CN103342823B - The method of hydrogel is prepared in a kind of enzymatic radical polymerization - Google Patents
The method of hydrogel is prepared in a kind of enzymatic radical polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of method that hydrogel is prepared in enzymatic radical polymerization, utilize peroxidase, beta-dicarbonyl compound and hydrogen peroxide to coordinate as enzymatic free radical initiator system for polymerization provides free radical.In use by even for the aqueous solution of peroxidase, beta-dicarbonyl compound and vinyl monomer, then hydrogen peroxide is added wherein, by regulating the concentration of component of peroxidase/beta-dicarbonyl compound/hydrogen peroxide ternary initiator system, can control at room temperature to prepare hydrogel in 20s ~ 30min.Preparation method of the present invention realizes at aqueous phase, reaction conditions is gentle, easy and simple to handle, gelation time is controlled fast, the Nanometer composite hydrogel material of high strength can be prepared, in fields such as fixed enzyme vector, drug controlled release, artificial cartilage, tissue engineering bracket materials, there is obvious application prospect.
Description
Technical field
The present invention relates to polyalcohol hydrogel field, especially relate to a kind of method that hydrogel is prepared in enzymatic radical polymerization.
Background technology
Hydrogel is the three-dimensional network material that one can absorb and retain large quantity of moisture (usual water content is greater than 70%), its network skeleton normally natural or synthesis polymer molecular chain.Because quite similar with the body tissue of full a large amount of aqueous solution, hydrogel is widely used in the fields such as biological medicine, biotechnology and biological chemistry, specifically comprises enzyme immobilization carrier, bio-sensing, wound dressing, drug release, organizational project (tissue bulking material, joint cartilage, cell cultures) etc.
The preparation of polyalcohol hydrogel is generally divided into physical crosslinking and chemically crosslinked two kinds.Physical crosslinking passes through non covalent bond reactive force as formation such as electrostatic interaction, hydrogen bond action, heat resistance and salt tolerance.Chemically crosslinked adds linking agent usually through in aqueous solutions of polymers, as glutaraldehyde, epoxy chloropropane, vulcabond etc., makes to be cross-linked to form between polymer molecular chain network; Or by means such as thermal initiation, UV-light initiation, gamma-ray irradiation initiations, make the comonomer solution polymerization containing unsaturated double-bond form the network of chemically crosslinked.But, chemical cross-linking agent or initiator remaining in system often causes material to there is cytotoxicity, and UV-irradiation, gamma-ray irradiation also may cause the necrocytosis (Biomaterials at illuminated position, 2009,30,344-353), these shortcomings greatly limit the application of chemically crosslinked aquagel in bio-medical field prepared with aforesaid method.
The advantage of biological enzyme (namely mild reaction conditions, high degree of specificity transform) is utilized to prepare polyalcohol hydrogel, for needing the traditional chemical preparation method of harsh reaction conditions to be a kind of eco-friendly selection scheme.Enzyme catalysis does not need to use chemical cross-linking agent or initiator, and the hydrogel biological material obtained has excellent biocompatibility (Biomaterials, 2012,33,1281-1290).Horseradish peroxidase (Horseradish peroxidase, EC1.11.1.7) when hydrogen peroxide exists, effectively catalysis can contain the oxidation cross-linked formation Space network of polymer between the biomacromolecule compound of phenolic hydroxyl group, thus obtain hydrogel, and (CN101439206A, US20120270810A1) is applied in medicine controlled releasing and cell cultures.But the preparation of this type of hydrogel needs first to use specified chemical reagent (as tyrasamine, para hydroxybenzene propionic acid etc.) to carry out chemically modified to biomacromolecule (as hyaluronic acid, alginates, gelatin etc.) generates phenolic hydroxyl group, and reaction process and purification of products are comparatively complicated; And prepared hydrogel General Mechanics intensity is poor, is typically used as injecting medicinal material.
