CN104418971B - Glucoseoxidase mediation free radical initiator system and the method preparing hydrogel thereof - Google Patents
Glucoseoxidase mediation free radical initiator system and the method preparing hydrogel thereof Download PDFInfo
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Abstract
The present invention relates to glucoseoxidase mediation free radical initiator system and the method preparing hydrogel thereof, initiator system is made up of N hydroxy imide derivant, glucoseoxidase and glucose, has initiation conditions gentleness, preparation simplicity, the pH value scope of application advantage wider, eco-friendly of reaction medium.Preparation method of the present invention is by regulating the pH value of reaction medium, or the concentration of component ratio of regulation ternary initiator system, can control at room temperature in 3～30min trigger monomer polymerization prepare hydrogel, and can be used for preparing the Nanometer composite hydrogel of high intensity, in fields such as drug controlled release, enzyme immobilization, organizational project, material separation, there is obvious application prospect.
Description
Technical field
The present invention relates to macromolecular compound field, especially relate to the mediation of a kind of Novel grape carbohydrate oxidase oneself
By base polymerization initiation system, and for the method preparing hydrogel.
Background technology
Macromolecular compound plays an important role at Material Field, and is widely used in industry, agricultural, biological doctor
, environmental conservation, domestic life equation field.Common macromolecular synthetic reaction typically require control temperature and
Pressure, requires higher to consersion unit, the most also needs to use poisonous catalyst.Along with human society sustainable development
The enhancing of exhibition consciousness, uses the high score needed for synthetic method efficient, non-toxic to humans, non-harmful to environment preparation
Sub-goods are the directions of polymer synthetic chemistry research.
Enzyme is a kind of to be had catalysis, active adjustable protein by what living cells produced, has following spy
Property: high catalytic efficiency;High selectivity;Stereospecificity.The mild condition of enzymic catalytic reaction (typically room temperature,
Under normal pressure), and need not the organic solvent using 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 cost, energy-saving and cost-reducing etc. significant.Therefore, with needs harsh reaction bar
The traditional chemical synthesis of part compares, and the polyreaction of enzyme mediation is that one is eco-friendly prepares high score
The superior method of sub-material.At present, the polyreaction research of enzyme mediation is concentrated mainly on polycondensation reaction (as gathered at wood
Under carbohydrase effect, β-1,4-.beta.-Xylobiose carries out polycondensation generation xylan by transglucosidation) and ring-opening polymerization (as
Under porcine pancreatic lipase effect, 6-caprolactone ring-opening polymerisation generates polycaprolactone) etc., and for the free radical of enzyme mediation
Polyreaction research is less.
Oxidoreductase can be catalyzed electron transfer reaction and produce free radical, causes the poly-of vinyl monomer in aqueous
Close.Document is reported, horseradish peroxidase (EC1.11.1.7)/beta-diketon/hydrogen peroxide ternary enzymatic system energy
Cause hydrophilic vinylic monomer (such as acrylamide) to carry out radical polymerization, or cause hydrophobic monomer (such as benzene
Ethylene) carry out mini-emulsion polymerization (Polym.Chem., 2012,3,900-906;Biom6crimolecules, 2006,7,
2927-2930;Chem.Rev, 2001,101,3793-3818).But, this reaction there will be the most reproducible,
The induction period of time longer (45～360min), and the price of horseradish peroxidase is relatively expensive, is unfavorable for reality
Border is applied.Make to add a kind of be distributed widely in animals and plants and microbial body, aerobic dehydrogenase that price is relatively low,
Glucoseoxidase (Glucose oxidase, EC1.1.3.4) is widely used to food, feedstuff, medicine, divides
In the industries such as analysis detection.It can the most specifically be catalyzed β-D-Glucose and be oxidized to gluconolactone,
Reduction oxygen generates hydrogen peroxide simultaneously.
