CN104418971A - Glucose oxidase mediation free radical initiating system and method for preparing hydrogel by using glucose oxidase mediation free radical initiating system - Google Patents
Glucose oxidase mediation free radical initiating system and method for preparing hydrogel by using glucose oxidase mediation free radical initiating system Download PDFInfo
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Abstract
The invention relates to a glucose oxidase mediation free radical initiating system and a method for preparing hydrogel by using the glucose oxidase mediation free radical initiating system. The glucose oxidase mediation free radical initiating system consists of a N-hydroxyphthalimide derivative, glucose oxidase and glucose and has the advantages that the initiation condition is gentle, the preparation is simple and convenient, the pH value application range of a reaction medium is relatively wide, and the environment can be protected. According to the method provided by the invention, by adjusting the pH value of the reaction medium or adjusting the concentration ratio of components of a ternary initiating system, monomer polymerization can be initiated within 3-30 minutes at the room temperature under control to prepare hydrogel, and high-strength nano composite hydrogel can be also prepared, so that the method has remarkable application prospect in fields such as controlled-release of medicines, enzyme immobilization, tissue engineering and substance separation.
Description
Technical field
The present invention relates to macromolecular compound field, especially relate to a kind of free radical polymerization initiation system of novel glucose oxidase mediates, and for the preparation of the method for hydrogel.
Background technology
Macromolecular compound plays an important role at Material Field, and is widely used in industry, agricultural, biomedicine, environment protection, a domestic life equation field.Common macromolecular synthetic reaction needs control temperature and pressure usually, requires higher to conversion unit, sometimes also needs to use poisonous catalyzer.Along with the enhancing of human social consciousness, adopts efficient, nontoxic to the mankind, prepared by the non-harmful synthetic method of environment needed for high molecular products be the direction that polymer synthetic chemistry is studied.
Biological enzyme be a kind of produced by viable cell there is catalysis, active adjustable protein, there is following characteristic: high catalytic efficiency; High selectivity; Stereospecificity.The mild condition (generally under normal temperature, normal pressure) of enzymic catalytic reaction, and do not need the organic solvent that uses a large amount of price higher and poisonous, can carry out in aqueous.Be thematic today in energy-saving and emission-reduction, water as a kind of cheap, environmental protection, reaction medium that heat transfer efficiency is high, to simplification of flowsheet, reduce costs, to save energy and reduce the cost etc. significant.Therefore, compared with needing the traditional chemical synthesis of harsh reaction conditions, the polyreaction of biological enzyme mediation is a kind of eco-friendly superior method preparing macromolecular material.At present, the polyreaction research of enzyme mediation mainly concentrates on polycondensation (as β-xylo-bioses carries out polycondensation generation xylan by transglycosylation under zytase effect) and ring-opening polymerization (as 6-caprolactone ring-opening polymerization generates polycaprolactone under porcine pancreatic lipase effect) etc., and less for the Raolical polymerizable research of enzyme mediation.
Oxydo-reductase can produce free radical by catalysis electron-transfer reaction, causes the polymerization of vinyl monomer in aqueous.Bibliographical information; horseradish peroxidase (EC1.11.1.7)/beta-diketon/hydrogen peroxide ternary enzymatic system can cause hydrophilic vinylic monomer (as acrylamide) and carry out radical polymerization; or mini-emulsion polymerization (Polym.Chem. is carried out in initiation hydrophobic monomer (as vinylbenzene); 2012; 3,900-906; Biom6crimolecules, 2006,7,2927-2930; Chem.Rev, 2001,101,3793-3818).But, there will be not reproducible, that the time is longer (45 ~ 360min) inductive phase in this reaction, and the price of horseradish peroxidase is relatively expensive, is unfavorable for practical application.Do to add a kind ofly be distributed widely in animals and plants and microbe, aerobic dehydrogenase that price is relatively low, glucose oxidase (Glucose oxidase, EC1.1.3.4) has been widely used in the industries such as food, feed, medicine, analyzing and testing.It at room temperature can be oxidized to glucono-lactone by the β-D-Glucose of catalysis specifically, simultaneously reduction oxygen Hydrogen Peroxide.
