CN103342823A - Method for preparing hydrogel by enzymatic free radical polymerization - Google Patents
Method for preparing hydrogel by enzymatic free radical polymerization Download PDFInfo
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Abstract
The invention relates to a method for preparing hydrogel by enzymatic free radical polymerization. According to the method, peroxidase, a beta-dicarbonyl compound and hydrogen peroxide are combined as an enzymatic free radical initiating system for providing free radicals for polymerization. The method comprises the following steps of: uniformly mixing an aqueous solution containing the peroxidase, the beta-dicarbonyl compound and alkene monomers in a using process; and then, adding hydrogen peroxide in the aqueous solution, adjusting the component concentration of a peroxidase/beta-dicarbonyl compound/hydrogen peroxide ternary initiating system, and controlling to obtain the hydrogel within 20 seconds to 30 minutes under the room temperature. The method for preparing the hydrogel by enzymatic free radical polymerization is realized in a water phase, gentle in reaction condition, simple and convenient to operate, quick and controllable in hydrogel forming time and capable of preparing the high-strength nanometer composite hydrogel material, and therefore, the method has an obvious application prospect in the fields including immobilized enzyme carriers, medicament controlled release, artificial cartilages, tissue engineering scaffold materials and the like.
Description
Technical field
The present invention relates to the polyalcohol hydrogel field, especially relate to the method that a kind of enzymatic radical polymerization prepares hydrogel.
Background technology
Hydrogel is a kind of three-dimensional network material that can absorb and keep large quantity of moisture (water content is greater than 70% usually), the polymer molecular chain that its network skeleton is normally natural or synthetic.Because it is quite similar with the body tissue of full a large amount of aqueous solution, hydrogel is widely used in fields such as biological medicine, biotechnology and biological chemistry, specifically comprises enzyme immobilization carrier, bio-sensing, wound dressing, drug release, organizational project (tissue filling material, joint cartilage, cell cultures) etc.
The preparation of polyalcohol hydrogel generally is divided into two kinds of physical crosslinking and chemically crosslinkeds.Physical crosslinking is by formation such as non covalent bond reactive force such as electrostatic interaction, hydrogen bond action, hydrophobic association effects.Chemically crosslinked often by add linking agent in aqueous solutions of polymers, as glutaraldehyde, epoxy chloropropane, vulcabond etc., makes and is cross-linked to form network between the polymer molecular chain; Or by means such as thermal initiation, UV-light initiation, gamma-ray irradiation initiations, make the comonomer solution polymerization that contains unsaturated double-bond form the network of chemically crosslinked.Yet, there is cytotoxicity in chemical cross-linking agent or the initiator residual material that often causes in system, and UV-irradiation, gamma-ray irradiation also may cause the necrocytosis (Biomaterials at illuminated position, 2009,30,344-353), these shortcomings have limited to a great extent and have used the chemically crosslinked aquagel of method for preparing in the application in bio-medical field.
Utilizing the advantage (be mild reaction conditions, high degree of specificity transform) of biological enzyme to prepare polyalcohol hydrogel, is a kind of eco-friendly selection scheme for the traditional chemical preparation method of the harsh reaction conditions of needs.Enzyme catalysis need not used chemical cross-linking agent or initiator, the hydrogel biological material that obtains have good biocompatibility (Biomaterials, 2012,33,1281-1290).Horseradish peroxidase (Horseradish peroxidase, EC1.11.1.7) when hydrogen peroxide exists, effectively catalysis contains the oxidation cross-linked formation three-dimensional polymer network between the biomacromolecule compound of phenolic hydroxyl group, thereby obtain hydrogel, and in medicine controlled releasing and cell cultures, be applied (CN101439206A, US20120270810A1).But the preparation of this type of hydrogel needs with particular chemical reagent (as tyrasamine, para hydroxybenzene propionic acid etc.) biomacromolecule (as hyaluronic acid, alginates, gelatin etc.) to be carried out chemically modified earlier generates phenolic hydroxyl group, and reaction process and purification of products are comparatively complicated; And prepared hydrogel General Mechanics intensity is relatively poor, is typically used as the injecting medicinal material.
