CN111825856B - Anti-ultraviolet hydrogel and preparation method and application thereof - Google Patents

Anti-ultraviolet hydrogel and preparation method and application thereof Download PDF

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CN111825856B
CN111825856B CN202010579809.XA CN202010579809A CN111825856B CN 111825856 B CN111825856 B CN 111825856B CN 202010579809 A CN202010579809 A CN 202010579809A CN 111825856 B CN111825856 B CN 111825856B
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hydrogel
titanium dioxide
natural polysaccharide
polydopamine
ultraviolet
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CN111825856A (en
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纪禹行
于珊
耿志杰
国翠平
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GUANGDONG INSTITUTE OF MEDICAL INSTRUMENTS
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Abstract

The invention discloses an anti-ultraviolet hydrogel and a preparation method and application thereof. The ultraviolet-proof hydrogel is formed by crosslinking polydopamine-coated titanium dioxide and natural polysaccharide-based hydrogel. The ultraviolet-proof hydrogel can be applied as a drug carrier or a medical dressing. The ultraviolet-proof hydrogel provided by the invention has stronger compressive resistance, obviously enhanced ultraviolet resistance, obviously improved comprehensive performance and wide application prospect.

Description

Anti-ultraviolet hydrogel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to an ultraviolet-proof hydrogel and a preparation method and application thereof.
Background
The hydrogel is a hydrophilic three-dimensional network structure high polymer which can swell but does not dissolve in water, integrates the characteristics of water absorption, moisture retention, slow release, softness and the like, and is widely applied to the biomedical fields of soft corneal contact lenses, cell and enzyme fixation, drug delivery, tissue engineering and the like. At present, various methods for preparing physical hydrogel, chemical hydrogel and dynamic chemical hydrogel are available, and the prepared hydrogel has various characteristics in structure and performance, but the preparation of multifunctional hydrogel is still a difficult point and a hot point.
The natural polymer hydrogel has the advantages of rich source and low price firstly, and good biocompatibility secondly, thereby arousing the attention of more and more scholars. The natural polymer hydrogel has the disadvantage that the use of the natural polymer hydrogel can only be applied to specific fields in consideration of obvious differences of mechanical properties and stability of materials.
Disclosure of Invention
In order to overcome the problems of the conventional hydrogel, the invention aims to provide a polydopamine-coated titanium dioxide-reinforced ultraviolet-proof hydrogel, the invention aims to provide a preparation method of the ultraviolet-proof hydrogel, and the invention aims to provide application of the ultraviolet-proof hydrogel.
The invention concept of the invention is as follows: polydopamine (PDA) is one of the main pigments in natural melanin, and has excellent photoelectric effect and good biocompatibility. Catechol, polyfunctional amine and imine in the chemical structure of PDA can be used as the starting point for covalent bond modification. PDA has light absorption properties similar to melanin, which has broad-band absorption in the range of ultraviolet light to visible light, and light absorption extends up to the near infrared region. Titanium dioxide (TiO) 2 ) The catalyst has the characteristics of no toxicity and stable chemical property, is the most commonly used catalyst in photocatalytic reaction, has high refractivity and high optical activity, so that the catalyst has a refraction effect on ultraviolet rays, and the refracted wavelength is closely related to the particle size. In order to solve the problem of poor mechanical property of the traditional hydrogel, the invention provides a polydopamine-coated titanium dioxide particle (TiO) 2 @ PDA) hydrogen bond enhanced uv blocking hydrogels. The hydrogel is obtained by the interaction of multiple action mechanisms such as hydrogen bonds among PDA substances, schiff base bonds and hydrogen bonds among natural polysaccharide-based hydrogel substrates, hydrogen bonds and amido bond crosslinks among PDA substances and natural polysaccharide-based substances, the compressive strength of the hydrogel can be obviously improved, and TiO is used for preparing the hydrogel 2 The @ PDA particles have the functions of absorbing and refracting ultraviolet raysThe ultraviolet-proof function of the hydrogel can be greatly enhanced. Therefore, the invention develops a novel hydrogel with excellent mechanical property and capability of preventing ultraviolet rays by introducing multiple hydrogen bond crosslinking networks for energy dissipation through the structural design of the hydrogel network.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an ultraviolet-proof hydrogel, which is formed by crosslinking polydopamine-coated titanium dioxide and natural polysaccharide-based hydrogel.
