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CN111840634A - Preparation method and application of grape seed extract hydrogel - Google Patents

Preparation method and application of grape seed extract hydrogel Download PDF

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Publication number
CN111840634A
CN111840634A CN202010815998.6A CN202010815998A CN111840634A CN 111840634 A CN111840634 A CN 111840634A CN 202010815998 A CN202010815998 A CN 202010815998A CN 111840634 A CN111840634 A CN 111840634A
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hydrogel
polymer
aqueous solution
grape seed
seed extract
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CN111840634B (en
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雒春辉
龚一铚
位宁
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North Minzu University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0023Polysaccharides
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    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
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    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0019Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0009Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
    • A61L26/0028Polypeptides; Proteins; Degradation products thereof
    • A61L26/0047Specific proteins or polypeptides not covered by groups A61L26/0033 - A61L26/0042
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    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
    • A61L26/0057Ingredients of undetermined constitution or reaction products thereof
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L26/00Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
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    • A61L26/008Hydrogels or hydrocolloids
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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Abstract

The invention belongs to the technical field of high polymer materials, and relates to a preparation method and application of grape seed extract hydrogel. The grape seed extract hydrogel is obtained by smearing nanometer glue on the surface of a hydrogel precursor; the hydrogel precursor is constructed by a polymer A aqueous solution and a polymer B aqueous solution by utilizing a phase separation micro-region and a hydrogen bond between the two polymers; the polymer A is one or a combination of water-soluble polymers with good biocompatibility and side chains containing hydrogen bonds for receptors, such as carboxymethyl cellulose, alginic acid, hyaluronic acid, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the polymer B is grape seed protein; the nano glue is formed by self-assembly of a polymer B aqueous solution and solid powder of the grape polyphenol by utilizing multiple hydrogen bonds between side chain hydroxyl groups of the grape polyphenol and GSP. The grape seed extract hydrogel has the characteristics of bacteriostasis, self-adhesion and easy stripping under temperature control, and can be applied to the field of chronic wound dressings.

Description

Preparation method and application of grape seed extract hydrogel
Technical Field
The invention belongs to the technical field of high polymer materials, relates to a green synthesis method and application of a hydrogel wound dressing, and particularly relates to a preparation method and application of grape seed extract hydrogel.
Background
The skin of a human body can cause wound when the skin is separated or damaged under the action of external force, and the wound healing comprises four processes of hemostasis, inflammatory reaction, granulation hyperplasia and tissue reconstruction. Whereas wound dressings are commonly used materials for dressing wounds. Traditional dressings such as gauze, bandage, band-aid and the like are generally composed of absorbent cotton or gauze and the like, but the dressings are weak in adhesive property, incapable of being attached to skin and lack in antibacterial property, risks of inducing wound inflammation exist, meanwhile, the mechanical property is weak, tissue discomfort is caused, materials are not degradable, the preparation process is not green enough, and the like, and the defects enable further application of the traditional dressings to be greatly limited. The ideal wound dressing should be cheap and easily available, and have the promoting functions of stopping bleeding, inhibiting bacteria, promoting collagen deposition and the like. The hydrogel has high water content and good histocompatibility, and can maintain a moist environment which is beneficial to wound healing, so that the hydrogel gradually becomes an ideal wound dressing. Currently, the research of wound dressings in the cross-fusion field of polymer science, life science, biomedical engineering and the like is an important strategic direction of the nation.
However, the existing hydrogel products have technical problems that cost, safety, bacteriostatic activity, reversible adhesion, mechanical properties and the like cannot be considered at the same time, and a novel hydrogel dressing product needs to be developed urgently.
The existing wound auxiliary materials constructed by adopting chitosan, honey and the like have safety and antibacterial activity, but when high-water-content hydrogel is contacted with a wound surface, the hydrogel cannot be adhered to the surface of the wound spontaneously due to the low adhesive energy of a water film. This makes the hydrogel inadequate for dressing irregular wounds or joint injuries. In addition, chronic wounds have a long healing period, require frequent dressing changes, and require that the dressing be easily peeled off without causing secondary damage.