Oxydo-reductase (as peroxidase, laccase etc.) can produce free radical by the catalysis electron-transfer reaction, causes the polymerization of vinyl monomer in the aqueous solution.Utilize the enzymatic mechanism of free-radical polymerization to prepare hydrogel and can realize that the comonomer range of choice is bigger at water, the reaction conditions gentleness, easy and simple to handle, and also gelation time is fast controllable.Different with the enzymatic oxidn cross-linking method, the enzymatic free radical polymerisation process of peroxidase mediation can be for the preparation of high-intensity Nanometer composite hydrogel, and is broader as the application prospect of bio-medical material.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of enzymatic mechanism of free-radical polymerization that utilizes to cause the method that the polymerization of alkene class comonomer prepares hydrogel for the defective that overcomes above-mentioned prior art existence.This method reaction conditions gentleness, easy and simple to handle, gelation time is fast controllable, and can be used for preparing high-intensity Nanometer composite hydrogel.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of enzymatic radical polymerization prepares the method for hydrogel, utilize peroxidase, beta-dicarbonyl compound and hydrogen peroxide to cooperate as enzymatic free radical initiator system, for polymerization provides free radical, aqueous solution with peroxidase, beta-dicarbonyl compound and vinyl monomer during preparation is even, regulating pH is 5.5～9, then to wherein adding hydrogen peroxide, at room temperature react 20s～30min, can produce the free radical trigger monomer and carry out polymerization formation three-dimensional polymer network, obtain hydrogel.
Described peroxidase be 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 the N-vinyl pyrrolidone.
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 N-N-isopropylacrylamide (NIPA).
The molar concentration rate of described hydrogen peroxide and peroxidase is 180～3500, and the beta-dicarbonyl compound that satisfies simultaneously and the molar concentration rate of hydrogen peroxide are not less than 2.6, join that the final volumetric molar concentration of hydrogen peroxide is not less than 400 μ M in the reaction system, the add-on of vinyl monomer accounts for 5～20% of reaction raw materials gross weight.
Can also add in the reactant have two or more two keys water-soluble cpds 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 the reactant and prepare high-intensity Nanometer composite hydrogel to adapt to different user demands, described inorganic nano material is clay nano sheet, nano silicon or nanometer hydroxyapatite, nano silicon or the lamella diameter 20～40nm of preferred median size 10～40nm, thickness 1nm, molecular formula is [Mg
5.34Li
0.66Si
8O
20(OH)
4] Na
0.66The clay 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 has proved in the enzymatic free radical initiator system of the present invention by spectrum (ESR) and has produced carbon center's free radical of being derived by beta-dicarbonyl compound.As shown in Figure 1, under with the situation of α-(4-pyridyl-1-oxygen)-N-tertiary butyl nitroketone (POBN) as the spin trapping agent, (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 free radical adducts, produced the free radical (Biotechnol.Lett. of carbon center that is derived by methyl ethyl diketone in the explanation system, 2000,22,1355-1361).Determined that by transmission electron microscope the inorganic nano component is evenly dispersed in the Nanometer composite hydrogel of the present invention preparation (Fig. 2), by and polymer molecular chain between non-covalent interaction power form the physical crosslinking point, hydrogel is played enhancement.The hydrogel Mechanical Properties is shown that the nano-hydrogel that the present invention prepares can resist the compressive strength of 400～2000kPa and can return to original state, and the ortho-water gel can only be resisted the compressive strength of about 20～50kPa and easily crushed.Studies show that by above-mentioned, adopt the enzymatic free radical polymerisation process of peroxidase mediation can the superior Nanometer composite hydrogel material as medicine control release, enzyme immobilization, separating substances, organizational project etc. of obtained performance, have the following advantages:
(1) compare with traditional chemically crosslinked polyalcohol hydrogel preparation method (as thermal initiation, UV-light initiation, radiation initiation etc.), technical solution of the present invention has environmental friendliness, reaction conditions gentleness (water room temperature reaction), advantage easy and simple to handle;
(2) preparation method of the present invention can be by regulating the concentration of component of peroxidase/beta-dicarbonyl compound/hydrogen peroxide ternary initiator system, control gelation time (20s～30min), be conducive to the practical application operation;
(3) compare with the enzymatic oxidn cross-linking method, the available raw material sources of preparation method of the present invention are extensive, and can prepare high-intensity Nanometer composite hydrogel.Good mechanical intensity is extremely important in the application of aspects such as fixed enzyme vector, artificial cartilage, tissue engineering bracket material, thereby the hydrogel of this method preparation is applied to field of biology and has tangible application prospect.
Description of drawings
Fig. 1 is the free radical signal that the detected enzymatic free radical of spectrum initiator system produces;
Fig. 2 is the transmission electron microscope photo with the Nanometer composite hydrogel of enzymatic radical polymerization preparation.
Among Fig. 2, A is not for containing the control sample of inorganic nano component; B is for containing 18wt%SiO
2The sample of nanoparticle (diameter is the dark spherical particle of 10～15nm among the figure).