Preferably, in the ultraviolet-proof hydrogel, the titanium dioxide is nano titanium dioxide; more preferably, the particle size of the titanium dioxide is 200nm to 400nm.
Among such uv-blocking hydrogels, the natural polysaccharide-based hydrogel is a hydrogel that has been formed by chemical crosslinking or physical crosslinking. Preferably, the natural polysaccharide-based hydrogel is at least one selected from chitosan, sodium alginate hydrogel, oxidized dextran hydrogel, gelatin hydrogel, pectin, carrageenan and starch; further preferably, the natural polysaccharide-based hydrogel is at least one selected from chitosan, sodium alginate hydrogel, oxidized dextran hydrogel and gelatin hydrogel.
Preferably, in the ultraviolet-proof hydrogel, the crosslinking mode comprises hydrogen bond crosslinking between polydopamine, schiff base bond and hydrogen bond crosslinking between natural polysaccharide-based hydrogels, and hydrogen bond and amide bond crosslinking between polydopamine and natural polysaccharide-based hydrogels.
The invention provides a preparation method of the ultraviolet-proof hydrogel in a second aspect.
A preparation method of an ultraviolet-proof hydrogel comprises the following steps:
1) Mixing a Dopamine (DA) solution and titanium dioxide for reaction to prepare polydopamine-coated titanium dioxide;
2) Mixing the first natural polysaccharide-based hydrogel solution with the polydopamine-coated titanium dioxide dispersion liquid to obtain a natural polysaccharide-based hydrogel precursor liquid containing polydopamine-coated titanium dioxide;
3) And (3) crosslinking the natural polysaccharide-based hydrogel precursor solution containing the polydopamine-coated titanium dioxide with a second natural polysaccharide-based hydrogel solution to obtain the ultraviolet-proof hydrogel.
Preferably, in the method for preparing the ultraviolet-proof hydrogel, the first natural polysaccharide-based hydrogel and the second natural polysaccharide-based hydrogel are respectively selected from any one of chitosan, sodium alginate hydrogel, oxidized dextran hydrogel, gelatin hydrogel, pectin, carrageenan and starch hydrogel.
Preferably, in the method for preparing the uv blocking hydrogel, the first natural polysaccharide-based hydrogel and the second natural polysaccharide-based hydrogel are different.
Preferably, in the preparation method of the ultraviolet-proof hydrogel, the step 1) is specifically as follows: and mixing the titanium dioxide dispersion liquid with the dopamine solution, and carrying out polymerization reaction under an alkaline condition to obtain the polydopamine-coated titanium dioxide.
Preferably, in step 1) of the preparation method, the mass ratio of titanium dioxide to dopamine is 1: (2-10); further preferably, in the step 1), the mass ratio of titanium dioxide to dopamine is 1: (3-5).
Preferably, in step 1) of the preparation method, the mass ratio of titanium dioxide to alkali is 1: (0.5 to 5); further preferably, in the step 1), the mass ratio of titanium dioxide to alkali is 1: (0.7-4).
Preferably, in step 1) of this production method, the titania content of the titania dispersion is 1 mg/mL-10 mg/mL; more preferably, in step 1), the titania content of the titania dispersion is 5mg/mL to 10mg/mL.
Preferably, in step 1) of the preparation method, the titanium dioxide is hydrophilic titanium dioxide nanoparticles, i.e. the titanium dioxide nanoparticles carry hydrophilic groups.