A chinese patent (201910132836. X) discloses a method of preparing an antibacterial hydrogel type skin dressing. The hydrogel is prepared by blending polyvinyl alcohol, chitosan salt and a high-molecular quaternary ammonium salt antibacterial material in an aqueous solution, has a better inhibiting effect on staphylococcus aureus than erythromycin, but does not have an effect on skinHas adhesion effect. Chinese patent (201811426211.6) discloses a polydopamine-chitosan oligosaccharide composite antibacterial hydrogel wound dressing and a preparation method thereof. The hydrogel is formed by polymerizing dopamine, modified chitosan, 2- (dimethylamino) ethyl methacrylate and acrylic acid monomers under the action of a cross-linking agent N' N-methylene bisacrylamide and an initiator. Because dopamine is easy to be oxidized and protein side chain-NH in tissues2or-SH forms permanent chemical crosslinks, so the dressing cannot be peeled off the wound bed. In addition, the cross-linking agent (glutaraldehyde) and residual monomers used in the synthesis process affect the biocompatibility and safety of the material.
In summary, the main problems of the existing hydrogel dressing are that biocompatibility, mechanical property, antibacterial property and adhesion property cannot be considered at the same time.
In order to solve the problem, a green and environment-friendly method is adopted to construct hydrogel while a biocompatible material is used; improving the bonding energy of the hydrogel and the wound surface needs to solve the problem of interface drainage macroscopically and improve the external force dissipated for destroying the interface microscopically; and the mild stripping is realized on the basis, and the adhesive force between the hydrogel and the wound surface is required to be rapidly reduced under the induction of external pH, temperature or light. Therefore, new materials and new methods for constructing multifunctional hydrogel wound dressings are urgently needed to be found, reversible adhesion and proper mechanical properties with wound tissues are considered while safety and antibacterial activity are guaranteed, and new products are developed to fill the market blank.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a grape seed extract hydrogel and a preparation method thereof.
It is another object of the present invention to provide a use of the above hydrogel, which can be used as a wound dressing.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a grape seed extract hydrogel is characterized in that the hydrogel is obtained by smearing nanometer glue on the surface of a hydrogel precursor; the hydrogel precursor is constructed by a polymer A aqueous solution and a polymer B aqueous solution by utilizing a phase separation micro-region and a hydrogen bond between the two polymers; the polymer A is one or a combination of water-soluble polymers with good biocompatibility and side chains containing hydrogen bonds for receptors, such as carboxymethyl cellulose, alginic acid, hyaluronic acid, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the polymer B is Grape Seed Protein (GSP); GSP is an abbreviation for Grape Seed Protein; the nano glue is formed by self-assembly of a polymer B aqueous solution and solid powder of the grape polyphenol by utilizing multiple hydrogen bonds between side chain hydroxyl groups of the grape polyphenol and GSP.
A preparation method of grape seed extract hydrogel is characterized by comprising the following steps: the method comprises the following steps:
s01, taking 10-20 parts of the polymer A, dissolving in 80-90 parts of deionized water, and preparing a polymer A water solution; the polymer A is a water-soluble polymer with good biocompatibility and a side chain containing a hydrogen bond donor-acceptor, and comprises one or the combination of two or more of carboxymethyl cellulose, alginic acid, hyaluronic acid, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the side chain of the polymer A contains a large number of hydrogen bond donor acceptors such as carboxyl and hydroxyl, and the safety of the polymer A is approved by the U.S. food and drug administration to be used clinically.
S02, taking 2-10 parts of the polymer B, dissolving in 90-98 parts of deionized water, and preparing a polymer B water solution; the polymer B is Grape Seed Protein (GSP) and can be extracted by an extraction method disclosed in Chinese patent application CN 201810129805.4; and the functional groups such as amino, carboxyl, hydroxyl and the like contained in the GSP side chain and the polymer A form an interpenetrating network through intermolecular hydrogen bonds in an aqueous solution.
S03, mixing 10-20 parts of the aqueous solution of the polymer A and 1-5 parts of the aqueous solution of the polymer B, stirring at room temperature for 2-4 hours to be uniform, and pouring into a mold; and adjusting the pH value of the mixed solution to 3.8, inducing the GSP to generate micro-phase separation, and constructing hydrogel by utilizing a phase separation micro-region and a hydrogen bond between two polymers to obtain a hydrogel precursor.
S04, taking 5-10 g of the aqueous solution of the polymer B, heating to 70-90 ℃, adding 0.1-1 g of the solid powder of the grape polyphenol while stirring, and stirring for 2-6 hours to fully dissolve the grape polyphenol; and (3) placing the obtained solution at 4 ℃ for 12-36 h, and forming G-NPs molecular glue by utilizing self-assembly of multiple hydrogen bonds between side chain hydroxyl groups of the glucan polyphenol and GSP, wherein the molecular glue is 'nano glue'.
G-NPs are abbreviations for nano particles of grape seed extracted polymers, i.e., grape seed extract nanoparticles.