Document reports a kind of redox initiation system using glucoseoxidase to mediate and at room temperature causes water
Soluble acrylic esters monomer and cross-linking agent carry out preparing the method (Chem.Mater. of hydrogel from going out base polymerization
2013,25,761-767;ACSAppl.Mater.Interf., 2010,2,1963-1972;Biomacromolecules,
2009,10,3114-3121).The component of this initiator system includes: ferrous sulfate (offer ferrous ion), Portugal
Glucoseoxidase and glucose.Its triggering mechanism is: in system in the presence of dissolved oxygen, glucoseoxidase is urged
Change the oxidation of Portugal's glucose;The hydrogen peroxide generated reacts generation hydroxyl radical free radical with ferrous ion by Fenton
(OH), thus trigger monomer carries out polymerization and obtains hydrogel.Above-mentioned document also indicates that simultaneously, in reaction system
Middle introducing ferrous ion both can produce the polymerization of hydroxyl radical free radical trigger monomer, also can consume a part and cause freely
Base, produces inhibitory action to polyreaction.Meanwhile, the oxidized generation of the ferrous ion in system ferric ion
After, also can suppress the propagation process of monomer radical, cause monomer polymerization not exclusively, thus the prepared water of impact
The subsequent applications of gel.Further, owing to the reproducibility of ferrous ion is relatively strong, the most easily aoxidize, therefore
After being made into aqueous solution as the ferrous sulfate causing one of component, storage stability is poor, also can affect actually used.
The polymerization initiation system of above-mentioned enzyme mediation (about 3 minutes) can prepare hydrogel in the short period of time, but about
It causes the Modulatory character of gelation time have not been reported.If the gelation time of gel rubber system can be regulated, will have
It is beneficial to the hydrogel for special-purpose, improves the controllable property in actual fabrication process.
Summary of the invention
It is an object of the invention to provide a kind of Portugal based on N-hydroxy imide derivant (N-Hydroxyimide)
The free radical polymerization initiation system of glucoseoxidase mediation.
Another object of the present invention is to use above-mentioned initiator system to cause vinyl monomer to be polymerized in aqueous
The method preparing hydrogel, the method reaction condition is gentle, and the pH value scope of application of reaction medium is wider, operation
Simplicity, gelation time is controlled, and can be used for preparing the Nanometer composite hydrogel of high intensity.
The purpose of the present invention can be achieved through the following technical solutions:
Glucoseoxidase mediation free radical initiator system, this free radical system is at room temperature with water as reaction medium
Cause vinyl monomer to carry out the initiator system of radical polymerization, comprise N-hydroxy imide derivant, Fructus Vitis viniferae glycosyloxy
Changing enzyme 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 glucose oxidase is 2250～52000, and N-hydroxy imide spreads out
Biological and glucose molar concentration rate is 0.2～4.0, the N-hydroxy imide derivant used in initiator system
Molar concentration is not less than 4.87mM, and the molar concentration of glucose is not less than 9mM.
Described N-hydroxy imide derivant is N-hydroxysuccinimide.
The initiator system preparation technology of the present invention is simple, and various ways can be used to prepare, can be by N-hydroxyl
Directly use after imide derivative, glucoseoxidase, glucose three mixing or use after reaction a period of time;
Or first by N-hydroxy imide derivant with after glucoseoxidase hybrid reaction a period of time, then with glucose
With the use of;Or first by N-hydroxy imide derivant with after glucose hybrid reaction a period of time, then with Portugal
Glucoseoxidase with the use of;Or first by glucoseoxidase with after glucose hybrid reaction a period of time, then with
N-hydroxy imide derivant with the use of;N-hydroxy imide derivant can add Portugal's glucose oxidase and glucose
In mixture, it is possible to be directly added in monomer/reaction medium;Or can be by a part of N-hydroxy imide derivant
Being charged first in monomer/reaction medium mixture, another part mixes with glucoseoxidase and glucose,
Use after can be used directly or mixing a period of time.The formula component of this initiator system also has storage after being made into aqueous solution
The advantage of good stability, even with the use of still keeping initiating activity after placing a few weeks or months.
It is different from the initiator system described in prior art and produces the mechanism of hydroxyl radical free radical initiation polymerization, the present invention's
Initiator system has novel free radical triggering mechanism.Demonstrate the present invention's by electron spin resonance (ESR)
Initiator system creates the Ionization Potential of C-Centered Radicals derived by saccharide compound.Such as, with a-(4-pyridine radicals-1-
Oxygen)-N-tert-butyl group nitroketone (POBN) as spin traps in the case of, the ternary initiator system of the present invention
(wherein the molar concentration rate of N-hydroxysuccinimide and glucose is 0.29, glucose and glucoseoxidase
Molar concentration rate be 12500) ESR that produces scanning signal is 6 features of POBN radical adduct
Peak (its hyperfine splitting constant aN=15.7G, aH=2.5G), explanation system creates and is spread out by saccharide compound
Raw Ionization Potential of C-Centered Radicals thus initiated polymerization are carried out.