A kind of redox initiation system adopting glucose oxidase to mediate of bibliographical information at room temperature causes method (Chem.Mater.2013,25, the 761-767 that water-soluble acrylic ester class monomer and linking agent carry out from going out base polymerization and prepare hydrogel; ACSAppl.Mater.Interf., 2010,2,1963-1972; Biomacromolecules, 2009,10,3114-3121).The component of this initiator system comprises: ferrous sulfate (providing ferrous ion), glucose oxidase and glucose.Its triggering mechanism is: in system dissolved oxygen existence under, the oxidation of glucose oxidase enzyme catalysis Portugal glucose; The hydrogen peroxide generated and ferrous ion are reacted by Fenton and produce hydroxyl radical free radical (OH), thus trigger monomer carries out polymerization obtains hydrogel.Above-mentioned document is also pointed out simultaneously, introduces ferrous ion and both can produce the polymerization of hydroxyl radical free radical trigger monomer, also can consume a part and cause free radical, produce restraining effect to polyreaction in reaction system.Meanwhile, after the oxidized generation ferric ion of the ferrous ion in system, also can suppress the propagation process of monomer radical, cause monomer polymerization incomplete, thus the subsequent applications of the prepared hydrogel of impact.Further, because the reductibility of ferrous ion is comparatively strong, be very easily oxidized in atmosphere, after being therefore made into the aqueous solution as the ferrous sulfate causing one of component, stability in storage is poor, also can affect actual use.The polymerization initiation system of above-mentioned enzyme mediation (about 3 minutes) can prepare hydrogel in the short period of time, but have not been reported about its Modulatory character causing gelation time.If the gelation time of gelling system can be regulated, will the hydrogel for specific end use be conducive to, improve in actual fabrication process can be handling.
Summary of the invention
The object of this invention is to provide a kind of free radical polymerization initiation system mediated based on the glucose oxidase of N-hydroxy imide derivative (N-Hydroxyimide).
Another object of the present invention adopts above-mentioned initiator system to cause vinyl monomer in aqueous to carry out being polymerized the method preparing hydrogel, the method reaction conditions is gentle, the pH value scope of application of reaction medium is wider, easy and simple to handle, gelation time is controlled, and can be used for the Nanometer composite hydrogel preparing high strength.
Object of the present invention can be achieved through the following technical solutions:
Glucose oxidase mediation free radical initiator system, this free radical system is be at room temperature the initiator system that reaction medium causes that vinyl monomer carries out radical polymerization with water, comprise N-hydroxy imide derivative, glucose oxidase and glucose, the pH value range that initiator system is suitable for is 3.5 ~ 10.5.
The molar concentration rate of described glucose and Portugal's notatin is 2250 ~ 52000, the molar concentration rate of N-hydroxy imide derivative and glucose is 0.2 ~ 4.0, the volumetric molar concentration of the N-hydroxy imide derivative adopted in initiator system is not less than 4.87mM, and the volumetric molar concentration of glucose is not less than 9mM.
Described N-hydroxy imide derivative is N-hydroxysuccinimide.
Initiator system preparation technology of the present invention is simple, and various ways can be adopted to prepare, and N-hydroxy imide derivative, glucose oxidase, glucose three can be mixed rear direct use or uses after reaction for some time; Or first by N-hydroxy imide derivative with after glucose oxidase hybrid reaction for some time, then with glucose with the use of; Or first by N-hydroxy imide derivative with after glucose hybrid reaction for some time, then with glucose oxidase with the use of; Or first by glucose oxidase with after glucose hybrid reaction for some time, then with N-hydroxy imide derivative with the use of; N-hydroxy imide derivative can add in Portugal's notatin and glucose mixture, also can directly add in monomer/reaction medium; Or first can join in monomer/reaction medium mixture by a part of N-hydroxy imide derivative, a part mixes with glucose oxidase and glucose in addition, directly can use or use after mixing for some time.After the formula component of this initiator system is made into the aqueous solution, also there is the good advantage of stability in storage, even after placement a few weeks or months with the use of still keeping initiating activity.
