CN109251330A - Nano-chitosan-PVA hydrogel and its preparation method and application - Google Patents
Nano-chitosan-PVA hydrogel and its preparation method and application Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The present invention provides a kind of nano-chitosan-PVA hydrogels and its preparation method and application, are related to biomedical material technology.The preparation method of nano-chitosan-PVA hydrogel includes the following steps: that (a) mixes nano-chitosan dispersion liquid with poly-vinyl alcohol solution, and physical crosslinking reaction occurs, the mixed dispersion liquid after obtaining physical crosslinking reaction；(b) crosslinking agent is added into the mixed dispersion liquid after physical crosslinking reaction, chemical crosslink reaction occurs, obtains nano-chitosan-PVA hydrogel.The preparation method of nano-chitosan-PVA hydrogel provided by the invention is mixed using nano-chitosan dispersion liquid with poly-vinyl alcohol solution, physical crosslinking reaction occurs, the mixed dispersion liquid after physical crosslinking reaction is mixed with crosslinking agent again, chemical crosslink reaction occurs, nano-chitosan-PVA hydrogel is obtained, preparation process is simple, at low cost, energy consumption is small, realizes the sustainable development of production.
Description
Technical field
The present invention relates to biomedical material technology, more particularly, to a kind of nano-chitosan-PVA hydrogel and its
Preparation method and application.
Background technique
Hydrogel is a kind of with three-dimensional crosslinked network structure, can absorb and keep large quantity of moisture, and not soluble in water
Functional polymer material.The special construction of hydrogel itself makes it be provided simultaneously with the property of solid and liquid, i.e. table on mechanics
Reveal class solid property, and thermodynamically then shows class I liquid I behavior.Hydrogel because its have low cost, porosity, compared with
The characteristics such as high strength, optical transparence, biodegradability, high swelling ratio, biocompatibility and stimulating responsive are wide
It is general to be applied to the fields such as food, cosmetics, medical and health, agricultural and environmental protection, already have become a hot topic of research.
Chitin is the natural polymer that nature biotechnology synthetic quantity is only second to cellulose, and main source is that Crustachia is dynamic
The cell wall of the object such as shell of shrimp, crab and certain mushrooms, algae, molecular structure are by 2- acetylaminohydroxyphenylarsonic acid 2- deoxidation-D- pyrans Portugal
Dextran and 2- amino -2- deoxidation-D- glucopyra glycan are with binary linear polymer made of β -1,4 glucosides key connections
The poly- polysaccharide of the unique a large amount of existing alkaline kations of nature.Chitin has good physiological compatibility and biodegradable
Property, it is a kind of important bio-medical material.
Currently, the preparation process of existing nano-chitosan-PVA hydrogel is complicated, at high cost, energy consumption is high, can not can hold
Supervention exhibition, the nano-chitosan-PVA hydrogel hole being prepared is uneven, and poor mechanical property is poor to the transitivity of drug.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of nano-chitosan-PVA hydrogel and preparation method thereof, existing to alleviate
There is preparation process present in technology complicated, at high cost, energy consumption is high, can not the technical problems such as sustainable development.
The preparation method of nano-chitosan-PVA hydrogel provided by the invention, includes the following steps:
(a) nano-chitosan dispersion liquid is mixed with poly-vinyl alcohol solution, physical crosslinking reaction occurs, is physical crosslinking
Mixed dispersion liquid after reaction；
(b) crosslinking agent is added into the mixed dispersion liquid after physical crosslinking reaction, chemical crosslink reaction occurs, obtains nanometer
Chitin-PVA hydrogel.
Further, in the step (a), the mass ratio of the nano-chitosan and polyvinyl alcohol is (1~9): (1~
9)；Preferably (1.5~8.5): (1.5~8.5)；Further preferably 5:5.
Further, in the step (b), the crosslinking agent includes glutaraldehyde, NN- methylene-bisacrylamide, epoxy
At least one of chloropropane, sodium trimetaphosphate or diene sulfone；Preferably, the crosslinking agent is glutaraldehyde；It is further preferred that
The crosslinking agent is glutaraldehyde water solution, and the mass concentration of the glutaraldehyde water solution is 0.1~0.5%；Still more preferably
, the mass concentration of the glutaraldehyde water solution is 0.2~0.5%.
Further, in the step (a), the mass concentration of the poly-vinyl alcohol solution is 5~10%；Preferably 6~
10%；Further preferably 6~9%；
And/or in the step (a), the temperature that the nano-chitosan dispersion liquid is mixed with poly-vinyl alcohol solution is 70
~90 DEG C；Preferably 75~90 DEG C；Further preferably 75~85 DEG C；
And/or in the step (a), the mass concentration of the nano-chitosan dispersion liquid is 1%~2%；Preferably 1
~1.8%；Further preferably 1.2~1.8%.
