CN109251330B - Nano chitin-PVA hydrogel and preparation method and application thereof - Google Patents
Nano chitin-PVA hydrogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nano chitin-PVA hydrogel and a preparation method and application thereof, relating to the technical field of biomedical materials. The preparation method of the nano chitin-PVA hydrogel comprises the following steps: (a) mixing the nano chitin dispersion liquid with a polyvinyl alcohol solution to perform a physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction; (b) and adding a cross-linking agent into the mixed dispersion liquid after the physical cross-linking reaction to perform a chemical cross-linking reaction to obtain the nano chitin-PVA hydrogel. The preparation method of the nano chitin-PVA hydrogel provided by the invention adopts the steps of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution to perform a physical crosslinking reaction, mixing the mixed dispersion liquid after the physical crosslinking reaction with the crosslinking agent to perform a chemical crosslinking reaction to obtain the nano chitin-PVA hydrogel, and the preparation method has the advantages of simple preparation process, low cost and low energy consumption, and realizes the sustainable development of production.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a nano chitin-PVA hydrogel and a preparation method and application thereof.
Background
The hydrogel is a functional polymer material which has a three-dimensional cross-linked network structure, can absorb and retain a large amount of water and is insoluble in water. The special structure of the hydrogel makes the hydrogel have the properties of both solid and liquid, namely, the hydrogel shows solid-like properties in mechanics and shows liquid-like behaviors in thermodynamics. The hydrogel has been a research hotspot because of its characteristics of low cost, porosity, higher mechanical strength, optical transparency, biodegradability, high swelling ratio, biocompatibility, stimulation responsiveness and the like, and is widely applied to the fields of food, cosmetics, medicine and health, agriculture, environmental protection and the like.
Chitin is a natural macromolecule with the second biosynthesis amount to cellulose in the nature, the main source of the chitin is shells of crustaceans such as shrimps and crabs and cell walls of certain fungi and algae, the molecular structure of the chitin is a binary linear polymer formed by connecting 2-acetamido-2-deoxy-D-glucopyranose and 2-amino-2-deoxy-D-glucopyranose by beta-1 and 4 glycosidic bonds, and the chitin is the only basic cationic polysaccharide which exists in large quantity in the nature. Chitin has good physiological compatibility and biodegradability, and is an important biomedical material.
At present, the existing nano chitin-PVA hydrogel is complex in preparation process, high in cost, high in energy consumption and incapable of sustainable development, and the prepared nano chitin-PVA hydrogel is uneven in pores, poor in mechanical property and poor in drug transferability.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a nano chitin-PVA hydrogel and a preparation method thereof, so as to solve the technical problems of complex preparation process, high cost, high energy consumption, incapability of sustainable development and the like in the prior art.
The preparation method of the nano chitin-PVA hydrogel provided by the invention comprises the following steps:
(a) mixing the nano chitin dispersion liquid with a polyvinyl alcohol solution to perform a physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
(b) and adding a cross-linking agent into the mixed dispersion liquid after the physical cross-linking reaction to perform a chemical cross-linking reaction to obtain the nano chitin-PVA hydrogel.
Further, in the step (a), the mass ratio of the nano chitin to the polyvinyl alcohol is (1-9): (1-9); preferably (1.5-8.5): (1.5-8.5); more preferably 5: 5.
further, in the step (b), the cross-linking agent comprises at least one of glutaraldehyde, NN-methylene bisacrylamide, epichlorohydrin, sodium trimetaphosphate or diene sulfone; preferably, the cross-linking agent is glutaraldehyde; preferably, the cross-linking agent is a glutaraldehyde aqueous solution, and the mass concentration of the glutaraldehyde aqueous solution is 0.1-0.5%; more preferably, the mass concentration of the glutaraldehyde aqueous solution is 0.2-0.5%.
Further, in the step (a), the mass concentration of the polyvinyl alcohol solution is 5-10%; preferably 6-10%; further preferably 6-9%;
and/or in the step (a), the mixing temperature of the nano chitin dispersion liquid and the polyvinyl alcohol solution is 70-90 ℃; preferably 75-90 ℃; further preferably 75-85 ℃;
and/or, in the step (a), the mass concentration of the nano chitin dispersion liquid is 1-2%; preferably 1-1.8%; more preferably 1.2 to 1.8%.
Further, the method also comprises the step (c): repeatedly freezing and thawing the nano chitin-PVA hydrogel;
preferably, in the step (c), the freezing temperature is-10 ℃ to-20 ℃; further preferably, the freezing temperature is-10 ℃ to-18 ℃; more preferably, the freezing temperature is-12 ℃ to-18 ℃.