The initiator system be different from described in prior art produces the mechanism of hydroxyl radical free radical initiated polymerization, and initiator system of the present invention has novel free radical triggering mechanism.The Ionization Potential of C-Centered Radicals creating in initiator system of the present invention and derived by saccharide compound is demonstrated by spectrum (ESR).Such as, when with a-(4-pyridyl-1-oxygen)-N-tertiary butyl nitroketone (POBN) as spin traps, the ESR sweep signal that ternary initiator system of the present invention (wherein the molar concentration rate of N-hydroxysuccinimide and glucose is 0.29, and the molar concentration rate of glucose and glucose oxidase is 12500) produces is 6 characteristic peaks (its hyperfine splitting constant a of POBN radical adduct
n=15.7G, a
h=2.5G), create the Ionization Potential of C-Centered Radicals derived by saccharide compound in explanation system thus initiated polymerization carries out.
Glucose oxidase mediation free radical system is utilized to prepare the method for hydrogel, utilize N-hydroxy imide derivative, glucose oxidase and glucose coordinate as free radical initiator system, for polymerization provides free radical, by N-hydroxy imide derivative during preparation, the aqueous solution of glucose oxidase and vinyl monomer is even, then glucose is added wherein, regulate the pH value of reaction medium or regulate the concentration of component of glucose oxidase/N-hydroxy imide derivative/glucose ternary initiator system, at room temperature control in 3min ~ 30min, produce free radical trigger monomer and carry out polymerization formation Space network of polymer, obtain hydrogel.
The pH value of reaction medium is adjusted to 3.5 ~ 10.5, the concentration of component of glucose oxidase/N-hydroxy imide derivative/glucose ternary initiator system is adjusted to: the molar concentration rate of glucose and glucose oxidase is 2250 ~ 52000, the molar concentration rate of N-hydroxy imide derivative and glucose is 0.2 ~ 4.0 simultaneously, the volumetric molar concentration of N-hydroxy imide derivative is not less than 4.87mM, and the volumetric molar concentration of glucose is not less than 9mM.
Described vinyl monomer is selected from one or more in water miscible acrylate derivative, acrylamide derivative or NVP, and the add-on of vinyl monomer accounts for 5 ~ 20% of reaction raw materials gross weight.
Described water miscible acrylate derivative is hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA) or polyoxyethylene glycol methacrylic acid formyl (PEGMA), described acrylamide derivative is acrylamide (AM), N,N-DMAA (DMAA) or NIPA (NIPA).
Water-soluble cpds with two or more double bonds can also be added as linking agent in reactant, comprise N, the protein of N-methylene-bisacrylamide (BIS), polyethyleneglycol diacrylate (PEGDA) or modified by vinyl, described dosage of crosslinking agent accounts for 1 ~ 6% of reaction raw materials gross weight.
The Nanometer composite hydrogel that water dispersible inorganic nano material prepares high strength can also be added in reactant, described inorganic nano material is clay nano sheet, nano silicon or nanometer hydroxyapatite, the nano silicon of preferred median size 10 ~ 40nm or lamella diameter 20 ~ 40nm, thickness 1nm, molecular formula is [Mg
5.34li
0.66si
8o
20(OH)
4] Na
0.66clay nano sheet, the consumption of described inorganic nano material accounts for 5 ~ 17% of reaction raw materials gross weight.
Common macromolecule hydrogel generally can only resist the compressive strength of about 20 ~ 100kPa and easily crushed.Nanometer composite hydrogel prepared by the present invention can be resisted the compressive strength of 1000 ~ 2300kPa and can return to original state, there is excellent mechanical property and biocompatibility, the fields such as drug controlled release, enzyme immobilization, organizational project, separating substances can be applied to.
