CN105670310A - Composite light-sensitive double-network hydrogel based on methyl vinyl ether maleic acid copolymer/alginic acid and preparation method of composite light-sensitive double-network hydrogel - Google Patents
Composite light-sensitive double-network hydrogel based on methyl vinyl ether maleic acid copolymer/alginic acid and preparation method of composite light-sensitive double-network hydrogel Download PDFInfo
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Abstract
The invention discloses composite light-sensitive double-network hydrogel based on methyl vinyl ether maleic acid copolymer/alginic acid and a preparation method of the composite light-sensitive double-network hydrogel. The composite light-sensitive double-network hydrogel is of a 3D network structure. The preparation method includes: dropwise adding a solution containing P(MVE-alt-MA)-g-beta-CD, sodium alginate and sodium lactate into a solution containing P(MVE-alt-MA)-g-azo and ferrous chloride, exposing in the air, allowing the P(MVE-alt-MA) in the solution to crosslink under the inclusion complexation effect of beta-CD and azo, and allowing the sodium alginate to crosslink through Fe<3+> generated by Fe<2+> oxidized by the air to obtain the P(MVE-alt-MA)/SA composite light-sensitive double-network hydrogel. The composite light-sensitive double-network hydrogel and the preparation method thereof have the advantages that the synthesizing process of the hydrogel is simple and green, and reaction condition is mild; the hydrogel is good in light responsiveness and has a penetrating microstructure, and the mechanical performance, degradability and the like of the hydrogel can be regulated flexibly.
Description
Technical field
The present invention relates to technical field of polymer materials, particularly to the one preparation method based on methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA))/alginic acid (SA) complex light sensitivity double-network hydrogel. The photaesthesia double-network hydrogel that specifically application inclusion complexation effect and ionomer are formed.
Background technology
Hydrogel is because having the poroelasticity hydration network similar with biological tissue, and is conducive to the transmission wherein of oxygen, nutrient substance and metabolic waste, can provide desirable three-dimensional microenvironment for cell adhesion, propagation and differentiation. Current hydrogel is widely used in the field of biomedical research such as medicine or albumen conveying, organizational project, cell in vitro dimensional culture. The cross-linking method preparing hydrogel mainly includes physical crosslinking and chemical crosslinking two kinds. Wherein the advantage of Physical cross linking methods is in that technique is simple, does not introduce the initiator of toxic component, cross-linking agent etc., and it is not high enough that inferior position is in that to form hydrogel intensity. For improving the mechanical property of hydrogel, occur in that such as the research of double; two cross-linked network constitution water gels, interpenetration network hydrogel, nano-composite gel and topology hydrogel etc. Wherein double; two cross-linked network constitution water gel development focus in utilizing convenient source, and simple method prepares the double-network hydrogel of high-moisture percentage, high intensity.
Progress in Intelligent Hydrogel is that a class stimulates the hydrogel that can produce sensitive response to external world, and environmental stimuli can be temperature, pH value, salinity, light, chemical substance etc. According to the response condition stimulated to external world, progress in Intelligent Hydrogel is divided into: temperature-responsive hydrogel, pH-responsiveness aquagel, optical Response hydrogel, pressure-responsive hydrogel, biomolecule responsiveness aquagel, electric field response hydrogel etc. Due to unique response of progress in Intelligent Hydrogel, chemical converter, memory cell switch, sensor, artificial muscle, chemical storage device, molecule separation system, organized enzyme fixing, organizational project, pharmaceutical carrier etc. in there is good application prospect. Wherein optical Response hydrogel is that a class can occur rapidly chemically or physically to change and the intelligent polymer material that responds under light action. Under normal circumstances, there is Volume-phase transition due to light radiation (photostimulation) in Photosensitive Polymer Hydrogel.As when ultraviolet radiation, the photaesthesia group generation photoisomerization in gel network, photodissociation, because the change of group conformation and dipole moment can make gel generation swelling.
Therefore, from biomedical sector application angle consider, develop have high-moisture percentage, high intensity, preparation method swelling progress in Intelligent Hydrogel simple, low be highly important.