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment, further specify 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 preparation modified by vinyl: get bovine serum albumin (BSA) 600mg, N-acryloxy succinimide 54mg is dissolved in the 30mL deionized water, magnetic agitation reaction at room temperature 2.5 hours.Reaction mixture is transferred in the dialysis tubing, places deionized water dialysis 3 days, lyophilize obtains the bovine serum albumin that white solid product is modified by vinyl.According to document (J.Biosci.Bioeng., 2005,100,551-555) reported method records and approximately modifies 4 two keys on average each bovine serum albumin molecule.
2) preparation precursor liquid: get N,N-DMAA 0.1021g, the bovine serum albumin 0.0608g of modified by vinyl, deionized water 1.7162g adds in the sample bottle, mixes with vortex mixer, and actual measurement pH value is 6.0.
3) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 7.784mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), mixing is used manual time-keeping simultaneously fast, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 3min.
Embodiment 2
1) prepares the bovine serum albumin of modified by vinyl and prepare precursor liquid with reference to embodiment 1.
2) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 14.60mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 5 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 58s.
Embodiment 3
1) prepares the bovine serum albumin of modified by vinyl and prepare precursor liquid with reference to embodiment 1.
2) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 36.01mg successively, horseradish peroxidase concentrated solution 100 μ L, (volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 12 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 20s.
Embodiment 4
1) prepares the bovine serum albumin of modified by vinyl and prepare precursor liquid with reference to embodiment 1.
2) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 14.60mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of hydrogen peroxide and horseradish peroxidase is 555 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 5), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 1min50s.
Embodiment 5
1) prepares the bovine serum albumin of modified by vinyl and prepare precursor liquid with reference to embodiment 1.
2) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 14.60mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of hydrogen peroxide and horseradish peroxidase is 1110 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 5), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 4min40s.
Embodiment 6
1) prepares the bovine serum albumin of modified by vinyl and prepare precursor liquid with reference to embodiment 1.
2) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 14.60mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of hydrogen peroxide and horseradish peroxidase is 2220 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the volumetric molar concentration of methyl ethyl diketone and hydrogen peroxide is 5), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 18min50s.
Embodiment 7
1) preparation precursor liquid: get N, N-DMAA 0.1213g, linking agent polyethyleneglycol diacrylate (molecular-weight average 250) 0.0831g, deionized water 1.3420g adds in the sample bottle, mix with vortex mixer, adding 0.1M aqueous acetic acid 300 μ L adjusting pH value again is 5.8.
2) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 7.784mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280 to aqueous hydrogen peroxide solution 50 μ L in the reaction system, 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: in above-mentioned precursor liquid, add methyl ethyl diketone 17.51mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of hydrogen peroxide and horseradish peroxidase is 641 to aqueous hydrogen peroxide solution 50 μ L in the reaction system, 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) with reference to the bovine serum albumin of embodiment 1 preparation modified by vinyl.
2) preparation precursor liquid: 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 the sample bottle, mixes with vortex mixer.
3) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 14.60mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 5 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 1min.
Embodiment 10
1) with reference to the bovine serum albumin of embodiment 1 preparation modified by vinyl.
2) preparation precursor liquid: 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 the sample bottle, mixes with vortex mixer.
3) preparation of hydrogel: in above-mentioned precursor liquid, add methyl ethyl diketone 14.60mg successively, horseradish peroxidase concentrated solution 100 μ L, (molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 5 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 1min.
Embodiment 11
1) preparation precursor liquid: get N, N-DMAA 0.1010g, clay nano sheet aqueous dispersions (10wt%) 1.0015g, deionized water 0.5860g add in the sample bottle, mix with vortex mixer, adding 0.1M aqueous acetic acid 200 μ L adjusting pH value again is 8.5.
2) preparation of hydrogel: in above-mentioned precursor liquid, add horseradish peroxidase concentrated solution 100 μ L successively, methyl ethyl diketone 7.784mg, (molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, the molar concentration rate of hydrogen peroxide and horseradish peroxidase is 280), quick mixing, airtight leaving standstill obtains light yellow transparent aquagel, gelation time 3min.
Embodiment 12
1) preparation precursor liquid: get N,N-DMAA 0.1020g, clay nano sheet 0.3005g, deionized water 1.2860g add in the sample bottle, high speed magnetic agitation 1h, and adding 0.1M aqueous acetic acid 200 μ L adjusting pH value again is 8.9.
