CN112625649B - Gelatin-based hydrogel adhesive initiated by Fenton reagent and preparation method and application thereof - Google Patents
Gelatin-based hydrogel adhesive initiated by Fenton reagent and preparation method and application thereof Download PDFInfo
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- 108010010803 Gelatin Proteins 0.000 title claims abstract description 68
- 239000008273 gelatin Substances 0.000 title claims abstract description 68
- 229920000159 gelatin Polymers 0.000 title claims abstract description 68
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 68
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 68
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 239000000017 hydrogel Substances 0.000 title claims abstract description 43
- 239000012028 Fenton's reagent Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 7
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- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 17
- -1 Acryloyl Cyclodextrin Chemical compound 0.000 claims abstract description 15
- CRPNQSVBEWWHIJ-UHFFFAOYSA-N 2,3,4-trihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1O CRPNQSVBEWWHIJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 7
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- KQZQZOQFUQXPLW-YFKPBYRVSA-N (2s)-2-amino-3-(3,4,5-trihydroxyphenyl)propanoic acid Chemical compound OC(=O)[C@@H](N)CC1=CC(O)=C(O)C(O)=C1 KQZQZOQFUQXPLW-YFKPBYRVSA-N 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
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- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
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- XGFJCRNRWOXGQM-UHFFFAOYSA-N hot-2 Chemical group CCSC1=CC(OC)=C(CCNO)C=C1OC XGFJCRNRWOXGQM-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/16—Cyclodextrin; Derivatives thereof
Abstract
The invention discloses a gelatin-based hydrogel adhesive initiated by Fenton reagent, which adopts gelatin (Gel) and Acryloyl Cyclodextrin (ACD) as raw materials, adds 2,3, 4-trihydroxy benzaldehyde (THB), and utilizes Fenton reagent (H)2O2And Fe2+) Initiating ACD free radical polymerization and thereby introducing Fe3+Thereby obtaining a hydrogel adhesive having broad adhesion to a variety of matrix materials. The hydrogel adhesive has wide adhesion to matrix materials such as PMMA, glass, pigskin and the like, and has great application prospect in the field of biomedicine.
Description
Technical Field
The invention relates to the technical field of hydrogel materials, in particular to a gelatin-based hydrogel adhesive initiated by a Fenton reagent and a preparation method and application thereof.
Background
Hydrogel refers to a three-dimensional network of polymer materials containing a large amount of water formed by crosslinking polymer molecular chains together through physical, ionic, or covalent interactions. Due to the structural particularity, particularly the characteristic of high water content, the hydrogel material has unique performance and has wide application prospect in the biomedical field.
Acute and chronic skin wounds are a common problem in the clinic, and wound dressings generally play a role in preventing wound infection, rapidly closing wounds, promoting wound healing, and reducing scar formation. Hydrogel wound dressings have advantages of being able to maintain a moist wound environment, absorb tissue exudate, permeate oxygen, cool the wound surface to relieve pain, etc., and various functional hydrogel wound dressings have been successively reported. Gel wound dressings are generally required to have certain tissue adhesion properties to enable them to conform and secure to a wound site, and to have mechanical compliance to spontaneously conform and conform to dynamic nonlinear surfaces to accommodate the movements of the body's limbs.
The tunicate can spontaneously heal the damage suffered by the tunicate, and the reason is that the tunicate protein contains a large amount of 3, 4-dihydroxyphenylalanine and 3,4, 5-trihydroxyphenylalanine, and the structures playing key roles in the protein are catechol and pyrogallol units. Inspired by the above, the pyrogallol structure can be applied to a hydrogel material to endow the hydrogel material with adhesiveness.