Summary of the invention
It is an object of the invention to provide a kind of based on methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA))/alginic acid (SA) complex light sensitivity double-network hydrogel and preparation method thereof, complicated to solve hydrogel synthesis step in prior art, the defects such as intensity is low, poor biocompatibility.
For achieving the above object, the technical solution used in the present invention is:
A kind of based on methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is 3D network structure, by containing P (MVE-alt-MA)-g-β-CD, the dropwise of sodium alginate (SA) and sodium lactate joins containing P (MVE-alt-MA)-g-azo and ferrous chloride (FeCl2) solution and expose in atmosphere, in solution, P (MVE-alt-MA) is cross-linked by inclusion complexation effect between β-CD and azo, and sodium alginate passes through Fe2+The Fe being oxidised with air to3+Crosslinking, obtains P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel; Described graft polymers P (MVE-alt-MA)-g-β-CD is with 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) for catalyst, 6-ethylenediamine-beta-schardinger dextrin-and P (MVE-alt-MA) is carried out graft reaction and obtains; Described P (MVE-alt-MA)-g-azo is with 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) for catalyst, P-aminoazobenzene (azo) and P (MVE-alt-MA) is carried out graft reaction and obtains.
A kind of method prepared based on methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel: comprise the steps:
Step one, prepare graft polymers P (MVE-alt-MA)-g-β-CD: by the N of methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)), dinethylformamide solution adds 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS), stir when room temperature lucifuge, it is added dropwise over the N of 6-ethylenediamine-beta-schardinger dextrin-again, dinethylformamide solution, at N2Stirring reaction under atmosphere and 25 DEG C～60 DEG C conditions, after terminating rear rotary evaporation removing solvent, is dissolved in water, dialyses 3 days～7 days, and lyophilizing obtains graft polymers P (MVE-alt-MA)-g-β-CD;
Step 2, prepare graft polymers P (MVE-alt-MA)-g-azo: by the N of methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)), dinethylformamide solution adds 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS), stir when room temperature lucifuge, it is added dropwise over the N of P-aminoazobenzene (azo) again, dinethylformamide solution, stirring reaction under 25 DEG C～60 DEG C conditions, after after end, rotary evaporation removes solvent, it is dissolved in water, dialyse 3 days～7 days, obtain graft polymers P (MVE-alt-MA)-g-azo,
Step 3, containing P (MVE-alt-MA)-g-β-CD, the dropwise of sodium alginate (SA) and sodium lactate joins containing P (MVE-alt-MA)-g-azo and ferrous chloride (FeCl2) solution and expose 3-24h in atmosphere and obtain P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel.
Further, in step, the concentration of the DMF solution of the DMF solution of described 6-ethylenediamine-beta-schardinger dextrin-and methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)) is 0.02g/ml～0.1g/ml.
Further, in step 2, the N of described methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)), the concentration of the DMF solution of dinethylformamide solution and P-aminoazobenzene (azo) is 0.02g/ml～0.1g/ml.
Further, the number-average molecular weight of described methyl vinyl ether maleic acid copolymer is 80000～311000.
Further, in step one, anhydride unit and the mol ratio of 6-ethylenediamine-beta-schardinger dextrin-in methyl vinyl ether maleic acid copolymer are 20～5:1; The mol ratio of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) is 0.5:1～1:1.5; 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and the total amount of N-hydroxy-succinamide (NHS) are 1:50～2 with the mol ratio of methyl vinyl ether maleic acid copolymer.
Further, in step 2, anhydride unit and the mol ratio of P-aminoazobenzene (azo) in methyl vinyl ether maleic acid copolymer are 10:1～2:1; The mol ratio of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) is 0.5:1～1:1.5; The mol ratio of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) total amount and polymethyl vinyl ether copolymerization maleic acid is 1:50～2.
Further, the response time of step one and step 2 is 8h～36h.