Further, in the step (a), the preparation of the nano chitin dispersion solution comprises the steps of pretreating, deacetylating, protonating and homogenizing a chitin raw material;
preferably, the chitin raw material comprises at least one of shrimp shells or crab shells.
Further, the deproteinization comprises: mixing a chitin raw material with an alkali solution to remove residual protein, and then washing the mixture to be neutral by deionized water; preferably, the concentration of the alkali solution is 0.5-1 mol/L; further preferably, the alkali solution comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution, or a calcium hydroxide solution;
and/or, the demineralization comprises: mixing the deproteinized chitin with inorganic acid to remove minerals, and washing with deionized water to neutrality; preferably, the concentration of the inorganic acid is 0.5-1 mol/L; further preferably, the inorganic acid comprises at least one of hydrochloric acid, sulfuric acid or acetic acid;
and/or, the bleaching comprises: mixing the chitin after removing the mineral substances with a bleaching agent for bleaching; preferably, the concentration of the bleaching agent is 0.5-1 mol/L; further preferably, the bleaching agent comprises at least one of sodium chlorite or calcium chlorite;
and/or, the deacetylation treatment comprises: carrying out deacetylation reaction on the pretreated chitin at 70-90 ℃ by using an alkali solution; preferably, the mass concentration of the alkali solution is 20-40%, and further preferably, the alkali solution comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution or a calcium hydroxide solution;
and/or the pH value of the protonation treatment is 3-4; preferably, the pH is 3.5-4; further preferably, the protonic acid comprises at least one of acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, aspartic acid, nucleotides, itaconic acid, malonic acid, or lucalytic acid.
Further, in the step (b), the pH value of the mixed dispersion liquid is 1-1.5; preferably, the pH is 1-1.2.
The second purpose of the invention is to provide the nano chitin-PVA hydrogel which has uniform pores and excellent mechanical properties.
The nano chitin-PVA hydrogel provided by the invention is prepared by the preparation method.
The third purpose of the invention is to provide an application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs, and the nano chitin-PVA hydrogel has a good delivery effect on drugs loaded in the hydrogel and a good slow release effect.
The application of the nano chitin-PVA hydrogel provided by the invention in preparing protein releasing medicaments;
preferably, the protein drug is at least one of glucose oxidase drug, insulin drug, interferon drug, collagen drug, heparin drug, superoxide dismutase drug, tissue growth factor drug or bovine serum albumin drug.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the nano chitin-PVA hydrogel provided by the invention adopts the steps of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution to perform a physical crosslinking reaction, mixing the mixed dispersion liquid after the physical crosslinking reaction with the crosslinking agent to perform a chemical crosslinking reaction to obtain the nano chitin-PVA hydrogel, and the preparation method has the advantages of simple preparation process, low cost and low energy consumption, and realizes the sustainable development of production.
The nano chitin-PVA hydrogel provided by the invention has uniform pores and excellent mechanical properties.
The nano chitin-PVA hydrogel provided by the invention has a good delivery effect on protein drugs loaded in the hydrogel, and is good in slow release effect, the prepared protein slow release drugs can prolong the action time of the drugs, the release period of the drugs is obviously increased, the side effect on human bodies is reduced, the release rate of the drugs is high, and the utilization rate of the drugs is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an AFM image of a nano chitin dispersion;
FIG. 2 is an electron micrograph of 90% PVA/10% nano chitin-PVA hydrogel;
FIG. 3 is an electron micrograph of 80% PVA/20% nano chitin-PVA hydrogel;
FIG. 4 is an electron micrograph of a 70% PVA/30% nano chitin-PVA hydrogel;
FIG. 5 is an electron micrograph of a 60% PVA/40% nano chitin-PVA hydrogel;
FIG. 6 is an electron micrograph of a 50% PVA/50% nano chitin-PVA hydrogel;
FIG. 7 is an electron micrograph of a 40% PVA/60% nano chitin-PVA hydrogel;
FIG. 8 is a graph showing the relationship between the absorbance and concentration of bovine serum albumin solution;
figure 9 is a drug release profile of a protein-loaded drug hydrogel.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, the present invention provides a method for preparing a nano chitin-PVA hydrogel, comprising the following steps:
(a) mixing the nano chitin dispersion liquid with a polyvinyl alcohol solution to perform a physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
(b) and adding a cross-linking agent into the mixed dispersion liquid after the physical cross-linking reaction to perform a chemical cross-linking reaction to obtain the nano chitin-PVA hydrogel.