Compared with prior art, the present invention has the following advantages:
(1) polymerization initiation system of the present invention has environmental friendliness, initiation conditions gentleness (aqueous phase room temperature reaction), prepares the wider advantage of the pH value scope of application that is easy, reaction medium, and can be used for the Nanometer composite hydrogel preparing high strength;
(2) polymerization initiation system N-hydroxy imide derivative of the present invention substitutes ferrous sulfate, provide the free radical triggering mechanism of a kind of novel glucose oxidase mediation, avoid the disadvantageous effect introduced ferrous ion and vinyl monomer Raolical polymerizable and hydrogel preparation are produced.Meanwhile, N-hydroxysuccinimide is better than the stability in storage of ferrous sulfate, avoids the shortcoming that ferrous ion is easily oxidated, is conducive to practical application;
(3) the present invention can by regulating the pH value of reaction medium, or regulate the concentration of component of glucose oxidase/N-hydroxy imide derivative/glucose ternary initiator system, control gelation time (3min ~ 30min), can for the hydrogel of specific end use, improve in actual fabrication process can be handling.
Accompanying drawing explanation
The Free Radical Signal that the free radical initiator system of the present invention that Fig. 1 detects for spectrum produces.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Further illustrate technical scheme of the present invention below in conjunction with specific embodiment, further illustrate the present invention below in conjunction with example, but these examples are not used for limiting the present invention.
Embodiment 1
1) precursor liquid is prepared: get N, N-DMAA 0.10 ~ 0.13g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.07 ~ 0.09g, deionized water 1.3 ~ 1.5g adds in sample bottle, mix with vortex mixer, actual measurement pH value is 7 ~ 8.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 100 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 1.74 to D/W 200 μ L, the molar concentration rate of glucose and glucose oxidase is 25000), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 3min30s.
Embodiment 2
1) precursor liquid is prepared: get N, N-DMAA 0.10 ~ 0.13g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.07 ~ 0.09g, deionized water 1.3 ~ 1.5g, 1M aqueous acetic acid 50 μ L adds in sample bottle, mix with vortex mixer, actual measurement pH value is 3.5 ~ 4.5.
2) preparation of hydrogel: step with embodiment 1, gelation time 3min.
Embodiment 3
1) precursor liquid is prepared: get N, N-DMAA 0.10 ~ 0.13g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.07 ~ 0.09g, deionized water 1.3 ~ 1.5g, 1M ammonia soln 125 μ L adds in sample bottle, mix with vortex mixer, actual measurement pH value is 9.5 ~ 10.5.
2) preparation of hydrogel: step with embodiment 1, gelation time 19min30s.
Embodiment 4
1) precursor liquid is prepared: get N, N-DMAA 0.10 ~ 0.13g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.07 ~ 0.09g, deionized water 1.6 ~ 1.7g adds in sample bottle, mixes with vortex mixer.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 1.74 to D/W 50 μ L, the molar concentration rate of glucose and glucose oxidase is 6250), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 4min20s.
Embodiment 5
1) precursor liquid is prepared: step is with embodiment 4.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 2.8 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 0.20 to D/W 50 μ L, the molar concentration rate of glucose and glucose oxidase is 6250), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 19min20s.
Embodiment 6
1) precursor liquid is prepared: get N, N-DMAA 0.10 ~ 0.13g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.07 ~ 0.09g, deionized water 1.6 ~ 1.8g adds in sample bottle, mixes with vortex mixer.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 20.4 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 100 μ L, in D/W 25 μ L(reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 2.84, the molar concentration rate of glucose and glucose oxidase is 3125), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 6min50s.
Embodiment 7
1) precursor liquid is prepared: step is with embodiment 6.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 20.4 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 4.0 to D/W 18 μ L, the molar concentration rate of glucose and glucose oxidase is 2250), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 7min30s.
Embodiment 8
1) precursor liquid is prepared: get N, N-DMAA 0.10 ~ 0.13g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.07 ~ 0.09g, deionized water 1.7 ~ 1.8g adds in sample bottle, mixes with vortex mixer.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 12 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 1.8 to D/W 50 μ L, the molar concentration rate of glucose and glucose oxidase is 52000), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 30min.