Further, in step 3, the concentration of P (MVE-alt-MA)-g-β-CD solution and P (MVE-alt-MA)-g-azo solution is 0.05g/mL～0.15g/mL, the mass fraction of sodium alginate is 1%～10%, sodium lactate concentration is 10～20mM, and ferrous chloride concentration is 10～30mM; P (MVE-alt-MA)-g-β-CD and P (MVE-alt-MA)-g-Azo active group mol ratio is 1:3～3:1.
Beneficial effect: the invention have the advantages that
1, cheaper starting materials of the present invention, synthetic route is simple, and the cycle is short, pollution-free, it is adaptable to large-scale production.
2, subject hydrogel is physical hydrogel, does not introduce the chemokineses such as chemical initiator, cross-linking agent, is of value to hydrogel practical application in biomedicine.
3, hydrogel had both needed material to have good biocompatibility and biological activity as tissue engineering bracket material, needed again have certain mechanical property. The tissue engineering bracket that homogenous material builds often cannot meet these requirements simultaneously. The present invention is by by differential responses ratio compound between artificial-synthetic copolymer P (MVE-alt-MA) and sodium alginate, can be easily obtained the mechanical strength meeting materials demand and good biological activity etc. simultaneously.
4, subject hydrogel, when irradiation under ultraviolet ray, gel conversion is colloidal sol, and light has good response, can be applicable to medicine controlled releasing and cell 3D culture carrier.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph based on P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel that embodiment 2 obtains.
Fig. 2 be embodiment 2 preparation based on P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel inversion of phases photo under ultraviolet irradiation condition.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further described.
Methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)) is the macromolecular material that human body and animal is nontoxic, have excellent hydrophilic, chemical stability, biocompatibility, the polycarboxylic acid polymers of bioadhesive and be widely used in biotechnology, pharmacology and healthcare applications. As stabilizer, plasticizer, binding agent and slow releasing agent etc. The micro array structure of P (MVE-alt-MA) can the sticking of backer's pluripotent stem cell (hPSCs) (HUES1, HUES9 and iPSCs), propagation and self renewal. Its characters and appearances can be maintained at the upper human pluripotent stem cells hPSCs cultivated of P (MVE-alt-MA), have expressed high level pluripotency marker's thing and keep normal karyotype. Based on the biocompatibility that this polymer is good, cyclodextrin, rimantadine hydrochloride are modified P (MVE-alt-MA) by the present invention respectively, and are assembled into pH sensitivity injectable self-healing hydrogel. Can be applicable to medicine controlled releasing and cell 3D culture carrier.
Alginic acid (alginicacid, HA), is the natural polysaccharide carbohydrate extracted from Thallus Laminariae (Thallus Eckloniae), has another name called alginic acid, seaweed gel. Alginic acid is by guluronic acid (α-L-guluronic, G unit) and mannuronic acid (β-D-mannuronic, M unit) the linear straight chain polysaccharide that is formed by connecting with (1 → 4) glycosidic bond, there is good biocompatibility, be widely used in food, cosmetics and field of medicaments. Sodium alginate (sodiumalginate, SA) is the sodium salt of alginic acid, and its aqueous solution has higher viscosity, can gelation in a mild condition, therefore, sodium alginate is widely used in the preparation of pharmaceutical carrier.
The present invention is based on P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel, by containing P (MVE-alt-MA)-g-β-CD, the dropwise of sodium alginate (SA) and sodium lactate joins containing P (MVE-alt-MA)-g-azo and ferrous chloride (FeCl2) solution and expose in atmosphere, in solution, P (MVE-alt-MA) is cross-linked by inclusion complexation effect between β-CD and azo, and sodium alginate passes through Fe2+The Fe being oxidised with air to3+Crosslinking, obtains P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel; Described graft polymers P (MVE-alt-MA)-g-β-CD is with EDC/NHS for catalyst, 6-ethylenediamine-beta-schardinger dextrin-and P (MVE-alt-MA) is carried out graft reaction and obtains; Described P (MVE-alt-MA)-g-azo is with EDC/NHS for catalyst, P-aminoazobenzene (azo) and P (MVE-alt-MA) is carried out graft reaction and obtains.
