CN112126084A - Casein-based double-network antibacterial composite hydrogel material and preparation method thereof - Google Patents
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Abstract
The invention discloses a casein-based double-network antibacterial composite hydrogel material and a preparation method thereof, and the technical scheme is as follows: the preparation method comprises the steps of taking casein as a base material, introducing zinc oxide nano particles, uniformly mixing casein dispersion liquid and nano zinc oxide particles through physical blending, promoting casein to be complexed and crosslinked in a self-crosslinking structure to form a double-network structure by taking metal ions as a crosslinking agent, coating and dispersing part of the zinc oxide nano particles in hydrogel in an antibacterial agent mode, and obtaining the casein-based double-network antibacterial composite hydrogel through UV (ultraviolet) photocuring. The casein-based double-network composite hydrogel obtained by the method has the advantages of high reaction rate and stable structure by utilizing the unique amphipathy, good swelling property, wide sources, low price and the like of casein; the prepared casein-based double-network composite hydrogel has the advantages that the nano particles are uniformly dispersed and effectively cross-linked among casein micelles, and the casein-based double-network composite hydrogel is environment-friendly, stable in performance and antibacterial.
Description
Technical Field
The invention belongs to the technical field of preparation of high-molecular biological materials, and particularly relates to a casein-based double-network antibacterial composite hydrogel material and a preparation method thereof.
Background
Hydrogels are water-soluble polymers with three-dimensional networks that can trap large amounts of water in their structures. The porous structure of the hydrogel makes it an excellent material for protection and transportation. The hydrogel has the following characteristics: (1) water swellable, cross-linked polymers. (2) Hydrophilic and can absorb thousands of times of water by weight. (3) Three-dimensional network structure, insoluble in water. (4) Can sense external micro stimulation. Hydrogel properties depend on polymer concentration, degree of crosslinking, temperature, pH, aging and salt concentration.
Casein is a spherical protein which can be completely biodegraded and regenerated, wherein 55 percent of amino acid contains polar groups such as carboxyl, amino, hydroxyl and the like, has better adhesive force, ironing resistance, polishing resistance, high temperature resistance and certain film forming property and toughness, and can be used for preparing food emulsifying agents, leather finishing, high-speed labeling glue and the like. Casein, a natural polymer having excellent swelling properties and a high level of polydispersity, is usually formed into a gel by destabilizing casein micelles by adding rennet, acid, denaturants (e.g., heat or ethanol), and the like. The casein hydrogel has attracted extensive attention due to its good encapsulation, controlled release, self-repair and other functionalities, as well as natural biocompatibility and degradability.
Casein, a natural substance, generally has the problems of easy mildew and rot, poor antibacterial performance and the like. It is therefore common to incorporate into the system some antimicrobial agents, including: organic, inorganic, and natural antimicrobial agents. The zinc oxide nano particles are used as an inorganic nano antibacterial material, and have the characteristics of high surface activity, large specific surface area and the like, so that the reaction area of the zinc oxide nano particles in contact with bacteria is large, and the zinc oxide nano particles have certain inhibition on the toxicity of the bacteria. In addition, the nano zinc oxide also has certain deodorization, photocatalysis and ultraviolet shielding properties, not only can play an effective role in resisting bacteria for coating materials, but also can endow the coating with better strength, toughness, water resistance and sanitary performance.
The metal ions can effectively connect the casein through polar groups such as active amino groups, carboxyl groups and the like, amino acid residues are complexed to form a plurality of crosslinking points, so that a double-network structure is formed by the metal ions and a network formed by self-crosslinking of the casein, and the defect of poor mechanical property of the bio-based hydrogel is effectively overcome. In the process, the nano zinc oxide can be used as a metal ion cross-linking agent to promote the formation of hydrogel, and after the cross-linking is completed, part of nano zinc oxide particles are encapsulated in a three-dimensional network of the nano zinc oxide particles to play a role in resisting bacteria and preventing mildew. Therefore, the nano zinc oxide forms a double-network structure for crosslinked casein and realizes antibiosis, and the casein-based double-network antibacterial composite hydrogel material has certain advantages.
