CN112062946A - Boric acid ester bond-based double-crosslinked self-repairing hydrogel and preparation method and application thereof - Google Patents
Boric acid ester bond-based double-crosslinked self-repairing hydrogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of biomedical high-molecular polymer materials, and discloses a boric acid ester bond-based double-crosslinked self-repairing hydrogel and a preparation method and application thereof. The gel has a structure shown as the following formula I, R1Is double-bond terminated four-arm polyethylene glycol acrylate PEG-QA, and double-bond terminated linear polyethylene glycol propyleneAcid ester PEG-DA, double bond terminated linear polycaprolactone acrylate PCL-DA or a mixture of double bond terminated linear polycaprolactone acrylate PCL-DA and double bond terminated linear polyethylene glycol acrylate PEG-DA. The hydrogel has certain self-healing capacity, can repair the cut surface to a certain extent in a short time (5 minutes), and provides a valuable preparation technology in the field of biological medicine in the future.
Description
Technical Field
The invention belongs to the technical field of biomedical high-molecular polymer materials, and particularly relates to a boric acid ester bond-based double-crosslinked self-repairing hydrogel and a preparation method and application thereof.
Background
Self-healing is a property originated from biology, and has self-healing capability and regeneration capability after being damaged by the outside world. In recent years, self-repairing materials are widely applied to the fields of aerospace, military industry, bridges, houses, biomedical engineering and the like. The intelligent self-repairing hydrogel is a system consisting of a three-dimensional network structure formed by crosslinking and polymerizing macromolecules and water, is very similar to biological tissues, can restore the structure and certain functions after being damaged by force, has the characteristic of self-repairing damage, has more advantages than common hydrogel in medical application, and is an intelligent gel material with great development potential in recent years.
At present, scientists construct self-healing gel mainly through two acting forces of supermolecule interaction and dynamic covalent bond. The stability and the mechanical property of the self-repairing gel constructed by dynamic covalent bonds such as hydrogen bonds, borate bonds, Diels-Alder reactions, acylhydrazone bonds, disulfide bonds and the like are superior to those of the gel formed by supermolecular acting force; meanwhile, due to the dynamic property of the dynamic covalent bond, the formed gel material has corresponding intelligent responsiveness, and attracts the attention of scientists.
The dynamic borate bond is used as a reversible chemical bond commonly used for constructing the chemical crosslinking self-healing hydrogel, the self-healing hydrogel based on the dynamic covalent borate bond has higher self-healing capability, the self-healing condition is mild, external stimulation is not needed, and the self-healing hydrogel has stimulation responsiveness to pH and saccharides and can be widely used in the fields of detectors, medicine carrying and the like. CN201810190965.X discloses a bio-based self-repairing gel based on a boric acid ester bond and a preparation method thereof, wherein the bio-based self-repairing gel is obtained through the electrostatic action of reversible ester bonds and positive and negative charges formed between phenylboronic acid and guar gum. CN201810678108.4 discloses a preparation method of a boric acid ester bond-containing dynamic covalent cross-linking agent and self-repairing hydrogel thereof, and the gel with super-long tensile property and rapid self-repairing property is obtained. However, the currently reported borate self-repairing hydrogel has more synthesis steps and more complex preparation process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a double-crosslinking self-repairing hydrogel based on a borate bond; the raw materials of the invention are safe, cheap and easily available, the preparation method is simple, the gelling condition is mild, and the invention has better application value.
The invention also aims to provide a preparation method of the borate bond-based double-crosslinked self-repairing hydrogel.
The invention further aims to provide application of the borate bond-based double-crosslinked self-repairing hydrogel.