The above-mentioned preparation method based on P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel, comprises the steps:
Step one, compound concentration are the N of 0.02g/ml～0.1g/ml methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)), dinethylformamide solution, add 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS), 2h is stirred under room temperature dark condition, it is added dropwise over the N of 0.02g/ml～0.1g/ml6-ethylenediamine-beta-schardinger dextrin-again, dinethylformamide solution, at N2Stirring 8h～36h with 600rpm～1700rpm under atmosphere and 25 DEG C～60 DEG C conditions, rotary evaporation is dissolved in water, dialyses 3 days～7 days after removing solvent, and lyophilizing obtains graft polymers P (MVE-alt-MA)-g-β-CD; Wherein, the number-average molecular weight of methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)) is 80000～311000, and carboxylic acid and the mol ratio of beta-schardinger dextrin-in methyl vinyl ether maleic acid copolymer are 20:1～5:1;The mol ratio of EDC and NHS is 0.5:1～1:1.5; The mol ratio of EDC and NHS total amount and methyl vinyl ether maleic acid copolymer is 1:50～2;
Step 2, compound concentration are the N of 0.02g/ml～0.1g/ml methyl vinyl ether maleic acid copolymer (P (MVE-alt-MA)), dinethylformamide solution, add EDC/NHS, 2h is stirred under room temperature dark condition, it is added dropwise over the N that concentration is 0.02g/ml～0.1g/mlazo again, dinethylformamide solution, 8h～36h is stirred with 600rpm～1700rpm under 25 DEG C～60 DEG C conditions, after rotary evaporation removes solvent, it is dissolved in water, dialyse 3 days～7 days, obtain graft polymers P (MVE-alt-MA)-g-azo; Wherein, the number-average molecular weight of P (MVE-alt-MA) is 80000～311000, and the carboxylic acid of methyl vinyl ether maleic acid copolymer and the mol ratio of azo are 10:1～2:1; The mol ratio of EDC and NHS is 0.5:1～1:1.5; The mol ratio of EDC and NHS total amount and methyl vinyl ether maleic acid copolymer is 1:50～2;
Step 3, containing P (MVE-alt-MA)-g-β-CD, the dropwise of sodium alginate (SA) and sodium lactate joins containing P (MVE-alt-MA)-g-azo and ferrous chloride (FeCl2) solution expose 3-24h in atmosphere and obtain P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel. The concentration of P (MVE-alt-MA)-g-β-CD solution and P (MVE-alt-MA)-g-azo solution is 0.05g/mL～0.15g/mL, sodium alginate mass fraction is 1%～10%, sodium lactate concentration is 10～20mM, and ferrous chloride concentration is 10～30mM. P (MVE-alt-MA)-g-β-CD and P (MVE-alt-MA)-g-Azo active group mol ratio is 1:3～3:1.
Raw material sources that following instance adopts illustrate: polymethyl vinyl ether maleic acid (P (MVE-alt-MA)) is purchased from lark prestige Science and Technology Ltd.; P-aminoazobenzene (azo) is purchased from Aladdin reagent (Shanghai) Co., Ltd.; Beta-schardinger dextrin-(β-CD), ethylenediamine (EDA), dimethylformamide (DMF), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC), N-hydroxy-succinamide (NHS) is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group. 6-ethylenediamine-β-CD (EDA-β-CD) is produced list of references (Y.Y.Liu, X.D.Fan, L.Gao, SynthesisandCharacterizationof β-CyclodextrinBasedFunctionalMonomersanditsCopolymerswithN-isopropylacrylamideMacromol.Biosci.2003,3,715 719)
Embodiment 1
(1), the synthesis of P (MVE-alt-MA)-g-β-CD
By P (MVE-alt-MA) (0.78g, 0.005mol) it is dissolved in the dry DMF of 20mL, add appropriate EDC/NHS (11 μ LEDC and 8mgNHS, mol ratio 1:1.2), 2h is stirred under room temperature dark condition, it is added dropwise over dissolved with EDA-β-CD (1.135g, DMF solution 0.001mol), 12h is stirred with 600rpm under N2 atmosphere and 60 DEG C of conditions, rotary evaporation is dissolved in appropriate water, dialyses 3 days after removing solvent, lyophilizing, obtains graft polymers P (MVE-alt-MA)-g-β-CD. The DMF solution concentration of EDA-β-CD is the DMF solution concentration of 0.06g/ml, P (MVE-alt-MA) is 0.05g/ml. Carboxylic acid and the EDA-β-CD mol ratio of P (MVE-alt-MA) are 5:1.