The fenton reagent belongs to a redox initiation system and has been used in many studies as a radical initiator in the polymerization or grafting of vinyl monomers. Fenton's reagent consisting of H2O2And ferrous salts, the main mechanism of action of which is H2O2With Fe2+The reaction can generate hydroxyl free radical and Fe3+And the hydroxyl radical can continue to initiate free radical polymerization of the double bond in the vinyl monomer.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art and provide a gelatin-based hydrogel adhesive initiated by Fenton's reagent, which adopts gelatin (Gel) and Acryloyl Cyclodextrin (ACD) as raw materials, adds 2,3, 4-Trihydroxybenzaldehyde (THB) and utilizes Fenton's reagent (H)2O2And Fe2+) Initiating ACD free radical polymerization and thereby introducing Fe3+Thereby obtaining a hydrogel adhesive having broad adhesion to a variety of matrix materials. The hydrogel adhesive has wide adhesion to matrix materials such as PMMA, ceramics, ferrous metals, glass, pigskin and the like, and has great application prospect in the field of biomedicine.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a method of preparing a gelatin-based hydrogel adhesive initiated by fenton's reagent comprising the steps of:
step 1: separately preparing FeCl2Or FeSO4Aqueous solutions and aqueous gelatin solutions;
step 2: subjecting the FeCl2Or FeSO4Adding the aqueous solution into gelatin aqueous solution heated to 55-65 ℃, and fully dissolving to obtain solution A;
and step 3: preparing mixed aqueous solution of 2,3, 4-Trihydroxybenzaldehyde (THB) and Acryloyl Cyclodextrin (ACD), and adding H2O2Uniformly mixing to obtain a solution B;
and 4, step 4: and adding the solution B into the solution A, fully and uniformly mixing, and standing to form gel to obtain the gelatin-based hydrogel adhesive.
In the above technical solution, in step 1, the FeCl2Aqueous solution or FeSO4The concentration of the aqueous solution is 0.2-0.3mol/L, preferably 0.2 mol/L; the mass ratio of the gelatin in the gelatin water solution to the volume of the water is (0.1-0.2): 400, gelatin mass unit is g, volume unit is ul, (0.1-0.2g gelatin and 400 μ L deionized water swelling volume is about 500-.
In the above technical solution, in step 2, the FeCl2Aqueous solution or FeSO4The ratio of the volume of the aqueous solution to the volume of water in the aqueous gelatin solution is 1: 4.
in the above technical scheme, in step 3, the mass ratio of 2,3, 4-trihydroxybenzaldehyde, acryloylated cyclodextrin and deionized water in the mixed aqueous solution is (1.54-30.8): (10-100): 200, preferably 15.4: (50-100): 200, wherein each part is mg; said H2O2The concentration of the aqueous solution was 30 wt%, said H2O2The volume ratio of the aqueous solution to the mixed aqueous solution is 3: 300.
in the above technical solution, in step 4, the volume ratio of the solution B to the solution a is 3: 7.
based on the above material ratio, FeCl2Or FeSO4The concentration in the gelatin-based hydrogel adhesive is 20-30mmol/L, preferably 20 mmol/L; the mass fraction of the gelatin in the gelatin-based hydrogel adhesive is 10-20 wt%; gelatin with 2,3, 4-trihydroxybenzaldehydeThe concentration in the base hydrogel adhesive is 0.01-0.2mol/L, preferably 0.1 mol/L; the mass fraction of the acrylated cyclodextrin in the gelatin based hydrogel adhesive is 1-10 wt%, preferably 5-10 wt%.
In the technical scheme, in the step 3, the temperature for standing and gelling is 30-40 ℃, preferably 37 ℃; the standing and gelling time is 3-5 min.
Another object of the present invention is a gelatin-based hydrogel adhesive prepared by the above-described preparation method.
In the technical scheme, when the concentration of the 2,3, 4-trihydroxybenzaldehyde is 0.1mol/L, the adhesive strength of the gelatin-based hydrogel adhesive is 20-140 KPa.
In the above solution, the adhesive strength of the gelatin-based hydrogel adhesive increases with increasing concentration of acrylated cyclodextrin.