The preparation method of the nano chitin-PVA hydrogel provided by the invention adopts the steps of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution to perform a physical crosslinking reaction, mixing the mixed dispersion liquid after the physical crosslinking reaction with the crosslinking agent to perform a chemical crosslinking reaction to obtain the nano chitin-PVA hydrogel, and the preparation method has the advantages of simple preparation process, low cost and low energy consumption, and realizes the sustainable development of production.
In a preferred embodiment, in the step (b), the mass ratio of the nano chitin to the polyvinyl alcohol is (1-9): (1-9); preferably (1.5-8.5): (1.5-8.5); more preferably 5: 5.
wherein, the mass ratio of the nano chitin to the polyvinyl alcohol can be, but is not limited to, 1: 9. 2: 8. 3: 7. 4: 6. 5: 5. 6: 4. 7: 3. 8: 2 or 9: 1.
the preparation method of the nano chitin-PVA hydrogel provided by the invention adopts the nano chitin dispersion liquid and the polyvinyl alcohol solution in a certain proportion to carry out physical crosslinking reaction, so that the nano chitin and the polyvinyl alcohol can be uniformly combined together in distribution, and the subsequent chemical crosslinking reaction is facilitated.
In a preferred embodiment, in step (b), the crosslinking agent comprises at least one of glutaraldehyde, NN-methylenebisacrylamide, epichlorohydrin, sodium trimetaphosphate, or diene sulfone; preferably, the cross-linking agent is glutaraldehyde; preferably, the cross-linking agent is a glutaraldehyde aqueous solution, and the mass concentration of the glutaraldehyde aqueous solution is 0.1-0.5%; more preferably, the mass concentration of the glutaraldehyde aqueous solution is 0.2-0.5%.
The cross-linking agent can convert the monomer, linear polymer or prepolymer into a three-dimensional network structure substance under certain conditions.
The mass concentration of the glutaraldehyde aqueous solution may be, for example, but not limited to, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.
The preparation method of the nano chitin-PVA hydrogel provided by the invention adopts glutaraldehyde aqueous solution with a certain concentration as a cross-linking agent to promote the nano chitin and polyvinyl alcohol to generate chemical cross-linking reaction, so as to obtain the nano chitin-PVA hydrogel.
In a preferred embodiment, in the step (a), the mass concentration of the polyvinyl alcohol solution is 5-10%; preferably 6-10%; more preferably 6 to 9%.
The polyvinyl alcohol is used as a raw material of the nano chitin-PVA hydrogel, the structure and the performance of the polyvinyl alcohol are closely related to the concentration of a polyvinyl alcohol solution, and when the mass concentration of the polyvinyl alcohol solution is 5-10%, the obtained nano chitin-PVA hydrogel has good mechanical properties and stable properties.
The mass concentration of the polyvinyl alcohol may be, for example, but not limited to, 5%, 6%, 7%, 8%, 9%, or 10%.
In a preferred embodiment, in the step (b), the temperature for mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution is 70-90 ℃; preferably 75-90 ℃; further preferably 75 to 85 ℃.
The temperature of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution can be, but is not limited to, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃ or 90 ℃.
In a preferred embodiment, in the step (a), the mass concentration of the nano chitin dispersion liquid is 1-2%; preferably 1-1.8%; more preferably 1.2 to 1.8%.
The mass concentration of the nano chitin dispersion liquid may be, but is not limited to, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%.
In a preferred embodiment, further comprising step (c): and (3) repeatedly freezing and thawing the nano chitin-PVA hydrogel. Repeated freezing-thawing can make the structural form of the nano chitin-PVA hydrogel more stable and the mechanical property more excellent.
In a preferred embodiment of this embodiment, the temperature of the freezing in step (c) is from-10 ℃ to-20 ℃; further preferably, the freezing temperature is-10 ℃ to-18 ℃; more preferably, the freezing temperature is-12 ℃ to-18 ℃.
The freezing temperature may be, for example, but not limited to, -10 ℃, -11 ℃, -12 ℃, -13 ℃, -14 ℃, -15 ℃, -16 ℃, -17 ℃, -18 ℃, -19 ℃, or-20 ℃.
In a preferred embodiment, in the step (a), the preparation of the nano chitin dispersion comprises pretreating, deacetylating, protonating and homogenizing the chitin raw material.