Preferably, in step 1) of the preparation method, the dopamine solution has a dopamine concentration of 10 mg/mL-50 mg/mL; further preferably, in the step 1), the dopamine concentration of the dopamine solution is 10 mg/mL-30 mg/mL.
Preferably, in step 1) of the preparation method, the alkaline condition refers to the reaction using an alkaline solution.
Preferably, in step 1) of the preparation method, the alkali solubility of the alkali solution is 5mg/mL to 50mg/mL; more preferably, in step 1), the alkali solubility of the alkali solution is 10mg/mL to 15mg/mL.
Preferably, in step 1) of this production method, the base is at least one selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate, and an alkali metal hydrogencarbonate; further preferably, in step 1), the base is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; still more preferably, in the step 1), the alkali is at least one selected from sodium hydroxide and potassium hydroxide.
Preferably, in step 1) of the preparation method, the volume ratio of the titanium dioxide dispersion to the dopamine solution is 1: (0.5 to 5); further preferably, in the step 1), the volume ratio of the titanium dioxide dispersion liquid to the dopamine solution is 1: (1-4).
Preferably, in step 1) of the preparation method, the volume ratio of the sum of the titanium dioxide dispersion liquid and the dopamine solution to the alkali solution is 1: (0.5 to 2); further preferably, in the step 1), the volume ratio of the sum of the titanium dioxide dispersion liquid and the dopamine solution to the alkali solution is 1.
Preferably, in step 1) of this production method, the reaction is carried out at 20 ℃ to 30 ℃; further preferably, in step 1), the reaction is carried out at room temperature (25 ℃).
Preferably, in step 1) of this preparation method, the reaction is carried out under protection from light.
Preferably, in step 1) of the preparation method, the reaction time is 1-48 h; further preferably, in the step 1), the reaction time is 12-36 h; still more preferably, in the step 1), the reaction time is 20 to 30 hours.
Preferably, in step 2) of the method for preparing the ultraviolet-proof hydrogel, the mass ratio of the polydopamine-coated titanium dioxide to the first natural polysaccharide-based hydrogel is 1: (1-10); further preferably, in the step 2), the mass ratio of the polydopamine-coated titanium dioxide to the first natural polysaccharide-based hydrogel is 1: (2-8).
Preferably, in step 2) of the method for preparing the ultraviolet blocking hydrogel, the first natural polysaccharide-based hydrogel solution has a first natural polysaccharide-based hydrogel concentration of 10mg/mL to 50mg/mL; further preferably, in the step 2), the first natural polysaccharide-based hydrogel concentration of the first natural polysaccharide-based hydrogel solution is 20mg/mL to 40mg/mL.
Preferably, in step 2) of the method for preparing the ultraviolet ray proof hydrogel, the first natural polysaccharide-based hydrogel solution further contains an acid; the mass percentage of the acid in the first natural polysaccharide-based hydrogel solution is preferably 0.5-2%; the acid in the first natural polysaccharide based hydrogel solution may be acetic acid.
Preferably, in step 2) of the method for preparing the uv-blocking hydrogel, the first natural polysaccharide-based hydrogel is at least one selected from chitosan, sodium alginate hydrogel, oxidized dextran hydrogel and gelatin hydrogel. The first natural polysaccharide-based hydrogel preferably comprises a hydrogel matrix having a plurality of hydroxyl and amino reactive groups. In some preferred embodiments of the present invention, the first natural polysaccharide-based hydrogel is chitosan.
Preferably, in step 2) of the preparation method of the ultraviolet-proof hydrogel, the content of the polydopamine-coated titanium dioxide in the polydopamine-coated titanium dioxide dispersion liquid is 5 mg/mL-40 mg/mL; further preferably, in the step 2), the content of the polydopamine-coated titanium dioxide in the polydopamine-coated titanium dioxide dispersion liquid is 10mg/mL to 20mg/mL.
