CN112745515A - Silver-loaded tannin polyphenol crosslinked polyvinyl alcohol antibacterial hydrogel and preparation method thereof - Google Patents
Silver-loaded tannin polyphenol crosslinked polyvinyl alcohol antibacterial hydrogel and preparation method thereof Download PDFInfo
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- CN112745515A CN112745515A CN202110060557.4A CN202110060557A CN112745515A CN 112745515 A CN112745515 A CN 112745515A CN 202110060557 A CN202110060557 A CN 202110060557A CN 112745515 A CN112745515 A CN 112745515A
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- 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
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention discloses a silver-loaded tannin polyphenol crosslinked polyvinyl alcohol antibacterial hydrogel and a preparation method thereof, belonging to the fields of biomedical materials and polymer chemistry. The hydrogel is prepared from the following materials: the antibacterial hydrogel with high mechanical strength is prepared from tannin polyphenol, silver nitrate, polyvinyl alcohol and the balance of deionized water by a ball milling and freezing thawing method. The characterization result shows that the hydrogel has higher water content, mechanical strength and high-dispersion silver nanoparticles. The method has the advantages that the tannin polyphenol is adopted in the hydrogel system to reduce the metallic silver in situ, so that the introduction of other reducing agents is avoided, and in addition, the mechanical ball milling method adopted in the preparation process is simpler to operate and is green and environment-friendly.
Description
Technical Field
The invention relates to a silver-loaded tannin polyphenol cross-linked polyvinyl alcohol antibacterial hydrogel and a preparation method thereof, belonging to the fields of biomedical materials and polymer chemistry.
Background
The polyvinyl alcohol hydrogel is a water-soluble polymer material commonly used in medicine, and is widely applied to the biomedical fields of wound dressings, artificial organ tissues, drug sustained-release carriers and the like due to the characteristics of low toxicity, high elastic modulus, high mechanical strength, high water absorption, good biocompatibility and the like. In recent years, in order to enrich the application range of polyvinyl alcohol hydrogel materials, many researchers have focused on the functional modification of hydrogels. For example, the mechanical strength and water absorption properties of PVA hydrogels have been altered by the introduction of some natural organic macromolecules; the doped nano particles change the anti-fouling performance, the antibacterial performance and the like of the polyvinyl alcohol hydrogel. However, the preparation process of the existing functional hydrogel is complicated, and the hydrogel doped with nanoparticles often needs to use an additional reducing agent.
The plant polyphenol is a secondary metabolite which is widely existed in plants and has a polyphenol structure, and the rich phenolic hydroxyl groups of the plant polyphenol lead the plant polyphenol to have stronger capacity of capturing active oxygen and oxidation resistance; the plurality of ortho-position phenolic hydroxyl groups can generate complex reaction with metal ions to form stable five-membered ring chelate, and in addition, the phenolic hydroxyl groups can be reduced from a high valence state to a low valence state metal nano particle while being complexed with the metal ions. Theoretically, plant polyphenol has great application potential in the field of biomedical materials, but the green biomedical materials based on the plant polyphenol which are reported at present are rare, and particularly, the polyphenol-based hydrogel with specific functions is rare.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing silver-loaded tannin polyphenol crosslinked polyvinyl alcohol antibacterial hydrogel, which is simple in process, simple and convenient to operate and environment-friendly.
Specifically, the invention firstly provides a preparation method of the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel, which comprises the following steps:
(1) ball milling and mixing the tannin polyphenol and silver nitrate to obtain a gray silver-loaded polyphenol hybrid;
(2) continuously ball-milling and mixing the silver-loaded polyphenol hybrid obtained in the step (1), polyvinyl alcohol and water to form a gel product preliminarily;
(3) and (3) placing the gel product obtained in the step (2) into a cold trap at the temperature of-77 to-10 ℃, and repeatedly freezing and unfreezing to obtain the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel.
In one embodiment of the present invention, the tannin polyphenol in step (1) is one or more of tannic acid, ellagic acid, and catechin.