S05, taking out the hydrogel precursor obtained in the step S03 from the mold, smearing the G-NPs molecular glue obtained in the step S04 on the surface of the hydrogel, and soaking the surface of the hydrogel in the G-NPs aqueous solution to improve the adhesive capacity of the hydrogel and skin tissues to obtain the target hydrogel, wherein the target hydrogel is the grape seed extract hydrogel finally obtained in the invention.
And (4) raising the temperature of the target hydrogel with the surface soaked with the G-NPs aqueous solution obtained in the step (S05), and inducing the G-NPs molecular glue to change from an aggregate into a linear molecular chain so as to diffuse into a hydrogel network, so that the hydrogel can be easily peeled at a temperature close to the body temperature.
All materials in the preparation process have good biocompatibility, so that the obtained hydrogel is safe and non-toxic, and the effects of inhibiting bacteria and removing free radicals of the grape seed extract are effectively maintained. The existence of the nanometer glue endows the hydrogel with dynamic and reversible self-adhesion performance with the wound surface.
Further, in step S01, polymer a is carboxymethyl cellulose or polyvinylpyrrolidone.
Further, the preparation method of the grape seed extract hydrogel specifically comprises the following steps:
s01, taking 20 parts of the polymer A, dissolving the polymer A in 80 parts of deionized water, and preparing a polymer A water solution; the polymer a is carboxymethyl cellulose.
S02, taking 10 parts of the polymer B, dissolving in 90 parts of deionized water, and preparing a polymer B water solution; the polymer B is Grape Seed Protein (GSP), and can be extracted by the extraction method disclosed in Chinese patent application CN 201810129805.4.
S03, mixing 15 parts of the aqueous solution of the polymer A with 2 parts of the aqueous solution of the polymer B, stirring for 2 hours at room temperature to be uniform, and pouring into a mold; and adjusting the pH value of the mixed solution to 3.8, and standing for 3-5 days at room temperature to obtain a hydrogel precursor.
S04, taking 5-10 g of the aqueous solution of the polymer B, heating to 70-90 ℃, adding 0.1-1 g of the solid powder of the grape polyphenol while stirring, and stirring for 4 hours to fully dissolve the grape polyphenol; and (3) placing the obtained solution at 4 ℃ for 12-36 h to obtain the G-NPs molecular glue, wherein the molecular glue is 'nano glue'.
S05, taking out the hydrogel precursor obtained in the step S03 from the mold, smearing the G-NPs molecular glue obtained in the step S04 on the surface of the hydrogel, and soaking the surface of the hydrogel in the G-NPs aqueous solution to improve the adhesive capacity of the hydrogel and skin tissues to obtain the target hydrogel, wherein the target hydrogel is the grape seed extract hydrogel finally obtained in the invention.
Furthermore, the peel strength of the target hydrogel with the surface being soaked in the G-NPs aqueous solution at room temperature can reach 50J/m2(ii) a When the temperature is increased to 45 ℃, the peel strength can be reduced to 1J/m2
Furthermore, the target hydrogel with the surface impregnated with the G-NPs aqueous solution has an antibacterial effect, and has an obvious antibacterial effect on staphylococcus aureus.
The invention also provides application of the target hydrogel obtained by the method, namely the grape seed extract hydrogel, in preparation of wound dressings.
The target hydrogel prepared by the method has wider application field. Can be used in the field of biological medicine.
The invention selects cellulose, polyvinyl alcohol, alginic acid, hyaluronic acid and the like with good biocompatibility and degradability as the polymer A, and the molecular side chains of the raw materials contain a large amount of hydrogen bond donor receptors such as carboxyl, hydroxyl and the like. The extraction method of the polymer B grape seed extract (GSP) used in the invention is shown in Chinese patent CN 201810129805.4. GSP has biological properties of keeping moisture, resisting bacteria, resisting oxidation, resisting coagulation, promoting cell adhesion and proliferation, and has hydrophilicity and degradability. The GSP side chain contains rich amino, carboxyl, hydroxyl, sulfydryl and other functional groups, and the groups and the polymer A can form an interpenetrating network through intermolecular hydrogen bonds in an aqueous solution, so that the crosslinking point density of the hydrogel is effectively improved, and the mechanical property of the obtained hydrogel material can be ensured; in addition, G-NPs molecular glue is formed by utilizing self-assembly of multiple hydrogen bonds between side chain hydroxyl groups of the glucosylphenol and GSP, G-NPs aqueous solution nanometer glue is soaked on the surface of a hydrogel precursor, and the adhesion capacity of the hydrogel and tissues is improved.