It further, further include step (c): by nano-chitosan-PVA hydrogel repeated freezing-thawing；
Preferably, in the step (c), the temperature of the freezing is -10 DEG C~-20 DEG C；It is further preferred that described cold
The temperature of jelly is -10 DEG C~-18 DEG C；Still more preferably, the temperature of the freezing is -12 DEG C~-18 DEG C.
Further, in the step (a), the preparation of the nano-chitosan dispersion liquid includes carrying out to chitin raw material
Pretreatment, it is deacetylated processing, protonation processing and it is homogeneous；
Preferably, the chitin raw material includes at least one of shrimp shell or crab shell.
Further, the deproteinized includes: that chitin raw material is mixed to removal residual protein with aqueous slkali, is then spent
Ion is washed to neutrality；Preferably, the concentration of the aqueous slkali is 0.5~1mol/L；It is further preferred that the aqueous slkali packet
Include at least one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution；
And/or it is described to remove minerals include: that the chitin after deproteinized is mixed minerals with inorganic acid, then use
Deionized water is washed till neutrality；Preferably, the concentration of the inorganic acid is 0.5~1mol/L；It is further preferred that the inorganic acid
Including at least one of hydrochloric acid, sulfuric acid or acetic acid；
And/or the bleaching includes: that will remove the chitin after minerals and bleaching agent mixed bleach；Preferably, the drift
White dose of concentration is 0.5~1mol/L；It is further preferred that the bleaching agent include in sodium chlorite or calcium chlorite at least
It is a kind of；
And/or the deacetylated processing includes: that pretreated chitin is carried out with aqueous slkali at 70~90 DEG C to de- second
Acyl reaction；Preferably, the mass concentration of the aqueous slkali is 20~40%, it is further preferred that the aqueous slkali includes hydrogen-oxygen
Change at least one of sodium solution, potassium hydroxide solution or calcium hydroxide solution；
And/or the pH of the protonation processing is 3~4；Preferably, the pH is 3.5~4；It is further preferred that institute
Stating Bronsted acid includes acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, aspartic acid, nucleotide, clothing health
Acid, malonic acid or coloured glaze clap at least one of acid.
Further, in the step (b), the pH of the mixed dispersion liquid is 1~1.5；Preferably, the pH be 1~
1.2。
The second object of the present invention is to provide a kind of nano-chitosan-PVA hydrogel, and the hydrogel hole is uniform, power
Have excellent performance.
Nano-chitosan-PVA hydrogel provided by the invention is prepared by above-mentioned preparation method.
The third object of the present invention is to provide a kind of nano-chitosan-PVA hydrogel and discharges protein medicaments in preparation
In application, the nano-chitosan-PVA hydrogel has good delivering effect to the drug being loaded into hydrogel, and delays
It is good to release effect.
Application of the nano-chitosan-PVA hydrogel provided by the invention in preparation release protein medicaments；
Preferably, the protein medicaments are glucose oxidase class drug, trypsin class medicine, interferons drug class
Drug, collagen class drug, heparin class drug, superoxide dismutase class drug, tissue growth factor class drug or ox blood
At least one of albumins drug.
Compared with prior art, the invention has the following advantages:
The preparation method of nano-chitosan-PVA hydrogel provided by the invention is using nano-chitosan dispersion liquid and poly- second
Enolate solution mixing occurs physical crosslinking reaction, then the mixed dispersion liquid after physical crosslinking reaction is mixed with crosslinking agent, occurs
Chemical crosslink reaction obtains nano-chitosan-PVA hydrogel, and preparation process is simple, and at low cost, energy consumption is small, realizes production
Sustainable development.
Nano-chitosan-PVA hydrogel hole provided by the invention is uniform, excellent in mechanical performance.
Nano-chitosan-PVA hydrogel provided by the invention has the protein medicaments being loaded into hydrogel good
Effect is delivered, and slow release effect is good, the protide slow releasing pharmaceutical being prepared is able to extend the action time of drug, significant to increase
Reduce the side effect to human body the deenergized period of dosing object, the release rate of drug is high, and utilization ratio of drug is high.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the AFM figure of nano-chitosan dispersion liquid；
Fig. 2 is the electron microscope of 90%PVA/10% nano-chitosan-PVA hydrogel；
Fig. 3 is the electron microscope of 80%PVA/20% nano-chitosan-PVA hydrogel；
Fig. 4 is the electron microscope of 70%PVA/30% nano-chitosan-PVA hydrogel；
Fig. 5 is the electron microscope of 60%PVA/40% nano-chitosan-PVA hydrogel；
Fig. 6 is the electron microscope of 50%PVA/50% nano-chitosan-PVA hydrogel；
Fig. 7 is the electron microscope of 40%PVA/60% nano-chitosan-PVA hydrogel；
Fig. 8 is the absorbance and concentration relationship curve graph of bovine serum albumen solution；
Fig. 9 is the drug release patterns figure for loading protein drug hydrogel.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument are not
Production firm person is indicated, is the conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, the present invention provides a kind of preparation sides of nano-chitosan-PVA hydrogel
Method includes the following steps:
(a) nano-chitosan dispersion liquid is mixed with poly-vinyl alcohol solution, physical crosslinking reaction occurs, is physical crosslinking
Mixed dispersion liquid after reaction；
(b) crosslinking agent is added into the mixed dispersion liquid after physical crosslinking reaction, chemical crosslink reaction occurs, obtains nanometer
Chitin-PVA hydrogel.
