CN112940291A - Transparent hydrogel based on chitosan and preparation method thereof - Google Patents

Transparent hydrogel based on chitosan and preparation method thereof Download PDF

Info

Publication number
CN112940291A
CN112940291A CN202110161784.6A CN202110161784A CN112940291A CN 112940291 A CN112940291 A CN 112940291A CN 202110161784 A CN202110161784 A CN 202110161784A CN 112940291 A CN112940291 A CN 112940291A
Authority
CN
China
Prior art keywords
chitosan
hydrogel
aldehyde
linking agent
transparent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110161784.6A
Other languages
Chinese (zh)
Other versions
CN112940291B (en
Inventor
马明明
李元亨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN202110161784.6A priority Critical patent/CN112940291B/en
Publication of CN112940291A publication Critical patent/CN112940291A/en
Application granted granted Critical
Publication of CN112940291B publication Critical patent/CN112940291B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention provides a chitosan-based transparent hydrogel with ultrahigh water content, high transparency and better mechanical property and a preparation method thereof. The chitosan hydrogel only contains chitosan as a unique macromolecule, and is crosslinked by using micromolecular glyoxylic acid, so that the synthesis method is simple and easy, and the water content and the mechanical strength of the final hydrogel can be adjusted by adjusting the initial feeding ratio and the feeding concentration. In addition, the chitosan hydrogel overcomes the defects that the existing hydrogel is difficult to have high water content, high transparency and high biocompatibility, the water content can reach 99.7-99.9%, the transparency is close to 100% in a visible light range, and meanwhile, the strength of the chitosan hydrogel is close to that of animal tendons, so that the chitosan hydrogel can be applied to the field of biological medicines.