Embodiment 9
1) precursor liquid is prepared: step is with embodiment 8.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 50 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 0.29 to D/W 50 μ L, the molar concentration rate of glucose and glucose oxidase is 12500), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 8min45s.
Embodiment 10
1) precursor liquid is prepared: step is with embodiment 8.
2) preparation of hydrogel: add the N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 200 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 1.8 to D/W 50 μ L, the molar concentration rate of glucose and glucose oxidase is 3125), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel, gelation time 4min.
Embodiment 11
1) precursor liquid is prepared: get NIPA 0.15 ~ 0.17g, clay nano sheet 0.15 ~ 0.25g, deionized water 1.5 ~ 1.7g adds in sample bottle, and high speed magnetic stirring 1.5h mixes.
3) the preparation and property test of hydrogel: add the N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 50 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 3.6 to D/W 25 μ L, the molar concentration rate of glucose and glucose oxidase is 6250), quick mixing, airtight leaving standstill obtains shallow white translucent hydrogel (containing 10wt% nanoclay sheet), gelation time 9min.After cylindric sample (diameter 15.7mm, high 7.3mm) made by above-mentioned hydrogel, use electronic universal tester to record compressive strength for 2250kPa (compressive strain 98%), do not rupture after test and can partly restore to the original state.
Embodiment 12
1) bovine serum albumin of modified by vinyl is prepared: get bovine serum albumin (BSA) 600mg, N-acryloxy succinimide 54mg, be dissolved in 30mL deionized water, at room temperature magnetic agitation reaction 2.5h.Be transferred to by reaction mixture in dialysis tubing, be placed in deionized water dialysis 3 days, lyophilize obtains the bovine serum albumin that white solid product is modified by vinyl.According to the method that document (J.Biosci. people oeng., 2005,100,551-555) is reported, record on average each bovine serum albumin molecule and approximately modify 4 double bonds.
2) precursor liquid is prepared: get NVP 0.09 ~ 0.11g, nano silicon aqueous dispersions (21wt%) 1.6 ~ 1.7g, bovine serum albumin 0.055 ~ the 0.065g of modified by vinyl adds in sample bottle, mixes with vortex mixer.
3) the preparation and property test of hydrogel: add the N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid successively, glucose oxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of N-hydroxysuccinimide and glucose is 1.74 to D/W 50 μ L, the molar concentration rate of glucose and glucose oxidase is 6250), quick mixing, airtight leaving standstill obtains light yellow translucent hydrogel (containing 17wt% nano silicon), gelation time 4min30s.After cylindric sample (diameter 15.7mm, high 7.5mm) made by above-mentioned hydrogel, use electronic universal tester to record compressive strength for 1250kPa (compressive strain 98%), can restore to the original state after test.
As shown in Figure 1, when with α-(4-pyridyl-1-oxygen)-N-tertiary butyl nitroketone (POBN) as spin traps, the ESR sweep signal that ternary initiator system of the present invention (wherein the molar concentration rate of N-hydroxysuccinimide and glucose is 0.29, and the molar concentration rate of glucose and glucose oxidase is 12500) produces is 6 characteristic peaks (its hyperfine splitting constant a of POBN radical adduct
n=15.7G, a
h=2.5G), create the Ionization Potential of C-Centered Radicals derived by saccharide compound in explanation system thus initiated polymerization carries out.
Above to invention has been exemplary description, but embodiments of the present invention are not restricted to the described embodiments.The amendment done under other any does not deviate from spirit of the present invention, replacement, combination, simplification, all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. glucose oxidase mediation free radical initiator system, it is characterized in that, this free radical system is be at room temperature the initiator system that reaction medium causes that vinyl monomer carries out radical polymerization with water, comprise N-hydroxy imide derivative, glucose oxidase and glucose, the pH value range that initiator system is suitable for is 3.5 ~ 10.5.
2. glucose oxidase mediation free radical initiator system according to claim 1, it is characterized in that, described glucose and the molar concentration rate of glucose oxidase are 2250 ~ 52000, the molar concentration rate of N-hydroxy imide derivative and glucose is 0.2 ~ 4.0, the volumetric molar concentration of the N-hydroxy imide derivative adopted in initiator system is not less than 4.87mM, and the volumetric molar concentration of glucose is not less than 9mM.