The method utilizing glucoseoxidase mediation free radical system to prepare hydrogel, utilizes N-hydroxy imide to spread out
Biology, glucoseoxidase and glucose coordinate as free radical initiator system, provide free radical, preparation for polymerization
Time by uniform for the aqueous solution of N-hydroxy imide derivant, glucoseoxidase and vinyl monomer, then to
Wherein adding glucose, pH value or the regulation glucoseoxidase/N-hydroxy imide of regulation reaction medium derive
The concentration of component of thing/glucose ternary initiator system, at room temperature controls to produce free radical in 3min～30min
Trigger monomer carries out polymerization and forms Space network of polymer, obtains hydrogel.
The pH value of reaction medium is adjusted to 3.5～10.5, glucoseoxidase/N-hydroxy imide derivant/Fructus Vitis viniferae
The concentration of component of sugar ternary initiator system is adjusted to: the molar concentration rate of glucose and glucoseoxidase is
2250～52000, the molar concentration rate of N-hydroxy imide derivant and glucose is 0.2～4.0 simultaneously, N-hydroxyl
The molar concentration of imide derivative is not less than 4.87mM, and the molar concentration of glucose is not less than 9mM.
Described vinyl monomer is selected from water miscible acrylate derivative, acrylamide derivative or N-vinyl
One or more in ketopyrrolidine, the addition of vinyl monomer accounts for the 5～20% of reaction raw materials gross weight.
Described water miscible acrylate derivative is hydroxyethyl methylacrylate (HEMA), acrylic acid hydroxypropyl
Ester (HPA) or Polyethylene Glycol methacrylic acid formyl (PEGMA), described acrylamide derivative is third
Acrylamide (AM), N, N-DMAA (DMAA) or NIPA (NIPA).
Reactant can also add the water soluble compound with two or more double bonds as cross-linking agent, including
N,N methylene bis acrylamide (BIS), polyethyleneglycol diacrylate (PEGDA) or modified by vinyl
Protein, described dosage of crosslinking agent accounts for the 1～6% of reaction raw materials gross weight,.
Reactant can also add water dispersible inorganic nano material and prepare the Nanometer composite hydrogel of high intensity,
Described inorganic nano material is clay nano sheet, nano silicon or nanometer hydroxyapatite, preferably average particle
The nano silicon in footpath 10～40nm or lamella diameter 20～40nm, thickness 1nm, molecular formula is
[Mg5.34Li0.66Si8O20(OH)4]Na0.66Clay nano sheet, the consumption of described inorganic nano material accounts for reaction
The 5～17% of raw material gross weight.
Common macromolecule hydrogel typically can only resist about 20～the compressive strength of 100kPa and the most crushed.
Nanometer composite hydrogel prepared by the present invention can be resisted the compressive strength of 1000～2300kPa and can return to former
Shape, has excellent mechanical property and biocompatibility, can apply to drug controlled release, enzyme immobilization, group
The fields such as weaver's journey, material separation.
Compared with prior art, the invention have the advantages that
(1) polymerization initiation system of the present invention have environmental friendliness, initiation conditions gentle (aqueous phase room temperature reaction),
The advantage that preparation is easy, the pH value scope of application of reaction medium is wider, and the nanometer that can be used for preparing high intensity is multiple
Heshui gel;
(2) polymerization initiation system of present invention N-hydroxy imide derivant substitutes ferrous sulfate, it is provided that one
The free radical triggering mechanism of kind novel glucoseoxidase mediation, it is to avoid introducing ferrous ion is to vinyl monomer
The adverse effect that Raolical polymerizable and hydrogel preparation produce.Meanwhile, N-hydroxysuccinimide is more sub-than sulphuric acid
The storage stability of ferrum is good, it is to avoid the shortcoming that ferrous ion is easily aoxidized, and is conducive to reality application;
(3) present invention by regulating the pH value of reaction medium, or can regulate glucoseoxidase/N-hydroxyl acyl
The concentration of component of imine derivative/glucose ternary initiator system, controls gelation time (3min～30min), can
With the hydrogel for special-purpose, improve the controllable property in actual fabrication process.