The invention mainly utilizes the grape seeds which are the wastes of wine making or agriculture to synthesize the hydrogel. The grape seeds have wide sources and low price, have the functions of oxidation resistance, beauty treatment and the like, and also have biocompatibility and environmental friendliness. Functional active substances are extracted from the grape seeds to synthesize the hydrogel, so that the additional value of the grape seeds can be improved.
The invention has the beneficial effects that:
compared with the prior art, the invention has the following outstanding substantive characteristics and remarkable progress.
(1) Compared with the traditional polymer hydrogel dressing, the grape seed extract hydrogel finally obtained by the invention has good biocompatibility, antibacterial property and self-adhesion property, and can be firmly adhered to the surface of skin under the conditions of sweating and water; meanwhile, the temperature control stripping device has the characteristic of easy stripping.
(2) Compared with the existing water-soluble natural polymer material such as sodium alginate, cellulose, chitosan, agar and other compound hydrogel, the construction process of the hydrogel only adjusts the pH value and temperature of the solution, does not use organic solvents and other chemical assistants, is very mild, and further ensures the safety of the material.
(3) The hydrogel precursor, which was not surface-modified, did not adhere to the skin surface. The surface of the hydrogel precursor is modified by dipping G-NPs aqueous solution 'nano glue', so that the hydrogel precursor has the characteristics of strong adhesion and easy stripping under temperature control.
(4) The raw materials used by the method are all natural high molecular materials with good biocompatibility, and the biocompatibility of the materials is ensured. More importantly, the grape seed extract hydrogel finally obtained by the invention has the characteristics of bacteriostasis, self-adhesion and easy peeling under temperature control, and has important significance for improving the application of the hydrogel in the field of chronic wound dressings.
Drawings
FIG. 1 is a photograph showing a gel formation of a hydrogel precursor obtained in example 1 of the present invention.
FIG. 2 is an SEM photograph of a hydrogel precursor obtained in example 1 of the present invention.
FIG. 3 is a graph showing the change of the particle size of the nanoparticles obtained in example 2 of the present invention with temperature.
FIG. 4 is a graph showing the effect of adhesion of the objective hydrogel obtained in example 3 of the present invention.
FIG. 5 is a comparison graph of the bacteriostatic effect of the hydrogel precursor obtained in example 1 of the present invention and the target hydrogel obtained in example 3.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to the accompanying drawings, but the implementation of the present invention is not limited thereto.
Example 1:
preparation of hydrogel precursors
20 g of carboxymethyl cellulose powder was dissolved in 80 g of deionized water to prepare 100g of a 20 wt% aqueous polymer solution (a). 100g of a 10 wt% aqueous GSP solution (b) was prepared. At room temperature, 2 g of GSP aqueous solution is slowly added into 15 g of carboxymethyl cellulose aqueous solution, and the mixture is stirred for 2 hours to be fully mixed. The mixed solution was then injected into a mold and the solution pH was adjusted to around the GSP isoelectric point (pI = 3.8). Standing for 3-5 days at room temperature, and constructing the three-dimensional network hydrogel (c) by utilizing a hydrophobic micro-region formed by GSP micro-phase separation and a hydrogen bond synergistic effect between GSP and carboxymethyl cellulose to obtain a hydrogel precursor.
When the carboxymethyl cellulose aqueous solution (a) and the GSP aqueous solution (b) are inverted, the solutions naturally flow from the bottom to the bottle cap under the action of gravity. When both form the three-dimensional network hydrogel (c), the gel remains at the bottom even when the sample vial is inverted.
A gel-forming photograph of the hydrogel precursor obtained in example 1 of the present invention is shown in FIG. 1.
The internal morphology of the hydrogel precursor was observed by scanning electron microscopy. And fully washing the hydrogel precursor with water, freeze-drying in a freeze dryer, and spraying gold on the surface for SEM observation.
SEM picture of hydrogel precursor obtained from example 1 is shown in fig. 2. As can be seen from fig. 2, the hydrogel precursor exhibits a typical honeycomb structure.
Example 2:
preparation of nano glue
Taking 10.0 g of GSP water solution with mass fraction of 8 wt%, slowly adding 1.0 g of gluglucosone powder at 70 deg.C, stirring for 4 hr to mix thoroughly. And then, quickly placing the mixed solution in a refrigerator at 4 ℃, placing for 12-36 h, and forming nanoparticles by utilizing strong multiple hydrogen bond action between the grape polyphenol and the grape seed protein to obtain the nano glue.