The preparation method of nano-chitosan-PVA hydrogel provided by the invention is using nano-chitosan dispersion liquid and poly- second
Enolate solution mixing occurs physical crosslinking reaction, then the mixed dispersion liquid after physical crosslinking reaction is mixed with crosslinking agent, occurs
Chemical crosslink reaction obtains nano-chitosan-PVA hydrogel, and preparation process is simple, and at low cost, energy consumption is small, realizes production
Sustainable development.
In one preferred embodiment, in the step (b), the mass ratio of the nano-chitosan and polyvinyl alcohol
For (1~9): (1~9)；Preferably (1.5~8.5): (1.5~8.5)；Further preferably 5:5.
Wherein, the mass ratio of nano-chitosan and polyvinyl alcohol such as can be, but be 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 nano-chitosan-PVA hydrogel provided by the invention is using a certain proportion of nano-chitosan point
Dispersion liquid and poly-vinyl alcohol solution occur physical crosslinking reaction, nano-chitosan can be made to combine with being evenly distributed with polyvinyl alcohol
Together, it is also beneficial to the progress of subsequent chemistry cross-linking reaction.
In one preferred embodiment, in the step (b), the crosslinking agent includes glutaraldehyde, NN- di-2-ethylhexylphosphine oxide
At least one of acrylamide, epoxychloropropane, sodium trimetaphosphate or diene sulfone；Preferably, the crosslinking agent is glutaraldehyde；
It is further preferred that the crosslinking agent is glutaraldehyde water solution, the mass concentration of the glutaraldehyde water solution is 0.1~0.5%；
Still more preferably, the mass concentration of the glutaraldehyde water solution is 0.2~0.5%.
Monomer, linear macromolecule or prepolymer can be transformed into the object of tridimensional network by crosslinking agent under certain condition
Matter.
Wherein, the mass concentration of glutaraldehyde water solution for example can be, but be not limited to 0.1%, 0.2%, 0.3%, 0.4%
Or 0.5%.
The preparation method of nano-chitosan-PVA hydrogel provided by the invention uses certain density glutaraldehyde water solution
As crosslinking agent, promotes nano-chitosan and polyvinyl alcohol that chemical crosslink reaction occurs, obtain nano-chitosan-PVA hydrogel.
In one preferred embodiment, in the step (a), the mass concentration of the poly-vinyl alcohol solution is 5~
10%；Preferably 6~10%；Further preferably 6~9%.
Raw material of the polyvinyl alcohol as nano-chitosan-PVA hydrogel, structure and performance and poly-vinyl alcohol solution it is dense
Spend closely related, when the mass concentration of poly-vinyl alcohol solution is 5~10%, obtained nano-chitosan-PVA hydrogel is mechanical
Functional, property is stablized.
Wherein, the mass concentration of polyvinyl alcohol for example can be, but be not limited to 5%, 6%, 7%, 8%, 9% or 10%.
In one preferred embodiment, in the step (b), the nano-chitosan dispersion liquid and polyvinyl alcohol are molten
The temperature of liquid mixing is 70~90 DEG C；Preferably 75~90 DEG C；Further preferably 75~85 DEG C.
Wherein, the temperature that nano-chitosan dispersion liquid is mixed with poly-vinyl alcohol solution for example can be, but be not limited to 70 DEG C,
72 DEG C, 74 DEG C, 76 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C or 90 DEG C.
In one preferred embodiment, in the step (a), the mass concentration of the nano-chitosan dispersion liquid is
1%~2%；Preferably 1~1.8%；Further preferably 1.2~1.8%.
Wherein, the mass concentration of nano-chitosan dispersion liquid for example can be, but be not limited to 1%, 1.1%, 1.2%,
1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2%.
It in one preferred embodiment, further include step (c): by nano-chitosan-PVA hydrogel repeated freezing-
Melt.Repeated freezing-thawing can make the structural form of nano-chitosan-PVA hydrogel more stable, and mechanical property is more excellent
It is good.