Accompanying drawing explanation
The Free Radical Signal that the free radical initiator system of the present invention that Fig. 1 detects for electron spin resonance produces.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Further illustrate technical scheme below in conjunction with specific embodiment, further illustrate below in conjunction with example
The present invention, but these examples are not intended to limit the present invention.
Embodiment 1
1) preparation precursor liquid: take N,N-DMAA 0.10～0.13g, cross-linking agent Polyethylene Glycol dipropyl
Olefin(e) acid ester (mean molecule quantity 250) 0.07～0.09g, deionized water 1.3～1.5g adds in sample bottle, with rotation
Whirlpool blender mix homogeneously, actual measurement pH value is 7～8.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 100 μ L in above-mentioned precursor liquid,
(in reaction system, N-maloyl is sub-for glucoseoxidase concentrated solution 100 μ L, D/W 200 μ L
The molar concentration rate of amine and glucose is 1.74, and the molar concentration rate of glucose and glucoseoxidase is 25000),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 3min30s.
Embodiment 2
1) preparation precursor liquid: take N,N-DMAA 0.10～0.13g, cross-linking agent Polyethylene Glycol dipropyl
Olefin(e) acid ester (mean molecule quantity 250) 0.07～0.09g, deionized water 1.3～1.5g, 1M aqueous acetic acid 50
μ L adds in sample bottle, uses vortex mixer mix homogeneously, and actual measurement pH value is 3.5～4.5.
2) preparation of hydrogel: step is with embodiment 1, gelation time 3min.
Embodiment 3
1) preparation precursor liquid: take N,N-DMAA 0.10～0.13g, cross-linking agent Polyethylene Glycol dipropyl
Olefin(e) acid ester (mean molecule quantity 250) 0.07～0.09g, deionized water 1.3～1.5g, 1M ammonia spirit 125 μ L
Adding in sample bottle, use vortex mixer mix homogeneously, actual measurement pH value is 9.5～10.5.
2) preparation of hydrogel: step is with embodiment 1, gelation time 19min30s.
Embodiment 4
1) preparation precursor liquid: take N,N-DMAA 0.10～0.13g, cross-linking agent Polyethylene Glycol dipropyl
Olefin(e) acid ester (mean molecule quantity 250) 0.07～0.09g, deionized water 1.6～1.7g adds in sample bottle, with rotation
Whirlpool blender mix homogeneously.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid,
(in reaction system, N-maloyl is sub-for glucoseoxidase concentrated solution 100 μ L, D/W 50 μ L
The molar concentration rate of amine and glucose is 1.74, and the molar concentration rate of glucose and glucoseoxidase is 6250),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 4min20s.
Embodiment 5
1) preparation precursor liquid: step is with embodiment 4.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 2.8 μ L in above-mentioned precursor liquid,
(in reaction system, N-maloyl is sub-for glucoseoxidase concentrated solution 100 μ L, D/W 50 μ L
The molar concentration rate of amine and glucose is 0.20, and the molar concentration rate of glucose and glucoseoxidase is 6250),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 19min20s.
Embodiment 6
1) preparation precursor liquid: take N,N-DMAA 0.10～0.13g, cross-linking agent Polyethylene Glycol dipropyl
Olefin(e) acid ester (mean molecule quantity 250) 0.07～0.09g, deionized water 1.6～1.8g adds in sample bottle, with rotation
Whirlpool blender mix homogeneously.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 20.4 μ L in above-mentioned precursor liquid,
Glucoseoxidase concentrated solution 100 μ L, in D/W 25 μ L(reaction system, N-maloyl is sub-
The molar concentration rate of amine and glucose is 2.84, and the molar concentration rate of glucose and glucoseoxidase is 3125),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 6min50s.
Embodiment 7
1) preparation precursor liquid: step is with embodiment 6.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 20.4 μ L in above-mentioned precursor liquid,
(in reaction system, N-maloyl is sub-for glucoseoxidase concentrated solution 100 μ L, D/W 18 μ L
The molar concentration rate of amine and glucose is 4.0, and the molar concentration rate of glucose and glucoseoxidase is 2250),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 7min30s.