Another object of the present invention is the use of the above-described gelatin-based hydrogel adhesive in the biomedical field.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the gelatin-based hydrogel adhesive initiated by the Fenton reagent, disclosed by the invention, the polymerization reaction can be completed under a mild condition through the Fenton reagent without stimulation of conditions such as light and heat, and when the gelatin-based hydrogel adhesive is used for preparing hydrogel, the gelling time can be controlled simply by controlling the dosage of the Fenton reagent.
2. The gelatin-based hydrogel adhesive provided by the invention has the advantages that the adhesive strength of the gel to various base materials is gradually increased along with the increase of the content of ACD, the crosslinking density of molecular chains is increased, the crosslinking network in the gel is more concentrated, the strength of the gel body is increased, and the reflected adhesive strength of the gel is increased.
3. Adopting gelatin (Gel) and Acryloyl Cyclodextrin (ACD) as raw materials, adding 2,3, 4-Trihydroxybenzaldehyde (THB), and using Fenton reagent (H)2O2And Fe2+) Initiating ACD free radical polymerization and thereby introducing Fe3+Thereby obtaining a hydrogel adhesive having broad adhesion to a variety of matrix materials. TheThe hydrogel adhesive has wide adhesion to PMMA, ceramics, ferrous metals, glass, pigskin and other matrix materials, and has great application prospect in the field of biomedicine.
Drawings
FIG. 1 shows the rheological time scan of a Gel (Gel-THB-ACD-20-0.1-10).
Figure 2 shows the adhesive strength of gels with different ACD contents for different matrix materials.
Wherein, a is Gel (Gel-THB-20-0.1), b is Gel (Gel-THB-ACD-20-0.1-5), and c is Gel (Gel-THB-ACD-20-0.1-10).
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the raw materials for preparing the hydrogel, gelatin, THB and FeSO4·7H2O and H2O2The aqueous solutions were all purchased reagents.
Wherein the gelatin is from Sigma-Aldrich company (specification: Type A, from pollen skin); THB was obtained from Tianjin Xiansi Biotechnology Ltd (purity 97%); FeSO4·7H2O is from Shanghai Aladdin Biotechnology Ltd (analytical pure), and the hydrogen peroxide solution (hydrogen peroxide) is from Shanghai Meclin Biotechnology Ltd (30 wt.% in H)2O)。
Acrylated Cyclodextrins (ACD) were prepared in the laboratory. Preparation method reference "mechanical resin, Injectable, and Bioadhesive macromolecular Gelatin Hydrogels cross linked by Weak Host-Guest Interactions and In Situ Tissue Regeneration" is specifically made as follows:
adding 10g of beta-cyclodextrin, 130mL of DMF and 7mL of triethylamine into a 500mL round-bottom flask placed in an ice-water bath, stirring to completely dissolve the beta-cyclodextrin, then slowly dropwise adding a 20mL DMF solution of 5mL of acryloyl chloride dissolved in an isopiestic dropping funnel into the round-bottom flask under the environment of the ice-water bath, stirring, maintaining the low-temperature environment of the ice-water bath after the dropwise adding is completed, and continuing the reaction for 12 hours. And after the reaction is finished, carrying out suction filtration, taking filtrate, carrying out vacuum rotary evaporation at 60 ℃ until about 20mL of concentrated solution is remained, carrying out sedimentation on the concentrated solution by using 600mL of acetone, and finally carrying out suction filtration and drying to obtain white powder, namely the Acryloyl Cyclodextrin (ACD).
Example 1
Preparing Gel with gelatin, THB, ACD content of 20 wt%, 0.1mol/L, 10 wt% respectively (Gel-THB-ACD-20-0.1-10).
0.2g of gelatin is weighed by an electronic balance into a 4mL centrifuge tube, 400 μ L of deionized water is accurately pipetted by a pipette gun and added, and then the centrifuge tube is placed at 60 ℃ to fully dissolve the gelatin to obtain a gelatin aqueous solution.
0.0556g of FeSO 4.7H 2O are weighed by an electronic balance to be dissolved in 1mL of deionized water, and the deionized water is swirled to be completely dissolved to prepare 0.2mol/L FeSO4The aqueous solution was set aside for use.