In a preferred embodiment of this embodiment, the chitin raw material comprises at least one of shrimp shells or crab shells.
The chitin raw material is derived from shrimp shells or crab shells in the ocean, is recycled, has low price and is green and environment-friendly.
In a preferred embodiment, the deproteinization comprises: mixing a chitin raw material with an alkali solution to remove residual protein, and then washing the mixture to be neutral by deionized water; preferably, the concentration of the alkali solution is 0.5-1 mol/L; further preferably, the alkali solution includes at least one of a sodium hydroxide solution, a potassium hydroxide solution, or a calcium hydroxide solution.
In a preferred embodiment, the demineralization agent comprises: mixing the deproteinized chitin with inorganic acid to remove minerals, and washing with deionized water to neutrality; preferably, the concentration of the inorganic acid is 0.5-1 mol/L; further preferably, the inorganic acid includes at least one of hydrochloric acid, sulfuric acid, or acetic acid.
In a preferred embodiment, the bleaching comprises: mixing the chitin after removing the mineral substances with a bleaching agent for bleaching; preferably, the concentration of the bleaching agent is 0.5-1 mol/L; further preferably, the bleaching agent comprises at least one of sodium chlorite or calcium chlorite.
In a preferred embodiment, the deacetylation treatment comprises: carrying out deacetylation reaction on the pretreated chitin at 70-90 ℃ by using an alkali solution; preferably, the mass concentration of the alkali solution is 20-40%, and further preferably, the alkali solution comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution or a calcium hydroxide solution.
In a preferred embodiment, the pH of the protonation treatment is 3 to 4; preferably, the pH is 3.5-4; further preferably, the protonic acid comprises at least one of acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, aspartic acid, nucleotides, itaconic acid, malonic acid, or lucalytic acid.
In a preferred embodiment, in the step (b), the pH of the mixed dispersion is 1 to 1.5; preferably, the pH is 1-1.2.
When the pH value of the mixed dispersion liquid is 1-1.5, the hydrogel obtained through the crosslinking reaction has good pore connectivity, uniform pores, good elasticity and excellent mechanical property, is stable in actual environment, and is not affected by the environment to damage the gel property.
The pH may be, but is not limited to, 1, 1.1, 1.2, 1.3, 1.4, or 1.5, for example.
According to a second aspect of the present invention, the present invention provides a nano chitin-PVA hydrogel.
The nano chitin-PVA hydrogel provided by the invention has uniform pores and excellent mechanical properties.
According to the third aspect of the invention, the invention provides an application of nano chitin-PVA hydrogel in preparation of protein releasing drugs.
The nano chitin-PVA hydrogel provided by the invention has a good delivery effect on protein drugs loaded in the hydrogel, and is good in slow release effect, the prepared protein slow release drugs can prolong the action time of the drugs, the release period of the drugs is obviously increased, the side effect on human bodies is reduced, the release rate of the drugs is high, and the utilization rate of the drugs is high.
In a preferred embodiment of this embodiment, the protein drug is at least one of a glucose oxidase drug, an insulin drug, an interferon drug, a collagen drug, a heparin drug, a superoxide dismutase drug, a tissue growth factor drug, or a bovine serum albumin drug.
In order to facilitate a clearer understanding of the present invention, the technical solution of the present invention will be further described below with reference to examples and comparative examples.
Example one
The embodiment provides a preparation method of a nano chitin dispersion liquid, which comprises the following steps:
20g of waste shrimp shells are soaked in 1mol/L sodium hydroxide solution, mechanically stirred for 2 hours, residual protein is removed, and the waste shrimp shells are washed to be neutral by deionized water; then soaking in 1mol/L hydrochloric acid, mechanically stirring for 2h, removing minerals, and washing with deionized water to neutrality; finally, soaking the chitin in 0.8mol/L sodium chlorite solution for 2 hours, and bleaching the treated chitin; drying after bleaching; soaking the dried chitin in 30 wt% sodium hydroxide solution, performing partial deacetylation treatment at 90 ℃ for 3h, simultaneously adding 5g of sodium borohydride, the deacetylation rate being 45%, then adding acetic acid to adjust the pH value to 3.5 to obtain chitin suspension, homogenizing the chitin suspension by a high-pressure homogenizer to obtain nano chitin dispersion, measuring the solid content of the nano chitin dispersion at the moment, adding deionized water to prepare the chitin dispersion with the mass concentration of 1.2%, and sealing and storing at 4 ℃. The grain size of the nano chitin is 10-150 nm. An AFM image of the nano chitin dispersion is shown in FIG. 1.