Oxydo-reductase (as peroxidase, laccase etc.) can produce free radical by catalysis electron-transfer reaction, causes the polymerization of vinyl monomer in aqueous.Utilize enzymatic mechanism of free-radical polymerization to prepare hydrogel to realize at aqueous phase, comonomer range of choice is comparatively large, and reaction conditions is gentle, easy and simple to handle, and gelation time is controlled fast.Different from enzymatic oxidn cross-linking method, the enzymatic free radical polymerisation process of peroxidase mediation may be used for the Nanometer composite hydrogel preparing high strength, and the application prospect as bio-medical material is broader.
Summary of the invention
Object of the present invention is exactly provide a kind of method utilizing enzymatic mechanism of free-radical polymerization to cause the polymerization of alkene class comonomer to prepare hydrogel to overcome defect that above-mentioned prior art exists.The method reaction conditions is gentle, and easy and simple to handle, gelation time is controlled fast, 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:
The method of hydrogel is prepared in a kind of enzymatic radical polymerization, peroxidase, beta-dicarbonyl compound and hydrogen peroxide is utilized to coordinate as enzymatic free radical initiator system, for polymerization provides free radical, by even for the aqueous solution of peroxidase, beta-dicarbonyl compound and vinyl monomer during preparation, pH is regulated to be 5.5 ~ 9, then hydrogen peroxide is added wherein, at room temperature react 20s ~ 30min, free radical trigger monomer can be produced and carry out polymerization formation Space network of polymer, obtain hydrogel.
Described peroxidase is horseradish peroxidase (HRP, 300units/mg).
Described beta-dicarbonyl compound is methyl ethyl diketone (ACAC).
Described vinyl monomer is selected from one or more in water miscible acrylate derivative, acrylamide derivative or NVP.
Described water miscible acrylate derivative is hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA) or polyoxyethylene glycol methyl methacrylate (PEGMA), described acrylamide derivative is acrylamide (AM), N,N-DMAA (DMAA) or NIPA (NIPA).
Described hydrogen peroxide and the molar concentration rate of peroxidase are 180 ~ 3500, and the molar concentration rate of the beta-dicarbonyl compound met and hydrogen peroxide is not less than 2.6 simultaneously, join the final volumetric molar concentration of hydrogen peroxide in reaction system and be not less than 400 μMs, the add-on of vinyl monomer accounts for 5 ~ 20% of reaction raw materials gross weight.
Water-soluble cpds with two or more double bonds can also be added in reactant as linking agent, comprise the protein of N,N methylene bis acrylamide (BIS), polyethyleneglycol diacrylate (PEGDA) or modified by vinyl.
The consumption of described linking agent accounts for 1 ~ 6% of reaction raw materials gross weight.
Also can add water dispersible inorganic nano material in reactant and prepare the Nanometer composite hydrogel of high strength to adapt to different user demands, 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 ~ 15% of reaction raw materials gross weight.
Compared with prior art, the present invention is demonstrated in enzymatic free radical initiator system of the present invention by spectrum (ESR) and creates the Ionization Potential of C-Centered Radicals derived by beta-dicarbonyl compound.As shown in Figure 1, when with α-(4-pyridyl-1-oxygen)-N-tertiary butyl nitroketone (POBN) as spin traps, (wherein the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to ternary initiator system of the present invention, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280) the ESR sweep signal that produces is 6 characteristic peaks of POBN radical adduct, Ionization Potential of C-Centered Radicals (the Biotechnol.Lett. derived by methyl ethyl diketone is created in explanation system, 2000,22,1355-1361).Determining inorganic nano component by transmission electron microscope is evenly dispersed in Nanometer composite hydrogel prepared by the present invention (Fig. 2), form physics cross-linking set by the non-covalent interaction power between polymer molecular chain, enhancement is played to hydrogel.The research of hydrogel mechanical property is shown that nano-hydrogel prepared by the present invention can be resisted the compressive strength of 400 ~ 2000kPa and can return to original state, and Common hydrogels can only resist the compressive strength of about 20 ~ 50kPa and easily crushed.Shown by above-mentioned research, adopt the enzymatic free radical polymerisation process of peroxidase mediation can obtain the Nanometer composite hydrogel material being used as drug controlled release, enzyme immobilization, separating substances, organizational project etc. of superior performance, have the following advantages:
(1) with traditional chemically crosslinked polyalcohol hydrogel preparation method (as thermal initiation, UV-light cause, radiation initiation etc.) compared with, technical solution of the present invention has environmental friendliness, reaction conditions gentleness (aqueous phase room temperature reaction), advantage easy and simple to handle;
(2) preparation method of the present invention by regulating the concentration of component of peroxidase/beta-dicarbonyl compound/hydrogen peroxide ternary initiator system, can control gelation time (20s ~ 30min), being conducive to actual operation;
(3) compared with enzymatic oxidn cross-linking method, the available raw material sources of preparation method of the present invention are extensive, and can prepare the Nanometer composite hydrogel of high strength.Extremely important in the application of good mechanical strength in fixed enzyme vector, artificial cartilage, tissue engineering bracket material etc., the hydrogel that thus prepared by the method is applied to field of biology and has obvious application prospect.