The particle size and temperature sensitivity of the nanoparticles were measured using a laser particle sizer, and the particle size of the nanoparticles obtained in example 2 was plotted as a function of temperature, as shown in FIG. 3. As can be seen from FIG. 3, the particle size of the nanoparticles was 116 nm at room temperature; when the temperature is increased to be higher than 42 ℃, the hydrodynamic diameter is reduced to about 1 nm, and a single molecular chain is correspondingly dissolved; the micelle is mainly assembled by hydrogen bonds, and the temperature sensitivity of the nano glue provides possibility for reversible adhesion.
Example 3:
preparation of target hydrogel-grape seed extract hydrogel and adhesion performance test
10 g of polyvinylpyrrolidone powder was dissolved in 90 g of deionized water to prepare 100g of a 10 wt% aqueous polymer solution. 100g of a 6 wt% aqueous GSP solution was prepared. The hydrogel precursor was prepared according to the method of example 1, using 20 g of a 10 wt% polyvinylpyrrolidone aqueous solution and 4 g of a 6 wt% GSP aqueous solution. And (3) at room temperature, coating 1 mL of the G-NPs aqueous solution obtained in the example 2 on the surface of the obtained hydrogel precursor for 2 min to obtain target hydrogel, wherein the target hydrogel is the finally obtained grape seed extract hydrogel.
The adhesion effect of the target hydrogel obtained in example 3 is shown in FIG. 4. As can be seen from FIG. 4, the target hydrogel obtained in example 3 spontaneously adhered firmly to the skin surface. As shown in fig. 4: the hydrogel does not fall off even if the finger or the joint is bent greatly. Further, it was found that the hydrogel could be firmly adhered to the skin surface under sweat, water conditions.
Example 4:
temperature-controlled exfoliation characteristics of target hydrogel-grape seed extract hydrogel
The target hydrogel obtained in example 3 was evaluated for its ability to adhere to a substrate according to GB/T2791-1995. The results show that the hydrogel has moderate adhesive strength with the substrate at room temperature, and the peeling strength is 50J/m2(ii) a When the temperature rises to 45 deg.CWhen the peel strength is lowered to 1J/m2
Example 5:
bacteriostatic property of target hydrogel-grape seed extract hydrogel
The inhibitory effect of the hydrogel precursor obtained in example 1 and the target hydrogel obtained in example 3 on staphylococcus aureus was evaluated by a plate colony counting method, and the results of the experiment are shown in fig. 5. As can be seen from the graph (A) in FIG. 5, when the hydrogel precursor obtained in example 1 is coated on the culture medium, the bacterial growth is not affected and the inhibition zone is almost zero. As can be seen from the graph (B) in FIG. 5, when the target hydrogel obtained in example 3 was coated on the medium, the bacterial growth around the hydrogel was significantly affected and the zone of inhibition was evident.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any technical solution that can be implemented in the scope of the claims covered by the present application, or any technical solution that can be made by the technical personnel skilled in the art by using the contents of the method disclosed in the above, is covered by the scope of the present invention.

Claims (8)

1. A grape seed extract hydrogel is characterized in that the hydrogel is obtained by smearing nanometer glue on the surface of a hydrogel precursor; the hydrogel precursor is constructed by a polymer A aqueous solution and a polymer B aqueous solution by utilizing a phase separation micro-region and a hydrogen bond between the two polymers; the polymer A is one or a combination of water-soluble polymers with good biocompatibility and side chains containing hydrogen bonds for receptors, such as carboxymethyl cellulose, alginic acid, hyaluronic acid, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the polymer B is GSP; the nano glue is formed by self-assembly of a polymer B aqueous solution and solid powder of the grape polyphenol by utilizing multiple hydrogen bonds between side chain hydroxyl groups of the grape polyphenol and GSP.