Embodiment 8
1) preparation precursor liquid: take N,N-DMAA 0.10～0.13g, cross-linking agent Polyethylene Glycol dipropyl
Olefin(e) acid ester (mean molecule quantity 250) 0.07～0.09g, deionized water 1.7～1.8g adds in sample bottle, with rotation
Whirlpool blender mix homogeneously.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid,
Glucoseoxidase concentrated solution 12 μ L, D/W 50 μ L (N-hydroxysuccinimide in reaction system
Being 1.8 with the molar concentration rate of glucose, the molar concentration rate of glucose and glucoseoxidase is 52000), soon
Speed mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 30min.
Embodiment 9
1) preparation precursor liquid: step is with embodiment 8.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid,
Glucoseoxidase concentrated solution 50 μ L, D/W 50 μ L (N-hydroxysuccinimide in reaction system
Being 0.29 with the molar concentration rate of glucose, the molar concentration rate of glucose and glucoseoxidase is 12500),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 8min45s.
Embodiment 10
1) preparation precursor liquid: step is with embodiment 8.
2) preparation of hydrogel: be sequentially added into N-hydroxysuccinimide aqueous solution 25 μ L in above-mentioned precursor liquid,
(in reaction system, N-maloyl is sub-for glucoseoxidase concentrated solution 200 μ L, D/W 50 μ L
The molar concentration rate of amine and glucose is 1.8, and the molar concentration rate of glucose and glucoseoxidase is 3125),
Quickly mixing, airtight standing obtains shallow white translucent hydrogel, gelation time 4min.
Embodiment 11
1) preparation precursor liquid: take NIPA 0.15～0.17g, clay nano sheet 0.15～0.25g,
Deionized water 1.5～1.7g adds in sample bottle, high speed magnetic stirring 1.5h mix homogeneously.
3) preparation of hydrogel and performance test: be sequentially added into N-hydroxysuccinimide water in above-mentioned precursor liquid
Solution 25 μ L, glucoseoxidase concentrated solution 50 μ L, D/W 25 μ L (N-hydroxyl in reaction system
The molar concentration rate of base succimide and glucose is 3.6, glucose and the molar concentration rate of glucoseoxidase
It is 6250), quickly mix, airtight standing 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, make
Recording compressive strength with electronic universal tester is 2250kPa (compression strain 98%), unbroken and can after test
Part restores to the original state.
Embodiment 12
1) bovine serum albumin of modified by vinyl is prepared: take bovine serum albumin (BSA) 600mg, N-third
Alkene acyloxysuccinimide 54mg, is dissolved in 30mL deionized water, at room temperature magnetic agitation reaction
2.5h.Being transferred in bag filter by reactant mixture, be placed in deionized water dialysis 3 days, lyophilization obtains white
Color solid product is the bovine serum albumin of modified by vinyl.According to document (J.Biosci. people oeng., 2005,100,
Method 551-555) reported, records and about modifies 4 double bonds on average each bovine serum albumin molecule.
2) preparation precursor liquid: take NVP 0.09～0.11g, nano silicon aqueous dispersions
(21wt%) 1.6～1.7g, the bovine serum albumin 0.055～0.065g of modified by vinyl adds in sample bottle,
Use vortex mixer mix homogeneously.
3) preparation of hydrogel and performance test: be sequentially added into N-hydroxysuccinimide water in above-mentioned precursor liquid
Solution 25 μ L, glucoseoxidase concentrated solution 100 μ L, D/W 50 μ L (N-hydroxyl in reaction system
The molar concentration rate of base succimide and glucose is 1.74, glucose and the molar concentration rate of glucoseoxidase
It is 6250), quickly mix, airtight standing obtains light yellow translucent hydrogel (containing 17wt% nanometer titanium dioxide
Silicon), gelation time 4min30s.Cylindric sample (diameter 15.7mm, high 7.5mm) made by above-mentioned hydrogel
After, using electronic universal tester to record compressive strength is 1250kPa (compression strain 98%), can be extensive after test
Restore shape.