Disclosure of Invention
The casein-based double-network antibacterial composite hydrogel material prepared by the method has uniform gaps and a stable structure, can effectively crosslink nano zinc oxide, is expected to improve the strength of the material and endow the material with antibacterial performance.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a casein-based dual-network antibacterial composite hydrogel material comprises the steps of taking casein as a base material, introducing zinc oxide nano particles, uniformly mixing casein dispersion liquid and nano zinc oxide particles through physical blending, promoting casein to be crosslinked in a self-crosslinking structure again by taking metal ions as a crosslinking agent at proper acidity to form a dual-network structure, coating and dispersing part of zinc oxide nano particles in the gel in an antibacterial agent mode, and finally obtaining the casein-based dual-network antibacterial composite hydrogel material through UV (ultraviolet) light curing.
The method specifically comprises the following steps:
the method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH to be 9-11 by adopting an alkaline solution; adding 1.25-1.65 parts by mass of casein powder into 97.65-98.65 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 40-55 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 0.5-1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: and adding 0.10-0.70 parts by mass of metal nanoparticles into deionized water, and magnetically stirring at normal temperature until the metal nanoparticles are uniformly dispersed to obtain the zinc oxide dispersion liquid. Slowly adding the mixture into casein dispersion liquid while stirring, and carrying out ultrasonic reaction at 30-50 ℃ for 0.5-1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH = 1-2, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20-30 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 2-3. Discarding the supernatant, and carrying out UV (ultraviolet) light curing to obtain the casein-based double-network antibacterial composite hydrogel material.
In the first step, the alkaline solution is triethanolamine solution, sodium hydroxide solution, ammonia water or phosphate buffer solution.
In the second step, the metal nanoparticles are zinc oxide nanoparticles or silver nanoparticles.
The casein-based double-network antibacterial composite hydrogel material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention utilizes the unique amphipathy, good swelling property, wide source, low price and other advantages of casein as a base material, introduces zinc oxide nano particles, uniformly mixes casein dispersion liquid and nano zinc oxide particles through physical blending, uses metal ions as a cross-linking agent to promote casein to be cross-linked in a self-cross-linked structure to form a double-network structure at proper acidity, disperses part of zinc oxide nano particles in the gel in an antibacterial agent form, and finally obtains casein-based double-network composite hydrogel through UV photocuring.
2) The casein-based double-network composite hydrogel prepared by the invention has the characteristics of uniform dispersion, effective crosslinking between casein micelles, environmental protection, stable performance, antibacterial property and the like, can endow the base material with excellent sanitary performance by applying the casein-based double-network composite hydrogel to the finishing of the base material such as leather or textile, can improve the added value of products, and has wide application prospect in the industries such as textile, leather, food, biological packaging and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a casein-based dual-network antibacterial composite hydrogel material prepared by the method;
FIG. 2 is a graph showing the antibacterial effect of casein-based double-network antibacterial composite hydrogel material (a Escherichia coli, b Staphylococcus aureus).
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
Based on the previous research foundation in the modification and functionalization of natural products of casein and chitosan and the aspect of functional water-based coatings, the inventor utilizes the unique amphipathy, good swelling property, wide sources, low price and the like of casein as a base material, introduces zinc oxide nanoparticles, uniformly mixes casein dispersion liquid and nano zinc oxide particles through physical blending, promotes the casein to be crosslinked again in a self-crosslinking structure to form a double-network structure by taking metal ions as a crosslinking agent at proper acidity, coats and disperses part of the zinc oxide nanoparticles in gel in the form of an antibacterial agent, and finally obtains the composite hydrogel through UV photocuring.
The method for preparing the casein-based double-network antibacterial composite hydrogel comprises the following specific steps:
the method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH to be 9-11 by using triethanolamine; adding 1.25-1.65 parts by mass of casein powder into 97.65-98.65 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 40-55 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 0.5-1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.10-0.70 parts by mass of zinc oxide nanoparticles into deionized water, and magnetically stirring at normal temperature until the zinc oxide nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid. Slowly adding the mixture into casein dispersion liquid while stirring, and carrying out ultrasonic reaction at 30-50 ℃ for 0.5-1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH = 1-2, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20-30 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 2-3. Discarding the supernatant, and carrying out UV (ultraviolet) photocuring to obtain the casein-based double-network antibacterial composite hydrogel.
Preferably, the triethanolamine solution for dissolving casein may be a sodium hydroxide solution, ammonia water, phosphate buffer solution; the zinc oxide nanoparticles can also be silver nanoparticles and other metal or metal oxide nanoparticles.
Example 1
The weight of the casein-based double-network composite hydrogel is 100 parts by weight.