Accurately transferring 100 mu L of FeSO by using a liquid transfer gun4Adding the aqueous solution into the dissolved gelatin solution while the aqueous solution is hot, and performing vortex to uniformly disperse the aqueous solution to obtain a solution A.
Weighing 0.0154g THB and 0.1g ACD in a 4mL centrifuge tube by using an electronic balance, accurately transferring 200 μ L deionized water by using a pipette gun, adding the deionized water into the centrifuge tube, dissolving the deionized water by vortex, and transferring 3 μ L H by using the pipette gun2O2An aqueous solution (30 wt%) was added and vortexed to disperse the solution uniformly to obtain solution B.
Adding the obtained solution B into the above solution A, quickly vortexing to mix the two solutions, and standing at 37 deg.C for a period of time to obtain 1g Gel (Gel-THB-ACD-20-0.1-10) with a volume of 1 mL. Wherein, FeSO4The concentration in Gel (Gel-THB-ACD-20-0.1-10) is 20 mmol/L; the mass fraction of the gelatin in the Gel (Gel-THB-ACD-20-0.1-10) is 20 wt%; the concentration of 2,3, 4-trihydroxybenzaldehyde in Gel (Gel-THB-ACD-20-0.1-10) is 0.1 mol/L; the mass fraction of the acryloyl cyclodextrin in the Gel (Gel-THB-ACD-20-0.1-10) is 10 wt%.
Fe is added into gelatin solution while it is hot2+Adding and adding H rapidly2O2ACD and THB ofAdding the mixed solution to avoid Fe2+Is oxidized in advance.
Fenton's reagent consisting of H2O2And Fe2+The mechanism of action is that the two react to generate hydroxyl free radical and Fe3+The hydroxyl free radical can continuously initiate double bonds in the ACD to carry out free radical polymerization, so that an interpenetrating network is formed by the hydroxyl free radical and gelatin molecules; during the process of standing and gelling, aldehyde group in THB and amino group in gelatin can react with Schiff base, so as to form imine bond to modify pyrogallol structure of THB onto gelatin molecular chain, and Fe3+On one hand, the pyrogallol can be oxidized to promote covalent coupling, and on the other hand, the pyrogallol can be complexed with carboxyl in gelatin to form ionic crosslinking, so that the crosslinking and entanglement among molecular chains are promoted to form a gel network. The annular cavity structure in the cyclodextrin can perform host-guest interaction with benzene rings in gelatin and THB, so that the internal crosslinking density of the gel is increased, and the crosslinking network is more concentrated.
Example 2
Preparing Gel with gelatin content of 20 wt%, THB content of 0.1mol/L, and ACD content of 5 wt% (Gel-THB-ACD-20-0.1-5).
0.2g of gelatin is weighed by an electronic balance into a 4mL centrifuge tube, 400 μ L of deionized water is accurately pipetted by a pipette gun and added, and then the centrifuge tube is placed at 60 ℃ to fully dissolve the gelatin to obtain a gelatin aqueous solution.
0.0556g of FeSO 4.7H 2O are weighed by an electronic balance to be dissolved in 1mL of deionized water, and the deionized water is swirled to be completely dissolved to prepare 0.2mol/L FeSO4The aqueous solution was set aside for use.
Accurately transferring 100 mu L of FeSO by using a liquid transfer gun4Adding the aqueous solution into the dissolved gelatin solution while the aqueous solution is hot, and performing vortex to uniformly disperse the aqueous solution to obtain a solution A.
Weighing 0.0154g THB and 0.05g ACD in a 4mL centrifuge tube by using an electronic balance, accurately transferring 200 μ L deionized water by using a pipette gun, adding the deionized water into the centrifuge tube, dissolving the deionized water by vortex, and transferring 3 μ L H by using the pipette gun2O2An aqueous solution (30 wt%) was added and vortexed to disperse the solution uniformly to obtain solution B.