Preferably, in step 2) of the method for preparing the ultraviolet-proof hydrogel, the volume ratio of the first natural polysaccharide-based hydrogel solution to the polydopamine-coated titanium dioxide dispersion is (0.5-5): 1; further preferably, in the step 2), the volume ratio of the first natural polysaccharide-based hydrogel solution to the polydopamine-coated titanium dioxide dispersion is (1-4): 1.
preferably, in step 3) of the method for preparing the ultraviolet-proof hydrogel, the mass ratio of the natural polysaccharide-based hydrogel containing the polydopamine-coated titanium dioxide to the second natural polysaccharide-based hydrogel is 1: (5-50); further preferably, in step 3), the mass ratio of the natural polysaccharide-based hydrogel containing the polydopamine-coated titanium dioxide to the second natural polysaccharide-based hydrogel is 1: (8 to 30).
Preferably, in step 3) of the method for preparing the uv blocking hydrogel, the concentration of the second natural polysaccharide-based hydrogel in the second natural polysaccharide-based hydrogel solution is 50mg/mL to 150mg/mL; further preferably, in step 3), the concentration of the second natural polysaccharide-based hydrogel in the second natural polysaccharide-based hydrogel solution is 80mg/mL to 120mg/mL.
Preferably, in step 3) of the method for preparing the uv-blocking hydrogel, the second natural polysaccharide-based hydrogel is at least one selected from chitosan, sodium alginate hydrogel, oxidized dextran hydrogel and gelatin hydrogel. The second natural polysaccharide-based hydrogel preferably comprises a hydrogel matrix having a plurality of hydroxyl and aldehyde-based reactive groups. In some preferred embodiments of the present invention, the second natural polysaccharide-based hydrogel is an oxidized dextran hydrogel.
In some preferred embodiments of the present invention, the natural polysaccharide-based hydrogel is selected from chitosan hydrogel and oxidized dextran hydrogel, and the two natural polysaccharide-based hydrogels not only contain hydroxyl groups, but also have amino groups and aldehyde groups, respectively, the combination of the two natural polysaccharide-based hydrogels can not only form hydrogen bonds but also form schiff base bonds, and the aldehyde groups in the polysaccharide and the amino groups in dopamine can also form schiff base bonds with each other. Therefore, the advantage of preferably forming hydrogel by the two polysaccharides is that not only hydrogen bonds and Schiff base bonds can be formed between the polysaccharides, but also the Schiff base bonds can be formed between the polysaccharides and the doped dopamine, so that the mechanical property is improved. Meanwhile, the two natural polysaccharide-based hydrogels also have the advantage of good biocompatibility from the viewpoint of biomedical applications.
Preferably, in step 3) of the method for preparing the ultraviolet-proof hydrogel, the volume ratio of the natural polysaccharide-based hydrogel precursor solution containing the polydopamine-coated titanium dioxide to the second natural polysaccharide-based hydrogel solution is 1: (1-10); further preferably, in step 3), the volume ratio of the natural polysaccharide-based hydrogel precursor solution containing the polydopamine-coated titanium dioxide to the second natural polysaccharide-based hydrogel solution is 1: (2.5-5).
In step 3) of the preparation method of the ultraviolet-proof hydrogel, the crosslinking method can be covalent bond crosslinking or non-covalent bond crosslinking. Preferably, in step 3), the crosslinking method is at least one selected from hydrogen bond crosslinking, schiff base bond crosslinking, double bond crosslinking, mercapto-double bond crosslinking and ionic crosslinking; further preferably, in step 3), the crosslinking method is Schiff base bond crosslinking and hydrogen bond crosslinking.
Preferably, in the step 3) of the preparation method of the ultraviolet-proof hydrogel, the crosslinking temperature is 20-30 ℃; further preferably, in step 3), the temperature for crosslinking is room temperature (25 ℃).
Preferably, in the step 3) of the preparation method of the ultraviolet-proof hydrogel, the crosslinking time is 5min to 30min; further preferably, in the step 3), the time for crosslinking is 10 to 15min.
In a third aspect, the present invention provides the use of the above-mentioned UV-blocking hydrogel.