2) preparation of hydrogel: in above-mentioned precursor liquid, add horseradish peroxidase concentrated solution 100 μ L successively, methyl ethyl diketone 7.784mg, (molar concentration rate of methyl ethyl diketone and hydrogen peroxide is 2.6 to aqueous hydrogen peroxide solution 6 μ L in the reaction system, 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 the compression performance test, various performance parameters is as shown in table 1.Compare with control sample, as seen it has good mechanical property.
The mechanical property of table 1 Nanometer composite hydrogel
Embodiment 13
The catalytic activity test of Nanometer composite hydrogel: the Nanometer composite hydrogel 10.05mg that gets embodiment 10 preparations, adding 100mL contains the toluene solution of 0.1082g O-Phenylene Diamine, add 200 μ L aqueous hydrogen peroxide solutions (30wt%) again, measuring the absorbance of oxidation products (2,3-diaminophenazine) at the 450nm place every 0.2min with ultraviolet-visible pectrophotometer under 25 degrees centigrade changes.With the absorbance in the 1min to the time map a straight line, calculating the catalyzed reaction initial velocity by its slope is 0.73 μ M/s.Get 20 μ g horseradish peroxidases (300units/mg), obtaining the catalyzed reaction initial velocity under above reaction conditions is 0.10 μ M/s.As seen the Nanometer composite hydrogel of the present invention's preparation has advantages of high catalytic activity in toluene, can be used as immobilized enzyme and is applied to the nonaqueous phase biocatalysis.
More than the present invention has been done exemplary description, but embodiments of the present invention are not restricted to the described embodiments.Other any do not deviate from modification, replacement, combination, the simplification of doing under the principle essence of the present invention, all should be the substitute mode of equivalence, is included within protection scope of the present invention.
Claims (10)
1. an enzymatic radical polymerization prepares the method for hydrogel, it is characterized in that, this method utilizes peroxidase, beta-dicarbonyl compound and hydrogen peroxide to cooperate as enzymatic free radical initiator system, for polymerization provides free radical, aqueous solution with peroxidase, beta-dicarbonyl compound and vinyl monomer during preparation is even, regulating pH is 5.5～9, then to wherein adding hydrogen peroxide, at room temperature react 20s～30min, can produce the free radical trigger monomer and carry out polymerization formation three-dimensional polymer network, obtain hydrogel.
2. a kind of enzymatic radical polymerization according to claim 1 prepares the method for hydrogel, it is characterized in that, described peroxidase be horseradish peroxidase (HRP, 300units/mg).
3. a kind of enzymatic radical polymerization according to claim 1 prepares the method for hydrogel, it is characterized in that, described beta-dicarbonyl compound is methyl ethyl diketone (ACAC).
4. a kind of enzymatic radical polymerization according to claim 1 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 the N-vinyl pyrrolidone.
5. a kind of enzymatic radical polymerization according to claim 1 prepares the method for hydrogel, it is characterized in that, 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 N-N-isopropylacrylamide (NIPA).
6. the method for preparing hydrogel according to each described a kind of enzymatic radical polymerization among the claim 1-5, it is characterized in that, the molar concentration rate of described hydrogen peroxide and peroxidase is 180～3500, and the beta-dicarbonyl compound that satisfies simultaneously and the molar concentration rate of hydrogen peroxide are not less than 2.6, join that the final volumetric molar concentration of hydrogen peroxide is not less than 400 μ M in the reaction system, the add-on of vinyl monomer accounts for 5～20% of reaction raw materials gross weight.
7. a kind of enzymatic radical polymerization according to claim 1 prepares the method for hydrogel, it is characterized in that, can also add in the reactant have two or more two keys water-soluble cpds as linking agent, the protein that comprises N,N methylene bis acrylamide (BIS), polyethyleneglycol diacrylate (PEGDA) or modified by vinyl.
8. a kind of enzymatic radical polymerization according to claim 7 prepares the method for hydrogel, it is characterized in that the consumption of described linking agent accounts for 1～6% of reaction raw materials gross weight.
9. a kind of enzymatic radical polymerization according to claim 1 prepares the method for hydrogel, it is characterized in that, also can add water dispersible inorganic nano material in the reactant and prepare high-intensity Nanometer composite hydrogel to adapt to different user demands, described inorganic nano material is clay nano sheet, nano silicon or nanometer hydroxyapatite, nano silicon or the lamella diameter 20～40nm of preferred median size 10～40nm, thickness 1nm, molecular formula is [Mg
5.34Li
0.66Si
8O
20(OH)
4] Na
0.66The clay nano sheet.
10. a kind of enzymatic radical polymerization according to claim 9 prepares the method for hydrogel, 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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