In a preferred embodiment of present embodiment, in the step (c), the temperature of the freezing is -10 DEG C
~-20 DEG C；It is further preferred that the temperature of the freezing is -10 DEG C~-18 DEG C；Still more preferably, the temperature of the freezing
Degree is -12 DEG C~-18 DEG C.
Wherein, cryogenic temperature for example can be, but be not limited to -10 DEG C, -11 DEG C, -12 DEG C, -13 DEG C, -14 DEG C, -15 DEG C, -
16 DEG C, -17 DEG C, -18 DEG C, -19 DEG C or -20 DEG C.
In one preferred embodiment, in the step (a), the preparation of the nano-chitosan dispersion liquid includes pair
Chitin raw material pre-processed, deacetylated processing, protonation processing and homogeneous.
In a preferred embodiment of present embodiment, the chitin raw material include in shrimp shell or crab shell at least
It is a kind of.
Shrimp shell or crab shell in the Yu Haiyang of chitin raw material source, utilize again, cheap, environmentally protective.
In one preferred embodiment, the deproteinized include: chitin raw material is mixed with aqueous slkali removal it is residual
Then remaining albumen is washed with deionized water to neutrality；Preferably, the concentration of the aqueous slkali is 0.5~1mol/L；Further preferably
, the aqueous slkali includes at least one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution.
In one preferred embodiment, it is described go minerals include: by after deproteinized chitin and inorganic acid-mixed
Minerals are removed in conjunction, are then washed with deionized water to neutrality；Preferably, the concentration of the inorganic acid is 0.5~1mol/L；Further
Preferably, the inorganic acid includes at least one of hydrochloric acid, sulfuric acid or acetic acid.
In one preferred embodiment, the bleaching includes: that the chitin after minerals will be gone to mix with bleaching agent
Bleaching；Preferably, the concentration of the bleaching agent is 0.5~1mol/L；It is further preferred that the bleaching agent includes sodium chlorite
Or at least one of calcium chlorite.
In one preferred embodiment, the deacetylated processing includes: by pretreated chitin aqueous slkali
In 70~90 DEG C of progress deacetylations；Preferably, the mass concentration of the aqueous slkali is 20~40%, it is further preferred that
The aqueous slkali includes at least one of sodium hydroxide solution, potassium hydroxide solution or calcium hydroxide solution.
In one preferred embodiment, the pH of the protonation processing is 3~4；Preferably, the pH be 3.5~
4；It is further preferred that the Bronsted acid includes acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, day
Aspartic acid, nucleotide, itaconic acid, malonic acid or coloured glaze clap at least one of acid.
In one preferred embodiment, in the step (b), the pH of the mixed dispersion liquid is 1~1.5；It is preferred that
, the pH is 1~1.2.
When the pH value of mixed dispersion liquid is 1~1.5, the hydrogel pore communication that cross-linking reaction obtains is good, and hole is equal
Even, elasticity is good, excellent in mechanical performance, and property is stablized in the actual environment, not affected by environment and destroy its gelling performance.
Wherein, pH for example can be, but be not limited to 1,1.1,1.2,1.3,1.4 or 1.5.
According to the second aspect of the invention, the present invention provides a kind of nano-chitosan-PVA hydrogels.
Nano-chitosan-PVA hydrogel hole provided by the invention is uniform, excellent in mechanical performance.
According to the third aspect of the present invention, the present invention provides a kind of nano-chitosan-PVA hydrogels discharges in preparation
Application in protein medicaments.
Nano-chitosan-PVA hydrogel provided by the invention has the protein medicaments being loaded into hydrogel good
Effect is delivered, and slow release effect is good, the protide slow releasing pharmaceutical being prepared is able to extend the action time of drug, significant to increase
Reduce the side effect to human body the deenergized period of dosing object, the release rate of drug is high, and utilization ratio of drug is high.
In a preferred embodiment of present embodiment, the protein medicaments be glucose oxidase class drug,
Trypsin class medicine, interferons drug class drug, collagen class drug, heparin class drug, superoxide dismutase class medicine
At least one of object, tissue growth factor class drug or bovine serum albumin class drug.
In order to facilitate the clearer understanding present invention, below in conjunction with embodiment and comparative example to technical side of the invention
Case is described further.