Adding the obtained solution B into the above solution A, quickly vortexing to mix the two solutions, and standing at 37 deg.C for a period of time to obtain Gel-THB-ACD-20-0.1-5.
Comparative example 1
A Gel (Gel-THB-20-0.1) was prepared in which the gelatin and THB contents were 20 wt% and 0.1mol/L, respectively.
0.2g of gelatin is weighed by an electronic balance into a 4mL centrifuge tube, 400 μ L of deionized water is accurately pipetted by a pipette gun and added, and then the centrifuge tube is placed at 60 ℃ to fully dissolve the gelatin to obtain a gelatin aqueous solution.
0.0556g of FeSO 4.7H 2O are weighed by an electronic balance to be dissolved in 1mL of deionized water, and the deionized water is swirled to be completely dissolved to prepare 0.2mol/L FeSO4The aqueous solution was set aside for use.
Accurately transferring 100 mu L of FeSO by using a liquid transfer gun4Adding the aqueous solution into the dissolved gelatin solution while the aqueous solution is hot, and performing vortex to uniformly disperse the aqueous solution to obtain a solution A.
Weighing 0.0154g THB in 4mL centrifuge tube with electronic balance, accurately transferring 200 μ L deionized water with pipette gun, adding into the centrifuge tube, vortex to dissolve, transferring 3 μ L H with pipette gun2O2An aqueous solution (30 wt%) was added and vortexed to disperse the solution uniformly to obtain solution B.
Adding the obtained solution B into the above solution A, quickly vortexing to mix the two solutions, and standing at 37 deg.C for a period of time to obtain Gel-THB-20-0.1.
Example 3
This example describes the properties of examples 1 and 2 and comparative example 1.
FIG. 1 is a time-course rheological scan of a Gel (Gel-THB-ACD-20-0.1-10) of example 1, in which Fenton's reagent H2O2And Fe2+Both 20mM, characterized for gel formation time and gel strength, and determined by testing conditions at a frequency of 1Hz, strain 1%, and temperature 37 ℃. Mixing gelatin with Fe2+Solution and addition of H2O2After the THB and ACD solutions are mixed, rheological time scanning is carried out immediately, and test results show that the gel forming time of the component gel is about 3min, and the G' number is increased along with the increase of the curing timeThe value increases, i.e. the gel strength increases, and the change in gel strength within 1h does not tend to be smooth, but still tends to increase.
After the mixed solution is quickly swirled to be uniformly mixed, the mixed solution is coated on the surfaces of various substrates in a viscous fluid state before gelation, and the in-situ cured hydrogel material can be adhered to the surfaces of the substrates through molecular penetration and various physical and chemical interactions (such as covalent coupling, hydrogen bonds, metal ion coordination and the like) related to the pyrogallol unit. The surfaces of two substrates were adhered together by the hydrogel adhesive and their adhesive strength was determined using a lap shear adhesion test.
The adhesive strength of the gel to various matrix materials is characterized by adopting a lap shear adhesion test, and the specific operation steps are as follows, about 200 mu L of viscous precursor solution which is not completely gelled is uniformly coated on the surface of a sheet-shaped substrate (the specification of the matrix material is 70 multiplied by 20 multiplied by 2mm), then another same substrate (the lap area is about 15 multiplied by 20mm) is immediately overlapped in a staggered way, the gel is more fit in the middle of the substrate by slight pressing, and then the overlapped adhesive sample is hermetically placed in a 37 ℃ thermostat for 2 h. The tensile rate is fixed at 50mm min < -1 > by adopting a universal tensile testing machine, and the Adhesive Strength (AS) is calculated according to F/S, wherein F is the maximum load (N) of the lapped sample during stretching, and S is the lapping area (m 2).
FIG. 2 shows the adhesion strength of gels with different ACD contents to different matrix materials (PMMA, glass, pigskin), wherein the gelatin and THB contents were determined to be 20 wt% and 0.1M unchanged, respectively. The test result shows that in the test range, the adhesive strength of the gel to various base materials is gradually increased along with the increase of the content of ACD, mainly because the content of ACD is increased, the crosslinking density of molecular chains is increased, the crosslinking network in the gel is more concentrated, the strength of the gel body is increased, and the adhesive strength of the reflected gel is increased.