2. A preparation method of grape seed extract hydrogel is characterized by comprising the following steps: the method comprises the following steps:
s01, taking 10-20 parts of the polymer A, dissolving in 80-90 parts of deionized water, and preparing a polymer A water solution; the polymer A is a water-soluble polymer with good biocompatibility and a side chain containing a hydrogen bond donor-acceptor, and comprises one or the combination of two or more of carboxymethyl cellulose, alginic acid, hyaluronic acid, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; the side chain of the polymer A contains a large number of hydrogen bond donor acceptors such as carboxyl, hydroxyl and the like;
s02, taking 2-10 parts of the polymer B, dissolving in 90-98 parts of deionized water, and preparing a polymer B water solution; the polymer B is GSP and can be extracted by an extraction method disclosed in Chinese patent application CN 201810129805.4; functional groups such as amino, carboxyl, hydroxyl and the like contained in the GSP side chain and the polymer A form an interpenetrating network through intermolecular hydrogen bonds in an aqueous solution;
s03, mixing 10-20 parts of the aqueous solution of the polymer A and 1-5 parts of the aqueous solution of the polymer B, stirring at room temperature for 2-4 hours to be uniform, and pouring into a mold; adjusting the pH value of the mixed solution to 3.8, inducing GSP to generate micro-phase separation, and constructing hydrogel by using a phase separation micro-region and a hydrogen bond between two polymers to obtain a hydrogel precursor;
s04, taking 5-10 g of the aqueous solution of the polymer B, heating to 70-90 ℃, adding 0.1-1 g of the solid powder of the grape polyphenol while stirring, and stirring for 2-6 hours to fully dissolve the grape polyphenol; placing the obtained solution at 4 ℃ for 12-36 h, and forming G-NPs molecular glue by utilizing self-assembly of multiple hydrogen bonds between side chain hydroxyl groups of the glucan polyphenol and GSP, wherein the molecular glue is 'nano glue';
s05, taking out the hydrogel precursor obtained in the step S03 from the mold, smearing the G-NPs molecular glue obtained in the step S04 on the surface of the hydrogel, and soaking the surface of the hydrogel in the G-NPs aqueous solution to improve the adhesive capacity of the hydrogel and skin tissues to obtain the target hydrogel, wherein the target hydrogel is the finally obtained grape seed extract hydrogel.
3. The method of preparing a hydrogel of grape seed extract as defined in claim 2, wherein: in step S01, polymer a is carboxymethyl cellulose or polyvinylpyrrolidone.
4. The method of preparing a hydrogel of grape seed extract as defined in claim 2, wherein: the method comprises the following specific steps:
s01, taking 20 parts of the polymer A, dissolving the polymer A in 80 parts of deionized water, and preparing a polymer A water solution; the polymer A is carboxymethyl cellulose;
s02, taking 10 parts of the polymer B, dissolving in 90 parts of deionized water, and preparing a polymer B water solution; the polymer B is GSP and can be extracted by an extraction method disclosed in Chinese patent application CN 201810129805.4;
s03, mixing 15 parts of the aqueous solution of the polymer A with 2 parts of the aqueous solution of the polymer B, stirring for 2 hours at room temperature to be uniform, and pouring into a mold; adjusting the pH value of the mixed solution to 3.8, and standing at room temperature for 3-5 days to obtain a hydrogel precursor;
s04, taking 5-10 g of the aqueous solution of the polymer B, heating to 70-90 ℃, adding 0.1-1 g of the solid powder of the grape polyphenol while stirring, and stirring for 4 hours to fully dissolve the grape polyphenol; placing the obtained solution at 4 ℃ for 12-36 h to obtain G-NPs molecular glue which is 'nano glue';
s05, taking out the hydrogel precursor obtained in the step S03 from the mold, smearing the G-NPs molecular glue obtained in the step S04 on the surface of the hydrogel, and soaking the surface of the hydrogel in the G-NPs aqueous solution to improve the adhesive capacity of the hydrogel and skin tissues to obtain the target hydrogel, wherein the target hydrogel is the finally obtained grape seed extract hydrogel.
5. The method of preparing a hydrogel of grape seed extract as defined in claim 2, wherein: the peel strength of the target hydrogel with the surface impregnated with the G-NPs aqueous solution at room temperature can reach 50J/m2(ii) a When the temperature is increased to 45 ℃, the peel strength can be reduced to 1J/m2
6. The method of preparing a hydrogel of grape seed extract as defined in claim 2, wherein: the target hydrogel with the surface impregnated with the G-NPs aqueous solution has an antibacterial effect, and has an obvious antibacterial effect on staphylococcus aureus.
7. Use of a grape seed extract hydrogel obtained by the method of any one of claims 2 to 6 in the preparation of a wound dressing.
8. The method of preparing a hydrogel of grape seed extract as defined in claim 2, wherein: and (4) raising the temperature of the target hydrogel with the surface impregnated with the G-NPs molecular glue obtained in the step S05, and inducing the G-NPs molecular glue to change from an aggregate into a linear molecular chain so as to diffuse into the hydrogel network, so that the hydrogel can be easily peeled at a near body temperature.
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