Accompanying drawing explanation
Fig. 1 is the Free Radical Signal of the enzymatic free radical initiator system generation that spectrum detects;
Fig. 2 is the transmission electron microscope photo of the Nanometer composite hydrogel prepared with enzymatic radical polymerization.
In Fig. 2, A is not containing the control sample of inorganic nano component; B is for containing 18wt%SiO
2the sample of nanoparticle (in figure, diameter is the dark spherical particle of 10 ~ 15nm).
Embodiment
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) 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 reacts 2.5 hours.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.Bioeng., 2005,100,551-555) is reported, record on average each bovine serum albumin molecule and approximately modify 4 double bonds.
2) prepare precursor liquid: get N,N-DMAA 0.1021g, the bovine serum albumin 0.0608g of modified by vinyl, deionized water 1.7162g adds in sample bottle, mixes with vortex mixer, actual measurement pH value is 6.0.
3) preparation of hydrogel: add methyl ethyl diketone 7.784mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing uses manual time-keeping simultaneously, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 3min.
Embodiment 2
1) prepare the bovine serum albumin of modified by vinyl with reference to embodiment 1 and prepare precursor liquid.
2) preparation of hydrogel: add methyl ethyl diketone 14.60mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 5 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 58s.
Embodiment 3
1) prepare the bovine serum albumin of modified by vinyl with reference to embodiment 1 and prepare precursor liquid.
2) preparation of hydrogel: add methyl ethyl diketone 36.01mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 12 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 20s.
Embodiment 4
1) prepare the bovine serum albumin of modified by vinyl with reference to embodiment 1 and prepare precursor liquid.
2) preparation of hydrogel: add methyl ethyl diketone 14.60mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 555 to aqueous hydrogen peroxide solution 6 μ L, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 5), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 1min50s.
Embodiment 5
1) prepare the bovine serum albumin of modified by vinyl with reference to embodiment 1 and prepare precursor liquid.
2) preparation of hydrogel: add methyl ethyl diketone 14.60mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 1110 to aqueous hydrogen peroxide solution 6 μ L, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 5), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 4min40s.
Embodiment 6
1) prepare the bovine serum albumin of modified by vinyl with reference to embodiment 1 and prepare precursor liquid.
2) preparation of hydrogel: add methyl ethyl diketone 14.60mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 2220 to aqueous hydrogen peroxide solution 6 μ L, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 5), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 18min50s.
Embodiment 7
1) precursor liquid is prepared: get N, N-DMAA 0.1213g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.0831g, deionized water 1.3420g adds in sample bottle, mix with vortex mixer, then to add 0.1M aqueous acetic acid 300 μ L adjust ph be 5.8.
2) preparation of hydrogel: add methyl ethyl diketone 7.784mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280 to aqueous hydrogen peroxide solution 50 μ L, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 2.6), quick mixing, airtight leaving standstill obtains the translucent hydrogel of light brown, gelation time 20min.
Embodiment 8
1) preparation steps of precursor liquid is the same.
2) preparation of hydrogel: add methyl ethyl diketone 17.51mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 641 to aqueous hydrogen peroxide solution 50 μ L, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 2.6), quick mixing, airtight leaving standstill obtains the translucent hydrogel of light brown, gelation time 28min.