The application of the ultraviolet-proof hydrogel in a drug carrier or a medical dressing.
Preferably, in use, the medical dressing is an anti-uv dressing.
The beneficial effects of the invention are:
the ultraviolet-proof hydrogel provided by the invention has stronger compressive resistance, obviously enhanced ultraviolet resistance, obviously improved comprehensive performance and wide application prospect.
Specifically, the method comprises the following steps: the invention provides a preparation method of polydopamine-coated titanium dioxide-enhanced ultraviolet-proof hydrogel, which is a method for post-treatment secondary enhancement of hydrogel rich in hydroxyl. The used preparation raw materials have good biocompatibility and biological stability, the mechanical property of the obtained hydrogel is obviously enhanced, the ultraviolet resistance is obviously improved, the comprehensive performance is good, and the hydrogel can be applied as a drug carrier or a medical dressing material.
Drawings
FIG. 1 is a macroscopic view of the hydrogel of comparative example 1 and the hydrogel of example 1;
FIG. 2 is a test chart of the hydrogel of comparative example 1 and the hydrogel of example 1 before swelling and swelling process;
FIG. 3 is a graph showing the ratio of volume change in swelling in water of the hydrogel of comparative example 1 and the hydrogel of example 1;
FIG. 4 is a graph showing the compression resistance test of the hydrogel of comparative example 1 and the hydrogel of example 1;
FIG. 5 is a graph showing UV-VIS absorption spectra of the hydrogel of comparative example 1 and the hydrogel of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or apparatus used in the examples and comparative examples were obtained from conventional commercial sources or can be obtained by a method of the prior art, unless otherwise specified. Unless otherwise indicated, the testing or testing methods are conventional in the art.
The titanium dioxide used in the examples was hydrophilic titanium dioxide particles having a particle size of 300nm.
Example 1
1. TiO2 2 Preparation of @ PDA nanoparticles
(1) Adding hydrophilic TiO 2 Dispersing the nano particles in an aqueous solution, and performing ultrasonic dispersion for 30 minutes to form a uniform dispersion liquid;
(2) Adding TiO into the mixture 2 Mixing the dispersion (5 mg/mL) and DA solution (20 mg/mL) according to a volume ratio of 1 2 @ PDA nano particle solution, finally freeze drying to obtain TiO 2 @ PDA nanoparticles.
2. TiO2 2 uV-proof hydrogel reinforced with @ PDA particles
(1) TiO obtained in the first step 2 Preparing 20mg/mL aqueous solution from the @ PDA nano particles, dropwise adding the aqueous solution into the prepared 20mg/mL aqueous solution of chitosan (containing 1wt% acetic acid), and mixing the chitosan solution and TiO 2 The volume ratio of the @ PDA nano particle aqueous solution is 2,to obtain a catalyst containing TiO 2 A chitosan precursor solution of @ PDA nanoparticles;
(2) Preparing 100mg/mL aqueous solution of oxidized dextran, blending the aqueous solution of oxidized dextran with chitosan precursor solution (V/V = 5/1), and after 10min at room temperature, forming TiO from the mixed solution 2 @ PDA nanoparticle doped chitosan/oxidized dextran hydrogel, tiO 2 @ PDA particles reinforced UV protected hydrogels.
Example 2
1. TiO2 2 Preparation of @ PDA nanoparticles
(1) Adding hydrophilic TiO 2 Dispersing the nano particles in an aqueous solution, and performing ultrasonic dispersion for 40 minutes to form a uniform dispersion liquid;
(2) Mixing TiO with 2 Mixing the dispersion (10 mg/mL) and the DA solution (30 mg/mL) according to a volume ratio of 1 2 @ PDA nano particle solution, finally freeze drying to obtain TiO 2 @ PDA nanoparticles.