Example two
The embodiment provides a preparation method of nano chitin-PVA hydrogel, which comprises the following steps:
fully stirring and uniformly mixing the nano chitin dispersion liquid prepared in the first embodiment and 10 wt% of polyvinyl alcohol AH-26 solution at normal temperature, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 9: 1, mechanically stirring for 2 hours in an oil bath at 70 ℃ to perform a physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
standing and cooling the mixed dispersion liquid after the physical crosslinking reaction to normal temperature, adjusting the pH to 1.5 by using HCl solution, adding 10g of 0.3 wt% glutaraldehyde solution, magnetically stirring uniformly and carrying out chemical crosslinking reaction to obtain nano chitin-PVA hydrogel, repeatedly washing the formed nano chitin-PVA hydrogel with deionized water, and removing residual crosslinking agent glutaraldehyde;
and (2) freezing the nano chitin-PVA hydrogel for 12h at-20 ℃, then taking out the nano chitin-PVA hydrogel to be thawed at room temperature, and performing circulating freeze thawing for three times to obtain the nano chitin-PVA hydrogel.
An electron micrograph of the 90% PVA/10% nano chitin-PVA hydrogel is shown in FIG. 2.
EXAMPLE III
The embodiment provides a preparation method of nano chitin-PVA hydrogel, which comprises the following steps:
fully stirring and uniformly mixing the nano chitin dispersion liquid prepared in the first embodiment and 9 wt% of polyvinyl alcohol AH-26 solution at normal temperature, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 8.5: 1.5, mechanically stirring for 1.8 hours in an oil bath at the temperature of 75 ℃ to perform physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
standing and cooling the mixed dispersion liquid after the physical crosslinking reaction to normal temperature, adjusting the pH to 1.2 by using HCl solution, adding 8g of 0.5 wt% glutaraldehyde solution, magnetically stirring uniformly and carrying out chemical crosslinking reaction to obtain nano chitin-PVA hydrogel, repeatedly washing the formed nano chitin-PVA hydrogel with deionized water, and removing residual crosslinking agent glutaraldehyde;
and (3) freezing the obtained hydrogel for 14h in a low-temperature environment of-18 ℃, then taking out the hydrogel to be thawed at room temperature, and performing circulating freeze thawing for three times to obtain the nano chitin-PVA hydrogel.
An electron micrograph of the 80% PVA/20% nano chitin-PVA hydrogel is shown in FIG. 3.
Example four
The embodiment provides a preparation method of nano chitin-PVA hydrogel, which comprises the following steps:
fully stirring and uniformly mixing the nano chitin dispersion liquid prepared in the first embodiment and 8 wt% of polyvinyl alcohol AH-26 solution at normal temperature, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 7: 3, mechanically stirring for 1.6 hours in an oil bath at the temperature of 85 ℃ to perform physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
standing and cooling the mixed dispersion liquid after the physical crosslinking reaction to normal temperature, adjusting the pH to 1.4 by using HCl solution, adding 9g of 0.4 wt% glutaraldehyde solution, magnetically stirring uniformly and carrying out chemical crosslinking reaction to obtain nano chitin-PVA hydrogel, repeatedly washing the formed nano chitin-PVA hydrogel with deionized water, and removing residual crosslinking agent glutaraldehyde;
and (3) freezing the obtained hydrogel for 18h in a low-temperature environment of-14 ℃, then taking out the hydrogel to be thawed at room temperature, and performing circulating freeze thawing for three times to obtain the nano chitin-PVA hydrogel.
An electron micrograph of the 70% PVA/30% nano chitin-PVA hydrogel is shown in FIG. 4.
EXAMPLE five
The embodiment provides a preparation method of nano chitin-PVA hydrogel, which comprises the following steps:
fully stirring and uniformly mixing the nano chitin dispersion liquid prepared in the first embodiment and 7 wt% of polyvinyl alcohol AH-26 solution at normal temperature, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 5: 5, mechanically stirring for 1.5 hours in an oil bath at the temperature of 80 ℃ to perform physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
standing and cooling the mixed dispersion liquid after the physical crosslinking reaction to normal temperature, adjusting the pH to 1.3 by using HCl solution, adding 12g of 0.3 wt% glutaraldehyde solution, magnetically stirring uniformly and carrying out chemical crosslinking reaction to obtain nano chitin-PVA hydrogel, repeatedly washing the formed nano chitin-PVA hydrogel with deionized water, and removing residual crosslinking agent glutaraldehyde;
and (3) freezing the obtained hydrogel for 20h in a low-temperature environment of-12 ℃, then taking out the hydrogel to be thawed at room temperature, and performing circulating freeze thawing for three times to obtain the nano chitin-PVA hydrogel.
