsive regenerative polymer P of pH up and down
aDBand P
aDBApartition ratio in the two-phase system formed.Known to MgSO4 concentration is 90mM, partition ratio reaches 1.99.
The distribution experiment of embodiment 6 Spiramycin Base in the responsive regenerative aqueous two-phase system of pH
Add 10mg Spiramycin Base and certain density salt ion in the responsive regenerative aqueous two-phase system of pH of the 2ml obtained in embodiment 4, dissolve vibration mixing, be settled into phase.Upper and lower Xiang Gequ 200 μ l solution, measures the spiramycin concentration in supernatant liquor according to known method after dilution, and the ratio of the concentration of phase Spiramycin Base is Spiramycin Base at the responsive regenerative polymer P of pH up and down
aDBand P
aDBApartition ratio in the two-phase system formed.Known to MgSO4 concentration is 90mM, partition ratio reaches 1.98.
The distribution that embodiment 7 is Ledermycined in the responsive regenerative aqueous two-phase system of pH is tested
Add 10mg in the responsive regenerative aqueous two-phase system of pH of the 2ml obtained in embodiment 4 to Ledermycin and certain density salt ion, dissolve vibration mixing, be settled into phase.Upper and lower Xiang Gequ 100 μ l solution, measures the concentration of Ledermycining in supernatant liquor according to known method after dilution, and the ratio of the concentration of Ledermycining mutually is up and down and Ledermycins at the responsive regenerative polymer P of pH
aDBand P
aDBApartition ratio in the two-phase system formed.Known when MgSO4 concentration is 60mM, partition ratio reaches minimum, is 0.0845.
The responsive regenerative polymer P of two kinds of pH prepared by the present invention
aDBand P
aDBA, these two kinds of polymers solns can form aqueous two-phase system.P
aDBwith vinylformic acid, dimethylaminoethyl methacrylate, butyl methacrylate for monomer, and P
aDBAwith vinylformic acid, dimethylaminoethyl methacrylate, butyl methacrylate, vinylcarbinol for monomer, take deionized water as solvent, sodium bisulfite, ammonium persulphate are initiator, adopt solution polymerization to be prepared from.Two polymkeric substance can both by the recovery regulating the pH value of its solution to reach polymkeric substance; Polymer P
aDBAiso-electric point be 3.91, the rate of recovery reaches 97.18%, and polymer P
aDBiso-electric point be 2.87, the rate of recovery reaches 98.87%.
In sum, the responsive invertible dissolution of two kinds of pH of the present invention responsive regenerative polymkeric substance pH, the regenerative aqueous two-phase system formed thus is pH susceptibility, twenty percent gathering compound can high efficiente callback, greatly reduce use cost, and reclaim easy, be suitable for large-scale promotion application.
In this description, the present invention is described with reference to its specific embodiment.But, still can make various amendment 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. for the formation of a pH responsive regenerative polymkeric substance I for aqueous two-phase system, it is characterized in that, the viscosity-average molecular weight of described pH responsive regenerative polymkeric substance I is 2.93 × 10
6g/mol, iso-electric point is 2.87, obtained through random copolymerization by compound shown in compound and formula (3) shown in compound formula (1) Suo Shi, formula (2), shown in wherein said formula (1), shown in compound, described formula (2), shown in compound and described formula (3), the molar ratio of compound is 23:2:1
2. prepare the method for the pH for the formation of aqueous two-phase system according to claim 1 responsive regenerative polymkeric substance I for one kind, it is characterized in that, compound shown in compound and described formula (3) shown in compound described formula (1) Suo Shi, described formula (2) is added in solvent by molar ratio 23:2:1, add initiator again, carry out polyreaction in the presence of an inert gas and obtain.
3. method according to claim 2, it is characterized in that, described solvent to be pH be 7.0 deionized water, described initiator is sodium bisulfite and ammonium persulphate, described rare gas element is nitrogen, described polyreaction be the condition of 200rpm at temperature, the rotating speed of 55 DEG C under oscillatory reaction within 24 hours, realize.
4. a pH responsive regenerative polymkeric substance II, is characterized in that, the viscosity-average molecular weight of described pH responsive regenerative polymkeric substance II is 3.37 × 10
5g/mol, iso-electric point is 3.91, obtained through random copolymerization by compound shown in compound and formula (4) shown in compound shown in compound formula (1) Suo Shi, formula (2), formula (3), shown in wherein said formula (1), shown in compound, described formula (2), shown in compound, described formula (3), the molar ratio of compound shown in compound and described formula (4) is 23:8:1:6
5. prepare the method for pH according to claim 4 responsive regenerative polymkeric substance II for one kind, it is characterized in that, compound shown in compound and described formula (4) shown in compound shown in compound described formula (1) Suo Shi, described formula (2), described formula (3) is added in solvent by molar ratio 23:8:1:6, add initiator again, carry out polyreaction in the presence of an inert gas and obtain.
6. method according to claim 5, it is characterized in that, described solvent to be pH be 7.0 deionized water, described initiator is sodium bisulfite and ammonium persulphate, described rare gas element is nitrogen, described polyreaction be the condition of 200rpm at temperature, the rotating speed of 55 DEG C under oscillatory reaction within 24 hours, realize.
7. a regenerative aqueous two-phase system, it is characterized in that, pH responsive regenerative polymkeric substance II prepared by the responsive regenerative polymkeric substance I of the pH for the formation of aqueous two-phase system prepared by the arbitrary described method of according to claim 1 or claim 2 ~ 3 and the according to claim 4 or arbitrary described method of claim 5 ~ 6 is formulated.
8. regenerative aqueous two-phase system according to claim 7 is distributing the application in microbiotic.
9. application according to claim 8, is characterized in that, described microbiotic is erythromycin, Spiramycin Base or Ledermycin.
10. one kind adopts regenerative aqueous two-phase system according to claim 7 to distribute antibiotic method, it is characterized in that, described microbiotic is added in described regenerative aqueous two-phase system, mix rear leaving standstill and be divided into upper and lower phase, described microbiotic on described mutually or described lower mutually in enrichment.
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| CN102875721B (en) * | 2012-10-18 | 2015-07-01 | 华东理工大学 | Two potential of hydrogen (pH) response regenerated polymers capable of forming acidic aqueous two-phase system and preparation methods and applications of two pH response regenerated polymers |
| 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 |
| CN103451259B (en) * | 2013-08-07 | 2015-09-30 | 南通康鑫药业有限公司 | In recyclable aqueous two-phase systems system, utilize immobilization penicillin acylated enzyme catalysis to synthesize the method for Prozef |
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| WO2010044842A1 (en) * | 2008-10-16 | 2010-04-22 | University Of Tennessee Research Foundation | Tamper resistant oral dosage forms containing an embolizing agent |
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| US4749762A (en) * | 1982-05-12 | 1988-06-07 | E. I. Du Pont De Nemours And Company | Acrylic amphoteric polymers |
| US5695925A (en) * | 1992-07-17 | 1997-12-09 | E. I. Du Pont De Nemours And Company | Analyte detection by means of an analyte-responsive polymer |
| CN1878539A (en) * | 2003-12-15 | 2006-12-13 | 科学与工业研究委员会 | Taste masked pharmaceutical compositions comprising bitter drug and pH sensitive polymer |
| WO2010044842A1 (en) * | 2008-10-16 | 2010-04-22 | University Of Tennessee Research Foundation | Tamper resistant oral dosage forms containing an embolizing agent |
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