In one embodiment of the invention, the mass ratio of the tannin polyphenol to the silver nitrate in the step (1) is 10: 1-50: 1.
In one embodiment of the invention, the oscillation frequency of the ball mill in the step (1) is 20-40HZ for 10-30 min.
In one embodiment of the present invention, the water in step (2) is preferably deionized water.
In one embodiment of the invention, the mass ratio of the polyvinyl alcohol to the tannin polyphenol in the step (2) is 1: 1-3: 1, the mass ratio of the water to the polyvinyl alcohol is 10-40: 1, the ball milling is continued for 10-30min, and the oscillation frequency is 20-40 HZ.
In one embodiment of the invention, the freezing time of the cold trap in the step (3) is 8-14 hours, and then the cold trap is thawed at 20-30 ℃, and the steps are repeated for 4-8 times.
The invention provides the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel prepared by the preparation method.
The invention provides a biomedical material containing the silver-loaded tannin polyphenol cross-linked polyvinyl alcohol hydrogel.
In one embodiment of the invention, the biomedical material comprises a wound dressing, an artificial organ tissue, a drug sustained release carrier, and the like.
The invention also provides the preparation method and application of the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel in the field of biomedicine.
The invention has the beneficial effects that:
(1) the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol antibacterial hydrogel adopts tannin polyphenol as a raw material, so that gold and silver ions can be stabilized and reduced in situ to be silver nanoparticles, and can be crosslinked with polyvinyl alcohol through hydrogen bonds, so that the introduction of an additional reducing agent and a crosslinking agent is avoided, and a hydrogel system is more environment-friendly and nontoxic;
(2) the preparation method is simple, has short preparation time and can be used for mass production;
(3) the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol antibacterial hydrogel has good water absorption rate and mechanical strength, and adjustable performance, and can be used as a medical wound dressing.
Drawings
FIG. 1A schematic representation of the structure of the silver-loaded tannin hybrid in example 1.
FIG. 2 sample of silver-loaded tannin crosslinked polyvinyl alcohol antimicrobial hydrogel of example 1 (left panel) and polyvinyl alcohol hydrogel without silver-loaded tannin addition (right panel).
FIG. 3X-ray diffraction (XRD) pattern of hydrogel of example 1.
FIG. 4 Fourier-Red (FT-IR) outer plot of the hydrogel of example 1.
FIG. 5 is measurement data of tensile strength and elongation at break of the hydrogels of example 1 and example 2.
FIG. 6 is a sample graph of the silver-loaded tannic acid crosslinked polyvinyl alcohol antimicrobial hydrogel of example 2.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Adding 1g of tannic acid and 0.05g of silver nitrate into a 50mL stainless steel ball milling tank, carrying out ball milling and mixing for 10min to obtain a gray silver-loaded polyphenol hybrid, adding 2g of polyvinyl alcohol and 20mL of deionized water, continuing ball milling for 10min, placing the obtained gel-like product into a cold trap at-25 ℃, freezing for 12 h, unfreezing at room temperature, and repeatedly freezing and unfreezing for 5 times in such a way to finally obtain the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel. The time for preparing the silver-loaded hydrogel by the conventional solution method is usually more than 10 hours, and the coordination and reduction time between silver and polyphenol is accelerated by adopting a ball milling method, so that the preparation time of the silver-loaded hydrogel is greatly accelerated.
Fig. 1 is a schematic structural diagram of the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel prepared in this example, and due to the specific composition structure of tannic acid, silver nanoparticles formed by reducing silver ions with phenolic hydroxyl groups can be highly dispersed in an organic framework material through coordination. FIG. 2 is a graph of a sample hydrogel showing that the silver-loaded tannic acid crosslinked polyvinyl alcohol antimicrobial hydrogel appears light gray (left panel), while the polyvinyl alcohol hydrogel without the addition of silver-loaded tannic acid appears white (right panel).