The purpose of the invention is realized by the following scheme:
a borate ester bond based double-crosslinked self-repairing hydrogel has a structure shown as the following formula:
R1the double-bond terminated four-arm polyethylene glycol acrylate PEG-QA, the double-bond terminated linear polyethylene glycol acrylate PEG-DA, the double-bond terminated linear polycaprolactone acrylate PCL-DA or a mixture of the double-bond terminated linear polycaprolactone acrylate PCL-DA and the double-bond terminated linear polyethylene glycol acrylate PEG-DA; in the mixture of the double-bond terminated linear polycaprolactone acrylate PCL-DA and the double-bond terminated linear polyethylene glycol acrylate PEG-DA, the molecular weights of the two are equal。
The preparation method of the borate ester bond-based double-crosslinked self-repairing hydrogel comprises the following operation steps: acrylate, dithiothreitol and a double-bond phenylboronic acid compound are mixed by a simple one-pot method and then subjected to two-stage ultraviolet curing operation to obtain the borate bond-based double-crosslinked self-repairing hydrogel.
The acrylate comprises double-bond terminated four-arm polyethylene glycol acrylate PEG-QA, double-bond terminated linear polyethylene glycol acrylate PEG-DA, double-bond terminated linear polycaprolactone acrylate PCL-DA, or a mixture of double-bond terminated linear polyethylene glycol acrylate PEG-DA and double-bond terminated linear polycaprolactone acrylate PCL-DA; in the mixture of the double-bond terminated linear polyethylene glycol acrylate PEG-DA and the double-bond terminated linear polycaprolactone acrylate PCL-DA, the molecular weights of the two are equal.
The PEG-QA is prepared by firstly carrying out dehydration condensation reaction on pentaerythritol and ethylene glycol for polymerization and then carrying out acylation reaction on acryloyl chloride;
the PEG-DA is prepared by acylation reaction of polyethylene glycol and acryloyl chloride;
the PCL-DA is prepared by acylation reaction of polycaprolactone and acryloyl chloride.
The molecular weight of the polyethylene glycol is 1000-4000; the molecular weight of the polycaprolactone is 1000-4000.
The double bond-containing phenylboronic acid compound is phenylboronic acid containing terminal group double bonds, and specifically is 4-vinyl phenylboronic acid (VPBA).
When the acrylate is double-bond-terminated four-arm polyethylene glycol acrylate PEG-QA, the molar ratio of the acrylate to dithiothreitol to the double-bond-containing phenylboronic acid compound is 1:4: 4;
when the acrylate is double-bond-terminated linear polyethylene glycol acrylate PEG-DA, the molar ratio of the acrylate to dithiothreitol to the double-bond-containing phenylboronic acid compound is 1:2: 2;
when the acrylate is double-bond terminated linear polycaprolactone acrylate PCL-DA, the molar ratio of the acrylate to dithiothreitol to the double-bond containing phenylboronic acid compound is 1:2: 2;
when the acrylate is a mixture of double-bond terminated linear polyethylene glycol acrylate PEG-DA and double-bond terminated linear polycaprolactone acrylate PCL-DA, the molar ratio of the double-bond terminated linear polyethylene glycol acrylate PEG-DA, the double-bond terminated linear polycaprolactone acrylate PCL-DA, dithiothreitol and the double-bond-containing phenylboronic acid compound is 1:1:4: 4.
In the ultraviolet curing operation, 400W ultraviolet light is adopted for 220 seconds in the first stage, 350W ultraviolet light is adopted for 105 seconds in the second stage, and the sum of curing time of the first stage and curing time of the second stage is controlled within 5-10 minutes.
The dithiothreitol is dissolved in PBS (phosphate buffer solution) with the pH value of 7-8 before use.
The boric acid ester bond-based double-crosslinked self-repairing hydrogel has potential value in the application of the biomedical field.
Compared with the prior art, the invention has the following advantages and effects:
the hydrogel is rapidly prepared by using cheap and easily-obtained materials, and the polyethylene glycol and polycaprolactone acrylate compound is a material widely applied to the fields of medicine, construction and high polymer, is cheap and easily-obtained and has better biocompatibility; the invention utilizes Michael addition reaction of sulfydryl and double bonds to introduce dithiothreitol and 4-vinylphenylboronic acid into polymer macromolecules, and then borate in a 4-vinylphenylboronic acid structure reacts with hydroxyl in a dithiothreitol structure to generate reversible borate bonds, thereby obtaining the double-crosslinking self-repairing hydrogel based on the borate bonds; the borate bond is a dynamic chemical bond and has a high forming speed, so that the hydrogel prepared by the reaction has self-repairing capability and a high gelling speed (can be self-repaired when being damaged by the outside so as to recover the original function and structure); the gel has self-repairability, injectability and excellent biocompatibility, and has wide application prospect in the field of biomedicine.