3. glucose oxidase mediation free radical initiator system according to claim 1, it is characterized in that, described N-hydroxy imide derivative is N-hydroxysuccinimide.
4. the glucose oxidase mediation free radical initiator system according to any one of claim 1-3, it is characterized in that, described N-hydroxy imide derivative, glucose oxidase, glucose are directly mixed to get the initiator system of radical polymerization;
Or by after N-hydroxy imide derivative and glucose oxidase or glucose mixing, then add glucose or glucose oxidase with the use of the initiator system obtaining radical polymerization.
Or after glucose oxidase and glucose mixing, then to add-hydroxy imide derivative is with the use of the initiator system obtaining radical polymerization.
5. utilize the mediation of the glucose oxidase according to any one of claim 1-4 free radical initiator system to prepare the method for hydrogel, it is characterized in that, the method utilizes N-hydroxy imide derivative, glucose oxidase and glucose coordinate as free radical initiator system, for polymerization provides free radical, by N-hydroxy imide derivative during preparation, the aqueous solution of glucose oxidase and vinyl monomer is even, then glucose is added wherein, regulate the pH value of reaction medium or regulate the concentration of component of glucose oxidase/N-hydroxy imide derivative/glucose ternary initiator system, at room temperature control in 3min ~ 30min, produce free radical trigger monomer and carry out polymerization formation Space network of polymer, obtain hydrogel.
6. glucose oxidase mediation free radical initiator system according to claim 5 prepares the method for hydrogel, it is characterized in that, the pH value of reaction medium is adjusted to 3.5 ~ 10.5, the concentration of component of glucose oxidase/N-hydroxy imide derivative/glucose ternary initiator system is adjusted to: the molar concentration rate of glucose and glucose oxidase is 2250 ~ 52000, the molar concentration rate of N-hydroxy imide derivative and glucose is 0.2 ~ 4.0 simultaneously, the volumetric molar concentration of N-hydroxy imide derivative is not less than 4.87mM, and the volumetric molar concentration of glucose is not less than 9mM.
7. glucose oxidase mediation free radical initiator system according to claim 5 prepares the method for hydrogel, it is characterized in that, described vinyl monomer is selected from one or more in water miscible acrylate derivative, acrylamide derivative or NVP, and the add-on of vinyl monomer accounts for 5 ~ 20% of reaction raw materials gross weight.
8. glucose oxidase mediation free radical initiator system according to claim 7 prepares the method for hydrogel, it is characterized in that, described water miscible acrylate derivative is hydroxyethyl methylacrylate (HEMA), vinylformic acid hydroxypropyl acyl (HPA) or polyoxyethylene glycol methyl methacrylate (PEGMA), described acrylamide derivative is acrylamide (AMM), N,N-DMAA (DMAA) or NIPA (NIPA).
9. glucose oxidase mediation free radical initiator system according to claim 5 prepares the method for hydrogel, it is characterized in that, water-soluble cpds with two or more double bonds can also be added as linking agent in reactant, comprise N, the protein of N-methylene-bisacrylamide (BIS), polyethyleneglycol diacrylate (PEGDA) or modified by vinyl, described dosage of crosslinking agent accounts for 1 ~ 6% of reaction raw materials gross weight.