2. TiO2 2 uV-proof hydrogel reinforced with @ PDA particles
(1) TiO obtained in the first step 2 Preparing 10mg/mL aqueous solution from the @ PDA nano particles, dropwise adding the aqueous solution into the prepared 20mg/mL aqueous solution of chitosan (containing 1wt% acetic acid), and mixing the chitosan solution and TiO 2 The volume ratio of the @ PDA nano particle aqueous solution is 4 2 A chitosan precursor solution of @ PDA nanoparticles;
(2) Preparing 100mg/mL aqueous solution of oxidized dextran, blending the aqueous solution of oxidized dextran with chitosan precursor solution (V/V = 5/2), and after 15min at room temperature, forming TiO from the mixed solution 2 @ PDA nanoparticle doped chitosan/oxidized dextran hydrogel, tiO 2 @ PDA particles reinforced UV protected hydrogels.
Example 3
1. TiO2 2 Preparation of @ PDA nanoparticles
(1) Adding hydrophilic TiO 2 The nanoparticles are dispersed in an aqueous solutionUltrasonically dispersing for 30 minutes to form uniform dispersion liquid;
(2) Mixing TiO with 2 Mixing the dispersion (10 mg/mL) and the DA solution (10 mg/mL) according to a volume ratio of 1 2 @ PDA nano particle solution, finally freeze drying to obtain TiO 2 @ PDA nanoparticles.
2. TiO2@ PDA particle reinforced UV-proof hydrogel
(1) TiO obtained in the first step 2 Preparing 20mg/mL aqueous solution from the @ PDA nano particles, dropwise adding the aqueous solution into the prepared 40mg/mL aqueous solution of chitosan (containing 1wt% acetic acid), and mixing the chitosan solution and TiO 2 The volume ratio of the @ PDA nano particle aqueous solution is 1 2 A chitosan precursor solution of @ PDA nanoparticles;
(2) Preparing 100mg/mL aqueous solution of oxidized dextran, blending the aqueous solution of oxidized dextran with chitosan precursor solution (V/V = 5/2), and after 10min at room temperature, forming TiO from the mixed solution 2 @ PDA nanoparticle doped chitosan/oxidized dextran hydrogel, tiO 2 @ PDA particles reinforced UV protected hydrogels.
Comparative example 1
1. Preparing chitosan solution and oxidized dextran aqueous solution
2g of chitosan was dissolved in 100mL of an aqueous solution (containing 1wt% acetic acid), and the solution was magnetically stirred for 3 hours to obtain an aqueous chitosan solution. 1g of oxidized dextran was dissolved in 10mL of the aqueous solution, and magnetically stirred for 3 hours to obtain an oxidized dextran aqueous solution.
2. Chitosan/oxidized dextran hydrogel
The aqueous solution of oxidized dextran was blended with the chitosan precursor solution (V/V = 5/1), and after 10min, the mixed solution formed a chitosan/oxidized dextran hydrogel.
TiO obtained in example 1 2 A macroscopic view of the UV-blocking hydrogel reinforced with @ PDA particles and the chitosan/oxidized dextran hydrogel prepared in comparative example 1 is shown in FIG. 1.
Performance testing
TiO from example 1 2 The performance test was performed on the UV blocking hydrogel reinforced with @ PDA particles and the chitosan/oxidized dextran hydrogel prepared in comparative example 1.
1. Comparison of swelling
Example 1TiO 2 @ PDA particle reinforced UV protected hydrogels and comparative example 1 Chitosan/oxidized dextran hydrogel swelled in water, FIG. 2 is example 1TiO 2 @ PDA particle enhanced UV protection hydrogel and comparative example 1 Chitosan/oxidized dextran hydrogel before swelling and swelling process test plots. Through TiO 2 The hydrogel reinforced with the @ PDA particles changed from white to tan indicating the presence of TiO 2 @ PDA particles exist in hydrogen bonding cross-links.
2. Change in swelling volume
FIG. 3 is example 1TiO 2 Graph of the volume change ratio of chitosan/oxidized dextran hydrogel swollen in water for the @ PDA particle-reinforced UV protection hydrogel and comparative example 1.