(2), the synthesis of P (MVE-alt-MA)-g-azo
By P (MVE-alt-MA) (1.56g, 0.01mol) it is dissolved in the dry DMF of 20mL, adds appropriate EDC/NHS (11 μ LEDC and 8mgNHS, mol ratio 1:1.2), it is added dropwise over dissolved with azo (0.197g, DMF solution 0.001mol), under 80 DEG C of conditions, with 600rpm stirring reaction 36h, rotary evaporation removes solvent, sample is dissolved in water, dialyses 3 days, obtains graft polymers P (MVE-alt-MA)-g-azo.The DMF solution concentration that DMF solution concentration is 0.08g/ml, azo of P (MVE-alt-MA) is 0.06g/ml. The carboxylic acid of P (MVE-alt-MA) and azo mol ratio are 10:1.
(3), the synthesis of P (MVE-alt-MA)/SA hydrogel
Take 500mgP (MVE-alt-MA)-g-β-CD, 50mg sodium alginate (SA) and 11.2mg sodium lactate are dissolved in 10mL deionized water, are joined by dropwise containing 350mgP (MVE-alt-MA)-g-azo and 12.68mg ferrous chloride (FeCl2) 10mL solution expose 6h in atmosphere and obtain P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel.
Embodiment 2
(1), the synthesis of P (MVE-alt-MA)-g-β-CD
By P (MVE-alt-MA) (1.56g, 0.01mol) it is dissolved in the dry DMF of 20mL, add appropriate EDC/NHS (11 μ LEDC and 8mgNHS, mol ratio 1:1.2), 2h is stirred under room temperature dark condition, it is added dropwise over the DMF solution dissolved with EDA-β-CD (1.135g, 0.001mol), at N2Stirring 8h with 1000rpm under atmosphere and 40 DEG C of conditions, rotary evaporation is dissolved in appropriate water, dialyses 7 days after removing solvent, and lyophilizing obtains graft polymers P (MVE-alt-MA)-g-β-CD. The DMF solution concentration of EDA-β-CD is the DMF solution concentration of 0.06g/ml, P (MVE-alt-MA) is 0.05g/ml. Carboxylic acid and the β-CD mol ratio of P (MVE-alt-MA) are 10:1.
(2), the synthesis of P (MVE-alt-MA)-g-azo
By P (MVE-alt-MA) (1.56g, 0.01mol) it is dissolved in the dry DMF of 20mL, adds appropriate EDC/NHS (11 μ LEDC and 8mgNHS, mol ratio 1:1.2), it is added dropwise over dissolved with azo (0.394g, DMF solution 0.002mol), under 40 DEG C of conditions, with 1000rpm stirring reaction 24h, rotary evaporation removes solvent, sample is dissolved in water, dialyses 7 days, obtains graft polymers P (MVE-alt-MA)-g-azo. The DMF solution concentration that DMF solution concentration is 0.08g/ml, azo of P (MVE-alt-MA) is 0.06g/ml. The carboxylic acid of P (MVE-alt-MA) and azo mol ratio are 5:1.
(3), the synthesis of P (MVE-alt-MA)/SA hydrogel
Take 500mgP (MVE-alt-MA)-g-β-CD, 58mg sodium alginate (SA) and 11.2mg sodium lactate are dissolved in 10mL deionized water, are joined by dropwise containing 350mgP (MVE-alt-MA)-g-azo and 14mg ferrous chloride (FeCl2) 10mL solution expose 6h in atmosphere and obtain P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel.