The gelatin-based hydrogels of the present invention were prepared according to the present disclosure with process parameter adjustments and exhibited substantially the same properties as example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (12)
1. A method of preparing a gelatin-based hydrogel adhesive initiated by fenton's reagent, comprising the steps of:
step 1: separately preparing FeCl2Or FeSO4Aqueous solutions and aqueous gelatin solutions;
step 2: subjecting the FeCl2Or FeSO4Adding the aqueous solution into gelatin aqueous solution heated to 55-65 ℃, and fully dissolving to obtain solution A;
and step 3: preparing mixed aqueous solution of 2,3, 4-trihydroxy benzaldehyde and acryloyl cyclodextrin, and adding H2O2Mixing the aqueous solution evenly to obtain solution B;
and 4, step 4: and adding the solution B into the solution A, fully and uniformly mixing, and standing to form gel to obtain the gelatin-based hydrogel adhesive.
2. The method of claim 1, wherein in step 1, the FeCl is2Aqueous solution or FeSO4The concentration of the aqueous solution is 0.2-0.3 mol/L; the mass ratio of the gelatin in the gelatin water solution to the volume of the water is (0.1-0.2): 400.
3. the method of claim 2, wherein the FeCl is prepared2Aqueous solution or FeSO4The concentration of the aqueous solution was 0.2 mol/L.
4. The method of claim 2, wherein in step 2, the FeCl is2Aqueous solution or FeSO4The ratio of the volume of the aqueous solution to the volume of water in the aqueous gelatin solution is 1: 4.
5. the method according to claim 4, wherein in step 3, the reaction is carried out in the presence of a catalystThe mass ratio of the 2,3, 4-trihydroxybenzaldehyde to the acryloyl cyclodextrin to the deionized water in the mixed aqueous solution is (1.54-30.8): (10-100): 200, preferably 15.4: (50-100): 200 of a carrier; said H2O2The concentration of the aqueous solution was 30 wt%, said H2O2The volume ratio of the aqueous solution to the mixed aqueous solution is 3: 300.
6. the method according to claim 5, wherein the mass ratio of 2,3, 4-trihydroxybenzaldehyde, acrylated cyclodextrin and deionized water in the mixed aqueous solution is 15.4: (50-100): 200.
7. the method according to claim 5, wherein in step 4, the volume ratio of the solution B to the solution A is 3: 7.
8. the method of claim 1, wherein in step 3, the temperature for standing to form gel is 30-40 ℃, preferably 37 ℃; the standing and gelling time is 3-5 min.
9. The method of claim 8, wherein the temperature of said gel on standing is 37 ℃.
10. A gelatin-based hydrogel adhesive prepared by the preparation method of any one of claims 1 to 9.
11. The gelatin-based hydrogel adhesive of claim 10 having an adhesive strength of 20 to 140KPa when the concentration of 2,3, 4-trihydroxybenzaldehyde is 0.1 mol/L.
12. The gelatin-based hydrogel adhesive of claim 10 wherein the adhesive strength of the gelatin-based hydrogel adhesive increases with increasing concentration of acrylated cyclodextrin.
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| CN105582572A (en) * | 2016-02-18 | 2016-05-18 | 深圳市第二人民医院 | Injectable cartilage repair supramolecular hydrogel and preparation method thereof |
| CN108641622A (en) * | 2018-04-25 | 2018-10-12 | 安徽盛美金属科技有限公司 | A kind of starch-base adhesive and preparation method thereof |
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| CN109206634A (en) * | 2017-06-30 | 2019-01-15 | 天津大学 | Gelatin-based high intensity hydrogel and preparation method thereof |
| CN108641622A (en) * | 2018-04-25 | 2018-10-12 | 安徽盛美金属科技有限公司 | A kind of starch-base adhesive and preparation method thereof |
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