Description

Transparent hydrogel based on chitosan and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogel, and particularly relates to transparent hydrogel based on chitosan and a preparation method thereof.
Background
With the development of biomaterials and biotechnology, the research of hydrogels based on biopolymers has been carried out. The biopolymer hydrogel combines the advantages of biopolymers and hydrogels: the biological polymer has better biocompatibility, and the mechanical property and flexible processability of the hydrogel are superior. Many naturally occurring polymers (referred to as natural polymers) have found applications in the fields of cell culture, tissue engineering, implantable devices, and the like. Biopolymer-based hydrogel materials are also gradually entering the field of view of researchers. The development of novel biological polymer hydrogel which is closer to biological tissues and more environment-friendly, and the application of the novel biological polymer hydrogel to the field of biological medicines is one of the future key directions in the field of biological materials.
Chitosan is a natural polysaccharide, also known as deacetylated chitin, obtained by partial deacetylation of chitin. Chitin is the second most abundant natural polymer (second to cellulose) in the earth, so chitosan is simple and easy to obtain, has large yield and low cost, and is suitable for being used as biopolymer hydrogel. In addition, the molecular chain of the chitosan is rich in amino and carboxyl, and the amino and the carboxyl can be crosslinked with other macromolecules or crosslinked with the amino and the carboxyl. In addition, the degradation product of the chitosan is nontoxic oligosaccharide, and is friendly to human body and environment. These properties make chitosan an ideal material for biomedical applications.
The hydrogel material based on chitosan has better biocompatibility, and the raw materials are simple and easy to obtain, so that a new idea for preparing the biopolymer hydrogel is provided. In recent years, some chitosan hydrogel materials have been used in the biomedical field, mostly multi-component hydrogels formed by chitosan and other polymers, such as carrageenan or polyacrylamide. There are two main ways of preparing chitosan hydrogel: physical crosslinking and chemical crosslinking. The chitosan hydrogel prepared by the physical method generally has poor chemical stability. Chemical crosslinking, while a relatively stable and tough chitosan hydrogel can be obtained, the method is often more complicated, and the addition of other types of polymers and crosslinking agents to the material can also impair the biocompatibility and transparency of the material. In view of biomedical applications, chitosan hydrogels should have good biocompatibility, high water content, and strength similar to human tissues. However, hydrogels often have difficulty achieving both higher water content and better mechanical properties: existing high water content chitosan hydrogels are generally soft and have high mechanical strength and a high probability of containing poorly biocompatible components.
The Ziliang Wu task group designs and prepares a Carrageenan-Chitosan Hydrogel film (Ultrathin kappa-Carrageenan/Chitosan Hydrogel Films with High Toughhness and additive property. ACS Appl. Mater. Interfaces 2018,10, 9002-9009) with High strength, the physical method is utilized to entangle Chitosan molecular chains with Carrageenan molecular chains, the water content of the obtained Hydrogel is 48-88%, and the tensile strength is 2-6.7 kPa. The hydrogel film has good biocompatibility, but has low water content and poor operability due to the limitation of the thickness of the film.
The Decheng Wu task group designs a double-network chitosan hydrogel (Yang, Y.Y.; Wang, X.; Yang, F.; Wang, L.N.; Wu, D.C. high Elastic and ultra high Hybrid-aqueous Hydrogels with a Tunable Structures and mechanical. advanced Materials 2018,30 (18)), which utilizes Ionic-Covalent crosslinking to obtain a double-network hydrogel composed of chitosan and polyacrylamide, has very good mechanical properties, can achieve a tensile stress at break of 5.6MPa, and can be repeatedly stretched tens of times. However, during the mechanical strengthening of the gel by treatment with a sulfate solution, the gel system changes from transparent to opaque, losing transparency and reducing the water content while improving mechanical properties. In addition, a large amount of reactants are introduced in the process of firstly chemically crosslinking and then treating by utilizing ions, so that the biocompatibility of the system is reduced, and the synthetic process is complicated.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a chitosan-based transparent hydrogel having ultra-high water content, high transparency and good mechanical properties, and a preparation method thereof.
The invention provides a transparent hydrogel based on chitosan, which is characterized by being formed by chitosan and an aldehyde micromolecule cross-linking agent; the aldehyde small molecule cross-linking agent comprises a carboxyl group.
Preferably, the aldehyde small molecule cross-linking agent is selected from glyoxylic acid; the viscosity of the chitosan is more than or equal to 400 mPas.
Preferably, the mass ratio of the chitosan to the aldehyde small molecule cross-linking agent is 1: (0.5 to 1.5).
Preferably, the water content of the transparent hydrogel after swelling is more than 99%.
Preferably, the fracture compression stress of the swollen transparent hydrogel is 19-45 kPa; the fracture compression strain is 16-30%.
The invention also provides a preparation method of the transparent hydrogel based on chitosan, which comprises the following steps:
s) mixing chitosan and an aldehyde micromolecule cross-linking agent in water, and heating for reaction to obtain the transparent hydrogel based on chitosan.
Preferably, the mass concentration of the chitosan in the mixed system is 2-4%; the mass concentration of the aldehyde micromolecule cross-linking agent in the mixed system is 1.4-2%.
Preferably, the step S) is specifically:
dispersing chitosan in water, adding an aqueous solution of an aldehyde micromolecule cross-linking agent under a heating condition, and stirring and mixing to obtain a viscous solution;
and heating the viscous solution for reaction to obtain the transparent chitosan-based hydrogel.
Preferably, the ratio of the chitosan to the water is (0.15-0.2) g: 3 ml; the concentration of the aldehyde micromolecule cross-linking agent in the aqueous solution of the aldehyde micromolecule cross-linking agent is 0.03-0.04 g/mL; the heating temperature is 45-50 ℃; the stirring and mixing time is more than or equal to 10-60 min.
Preferably, the viscous solution is subjected to defoaming treatment and then is subjected to heating reaction to obtain the transparent hydrogel based on chitosan; the temperature of the heating reaction is 70-80 ℃; the heating reaction time is 4-6 h.
The invention provides a transparent hydrogel based on chitosan, which is formed by chitosan and an aldehyde micromolecule cross-linking agent; the aldehyde small molecule cross-linking agent comprises a carboxyl group. Compared with the prior art, the chitosan-based transparent hydrogel provided by the invention takes the chitosan as the only macromolecule in the hydrogel, and the crosslinking is carried out by utilizing the aldehyde micromolecule crosslinking agent containing carboxyl, so that the obtained hydrogel has ultrahigh water content, high transparency and better mechanical property.