Fig. 1 is the scanning electron microscope (SEM) photograph based on P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel prepared by the present embodiment, and this hydrogel internal structure is continuous print network structure, and this kind of structure makes hydrogel have bigger specific surface area. Fig. 2 be the present embodiment prepare based on P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel when irradiation under ultraviolet ray, gel conversion is colloidal sol, illustrates that light is had good response by this hydrogel.
Embodiment 3
(1) synthesis of P (MVE-alt-MA)-g-β-CD
By P (MVE-alt-MA) (3.12g, 0.02mol) it is dissolved in the dry DMF of 20mL, add appropriate EDC/NHS (11 μ LEDC and 8mgNHS, mol ratio 1:1.2), 2h is stirred under room temperature dark condition, it is added dropwise over the DMF solution dissolved with EDA-β-CD (1.135g, 0.001mol), at N2Stirring 8h with 1700rpm under atmosphere and 25 DEG C of conditions, rotary evaporation is dissolved in appropriate water, dialyses 7 days after removing solvent, and lyophilizing obtains graft polymers P (MVE-alt-MA)-g-β-CD.The DMF solution concentration of EDA-β-CD is the DMF solution concentration of 0.06g/ml, P (MVE-alt-MA) is 0.05g/ml. Carboxylic acid and the β-CD mol ratio of P (MVE-alt-MA) are 20:1.
(2) synthesis of P (MVE-alt-MA)-g-azo
By P (MVE-alt-MA) (1.56g, 0.01mol) it is dissolved in the dry DMF of 20mL, adds appropriate EDC/NHS (11 μ LEDC and 8mgNHS, mol ratio 1:1.2), it is added dropwise over dissolved with azo (0.985g, DMF solution 0.005mol), under 25 DEG C of conditions, with 1700rpm stirring reaction 12h, rotary evaporation removes solvent, sample is dissolved in water, dialyses 7 days, obtains graft polymers P (MVE-alt-MA)-g-azo. The DMF solution concentration that DMF solution concentration is 0.08g/ml, azo of P (MVE-alt-MA) is 0.06g/ml. The carboxylic acid of P (MVE-alt-MA) and azo mol ratio are 2:1.
(3) synthesis of P (MVE-alt-MA)/SA hydrogel
Take 500mgP (MVE-alt-MA)-g-β-CD, 58mg sodium alginate (SA) and 11.2mg sodium lactate are dissolved in 10mL deionized water, are joined by dropwise containing 200mgP (MVE-alt-MA)-g-azo and 14mg ferrous chloride (FeCl2) 10mL solution expose 6h in atmosphere and obtain P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel.
The above is only the preferred embodiment of the present invention; it is noted that, for those skilled in the art; under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (9)
1. one kind based on methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterized in that: it is 3D network structure, by containing P (MVE-alt-MA)-g-β-CD, the dropwise of sodium alginate and sodium lactate joins containing P (MVE-alt-MA)-g-azo and solution of ferrous chloride and exposes in atmosphere, P (MVE-alt-MA) in solution is cross-linked by inclusion complexation effect between β-CD and azo, and sodium alginate passes through Fe2+The Fe being oxidised with air to3+Crosslinking, obtains P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel; Described graft polymers P (MVE-alt-MA)-g-β-CD is with 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide for catalyst, 6-ethylenediamine-beta-schardinger dextrin-and P (MVE-alt-MA) is carried out graft reaction and obtains; Described P (MVE-alt-MA)-g-azo is with 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide for catalyst, P-aminoazobenzene and P (MVE-alt-MA) is carried out graft reaction and obtains.