Embodiment 9
1) bovine serum albumin of modified by vinyl is prepared with reference to embodiment 1.
2) precursor liquid is prepared: get N, N-DMAA 0.1018g, nano silicon aqueous dispersions (21wt%) 0.5735g, the bovine serum albumin 0.0602g of modified by vinyl, deionized water 1.1476g adds in sample bottle, mixes with vortex mixer.
3) preparation of hydrogel: add methyl ethyl diketone 14.60mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 5 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 1min.
Embodiment 10
1) bovine serum albumin of modified by vinyl is prepared with reference to embodiment 1.
2) precursor liquid is prepared: get N,N-DMAA 0.1010g, nano silicon aqueous dispersions (21wt%) 1.7205g, the bovine serum albumin 0.0608g of modified by vinyl adds in sample bottle, mixes with vortex mixer.
3) preparation of hydrogel: add methyl ethyl diketone 14.60mg successively in above-mentioned precursor liquid, horseradish peroxidase concentrated solution 100 μ L, (in reaction system, the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 5 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 1min.
Embodiment 11
1) precursor liquid is prepared: get N, N-DMAA 0.1010g, clay nano sheet aqueous dispersions (10wt%) 1.0015g, deionized water 0.5860g adds in sample bottle, mix with vortex mixer, then to add 0.1M aqueous acetic acid 200 μ L adjust ph be 8.5.
2) preparation of hydrogel: add horseradish peroxidase concentrated solution 100 μ L in above-mentioned precursor liquid successively, methyl ethyl diketone 7.784mg, (in reaction system, the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow clear hydrogel, gelation time 3min.
Embodiment 12
1) prepare precursor liquid: get N,N-DMAA 0.1020g, clay nano sheet 0.3005g, deionized water 1.2860g adds in sample bottle, high speed magnetic stirring 1h, then to add 0.1M aqueous acetic acid 200 μ L adjust ph be 8.9.
2) preparation of hydrogel: add horseradish peroxidase concentrated solution 100 μ L in above-mentioned precursor liquid successively, methyl ethyl diketone 7.784mg, (in reaction system, the molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to aqueous hydrogen peroxide solution 6 μ L, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow translucent hydrogel, gelation time 3min.
For the Nanometer composite hydrogel sample (being of a size of diameter 15.7mm, the cylinder of high 7 ~ 8mm) of above preparation, use electronic universal tester to carry out compression performance test, various performance parameters is as shown in table 1.Compared with control sample, it has good mechanical property as seen.
The mechanical property of table 1 Nanometer composite hydrogel
Embodiment 13
The catalytic activity test of Nanometer composite hydrogel: Nanometer composite hydrogel 10.05mg prepared by Example 10, add the toluene solution that 100mL contains 0.1082g O-Phenylene Diamine, add 200 μ L aqueous hydrogen peroxide solutions (30wt%) again, the absorbance change of oxidation products (2,3-diaminophenazine) at 450nm place is measured every 0.2min ultraviolet-visible pectrophotometer under 25 degrees Celsius.To map to obtain a straight line to the time with the absorbance in 1min, calculating catalyzed reaction initial velocity by its slope is 0.73 μM/s.Get 20 μ g horseradish peroxidases (300units/mg), under above reaction conditions, obtain catalyzed reaction initial velocity is 0.10 μM/s.Nanometer composite hydrogel prepared by visible the present invention has higher catalytic activity in toluene, can be used as immobilized enzyme and is applied to nonaqueous biocatalysis.
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. the method for hydrogel is prepared in an enzymatic radical polymerization, it is characterized in that, the method utilizes peroxidase, beta-dicarbonyl compound and hydrogen peroxide to coordinate as enzymatic free radical initiator system, for polymerization provides free radical, by even for the aqueous solution of peroxidase, beta-dicarbonyl compound and vinyl monomer during preparation, pH is regulated to be 5.5 ~ 9, then hydrogen peroxide is added wherein, at room temperature react 20s ~ 30min, free radical trigger monomer can be produced and carry out polymerization formation Space network of polymer, obtain hydrogel;
Described hydrogen peroxide and the molar concentration rate of peroxidase are 180 ~ 3500, and the molar concentration rate of the beta-dicarbonyl compound met and hydrogen peroxide is not less than 2.6 simultaneously, join the final volumetric molar concentration of hydrogen peroxide in reaction system and be not less than 400 μMs, the add-on of vinyl monomer accounts for 5 ~ 20% of reaction raw materials gross weight.
2. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 1, and it is characterized in that, described peroxidase is horseradish peroxidase.
3. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 1, and it is characterized in that, described beta-dicarbonyl compound is methyl ethyl diketone.
4. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 1, and it is characterized in that, described vinyl monomer is selected from one or more in water miscible acrylate derivative, acrylamide derivative or NVP.
5. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 4, it is characterized in that, described water miscible acrylate derivative is hydroxyethyl methylacrylate, Propylene glycol monoacrylate or polyoxyethylene glycol methyl methacrylate, described acrylamide derivative is acrylamide, N,N-DMAA or NIPA.
6. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 1, it is characterized in that, water-soluble cpds with two or more double bonds can also be added as linking agent in reactant, comprise the protein of N,N methylene bis acrylamide, polyethyleneglycol diacrylate or modified by vinyl.
7. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 6, and it is characterized in that, the consumption of described linking agent accounts for 1 ~ 6% of reaction raw materials gross weight.
8. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 1, it is characterized in that, also can add water dispersible inorganic nano material in reactant and prepare the Nanometer composite hydrogel of high strength to adapt to different user demands, described inorganic nano material is clay nano sheet, nano silicon or nanometer hydroxyapatite.
9. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 8, it is characterized in that, inorganic nano material is nano silicon or lamella diameter 20 ~ 40nm, the thickness 1nm of median size 10 ~ 40nm, and molecular formula is [Mg
5.34li
0.66si
8o
20(OH)
4] Na
0.66clay nano sheet.
10. the method for hydrogel is prepared in a kind of enzymatic radical polymerization according to claim 8, and it is characterized in that, the consumption of described inorganic nano material accounts for 5 ~ 15% of reaction raw materials gross weight.
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| CN104892835B (en) * | 2015-05-06 | 2017-05-24 | 同济大学 | Method for preparing microgel through enzymatic polymerization |
| CN105133065B (en) * | 2015-07-21 | 2017-06-30 | 东华大学 | A kind of preparation method of the PEGMA/PEGDA aquagel fibres with supper-fast anisotropy water absorbing properties |
| CN107153052B (en) * | 2016-03-03 | 2020-10-09 | 湖北中医药大学 | Free radical polymerization reaction initiated by enzyme and detection application |
| CN106750395A (en) * | 2016-11-23 | 2017-05-31 | 华中科技大学同济医学院附属协和医院 | A kind of method of the sericin hydrogel for preparing water white transparency |
| 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 |
| CN107474264B (en) * | 2017-08-31 | 2020-05-15 | 济南大学 | Nano ferroferric oxide mediated free radical polymerization initiation system and method for preparing magnetic hydrogel by using same |
| CN109438730A (en) * | 2018-11-07 | 2019-03-08 | 常州清大智造科技有限公司 | A kind of preparation method of 3D printing technique enzymatic polymerization class hydrogel |
| CN110257028B (en) * | 2019-06-17 | 2022-04-05 | 同济大学 | Enzymatic polymerization macromolecule composite slurry and preparation method thereof |
| CN110343214B (en) * | 2019-07-12 | 2021-08-10 | 东华大学 | Method for preparing cellulose graft copolymer in homogeneous phase by using enzymatic system |
| CN111321174B (en) * | 2020-04-30 | 2022-08-30 | 福州大学 | Application of laccase in catalyzing polymerization of methacrylate monomer |
| CN112683890A (en) * | 2020-12-03 | 2021-04-20 | 南京师范大学 | Kit for rapidly detecting glucose based on double-enzyme-hydrogel composite material and detection method thereof |
| CN114736332B (en) * | 2022-03-28 | 2023-07-04 | 同济大学 | Preparation method and application of enzymatic biogenic salt gel |
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