The self-repairing gel can realize self-repairing when the pH value is 7.4-8.6; when the gel cut into two halves is aligned with the section and spliced again, hydroxyl groups and borate ions on the two sections of the gel are recombined to form a borate bond, so that the repair of the section of the hydrogel is completed; when a section of the gel is wetted with a little deionized water, the equilibrium of exposed borate groups on the gel surface shifts to a dissociated state, so that more borate ions and hydroxyl groups are generated on the section, and the section of the gel can be repaired more quickly (5 minutes). (as in FIG. 1)
Drawings
FIG. 1 shows the self-healing principle of a double-crosslinking self-healing hydrogel based on borate bonds.
FIG. 2 is a diagram of the formation of hydrogel 1 of example 1, wherein (a) the solution is mixed; (b) irradiating the mixed solution by 400W ultraviolet light, and curing in the first stage (220 s); (c) the mixed solution was irradiated with 350W of UV light, cured in the second stage (105s), and the gel was formed.
FIG. 3 shows the nuclear magnetic hydrogen spectrum of hydrogel 1 of example 1, wherein (A) is a solution which is not cured by UV irradiation and (B) is a solution which is cured for 220 seconds by UV irradiation.
FIG. 4 is an IR spectrum of hydrogel 1 of example 1 wherein (A) is PEG2000-QA and (B) is an IR spectrum of a stimulus responsive gel based on borate bonds (after 1 h).
FIG. 5 is a self-healing performance test of the gel of example 5, wherein (a) is the prepared gel; (b) cutting the gel along the middle part; (c) two gel slices are rapidly contacted and compacted in alignment with the section, and are self-healed for 5 minutes at room temperature without external stimulation.
FIG. 6 is an abstracted spatial structure of the double-crosslinked self-repairing hydrogel obtained by the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The sources of reagents used in the following examples are all commercially available.
Example 1: preparation of double-crosslinking self-repairing hydrogel (PEG 2000-QA: VPBA: DTT ═ 1:4: 4) with precursor PEG2000-QA (double-bond end-capped four-arm polyethylene glycol acrylate prepared from polyethylene glycol with molecular weight of 2000)
(1) Preparing a PBS buffer solution: 74.10mg of sodium dihydrogen phosphate dihydrate (NaH) were weighed out using an analytical balance2PO4·2H2O) and 72.49mg of disodium hydrogen phosphate dodecahydrate (Na)2HPO4·12H2O), added to a 100mL beaker, and then deionized water was added to the beaker and mixed well to make 50mL of PBS buffer.
(2) Preparing NaOH aqueous solution: 40.00mg of sodium hydroxide (NaOH) was weighed using an analytical balance and added to a 200mL beaker, and then deionized water was added to the beaker to prepare 100mL of an aqueous NaOH solution.