An XRD diffraction pattern of the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel is shown in figure 3, and obvious diffraction peaks (38 degrees, 44 degrees, 64 degrees, 78 degrees and 81 degrees) of silver nanoparticles can be seen, so that the tannic acid successfully reduces silver ions into zero-valent silver particles in situ.
The FT-IR spectrum of the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel is shown in FIG. 4, and is 3300cm-1Nearby appears very strongHydroxyl group stretching vibration peaks indicate that the hydrogel contains abundant hydroxyl groups, which is also a main reason for high water content of the hydrogel.
The tensile strength and the elongation at break of the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel are shown in figure 5, and the tensile strength and the elongation at break respectively reach 0.9MPa and 700 percent, which shows that the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel has good mechanical strength and elasticity.
Example 2
Adding 1g of tannic acid and 0.05g of silver nitrate into a 50mL stainless steel ball milling tank, carrying out ball milling and mixing for 30min to obtain a gray silver-loaded polyphenol hybrid, adding 1g of polyvinyl alcohol and 20mL of deionized water, continuing ball milling for 30min, placing the obtained gel-like product into a cold trap at-25 ℃, freezing for 12 h, unfreezing at room temperature, and repeatedly freezing and unfreezing for 5 times in such a way to finally obtain the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel. Fig. 6 is a photograph of the resulting sample.
As can be seen in FIG. 5, when the ratio of silver-loaded tannic acid to polyvinyl alcohol was increased, the resulting hydrogel still had good elasticity and mechanical strength.
Example 3
Adding 1g of ellagic acid and 0.05g of silver nitrate into a 50mL stainless steel ball milling tank, carrying out ball milling and mixing for 30min to obtain a gray silver-loaded polyphenol hybrid, adding 2g of polyvinyl alcohol and 20mL of deionized water, continuing ball milling for 30min, placing the obtained gelatinous product into a cold trap at-25 ℃, freezing for 12 h, unfreezing at room temperature, and repeatedly freezing and unfreezing for 5 times in such a way to finally obtain the silver-loaded ellagic acid crosslinked polyvinyl alcohol antibacterial hydrogel.
Comparative example 1
Adding 1g of tannic acid and 0.05g of silver nitrate into a 50mL round-bottom flask, reacting for at least 20h in a water-bath stirring reactor at 70 ℃ until the color of the solution becomes gray, adding 2g of polyvinyl alcohol and 20mL of deionized water, continuing stirring for 6h, placing the obtained gelatinous product into a cold trap at-25 ℃ for freezing for 12 h, unfreezing at room temperature, and repeatedly freezing and unfreezing for 5 times in such a way to finally obtain the silver-loaded tannic acid crosslinked polyvinyl alcohol antibacterial hydrogel. Therefore, the early-stage tannin and silver coordination of the silver-loaded hydrogel prepared by the hydrothermal method needs heating and takes a long time.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel is characterized by comprising the following steps:
(1) ball milling and mixing the tannin polyphenol and silver nitrate to obtain a gray silver-loaded polyphenol hybrid;
(2) continuously ball-milling and mixing the silver-loaded polyphenol hybrid obtained in the step (1), polyvinyl alcohol and water to form a gel product preliminarily;
(3) and (3) placing the gel product obtained in the step (2) into a cold trap at the temperature of-77 to-10 ℃, and repeatedly freezing and unfreezing to obtain the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel.
2. The method for preparing the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel according to claim 1, wherein the tannin polyphenol in the step (1) is one or more of tannic acid, ellagic acid and catechin.
3. The preparation method of the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel according to claim 2, wherein the tannin polyphenol and silver nitrate in the step (1) are in a mass ratio of 10: 1-50: 1.
4. The method for preparing the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel as claimed in claim 1, wherein the oscillation frequency of the ball milling in the step (1) is 20-40HZ and 10-30 min.