As it is shown in figure 1, with α-(4-pyridine radicals-1-oxygen)-N-tert-butyl group nitroketone (POBN) as Active oxygen radical
In the case of agent, (wherein N-hydroxysuccinimide and glucose is mole dense for the ternary initiator system of the present invention
Degree ratio is 0.29, and the molar concentration rate of glucose and glucoseoxidase is 12500) ESR that produces scanning believes
Number it is 6 characteristic peaks (its hyperfine splitting constant a of POBN radical adductN=15.7G, aH=2.5
G), explanation system creates the Ionization Potential of C-Centered Radicals derived by saccharide compound thus initiated polymerization is carried out.
Above the present invention is done exemplary description, but embodiments of the present invention have not been limited by above-described embodiment
System.Other any without departing from the amendment made under the spirit of the present invention, replace, combine, simplify, all should
For equivalence substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. glucoseoxidase mediation free radical initiator system, it is characterised in that this free radical initiator system be
Cause vinyl monomer to carry out the initiator system of radical polymerization with water for reaction medium under room temperature, comprise N-hydroxyl acyl
Imines, glucoseoxidase and glucose, the pH value range that initiator system is suitable for is 3.5～10.5；
Wherein the molar concentration rate of glucose and glucoseoxidase is 2250～52000:1, N-hydroxy imide and
The molar concentration rate of glucose is 0.2～4.0:1, and the molar concentration of the N-hydroxy imide used in initiator system is not
Less than 4.87mM, the molar concentration of glucose is not less than 9mM.
Glucoseoxidase the most according to claim 1 mediation free radical initiator system, it is characterised in that
Described N-hydroxy imide is N-hydroxysuccinimide.
Glucoseoxidase the most according to claim 1 and 2 mediation free radical initiator system, its feature exists
In, N-hydroxy imide, glucoseoxidase, glucose are directly mixed to get free radical initiator system；
Or by after N-hydroxy imide and glucoseoxidase or glucose mixing, add glucose or Fructus Vitis viniferae
Carbohydrate oxidase is with the use of obtaining free radical initiator system；
Or after glucoseoxidase and glucose mix, add N-hydroxy imide with the use of obtaining freedom
Base initiator system.
4. utilize the mediation free radical initiator system of the glucoseoxidase according to any one of claim 1-3 to prepare
The method of hydrogel, it is characterised in that the method utilizes N-hydroxy imide, glucoseoxidase and glucose
Coordinate as free radical initiator system, provide free radical for polymerization, by N-hydroxy imide, glucose during preparation
Oxidase is uniform with the aqueous solution of vinyl monomer, is then added thereto to glucose, regulation reaction medium
PH value or the concentration of component of regulation glucoseoxidase/N-hydroxy imide/glucose ternary initiator system, in room
The lower free radical trigger monomer that produces of temperature carries out polymerization formation Space network of polymer, obtains hydrogel, controls into gel
Time is 3min～30min.
Method the most according to claim 4, it is characterised in that described vinyl monomer is selected from acrylamide
One or more in derivant, NVP or water miscible acrylate derivative, vinyl monomer
Addition account for the 5～20% of reaction raw materials gross weight, described reaction raw materials includes reaction medium.
Method the most according to claim 5, it is characterised in that described water miscible acrylate derives
Thing is hydroxyethyl methylacrylate or Hydroxypropyl acrylate, and described acrylamide derivative is acrylamide, N, N-
DMAA or NIPA.
Method the most according to claim 4, it is characterised in that be also added with in reactant with more than 2
The water soluble compound of double bond as cross-linking agent, described cross-linking agent include N, N '-methylene-bisacrylamide,
Polyethyleneglycol diacrylate or the protein of modified by vinyl, described dosage of crosslinking agent accounts for reaction raw materials gross weight
1～6%, described reaction raw materials includes reaction medium.
Method the most according to claim 4, it is characterised in that be also added with water dispersible nothing in reactant
Machine nano material prepares the Nanometer composite hydrogel of high intensity, and described inorganic nano material is clay nano sheet, receives
Rice silicon dioxide or nanometer hydroxyapatite, the consumption of described inorganic nano material accounts for reaction raw materials gross weight
5～17%, described reaction raw materials includes reaction medium.
Method the most according to claim 8, it is characterised in that described inorganic nano material is average particle
The nano silicon in footpath 10～40nm or lamella a diameter of 20～40nm, thickness is 1nm, and molecular formula is
[Mg5.34Li0.66Si8O20(OH)4]Na0.66Clay nano sheet.
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| 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 |
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