Embodiment one
The preparation method for present embodiments providing a kind of nano-chitosan dispersion liquid, includes the following steps:
The 20g shrimp shell discarded is immersed in 1mol/L sodium hydroxide solution, mechanical stirring 2h, removes residual protein, and
It is washed with deionized water to neutrality；Then it is immersed in 1mol/L hydrochloric acid, mechanical stirring 2h demineralizes, and uses deionized water
It is washed till neutrality；It is finally immersed in 2h in 0.8mol/L sodium chlorite solution, chitin is bleached to treated；It is dried after bleaching
It is dry；Chitin after drying is immersed in the sodium hydroxide solution of 30wt% the progress deacetylated processing 3h in part at 90 DEG C,
5g sodium borohydride is added simultaneously, deacetylated rate is 45%, is subsequently added into vinegar acid for adjusting pH to 3.5, obtains chitin suspension, incite somebody to action
Chitin suspension obtains nano-chitosan dispersion liquid by high pressure homogenizer homogeneous, measures nano-chitosan dispersion liquid at this time
Solid content, addition deionized water be configured to 1.2% mass concentration chitin dispersion liquid, be placed at 4 DEG C and be sealed.The nanometer
The partial size of chitin is between 10~150nm.The AFM figure of nano-chitosan dispersion liquid is as shown in Figure 1.
Embodiment two
The preparation method for present embodiments providing a kind of nano-chitosan-PVA hydrogel, includes the following steps:
The polyvinyl alcohol AH-26 solution for the nano-chitosan dispersion liquid and 10wt% that embodiment one is prepared is in room temperature
Under be thoroughly mixed uniformly, the mass ratio of nano-chitosan dispersion liquid and polyvinyl alcohol AH-26 solution is 9:1, then 70
Mechanical stirring 2h in DEG C oil bath brings it about physical crosslinking reaction, the mixed dispersion liquid after obtaining physical crosslinking reaction；
Will physical crosslinking reaction after mixed dispersion liquid standing is cooled to room temperature, with HCl solution adjust PH to 1.5, then plus
Enter the glutaraldehyde solution of 10g 0.3wt%, the uniform concurrent biochemical cross-linking reaction of magnetic agitation obtains nano-chitosan-PVA water
Nano-chitosan-PVA the hydrogel of formation is rinsed with deionized water repeatedly, removes remaining crosslinking agent glutaraldehyde by gel；
Nano-chitosan-PVA hydrogel is placed in -20 DEG C of freezing 12h, then takes out and melts in room temperature, circulating freezing resistance three
It is secondary, obtain nano-chitosan-PVA hydrogel.
The electron microscope of 90%PVA/10% nano-chitosan-PVA hydrogel is as shown in Figure 2.
Embodiment three
The preparation method for present embodiments providing a kind of nano-chitosan-PVA hydrogel, includes the following steps:
The polyvinyl alcohol AH-26 solution for the nano-chitosan dispersion liquid and 9wt% that embodiment one is prepared is in room temperature
Under be thoroughly mixed uniformly, the mass ratio of nano-chitosan dispersion liquid and polyvinyl alcohol AH-26 solution is 8.5:1.5, then
The mechanical stirring 1.8h in 75 DEG C of oil baths brings it about physical crosslinking reaction, the mixed dispersion liquid after obtaining physical crosslinking reaction；
Will physical crosslinking reaction after mixed dispersion liquid standing is cooled to room temperature, with HCl solution adjust PH to 1.2, then plus
Enter the glutaraldehyde solution of 8g 0.5wt%, the uniform concurrent biochemical cross-linking reaction of magnetic agitation obtains nano-chitosan-PVA water
Nano-chitosan-PVA the hydrogel of formation is rinsed with deionized water repeatedly, removes remaining crosslinking agent glutaraldehyde by gel；
Resulting hydrogel is carried out to be placed in -18 DEG C of low temperature environment freezing 14h, then takes out and melts in room temperature, circulation is frozen
Melt three times, obtains nano-chitosan-PVA hydrogel.
The electron microscope of 80%PVA/20% nano-chitosan-PVA hydrogel is as shown in Figure 3.
Example IV
The preparation method for present embodiments providing a kind of nano-chitosan-PVA hydrogel, includes the following steps:
The polyvinyl alcohol AH-26 solution for the nano-chitosan dispersion liquid and 8wt% that embodiment one is prepared is in room temperature
Under be thoroughly mixed uniformly, the mass ratio of nano-chitosan dispersion liquid and polyvinyl alcohol AH-26 solution is 7:3, then 85
Mechanical stirring 1.6h in DEG C oil bath brings it about physical crosslinking reaction, the mixed dispersion liquid after obtaining physical crosslinking reaction；
Will physical crosslinking reaction after mixed dispersion liquid standing is cooled to room temperature, with HCl solution adjust PH to 1.4, then plus
Enter the glutaraldehyde solution of 9g 0.4wt%, the uniform concurrent biochemical cross-linking reaction of magnetic agitation obtains nano-chitosan-PVA water
Nano-chitosan-PVA the hydrogel of formation is rinsed with deionized water repeatedly, removes remaining crosslinking agent glutaraldehyde by gel；
Resulting hydrogel is carried out to be placed in -14 DEG C of low temperature environment freezing 18h, then takes out and melts in room temperature, circulation is frozen
Melt three times, obtains nano-chitosan-PVA hydrogel.