5. The method for preparing the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel according to any one of claims 1 to 4, wherein the mass ratio of the polyvinyl alcohol to the tannin polyphenol in the step (2) is 1:1 to 3:1, the mass ratio of the water to the polyvinyl alcohol is 10 to 40:1, the ball milling is continued for 10 to 30min, and the oscillation frequency is 20 to 40 HZ.
6. The method for preparing the silver-loaded tannin polyphenol crosslinked polyvinyl alcohol hydrogel as claimed in any one of claims 1 to 5, wherein the freezing time of the cold trap in the step (3) is 8 to 14 hours, and then the cold trap is thawed at 20 to 30 ℃, and the steps are repeated for 4 to 8 times.
7. The silver-loaded tannin polyphenol cross-linked polyvinyl alcohol hydrogel prepared by the preparation method of the silver-loaded tannin polyphenol cross-linked polyvinyl alcohol hydrogel according to any one of claims 1 to 6.
8. A biomedical material comprising the silver-loaded tannin polyphenol cross-linked polyvinyl alcohol hydrogel of claim 7.
9. The biomedical material according to claim 8, characterized in that it comprises wound dressing, artificial organ tissue, drug slow release carrier.
10. The method for preparing the silver-loaded tannin polyphenol cross-linked polyvinyl alcohol hydrogel as claimed in any one of claims 1 to 6 or the application of the silver-loaded tannin polyphenol cross-linked polyvinyl alcohol hydrogel as claimed in claim 7 in the biomedical field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214508A (en) * | 2021-05-29 | 2021-08-06 | 山东大学 | Natural antibacterial gel for skin repair and preparation method thereof |
| CN114344558A (en) * | 2022-01-20 | 2022-04-15 | 哈尔滨工业大学重庆研究院 | Cannabidiol-tannin-polyvinyl alcohol hydrogel wound dressing and preparation method thereof |
| CN114515267A (en) * | 2022-01-24 | 2022-05-20 | 武汉理工大学 | Polymer soluble microneedle patch and preparation method thereof |
| CN115501173A (en) * | 2022-08-31 | 2022-12-23 | 四川大学 | Multistage-pore hydrogel drug sustained release system based on natural polyphenol and preparation method thereof |
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| CN110117369A (en) * | 2019-05-16 | 2019-08-13 | 吉林大学 | A kind of conductive hydrogel and its preparation method and application of antibacterial adherency |
| CN111518290A (en) * | 2020-06-28 | 2020-08-11 | 河南省科学院同位素研究所有限责任公司 | High-transparency high-toughness antibacterial polyvinyl alcohol hydrogel and preparation method thereof |
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- 2021-01-18 CN CN202110060557.4A patent/CN112745515B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150313912A1 (en) * | 2013-05-02 | 2015-11-05 | Medical Technology Research Inc | Antimicrobial compositions and methods of making the same |
| CN110117369A (en) * | 2019-05-16 | 2019-08-13 | 吉林大学 | A kind of conductive hydrogel and its preparation method and application of antibacterial adherency |
| CN111518290A (en) * | 2020-06-28 | 2020-08-11 | 河南省科学院同位素研究所有限责任公司 | High-transparency high-toughness antibacterial polyvinyl alcohol hydrogel and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214508A (en) * | 2021-05-29 | 2021-08-06 | 山东大学 | Natural antibacterial gel for skin repair and preparation method thereof |
| CN113214508B (en) * | 2021-05-29 | 2022-06-10 | 山东大学 | Natural antibacterial gel for skin repair and preparation method thereof |
| CN114344558A (en) * | 2022-01-20 | 2022-04-15 | 哈尔滨工业大学重庆研究院 | Cannabidiol-tannin-polyvinyl alcohol hydrogel wound dressing and preparation method thereof |
| CN114515267A (en) * | 2022-01-24 | 2022-05-20 | 武汉理工大学 | Polymer soluble microneedle patch and preparation method thereof |
| CN115501173A (en) * | 2022-08-31 | 2022-12-23 | 四川大学 | Multistage-pore hydrogel drug sustained release system based on natural polyphenol and preparation method thereof |
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