An electron micrograph of the 60% PVA/40% nano chitin-PVA hydrogel is shown in FIG. 5.
EXAMPLE six
The embodiment provides a preparation method of nano chitin-PVA hydrogel, which comprises the following steps:
fully stirring and uniformly mixing the nano chitin dispersion liquid prepared in the first embodiment and 6 wt% of polyvinyl alcohol AH-26 solution at normal temperature, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 3.5: 6.5, mechanically stirring for 1h in an oil bath at 90 ℃ to perform physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
standing and cooling the mixed dispersion liquid after the physical crosslinking reaction to normal temperature, adjusting the pH to 1.1 by using HCl solution, adding 20g of 0.1 wt% glutaraldehyde solution, magnetically stirring uniformly and carrying out chemical crosslinking reaction to obtain nano chitin-PVA hydrogel, repeatedly washing the formed nano chitin-PVA hydrogel with deionized water, and removing residual crosslinking agent glutaraldehyde;
and (3) freezing the obtained hydrogel for 16h in a low-temperature environment of-16 ℃, then taking out the hydrogel to be thawed at room temperature, and performing circulating freeze thawing for three times to obtain the nano chitin-PVA hydrogel.
An electron micrograph of the 50% PVA/50% nano chitin-PVA hydrogel is shown in FIG. 6.
EXAMPLE seven
The embodiment provides a preparation method of nano chitin-PVA hydrogel, which comprises the following steps:
fully stirring and uniformly mixing the nano chitin dispersion liquid prepared in the first embodiment and 5 wt% of polyvinyl alcohol AH-26 solution at normal temperature, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 3: 7, mechanically stirring for 1.3 hours in an oil bath at 88 ℃ to perform physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction;
standing and cooling the mixed dispersion liquid after the physical crosslinking reaction to normal temperature, adjusting the pH to 1.3 by using HCl solution, adding 13g of 0.2 wt% glutaraldehyde solution, magnetically stirring uniformly and carrying out chemical crosslinking reaction to obtain nano chitin-PVA hydrogel, repeatedly washing the formed nano chitin-PVA hydrogel with deionized water, and removing residual crosslinking agent glutaraldehyde;
and (3) freezing the obtained hydrogel for 24h in a low-temperature environment of-10 ℃, then taking out the hydrogel to be thawed at room temperature, and performing circulating freeze thawing for three times to obtain the nano chitin-PVA hydrogel.
An electron micrograph of the 40% PVA/60% nano chitin-PVA hydrogel is shown in FIG. 7.
Comparative example 1
The comparative example provides a preparation method of nano chitin-PVA hydrogel, which is different from the fifth example in that a nano chitin dispersion liquid and a 7 wt% polyvinyl alcohol AH-26 solution are fully stirred and mixed uniformly at normal temperature, and the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol AH-26 solution is 20: 1, the other steps are the same as the preparation method of the fifth embodiment.
Comparative example No. two
The comparative example provides a preparation method of nano chitin-PVA hydrogel, which is different from the fifth example in that the step of physical crosslinking reaction is omitted, and the other steps are the same as the preparation method of the fifth example.
Comparative example No. three
The comparative example provides a preparation method of nano chitin-PVA hydrogel, which is different from the fifth example in that the step of chemical crosslinking reaction is omitted, and the other steps are the same as the preparation method of the fifth example.
Test example 1
The drug loading per unit mass and the maximum stress of the nano chitin-PVA hydrogel provided in each example and comparative example were measured, and the measurement results are shown in table 1.
TABLE 1 drug loading per unit mass and maximum stress of nano chitin-PVA hydrogels
As can be seen from table 1, the drug loading and the maximum stress per unit mass of the nano chitin-PVA hydrogel provided in the second to seventh embodiments of the present invention are much higher than those of the nano chitin-PVA hydrogels provided in the first to third embodiments, wherein the maximum stress is 5.12 to 6.68MPa, and the hydrogel can withstand the pressure of the environment in the human body, and is suitable for use as a drug carrier.