The method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH value to be =10 by using triethanolamine; adding 1.25 parts by mass of casein powder into 98.65 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 45 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.10 mass part of zinc oxide nanoparticles into deionized water, and magnetically stirring at normal temperature until the zinc oxide nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid. Slowly adding the mixture into casein dispersion liquid while stirring, and performing ultrasonic reaction at 45 ℃ for 1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH =1, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 3. Discarding the supernatant, and carrying out UV (ultraviolet) photocuring to obtain the casein-based double-network antibacterial composite hydrogel.
Example 2
The weight of the casein-based double-network composite hydrogel is 100 parts by weight.
The method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH value to be =10 by using triethanolamine; adding 1.35 parts by mass of casein powder into 98.40 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring with a stirrer, heating in water bath to 45 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.25 part by mass of zinc oxide nanoparticles into deionized water, and magnetically stirring at normal temperature until the zinc oxide nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid. Slowly adding the mixture into casein dispersion liquid while stirring, and performing ultrasonic reaction at 45 ℃ for 1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH =1, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 3. Discarding the supernatant, and carrying out UV (ultraviolet) photocuring to obtain the casein-based double-network antibacterial composite hydrogel.
Example 3
The weight of the casein-based double-network composite hydrogel is 100 parts by weight.
The method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH value to be =10 by using triethanolamine; adding 1.45 parts by mass of casein powder into 98.15 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 45 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.40 mass part of zinc oxide nanoparticles into deionized water, and magnetically stirring at normal temperature until the zinc oxide nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid. Slowly adding the mixture into casein dispersion liquid while stirring, and performing ultrasonic reaction at 45 ℃ for 1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH =1, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 3. Discarding the supernatant, and carrying out UV (ultraviolet) photocuring to obtain the casein-based double-network antibacterial composite hydrogel.
Example 4
The weight of the casein-based double-network composite hydrogel is 100 parts by weight.
The method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH value to be =10 by using triethanolamine; adding 1.55 parts by mass of casein powder into 97.90 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 45 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.55 part by mass of zinc oxide nanoparticles into deionized water, and magnetically stirring at normal temperature until the zinc oxide nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid. Slowly adding the mixture into casein dispersion liquid while stirring, and performing ultrasonic reaction at 45 ℃ for 1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH =1, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 3. Discarding the supernatant, and carrying out UV (ultraviolet) photocuring to obtain the casein-based double-network antibacterial composite hydrogel.
Example 5
The weight of the casein-based double-network composite hydrogel is 100 parts by weight.
The method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH value to be =10 by using triethanolamine; adding 1.65 parts by mass of casein powder into 97.65 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 45 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.70 mass part of zinc oxide nanoparticles into deionized water, and magnetically stirring at normal temperature until the zinc oxide nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid. Slowly adding into casein dispersion liquid while stirring, and performing ultrasonic reaction at 45 deg.C for 1 hr to uniformly disperse nanometer zinc oxide among casein molecules to obtain mixed dispersion liquid
Step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH =1, and gradually flocculating casein in the dispersion liquid; and adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 3. Discarding the supernatant, and carrying out UV (ultraviolet) photocuring to obtain the casein-based double-network antibacterial composite hydrogel.
SEM test of the casein-based double-network antibacterial composite hydrogel material prepared in example 1 shows that the hydrogel has a dense three-dimensional network structure and uniformly dispersed pores, and the surface of the hydrogel has a rougher surface appearance. The composite hydrogel has a uniform double-network structure.
An antibacterial effect diagram shown in figure 2 is obtained by performing an antibacterial property test on the casein-based dual-network antibacterial composite hydrogel material prepared in example 1, and as can be seen from figure 2, the composite hydrogel added with zinc oxide nanoparticles generates an obvious inhibition zone for two kinds of bacteria; by changing the content of the zinc oxide nanoparticles, it was observed that the bacteriostatic effect was improved with the increase of the nanoparticle content. Through the surface appearance and the antibacterial effect diagram, and theoretical analysis, the judgment can be carried out, the zinc oxide nanoparticles are combined with casein through the mutual crosslinking combination of various forces such as metal complexing action, electrostatic attraction and the like, the casein-based double-network antibacterial composite hydrogel is successfully prepared, and the result proves that the preparation scheme is effective; in addition, the casein-based dual-network antibacterial composite hydrogel material is applied to finishing of base materials such as leather or textile fabrics, can endow the base materials with antibacterial hygienic performance, improves the added value of products, and has wide application prospects in the industries such as textile, leather, food, biological packaging and the like.