2. the method prepared based on methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterised in that: comprise the steps:
Step one, prepare graft polymers P (MVE-alt-MA)-g-β-CD: by the N of methyl vinyl ether maleic acid copolymer, dinethylformamide solution adds 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide, stir when room temperature lucifuge, it is added dropwise over the N of 6-ethylenediamine-beta-schardinger dextrin-again, dinethylformamide solution, at N2Stirring reaction under atmosphere and 25 DEG C～60 DEG C conditions, after terminating rear rotary evaporation removing solvent, is dissolved in water, dialyses 3 days～7 days, and lyophilizing obtains graft polymers P (MVE-alt-MA)-g-β-CD;
Step 2, prepare graft polymers P (MVE-alt-MA)-g-azo: by the N of methyl vinyl ether maleic acid copolymer, dinethylformamide solution adds 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide, stir when room temperature lucifuge, it is added dropwise over the N of P-aminoazobenzene again, dinethylformamide solution, stirring reaction under 25 DEG C～60 DEG C conditions, after after end, rotary evaporation removes solvent, it is dissolved in water, dialyse 3 days～7 days, obtain graft polymers P (MVE-alt-MA)-g-azo;
Step 3, containing P (MVE-alt-MA)-g-β-CD, the dropwise of sodium alginate and sodium lactate joins the solution containing P (MVE-alt-MA)-g-azo and ferrous chloride and exposes 3-24h in atmosphere and obtain P (MVE-alt-MA)/SA complex light sensitivity double-network hydrogel.
3. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterized in that: in step one, the N of described 6-ethylenediamine-beta-schardinger dextrin-, the concentration of the DMF solution of dinethylformamide solution and methyl vinyl ether maleic acid copolymer is 0.02g/ml～0.1g/ml.
4. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterized in that: in step 2, the N of described methyl vinyl ether maleic acid copolymer, the concentration of the DMF solution of dinethylformamide solution and P-aminoazobenzene is 0.02g/ml～0.1g/ml.
5. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterised in that: the number-average molecular weight of described methyl vinyl ether maleic acid copolymer is 80000～311000.
6. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterized in that: in step one, anhydride unit and the mol ratio of 6-ethylenediamine-beta-schardinger dextrin-in methyl vinyl ether maleic acid copolymer are 20～5:1; The mol ratio of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide is 0.5:1～1:1.5; 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and the total amount of N-hydroxy-succinamide are 1:50～2 with the mol ratio of methyl vinyl ether maleic acid copolymer.
7. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterized in that: in step 2, anhydride unit and the mol ratio of P-aminoazobenzene in methyl vinyl ether maleic acid copolymer are 10:1～2:1; The mol ratio of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide is 0.5:1～1:1.5; 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and the total amount of N-hydroxy-succinamide are 1:50～2 with the mol ratio of methyl vinyl ether maleic acid copolymer.
8. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterised in that: the response time of step one and step 2 is 8h～36h.
9. preparation according to claim 2 is based on the method for methyl vinyl ether maleic acid copolymer/alginic acid complex light sensitivity double-network hydrogel, it is characterized in that: in step 3, the concentration of P (MVE-alt-MA)-g-β-CD solution and P (MVE-alt-MA)-g-azo solution is 0.05g/mL～0.15g/mL, the mass fraction of sodium alginate is 1%～10%, sodium lactate concentration is 10～20mM, and ferrous chloride concentration is 10～30mM; P (MVE-alt-MA)-g-β-CD and P (MVE-alt-MA)-g-Azo active group mol ratio is 1:3～3:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105936674A (en) * | 2016-06-29 | 2016-09-14 | 武汉纺织大学 | Preparation method of alginic acid hydrogel matrix for UV 3D printing |
| WO2019222635A1 (en) * | 2018-05-18 | 2019-11-21 | Northwestern University | Photocontrolled dynamic covalent linkers for polymer networks |
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| CN109879984A (en) * | 2019-03-27 | 2019-06-14 | 华东理工大学 | A kind of vinyl etherificate modified sodium alginate and the preparation method and application thereof |
| CN109879984B (en) * | 2019-03-27 | 2021-02-12 | 华东理工大学 | Vinyl etherification modified sodium alginate and preparation method and application thereof |
| CN113088511A (en) * | 2021-04-29 | 2021-07-09 | 江苏师范大学 | Enzyme immobilization compound based on photoinduced reusable immobilization material and preparation method thereof |
| CN116284504A (en) * | 2023-01-04 | 2023-06-23 | 昆明理工大学 | Series of crosslinked cyclodextrin polymers, and preparation method and application thereof |
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