3. Mechanical testing (compression test)
The modulus of the hydrogels was determined by an universal mechanical tester (Instron 5540A). The hydrogel was demolded into a cylinder 15mm in diameter and 3mm in height. The compression rate during the test was 5mm/min. The slope (5-10%) at the linear region of the stress-strain curve is defined as the compressive property of the hydrogel.
FIG. 4 is example 1TiO 2 The compression resistance test plots for the @ PDA particle reinforced UV protected hydrogel and comparative example 1 chitosan/oxidized dextran hydrogel. As can be seen in FIG. 4, the mechanical strength of the chitosan/oxidized dextran hydrogel was about 57kPa 2 The mechanical strength of the ultraviolet-proof hydrogel reinforced by the @ PDA particles is about 18kPa, and the elastic strength is enhanced by more than 3 times, which indicates that the TiO 2 The compression resistance of the uV-protected hydrogel reinforced with @ PDA particles is significantly enhanced.
4. Ultraviolet resistance test
Example 1TiO testing Using UV-Vis absorption Spectroscopy 2 @ PDA particle enhanced UV blocking hydrogel and comparative example 1 Chitosan/oxidized dextran hydrogel vs. UVLight absorption intensity. The hydrogel obtained in the example 1 and the hydrogel obtained in the comparative example 1 are placed in a sample cell of an ultraviolet visible absorption spectrometer, ultraviolet scanning is carried out on the hydrogel, the scanning wavelength is 200-800nm, and the absorption peak wavelength and the absorption peak intensity of the sample are observed.
FIG. 5 is example 1TiO 2 Uv-vis absorption spectra of @ PDA particle enhanced uv blocking hydrogel and comparative example 1 chitosan/oxidized dextran hydrogel. As can be seen from the comparison in FIG. 5, the results obtained by TiO 2 The doping of the @ PDA particles enables the ultraviolet light absorption intensity of the hydrogel to be remarkably enhanced near 300nm, and the ultraviolet light absorption hydrogel has an ultraviolet resistance function.
As shown by the results of the performance tests, the TiO prepared in example 1 2 Compared with the chitosan/oxidized glucan hydrogel in the comparative example 1, the ultraviolet-proof hydrogel reinforced by the @ PDA particles has stronger compression resistance, enhanced ultraviolet resistance and relatively better comprehensive performance.
In summary, the invention takes polysaccharide (chitosan/oxidized dextran) as raw material and adopts TiO to treat 2 The @ PDA particles are doped, and hydrogen bond self-crosslinking and intermolecular hydrogen bond crosslinking are introduced into a hydrogel system to obtain the novel reinforced hydrogel. TiO prepared by the method 2 The @ PDA/chitosan/oxidized glucan hydrogel has the characteristics of obviously enhanced and controllable anti-compression performance, obviously enhanced anti-ultraviolet effect, excellent biocompatibility and the like. The preparation method is simple and feasible, has low energy consumption, saves time and materials, has good repeatability, and the constructed TiO 2 The @ PDA/chitosan/oxidized glucan hydrogel can be widely applied to the field of tissue engineering, can be used as a drug carrier or a medical dressing material (such as an anti-ultraviolet medical dressing), and has good clinical application prospect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. An ultraviolet-protective hydrogel, which is characterized in that: the anti-ultraviolet hydrogel is formed by crosslinking polydopamine-coated titanium dioxide and natural polysaccharide-based hydrogel; the titanium dioxide is nano titanium dioxide; the natural polysaccharide-based hydrogel is chitosan and oxidized glucan hydrogel;
the ultraviolet-proof hydrogel is prepared by the preparation method comprising the following steps:
1) Mixing the dopamine solution and titanium dioxide for reaction to prepare polydopamine-coated titanium dioxide;
2) Mixing the first natural polysaccharide-based hydrogel solution with the polydopamine-coated titanium dioxide dispersion liquid to obtain a natural polysaccharide-based hydrogel precursor liquid containing polydopamine-coated titanium dioxide;
3) Crosslinking a natural polysaccharide-based hydrogel precursor solution containing polydopamine-coated titanium dioxide with a second natural polysaccharide-based hydrogel solution to obtain the anti-ultraviolet hydrogel;
the first natural polysaccharide-based hydrogel is chitosan;
the second natural polysaccharide-based hydrogel is an oxidized dextran hydrogel.