Compared with the fifth embodiment, the first embodiment shows that the hydrogel with excellent mechanical properties can be obtained only by reacting the nano chitin dispersion liquid and the polyvinyl alcohol solution within the protection range of the invention according to a certain mass ratio; compared with the fifth embodiment, the second embodiment shows that the physical crosslinking reaction can uniformly combine the nano chitin and the polyvinyl alcohol, and if the step is omitted, the pore distribution of the hydrogel generated by the reaction is not uniform, so that the drug loading and the mechanical property of the hydrogel are influenced; comparing the third comparative example with the fifth example, it is demonstrated that the chemical crosslinking reaction can stabilize the structure and properties of the hydrogel, and if this step is omitted, the mechanical properties of the hydrogel are affected.
Test example two
Bovine serum albumin solutions with the concentrations of 0.02mg/mL, 0.04mg/mL, 0.06mg/mL, 0.08mg/mL, 0.1mg/mL, 0.12mg/mL and 0.14mg/mL are prepared respectively, the absorbance of the prepared solution at 280nm is measured by a spectrophotometer, and a standard curve of the absorbance and the concentration is established, wherein the standard curve equation is that y is 0.60375x +0.00121, wherein x is the concentration, and y is the absorbance. FIG. 8 is a graph of absorbance versus concentration for bovine hemoglobin solutions.
After the nano chitin-PVA hydrogel provided in the second to seventh embodiments is dried in vacuum for 5 hours, 1g of the nano chitin-PVA hydrogel is weighed and placed in 50mL of release medium at the temperature of 37 ℃, the nano chitin-PVA hydrogel is swelled for at least 24 hours, the drug is loaded into the nano chitin-PVA hydrogel, 5mL of solution is taken out after a fixed interval of 1 hour, the absorbance of the prepared solution at 280nm is measured by a spectrophotometer, a standard curve of the absorbance and the concentration is established, and the bovine serum albumin slow release amount at different time points is calculated. FIG. 9 is a drug release curve of nano chitin-PVA hydrogel. Wherein CHINFS-10% represents 10% nano chitin, CHINFS-20% represents 20% nano chitin, CHINFS-30% represents 30% nano chitin, CHINFS-40% represents 40% nano chitin, CHINFS-50% represents 50% nano chitin, and CHINFS-60% represents 60% nano chitin.
As can be seen from FIG. 9, the nano chitin-PVA hydrogel provided by the invention is loaded with a drug to prepare a nano biomass-based anticancer drug, the drug release time can be as long as more than 80h, the action time of the drug is prolonged, the release period of the drug is remarkably increased, the side effect on a human body is reduced, and under the drug loading, the release rate of the drug is 50-80%, and the drug utilization rate is high.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (38)
1. An application of nano chitin-PVA hydrogel in preparing release protein drugs is characterized in that the preparation method of the nano chitin-PVA hydrogel comprises the following steps:
(a) mixing the nano chitin dispersion liquid with a polyvinyl alcohol solution to perform a physical crosslinking reaction to obtain a mixed dispersion liquid after the physical crosslinking reaction; the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol solution is (1-9): (1-9); the mass concentration of the polyvinyl alcohol solution is 5-10%;
(b) adding a cross-linking agent into the mixed dispersion liquid after the physical cross-linking reaction to perform a chemical cross-linking reaction to obtain the nano chitin-PVA hydrogel;
in the step (a), the preparation of the nano chitin dispersion solution comprises the steps of pretreating, deacetylating, protonating and homogenizing a chitin raw material;
wherein, the nano chitin dispersion solution and the polyvinyl alcohol solution in the step (a) are fully stirred and mixed evenly at normal temperature, and then stirred in an oil bath machine to generate physical crosslinking reaction.
2. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 1, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol solution is (1.5-8.5): (1.5-8.5).
3. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 1, wherein the mass ratio of the nano chitin dispersion liquid to the polyvinyl alcohol solution is 5: 5.
4. the use of the nano chitin-PVA hydrogel according to claim 1, wherein in the step (b), the cross-linking agent comprises at least one of glutaraldehyde, NN-methylenebisacrylamide, epichlorohydrin, sodium trimetaphosphate, or diene sulfone.
5. The use of the nano chitin-PVA hydrogel according to claim 1, wherein in the step (b), the cross-linking agent is glutaraldehyde.
6. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 1, wherein in the step (b), the cross-linking agent is glutaraldehyde aqueous solution, and the mass concentration of the glutaraldehyde aqueous solution is 0.1-0.5%.
7. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 6, wherein in the step (b), the mass concentration of the glutaraldehyde aqueous solution is 0.2-0.5%.
8. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 1, wherein in the step (a), the mass concentration of the polyvinyl alcohol solution is 6-10%.
9. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 1, wherein in the step (a), the mass concentration of the polyvinyl alcohol solution is 6-9%.
10. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 1, wherein in the step (a), the temperature of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution is 70-90 ℃.
11. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 10, wherein the temperature of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution is 75-90 ℃.
12. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 10, wherein the temperature of mixing the nano chitin dispersion liquid and the polyvinyl alcohol solution is 75-85 ℃.
13. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of a drug for releasing proteins, wherein in the step (a), the mass concentration of the nano chitin dispersion liquid is 1% -2%.
14. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 13, wherein the mass concentration of the nano chitin dispersion liquid is 1-1.8%.
15. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 13, wherein the mass concentration of the nano chitin dispersion liquid is 1.2-1.8%.
16. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of a drug for releasing proteins, further comprising the step (c): and (3) repeatedly freezing and thawing the nano chitin-PVA hydrogel.
17. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 16, wherein in the step (c), the freezing temperature is-10 ℃ to-20 ℃.
18. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 16, wherein in the step (c), the freezing temperature is-10 ℃ to-18 ℃.
19. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 16, wherein in the step (c), the freezing temperature is-12 ℃ to-18 ℃.
20. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of a drug for releasing proteins, wherein the chitin raw material comprises at least one of shrimp shell or crab shell.
21. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of a drug for releasing proteins, wherein the deproteinization in the pretreatment comprises: mixing chitin raw material with alkali solution to remove residual protein, and washing with deionized water to neutrality.
22. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 21, wherein the concentration of the alkali solution is 0.5-1 mol/L.
23. The use of the nano chitin-PVA hydrogel according to claim 21, wherein the alkali solution comprises at least one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution.
24. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of protein releasing drugs, wherein the demineralization in the pretreatment comprises: mixing the deproteinized chitin with inorganic acid to remove minerals, and washing with deionized water to neutrality.
25. The application of the nano chitin-PVA hydrogel in the preparation of protein releasing drugs according to claim 24, wherein the concentration of the inorganic acid is 0.5-1 mol/L.
26. The use of the nano chitin-PVA hydrogel according to claim 24, wherein the inorganic acid comprises at least one of hydrochloric acid and sulfuric acid.
27. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of a drug for releasing proteins, wherein the bleaching in the pretreatment comprises: mixing the chitin after removing minerals with bleaching agent for bleaching.
28. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 27, wherein the concentration of the bleaching agent is 0.5-1 mol/L.
29. The use of the nanochitin-PVA hydrogel according to claim 27, wherein the bleaching agent comprises at least one of sodium chlorite or calcium chlorite for the preparation of a drug that releases proteins.
30. The use of the nano chitin-PVA hydrogel according to claim 1 in the preparation of a drug for releasing proteins, wherein the deacetylation treatment comprises: and performing deacetylation reaction on the pretreated chitin at 70-90 ℃ by using an alkali solution.
31. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 30, wherein the mass concentration of the alkali solution is 20-40%.
32. The use of the nano chitin-PVA hydrogel according to claim 30, wherein the alkali solution comprises at least one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution.
33. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 1, wherein the pH of the protonation treatment is 3-4.
34. The use of the nano chitin-PVA hydrogel according to claim 33 in the preparation of a drug for releasing proteins, wherein the pH is 3.5-4.
35. The use of the nano chitin-PVA hydrogel according to claim 33, wherein the protonation treatment is performed with protonic acid, and the protonic acid comprises at least one of acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, aspartic acid, nucleotide, itaconic acid, malonic acid or ulfenac.
36. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 1, wherein in the step (b), the pH of the mixed dispersion liquid is 1-1.5.
37. The application of the nano chitin-PVA hydrogel in preparation of protein releasing drugs according to claim 1, wherein in the step (b), the pH of the mixed dispersion liquid is 1-1.2.
38. The use of the nano chitin-PVA hydrogel in the preparation of a drug for releasing protein according to claim 1, wherein the protein drug is at least one of glucose oxidase drug, insulin drug, interferon drug, collagen drug, heparin drug, superoxide dismutase drug, tissue growth factor drug or bovine serum albumin drug.
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Application publication date: 20190122 Assignee: Huagong Liyan (Guangdong) new material technology Co.,Ltd. Assignor: SOUTH CHINA University OF TECHNOLOGY Contract record no.: X2022980008303 Denomination of invention: Nano chitin PVA hydrogel and its preparation method and Application Granted publication date: 20211001 License type: Common License Record date: 20220628 |