(3) Preparing a hydrogel: 70.46mg of 4-vinylphenylboronic acid (VPBA), 249.98mg of tetraacrylate polyethylene glycol (PEG2000-QA) and 73.45mg of Dithiothreitol (DTT) were weighed using an analytical balance so that the molar ratio of the gel raw materials (PEG 2000-QA: VPBA: DTT) was 1:4: 4. dissolving DTT in a 1.5mL centrifuge tube by using 50 mu L of PBS buffer solution to prepare a DTT solution, mixing PEG2000-QA and VPBA in a 5mL small beaker, uniformly mixing by using a capillary tube, adding the prepared DTT solution into the mixed PEG2000-QA and VPBA, carrying out light-shielding treatment on the beaker by using tinfoil paper in advance, uniformly mixing by using the capillary tube, and then carrying out ultraviolet light curing on the mixed solution, wherein 400W ultraviolet light is adopted for 220 seconds in the first stage, 350W ultraviolet light is adopted for 105 seconds in the second stage, and the sum of the curing time of the first stage and the curing time of the second stage is controlled within 5-10 minutes. The phenomenon of the solution after each exposure to ultraviolet light was recorded. After two stages of uv irradiation, hydrogel 1 was obtained. The synthesis reaction is shown in formula (1), and the spatial structure is shown in FIG. 6. The observation in fig. 2 shows that the mixture becomes more viscous and less fluid after the first stage of uv irradiation. After the second stage of curing, colorless and transparent hydrogel without fluidity is formed. The molecular structure and composition were analyzed by nuclear magnetic (fig. 3) and infrared (fig. 4), and the results showed that the reaction of the raw materials was relatively thorough and the product gelled well rapidly.
Example 2: the precursor is the preparation of double-crosslinking self-repairing hydrogel of PEG2000-DA (double-bond end-capped linear polyethylene glycol acrylate prepared from polyethylene glycol with molecular weight of 2000). (PEG 2000-DA: VPBA: DTT ═ 1:2: 2)
The hydrogel was prepared according to the method of example 1, except that PEG2000-QA was changed to PEG2000-DA, PEG 2000-DA: VPBA: the molar ratio of DTT is 1:2: 2.
example 3: the precursor is the preparation of double-crosslinking self-repairing hydrogel of PCL2000-DA (double-bond terminated linear polycaprolactone acrylate prepared from polycaprolactone with molecular weight of 2000). (PCL 2000-DA: VPBA: DTT ═ 1:2: 2)
A hydrogel was prepared according to the method of example 1, except that the four-arm PEG2000-QA was changed to PCL2000-DA, PCL 2000-DA: VPBA: DTT molar ratio 1:2: 2.
example 4: the precursor is the preparation of double-crosslinking self-repairing hydrogel of a blend of PEG2000-DA (double-bond terminated linear polyethylene glycol acrylate prepared from polyethylene glycol with molecular weight of 2000) and PCL2000-DA (double-bond terminated linear polycaprolactone acrylate prepared from polycaprolactone with molecular weight of 2000). (PEG 2000-DA: PCL 2000-DA: VPBA: DTT molar ratio is 1:1:4: 4)
A hydrogel was prepared according to the method of example 1, except that the four-arm PEG2000-QA was changed to a blend of PEG2000-DA and PCL2000-DA, PEG 2000-DA: PCL 2000-DA: VPBA: DTT molar ratio 1:1:4: 4.
example 5: self-healing performance test
The self-healing properties of the gel prepared in example 1 were macroscopically characterized by observation, the prepared gel was dried in a dryer together with a beaker, the gel was removed from the small beaker, cut through the middle of the hydrogel, and the two hydrogel sections were rapidly contacted and compressed, indicating that the gel sections were rapidly contacted and compressed in alignment with the section, and that the hydrogel section could have some repair after 5 minutes at room temperature without external stimulus (see fig. 5).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A boric acid ester bond-based double-crosslinked self-repairing hydrogel is characterized in that: the hydrogel has a structure shown as the following formula I:
R1the double-bond terminated four-arm polyethylene glycol acrylate PEG-QA, the double-bond terminated linear polyethylene glycol acrylate PEG-DA, the double-bond terminated linear polycaprolactone acrylate PCL-DA or a mixture of the double-bond terminated linear polycaprolactone acrylate PCL-DA and the double-bond terminated linear polyethylene glycol acrylate PEG-DA; in the mixture of the double-bond terminated linear polycaprolactone acrylate PCL-DA and the double-bond terminated linear polyethylene glycol acrylate PEG-DA, the molecular weights of the two are equal.
2. The preparation method of the borate ester bond-based double-crosslinked self-repairing hydrogel according to claim 1, characterized by comprising the following steps: acrylate, dithiothreitol and a double-bond phenylboronic acid compound are mixed by a simple one-pot method and then subjected to two-stage ultraviolet curing operation to obtain the borate bond-based double-crosslinked self-repairing hydrogel.