2. The uv-blocking hydrogel according to claim 1, wherein: the crosslinking mode comprises hydrogen bond crosslinking among polydopamine, schiff base bond and hydrogen bond crosslinking among natural polysaccharide-based hydrogels, and hydrogen bond and amido bond crosslinking among polydopamine and natural polysaccharide-based hydrogels.
3. A method for preparing the UV blocking hydrogel of claim 1, wherein: the method comprises the following steps:
1) Mixing the dopamine solution and titanium dioxide for reaction to prepare polydopamine-coated titanium dioxide;
2) Mixing the first natural polysaccharide-based hydrogel solution with the polydopamine-coated titanium dioxide dispersion liquid to obtain a natural polysaccharide-based hydrogel precursor liquid containing polydopamine-coated titanium dioxide;
3) Crosslinking a natural polysaccharide-based hydrogel precursor solution containing polydopamine-coated titanium dioxide with a second natural polysaccharide-based hydrogel solution to obtain the anti-ultraviolet hydrogel;
the first natural polysaccharide-based hydrogel is chitosan;
the second natural polysaccharide-based hydrogel is an oxidized dextran hydrogel.
4. The production method according to claim 3, characterized in that: the step 1) is specifically as follows: and mixing the titanium dioxide dispersion liquid and the dopamine solution, and carrying out polymerization reaction under an alkaline condition to obtain the polydopamine-coated titanium dioxide.
5. The method of claim 4, wherein: in the step 1), the mass ratio of the titanium dioxide to the dopamine is 1: (2 to 10).
6. The production method according to claim 3, characterized in that: in the step 2), the mass ratio of the titanium dioxide coated with the polydopamine to the first natural polysaccharide-based hydrogel is 1: (1 to 10).
7. The production method according to claim 3, characterized in that: in the step 3), the mass ratio of the natural polysaccharide-based hydrogel containing the polydopamine-coated titanium dioxide to the second natural polysaccharide-based hydrogel is 1: (5 to 50).
8. Use of the uv-blocking hydrogel of any one of claims 1 to 2 in a pharmaceutical carrier or a medical dressing.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107641179A (en) * 2017-09-30 2018-01-30 西南交通大学 A kind of preparation method of the self-adhesion attached water gel with freeze proof/heat resistanceheat resistant performance
CN110237782A (en) * 2019-06-26 2019-09-17 中南民族大学 A kind of preparation method of high-strength, antioxidant chitosan/poly-dopamine composite hydrogel
CN111286045A (en) * 2020-03-11 2020-06-16 广东省医疗器械研究所 Polyphenol substance hydrogen bond-enhanced hydrogel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107641179A (en) * 2017-09-30 2018-01-30 西南交通大学 A kind of preparation method of the self-adhesion attached water gel with freeze proof/heat resistanceheat resistant performance
CN110237782A (en) * 2019-06-26 2019-09-17 中南民族大学 A kind of preparation method of high-strength, antioxidant chitosan/poly-dopamine composite hydrogel
CN111286045A (en) * 2020-03-11 2020-06-16 广东省医疗器械研究所 Polyphenol substance hydrogen bond-enhanced hydrogel

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Nanohybrid organic-inorganic chitosan/dopamine/TiO2 composites with controlled drug-delivery properties";Mostafa safari等;《Applied surface science》;20150314;第342卷;第26-33页 *
"PVDF/多巴胺改性二氧化钛复合膜光阻隔性研究";李同兵等;《工程塑料应用》;20160610;第44卷(第6期);第26-31页 *

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