The electron microscope of 70%PVA/30% nano-chitosan-PVA hydrogel is as shown in Figure 4.
Embodiment five
The preparation method for present embodiments providing a kind of nano-chitosan-PVA hydrogel, includes the following steps:
The polyvinyl alcohol AH-26 solution for the nano-chitosan dispersion liquid and 7wt% that embodiment one is prepared is in room temperature
Under be thoroughly mixed uniformly, the mass ratio of nano-chitosan dispersion liquid and polyvinyl alcohol AH-26 solution is 5:5, then 80
Mechanical stirring 1.5h in DEG C oil bath brings it about physical crosslinking reaction, the mixed dispersion liquid after obtaining physical crosslinking reaction；
Will physical crosslinking reaction after mixed dispersion liquid standing is cooled to room temperature, with HCl solution adjust PH to 1.3, then plus
Enter the glutaraldehyde solution of 12g 0.3wt%, the uniform concurrent biochemical cross-linking reaction of magnetic agitation obtains nano-chitosan-PVA water
Nano-chitosan-PVA the hydrogel of formation is rinsed with deionized water repeatedly, removes remaining crosslinking agent glutaraldehyde by gel；
Resulting hydrogel is carried out to be placed in -12 DEG C of low temperature environment freezing 20h, then takes out and melts in room temperature, circulation is frozen
Melt three times, obtains nano-chitosan-PVA hydrogel.
The electron microscope of 60%PVA/40% nano-chitosan-PVA hydrogel is as shown in Figure 5.
Embodiment six
The preparation method for present embodiments providing a kind of nano-chitosan-PVA hydrogel, includes the following steps:
The polyvinyl alcohol AH-26 solution for the nano-chitosan dispersion liquid and 6wt% that embodiment one is prepared is in room temperature
Under be thoroughly mixed uniformly, the mass ratio of nano-chitosan dispersion liquid and polyvinyl alcohol AH-26 solution is 3.5:6.5, then
The mechanical stirring 1h in 90 DEG C of oil baths brings it about physical crosslinking reaction, the mixed dispersion liquid after obtaining physical crosslinking reaction；
Will physical crosslinking reaction after mixed dispersion liquid standing is cooled to room temperature, with HCl solution adjust PH to 1.1, then plus
Enter the glutaraldehyde solution of 20g 0.1wt%, the uniform concurrent biochemical cross-linking reaction of magnetic agitation obtains nano-chitosan-PVA water
Nano-chitosan-PVA the hydrogel of formation is rinsed with deionized water repeatedly, removes remaining crosslinking agent glutaraldehyde by gel；
Resulting hydrogel is carried out to be placed in -16 DEG C of low temperature environment freezing 16h, then takes out and melts in room temperature, circulation is frozen
Melt three times, obtains nano-chitosan-PVA hydrogel.
The electron microscope of 50%PVA/50% nano-chitosan-PVA hydrogel is as shown in Figure 6.
Embodiment seven
The preparation method for present embodiments providing a kind of nano-chitosan-PVA hydrogel, includes the following steps:
The polyvinyl alcohol AH-26 solution for the nano-chitosan dispersion liquid and 5wt% that embodiment one is prepared is in room temperature
Under be thoroughly mixed uniformly, the mass ratio of nano-chitosan dispersion liquid and polyvinyl alcohol AH-26 solution is 3:7, then 88
Mechanical stirring 1.3h in DEG C oil bath brings it about physical crosslinking reaction, the mixed dispersion liquid after obtaining physical crosslinking reaction；
Will physical crosslinking reaction after mixed dispersion liquid standing is cooled to room temperature, with HCl solution adjust PH to 1.3, then plus
Enter the glutaraldehyde solution of 13g 0.2wt%, the uniform concurrent biochemical cross-linking reaction of magnetic agitation obtains nano-chitosan-PVA water
Nano-chitosan-PVA the hydrogel of formation is rinsed with deionized water repeatedly, removes remaining crosslinking agent glutaraldehyde by gel；
Resulting hydrogel is carried out to be placed in -10 DEG C of low temperature environment freezings for 24 hours, then takes out and melts in room temperature, circulation is frozen
Melt three times, obtains nano-chitosan-PVA hydrogel.
The electron microscope of 40%PVA/60% nano-chitosan-PVA hydrogel is as shown in Figure 7.
Comparative example one
This comparative example provides a kind of preparation method of nano-chitosan-PVA hydrogel, unlike embodiment five,
The polyvinyl alcohol AH-26 solution of nano-chitosan dispersion liquid and 7wt% are thoroughly mixed uniformly at normal temperature, nano-chitosan
The mass ratio of dispersion liquid and polyvinyl alcohol AH-26 solution is 20:1, other identical as the preparation method of embodiment five.