The invention is not limited to the examples given, and any equivalent alterations to the technical solution of the invention which are made by those skilled in the art after reading the description of the invention are all covered by the claims of the invention.
Claims (5)
1. A preparation method of a casein-based double-network antibacterial composite hydrogel material is characterized by comprising the following steps:
casein is used as a base material, zinc oxide nano particles are introduced, casein dispersion liquid and the nano zinc oxide particles are uniformly mixed through physical blending, metal ions are used as a cross-linking agent to promote the casein to be cross-linked in a self-cross-linked structure to form a double-network structure at proper acidity, part of the zinc oxide nano particles are coated and dispersed in gel in an antibacterial agent form, and finally, the casein-based double-network antibacterial composite hydrogel material is obtained through UV photocuring.
2. The preparation method of the casein-based double-network antibacterial composite hydrogel material according to claim 1, which comprises the following steps:
the method comprises the following steps: taking a certain amount of deionized water, and adjusting the pH to be 9-11 by adopting an alkaline solution; adding 1.25-1.65 parts by mass of casein powder into 97.65-98.65 parts by mass of triethanolamine solution, mixing, adding into a three-neck flask, continuously stirring by using a stirrer, heating in a water bath to 40-55 ℃, controlling the magnetic stirring speed to be 500 r/min, and continuously stirring for 0.5-1 h until the casein powder is dissolved to obtain casein dispersion liquid;
step two: adding 0.10-0.70 parts by mass of metal nanoparticles into deionized water, and magnetically stirring at normal temperature until the metal nanoparticles are uniformly dispersed to obtain a zinc oxide dispersion liquid;
slowly adding the mixture into casein dispersion liquid while stirring, and carrying out ultrasonic reaction at 30-50 ℃ for 0.5-1 h to uniformly disperse the nano zinc oxide among casein molecules to obtain mixed dispersion liquid;
step three: slowly dropwise adding a hydrochloric acid solution to the mixed dispersion liquid obtained in the second step, adjusting the acidity to be pH = 1-2, and gradually flocculating casein in the dispersion liquid; adding the suspension into a centrifugal tube, controlling the magnetic stirring speed to be 6000 r/min, centrifuging for 20-30 min, and repeating the operation for 3-5 times until the pH value of the supernatant is measured to be 2-3;
discarding the supernatant, and carrying out UV (ultraviolet) light curing to obtain the casein-based double-network antibacterial composite hydrogel material.
3. The preparation method of the casein-based double-network antibacterial composite hydrogel material according to claim 2, wherein the preparation method comprises the following steps:
in the first step, the alkaline solution is triethanolamine solution, sodium hydroxide solution, ammonia water or phosphate buffer solution.
4. The preparation method of the casein-based double-network antibacterial composite hydrogel material according to claim 2, wherein the preparation method comprises the following steps:
in the second step, the metal nanoparticles are zinc oxide nanoparticles or silver nanoparticles.
5. The casein-based double-network antibacterial composite hydrogel material prepared by the preparation method of claim 1.
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| CN113321822A (en) * | 2021-06-08 | 2021-08-31 | 陕西科技大学 | High-strength casein/graphene composite hydrogel and preparation method thereof |
| CN114437371A (en) * | 2022-01-14 | 2022-05-06 | 陕西科技大学 | Preparation method of casein-based nano hybrid hydrogel based on double cross-linking mechanism |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112843239A (en) * | 2021-03-29 | 2021-05-28 | 烟台鲁量新材料科技有限公司 | Gel matrix, nano zinc oxide antibacterial gel and preparation method thereof |
| CN113321822A (en) * | 2021-06-08 | 2021-08-31 | 陕西科技大学 | High-strength casein/graphene composite hydrogel and preparation method thereof |
| CN113321822B (en) * | 2021-06-08 | 2022-11-08 | 陕西科技大学 | High-strength casein/graphene composite hydrogel and preparation method thereof |
| CN114437371A (en) * | 2022-01-14 | 2022-05-06 | 陕西科技大学 | Preparation method of casein-based nano hybrid hydrogel based on double cross-linking mechanism |
| CN114437371B (en) * | 2022-01-14 | 2023-09-05 | 陕西科技大学 | Preparation method of casein-based nano hybrid hydrogel based on double crosslinking mechanism |
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