3. The method of claim 2, wherein: the acrylate comprises double-bond terminated four-arm polyethylene glycol acrylate PEG-QA, double-bond terminated linear polyethylene glycol acrylate PEG-DA, double-bond terminated linear polycaprolactone acrylate PCL-DA, or a mixture of double-bond terminated linear polyethylene glycol acrylate PEG-DA and double-bond terminated linear polycaprolactone acrylate PCL-DA; in the mixture of the double-bond terminated linear polyethylene glycol acrylate PEG-DA and the double-bond terminated linear polycaprolactone acrylate PCL-DA, the molecular weights of the two are equal.
4. The production method according to claim 3, characterized in that: the PEG-QA is prepared by firstly carrying out polymerization on pentaerythritol and polyethylene glycol through dehydration condensation reaction and then carrying out acylation reaction on acryloyl chloride;
the PEG-DA is prepared by acylation reaction of polyethylene glycol and acryloyl chloride;
the PCL-DA is prepared by acylation reaction of polycaprolactone and acryloyl chloride.
5. The method of claim 4, wherein: the molecular weight of the polyethylene glycol is 1000-4000; the molecular weight of the polycaprolactone is 1000-4000.
6. The method of claim 2, wherein: the double-bond phenylboronic acid compound is phenylboronic acid containing terminal group double bonds, and specifically is 4-vinyl phenylboronic acid.
7. The method of claim 2, wherein:
when the acrylate is double-bond-terminated four-arm polyethylene glycol acrylate PEG-QA, the molar ratio of the acrylate to dithiothreitol to the double-bond-containing phenylboronic acid compound is 1:4: 4;
when the acrylate is double-bond-terminated linear polyethylene glycol acrylate PEG-DA, the molar ratio of the acrylate to dithiothreitol to the double-bond-containing phenylboronic acid compound is 1:2: 2;
when the acrylate is double-bond terminated linear polycaprolactone acrylate PCL-DA, the molar ratio of the acrylate to dithiothreitol to the double-bond containing phenylboronic acid compound is 1:2: 2;
when the acrylate is a mixture of double-bond terminated linear polyethylene glycol acrylate PEG-DA and double-bond terminated linear polycaprolactone acrylate PCL-DA, the molar ratio of the double-bond terminated linear polyethylene glycol acrylate PEG-DA, the double-bond terminated linear polycaprolactone acrylate PCL-DA, dithiothreitol and the double-bond-containing phenylboronic acid compound is 1:1:4: 4.
8. The method of claim 2, wherein: in the ultraviolet curing operation, 400W ultraviolet light is adopted for 220 seconds in the first stage, 350W ultraviolet light is adopted for 105 seconds in the second stage, and the sum of curing time of the first stage and curing time of the second stage is controlled within 5-10 minutes.
9. The method of claim 2, wherein: the dithiothreitol is dissolved in PBS (phosphate buffer solution) with the pH value of 7-8 before use.
10. The application of the borate ester bond-based double-crosslinked self-repairing hydrogel in the biomedical field according to claim 1.
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| CN114058359A (en) * | 2021-12-10 | 2022-02-18 | 中海石油(中国)有限公司湛江分公司 | Preparation method and application of efficient degradation gel system for drilling and plugging deep-water and ultra-deep-water fractured reservoir |
| CN115160630A (en) * | 2022-07-18 | 2022-10-11 | 浙江大学 | Method for preparing high-water-absorption porous material based on water-induced powder crosslinking, product and application thereof |
| CN115477741A (en) * | 2022-09-14 | 2022-12-16 | 浙江中医药大学 | Degradable polymer and preparation method and application thereof |
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| CN115477741A (en) * | 2022-09-14 | 2022-12-16 | 浙江中医药大学 | Degradable polymer and preparation method and application thereof |
| CN115477741B (en) * | 2022-09-14 | 2023-08-18 | 浙江中医药大学 | Degradable polymer and preparation method and application thereof |
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