Comparative example two
This comparative example provides a kind of preparation method of nano-chitosan-PVA hydrogel, unlike embodiment five,
The step of omitting physical crosslinking reaction, it is other identical as the preparation method of embodiment five.
Comparative example three
This comparative example provides a kind of preparation method of nano-chitosan-PVA hydrogel, unlike embodiment five,
The step of omitting chemical crosslink reaction, it is other identical as the preparation method of embodiment five.
Test example one
By the drugloading rate of the unit mass of the provided nano-chitosan-PVA hydrogel of each embodiment and comparative example with
And maximum stress is detected, testing result is as shown in table 1.
The drugloading rate and maximum stress of the unit mass of 1 nano-chitosan-PVA hydrogel of table
As shown in Table 1, using the unit matter of nano-chitosan-PVA hydrogel provided by the embodiment of the present invention two to seven
The drugloading rate and maximum stress of amount are significantly larger than the unit matter of nano-chitosan-PVA hydrogel provided by comparative example one to three
The drugloading rate and maximum stress of amount, wherein maximum stress is 5.12~6.68MPa, is able to bear the pressure of human internal environment, is fitted
For as pharmaceutical carrier hydrogel.
Comparative example one illustrates nano-chitosan point only within protection scope of the present invention compared with embodiment five
Dispersion liquid and poly-vinyl alcohol solution can just obtain the hydrogel of good mechanical performance according to certain mass ratio by reaction；Comparative example
Two compared with embodiment five, illustrates that physical crosslinking reaction can be such that nano-chitosan is incorporated in being evenly distributed with polyvinyl alcohol
Together, if omitting this step, the hydrogel distribution of pores for reacting generation is uneven, influences the drugloading rate and mechanical property of hydrogel
Energy；Comparative example three illustrates that chemical crosslink reaction can make the structure of hydrogel and property more stable compared with embodiment five,
If omitting this step, the mechanical property of hydrogel is influenced.
Test example two
Respectively compound concentration be 0.02mg/mL, 0.04mg/mL, 0.06mg/mL, 0.08mg/mL, 0.1mg/mL,
The bovine serum albumen solution of 0.12mg/mL and 0.14mg/mL prepares suction of the solution at 280nm using spectrophotometric determination
Luminosity establishes the standard curve of absorbance and concentration, and calibration curve equation y=0.60375x+0.00121, wherein x is dense
Degree, y is absorbance.Fig. 8 is the relation curve that ox blood asks protein solution absorbance and concentration.
After nano-chitosan-PVA hydrogel provided by embodiment two to seven is dried in vacuo 5h, respectively weighs 1g and be placed in 37
In the release culture medium of 50mL at a temperature of DEG C, swelling at least for 24 hours, makes it be loaded into drug, takes out 5mL behind the fixed interval 1h
Solution prepares absorbance of the solution at 280nm using spectrophotometric determination, establishes the standard curve of absorbance and concentration,
Calculate different time points bovine serum albumin sustained release amount.Fig. 9 is the medicament slow release curve of nano-chitosan-PVA hydrogel.Wherein
CHINFS-10% indicates that 10% nano-chitosan, CHINFS-20% indicate that 20% nano-chitosan, CHINFS-30% indicate
30% nano-chitosan, CHINFS-40% indicate that 40% nano-chitosan, CHINFS-50% indicate 50% nano-chitosan,
CHINFS-60% indicates 60% nano-chitosan.
As shown in Figure 9, nano biological matter base is made after being loaded into drug in nano-chitosan-PVA hydrogel provided by the invention
Anticarcinogen, medicament slow release time can be up to 80h or more, extend the action time of drug, the deenergized period of significantly increasing medicament,
The side effect to human body is reduced, and under above-mentioned drugloading rate, the release rate of drug is 50~80%, and utilization ratio of drug is high.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of nano-chitosan-PVA hydrogel, which comprises the steps of:
(a) nano-chitosan dispersion liquid is mixed with poly-vinyl alcohol solution, physical crosslinking reaction occurs, obtain physical crosslinking reaction
Mixed dispersion liquid afterwards；
(b) crosslinking agent is added into the mixed dispersion liquid after physical crosslinking reaction, chemical crosslink reaction occurs, obtains a nanometer crust
Element-PVA hydrogel.
2. the preparation method of nano-chitosan-PVA hydrogel according to claim 1, which is characterized in that the step
(a) in, the mass ratio of the nano-chitosan and polyvinyl alcohol is (1~9): (1~9)；Preferably (1.5~8.5): (1.5~
8.5)；Further preferably 5:5.