10. glucose oxidase mediation free radical initiator system according to claim 5 prepares the method for hydrogel, it is characterized in that, the Nanometer composite hydrogel that water dispersible inorganic nano material prepares high strength can also be added in reactant, described inorganic nano material is clay nano sheet, nano silicon or nanometer hydroxyapatite, the nano silicon of preferred median size 10 ~ 40nm or lamella diameter 20 ~ 40nm, thickness Inm, molecular formula is [Mg
5.34li
0.66si
8o
20(OH)
4] Na
0.66clay nano sheet, the consumption of described inorganic nano material accounts for 5 ~ 17% of reaction raw materials gross weight.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892835A (en) * | 2015-05-06 | 2015-09-09 | 同济大学 | Method for preparing microgel through enzymatic polymerization |
| CN106011203A (en) * | 2016-05-10 | 2016-10-12 | 同济大学 | Nano-silicon dioxide composite hydrogel for 3D printing and wound repair |
| CN107242997A (en) * | 2017-05-08 | 2017-10-13 | 同济大学 | A kind of gel rubber material efficiently treated for tumour and preparation method thereof |
| CN110257028A (en) * | 2019-06-17 | 2019-09-20 | 同济大学 | A kind of enzymatic polymerization macromolecule composite mortar and preparation method thereof |
| CN110859997A (en) * | 2018-12-20 | 2020-03-06 | 四川大学 | Dental implant with osteogenesis-anti-inflammatory-blood sugar three-dimensional response structure and preparation method thereof |
| CN112210041A (en) * | 2020-09-24 | 2021-01-12 | 同济大学 | Hydrated ionic liquid gel and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866660A (en) * | 1997-03-13 | 1999-02-02 | Isp Investments Inc. | Polyvinyl prolidone and crosslinker with divinyl and chelation group |
| CN101668586A (en) * | 2007-04-26 | 2010-03-10 | 巴斯夫欧洲公司 | Enzymatic method for the production of microcapsules |
| CN103045702A (en) * | 2012-12-11 | 2013-04-17 | 淄博兰雁集团有限责任公司 | Method for producing modified starch size through bio-enzyme |
-
2013
- 2013-09-09 CN CN201310407843.9A patent/CN104418971B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866660A (en) * | 1997-03-13 | 1999-02-02 | Isp Investments Inc. | Polyvinyl prolidone and crosslinker with divinyl and chelation group |
| CN101668586A (en) * | 2007-04-26 | 2010-03-10 | 巴斯夫欧洲公司 | Enzymatic method for the production of microcapsules |
| CN103045702A (en) * | 2012-12-11 | 2013-04-17 | 淄博兰雁集团有限责任公司 | Method for producing modified starch size through bio-enzyme |
Non-Patent Citations (3)
| Title |
|---|
| RAVEESH SHENOY等: ""Kinetics of interfacial radical polymerization initiated by a glucose-oxidase mediated redox system"", 《BIOMATERIALS》 * |
| REGINA A. DERANGO等: ""ENZYME-MEDIATED POLYMERIZATION OF ACRYLIC MONOMERS"", 《BIOTECHNOLOGY TECHNIQUES》 * |
| 吴斌杰等: ""胶囊固定化辣根过氧化物酶酶促体系引发丙烯酰胺聚合研究"", 《功能高分子学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892835A (en) * | 2015-05-06 | 2015-09-09 | 同济大学 | Method for preparing microgel through enzymatic polymerization |
| CN106011203A (en) * | 2016-05-10 | 2016-10-12 | 同济大学 | Nano-silicon dioxide composite hydrogel for 3D printing and wound repair |
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| CN110859997A (en) * | 2018-12-20 | 2020-03-06 | 四川大学 | Dental implant with osteogenesis-anti-inflammatory-blood sugar three-dimensional response structure and preparation method thereof |
| CN110859997B (en) * | 2018-12-20 | 2020-06-23 | 四川大学 | Dental implant with osteogenesis-anti-inflammatory-blood sugar three-dimensional response structure and preparation method thereof |
| CN110257028A (en) * | 2019-06-17 | 2019-09-20 | 同济大学 | A kind of enzymatic polymerization macromolecule composite mortar and preparation method thereof |
| CN110257028B (en) * | 2019-06-17 | 2022-04-05 | 同济大学 | Enzymatic polymerization macromolecule composite slurry and preparation method thereof |
| CN112210041A (en) * | 2020-09-24 | 2021-01-12 | 同济大学 | Hydrated ionic liquid gel and preparation method and application thereof |
| CN114767941A (en) * | 2022-03-28 | 2022-07-22 | 同济大学 | Enzyme complex hydrogel prepared based on catalysis of glucose oxidase/amino acid metal complex and preparation method thereof |
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