3. the preparation method of nano-chitosan-PVA hydrogel according to claim 1, which is characterized in that the step
(b) in, the crosslinking agent includes glutaraldehyde, NN- methylene-bisacrylamide, epoxychloropropane, sodium trimetaphosphate or diene sulfone
At least one of；Preferably, the crosslinking agent is glutaraldehyde；It is further preferred that the crosslinking agent is glutaraldehyde water solution,
The mass concentration of the glutaraldehyde water solution is 0.1~0.5%；Still more preferably, the quality of the glutaraldehyde water solution
Concentration is 0.2~0.5%.
4. the preparation method of nano-chitosan-PVA hydrogel according to claim 1, which is characterized in that the step
(a) in, the mass concentration of the poly-vinyl alcohol solution is 5~10%；Preferably 6~10%；Further preferably 6~9%；
And/or in the step (a), the temperature that the nano-chitosan dispersion liquid is mixed with poly-vinyl alcohol solution is 70~90
℃；Preferably 75~90 DEG C；Further preferably 75~85 DEG C；
And/or in the step (a), the mass concentration of the nano-chitosan dispersion liquid is 1%~2%；Preferably 1~
1.8%；Further preferably 1.2~1.8%.
5. the preparation method of nano-chitosan-PVA hydrogel according to claim 1, which is characterized in that further include step
(c): by nano-chitosan-PVA hydrogel repeated freezing-thawing；
Preferably, in the step (c), the temperature of the freezing is -10 DEG C~-20 DEG C；It is further preferred that the freezing
Temperature is -10 DEG C~-18 DEG C；Still more preferably, the temperature of the freezing is -12 DEG C~-18 DEG C.
6. the preparation method of nano-chitosan-PVA hydrogel according to claim 1, which is characterized in that the step
(a) in, the preparation of the nano-chitosan dispersion liquid include chitin raw material is pre-processed, deacetylated processing, protonation
It handles and homogeneous；
Preferably, the chitin raw material includes at least one of shrimp shell or crab shell.
7. the preparation method of nano-chitosan-PVA hydrogel according to claim 6, which is characterized in that the deproteinized
Include: that chitin raw material is mixed to removal residual protein with aqueous slkali, is then washed with deionized water to neutrality；Preferably, described
The concentration of aqueous slkali is 0.5~1mol/L；It is further preferred that the aqueous slkali includes that sodium hydroxide solution, potassium hydroxide are molten
At least one of liquid or calcium hydroxide solution；
And/or it is described to remove minerals include: that the chitin after deproteinized is mixed minerals with inorganic acid, then spend from
Son is washed to neutrality；Preferably, the concentration of the inorganic acid is 0.5~1mol/L；It is further preferred that the inorganic acid includes
At least one of hydrochloric acid, sulfuric acid or acetic acid；
And/or the bleaching includes: that will remove the chitin after minerals and bleaching agent mixed bleach；Preferably, the bleaching agent
Concentration be 0.5~1mol/L；It is further preferred that the bleaching agent includes at least one in sodium chlorite or calcium chlorite
Kind；
And/or it is described it is deacetylated processing include: pretreated chitin is carried out with aqueous slkali at 70~90 DEG C it is deacetylated instead
It answers；Preferably, the mass concentration of the aqueous slkali is 20~40%, it is further preferred that the aqueous slkali includes sodium hydroxide
At least one of solution, potassium hydroxide solution or calcium hydroxide solution；
And/or the pH of the protonation processing is 3~4；Preferably, the pH is 3.5~4；It is further preferred that the matter
Sub- acid include acetic acid, folic acid, gluconic acid, oxalic acid, lysine, linolenic acid, citric acid, aspartic acid, nucleotide, itaconic acid,
Malonic acid or coloured glaze clap at least one of acid.
8. the preparation method of nano-chitosan-PVA hydrogel according to claim 1, which is characterized in that the step
(b) in, the pH of the mixed dispersion liquid is 1~1.5；Preferably, the pH is 1~1.2.
9. a kind of nano-chitosan-PVA hydrogel being prepared by preparation method according to any one of claims 1 to 8.
10. a kind of nano-chitosan-PVA hydrogel being prepared by preparation method according to any one of claims 1 to 8 or
Application of the nano-chitosan-PVA hydrogel as claimed in claim 9 in preparation release protein medicaments；
Preferably, the protein medicaments are glucose oxidase class drug, trypsin class medicine, interferons drug class medicine
Object, collagen class drug, heparin class drug, superoxide dismutase class drug, tissue growth factor class drug or cow's serum
At least one of protein medicaments.
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| CN113307989B (en) * | 2021-06-07 | 2022-07-29 | 中山大学 | Preparation method and application of in-situ growth nano calcium carbonate hydrogel sponge marine antifouling material |
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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 |