The invention further provides a preparation method of the transparent hydrogel based on chitosan, in the method, chitosan is subjected to secondary crosslinking under the action of aldehyde micromolecules to form hydrogel, and the mechanical strength and the saturated water content of the hydrogel can be adjusted by adjusting the initial feeding ratio and the feeding concentration, so that the preparation method is practical and flexible.
Experiments show that the water content of the CSG hydrogel prepared by the invention can reach 99.7-99.9 percent, and the transparency is close to 100 percent in the visible light range; meanwhile, the breaking compression strength of the CSG hydrogel is 20-45 kPa, and the breaking compression strength is similar to that of animal tendons. The ultra-high water content, high transparency and strength comparable to biological tissues of the hydrogel enable the hydrogel to be applied to the field of biological medicine.
Drawings
FIG. 1 is a photograph showing the preparation process and the final product of a transparent chitosan-based hydrogel in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of the hydrogel after freeze-drying treatment in example 1 of the present invention;
FIG. 3 is a graph showing the compression curves of CSG hydrogels of different compositions in examples 1 to 4 of the present invention;
FIG. 4 is a chart of an ultraviolet-visible light spectrum of a CSG hydrogel obtained in example 1 of the present invention;
FIG. 5 is a photograph of a CSG hydrogel obtained in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 invention provides a transparent hydrogel based on chitosan, which is formed by chitosan and an aldehyde micromolecule cross-linking agent; the aldehyde small molecule cross-linking agent comprises a carboxyl group.
The chitosan is preferably high-viscosity chitosan; the viscosity of the chitosan is preferably more than or equal to 400 mPas, and is more preferably 400 to 800 mPas; the aldehyde small molecule cross-linking agent is preferably glyoxylic acid.
The mass ratio of the chitosan to the aldehyde small molecule cross-linking agent is preferably 1: (0.5 to 1.5), more preferably 1: (0.7-1.5), and more preferably 1: (0.78 to 1.4); in some embodiments provided herein, the mass ratio of chitosan to aldehyde small molecule crosslinker is specifically 1:1.05, 1:0.78 or 1: 1.4.
the water content of the chitosan-based transparent hydrogel adhesive after swelling is preferably more than 99%, and the water content can be correspondingly adjusted through the feeding ratio and the feeding concentration; in the examples provided herein, the chitosan-based transparent hydrogel has a water content after swelling of 99.7%, 99.2%, 99.4%, or 99.9%.
The fracture compressive stress of the chitosan-based transparent hydrogel after swelling is preferably 19-45 kPa; in the examples provided by the present invention, the fracture compressive stress of the chitosan-based transparent hydrogel after swelling is specifically 45kPa, 23kPa, 21kPa or 19 kPa; the fracture compressive strain is preferably 16 to 30 percent; in embodiments provided herein, the chitosan-based transparent hydrogel has a specific compressive strain at break after swelling of 26%, 19%, 30%, or 16%.
The chitosan-based transparent hydrogel provided by the invention takes chitosan as the only macromolecule in the hydrogel, and is crosslinked by using the aldehyde micromolecule crosslinking agent containing carboxyl, so that the obtained hydrogel has ultrahigh water content, high transparency and better mechanical property.
The invention also provides a preparation method of the transparent hydrogel based on chitosan, which comprises the following steps: s) mixing chitosan and an aldehyde micromolecule cross-linking agent in water, and heating for reaction to obtain the transparent hydrogel based on chitosan.
Wherein, the sources of all raw materials are not specially limited and can be sold in the market; the types and the proportions of the chitosan and the aldehyde micromolecule cross-linking agent are the same as those described above, and are not described again; in the present invention, the amount of the substance of chitosan is calculated as its single-stranded segment, unless otherwise specified.
Mixing chitosan and an aldehyde micromolecule cross-linking agent in water; in the invention, preferably, the chitosan is dispersed in water, then the aqueous solution of the aldehyde micromolecule cross-linking agent is added under the heating condition, and the mixture is stirred and mixed; the preferable ratio of the chitosan to the water is (0.15-0.2) g: 3 ml; the concentration of the aldehyde micromolecule cross-linking agent in the aqueous solution of the aldehyde micromolecule cross-linking agent is preferably 0.03-0.04 g/mL; the heating temperature is preferably 45-50 ℃; the stirring and mixing time is preferably more than or equal to 10min, and more preferably 20-30 min; the mass concentration of the chitosan in the mixed system is preferably 2-4%, more preferably 2.39-3.17%; the mass concentration of the aldehyde small-molecule cross-linking agent in the mixed system is preferably 1.4-2%, and more preferably 1.43-1.91%.
Mixing to obtain a viscous solution, and heating the viscous solution for reaction to obtain transparent hydrogel based on chitosan; in the invention, the viscous solution is preferably subjected to defoaming treatment and then subjected to heating reaction to obtain the transparent hydrogel based on chitosan; the method of the defoaming treatment is a method well known to those skilled in the art, and is not particularly limited, and in the present invention, standing or ultrasonic treatment is preferable; the viscous solution after bubble removal is preferably sucked into an injector and then is subjected to heating reaction; the volume of the syringe is selected according to the volume of the viscous solution; the temperature of the heating reaction is preferably 70-80 ℃; the heating reaction time is preferably 4-6 h.
After the heating reaction, the hydrogel is preferably fully swelled in water or aqueous solution, so that the transparent hydrogel with ultrahigh water content, high transparency and better mechanical property can be obtained, and the strength of the transparent hydrogel is comparable to that of tendon.
According to the invention, amino on a chitosan molecular chain is reacted to be carbonyl through the reaction of chitosan and glyoxylic acid, and the generated carbonyl is crosslinked with other amino on a chitosan chain so as to obtain the transparent hydrogel; the invention avoids introducing other high molecules or toxic cross-linking agents when synthesizing the hydrogel, adopts one-step synthesis, has simple and harmless process, solves the problem that high water content and high mechanical strength can not coexist, and can adjust the feed ratio according to the requirement to obtain the transparent hydrogel with different strength and water content.
In order to further illustrate the present invention, the following will describe a chitosan-based transparent hydrogel and a method for preparing the same in detail with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
(1) 0.12g glyoxylic acid monohydrate was dissolved in 3mL deionized water at room temperature to give solution A.
(2) Dispersing 0.2g of high-viscosity chitosan (>400 mPas) in 3mL of deionized water, adding the solution A in the whole volume under the conditions of heating at 50 ℃ and magnetic stirring, and continuously heating and stirring for 20min to obtain a clear yellowish and viscous solution B.
(3) The solution B was sonicated for one minute to remove small bubbles, pipetted into a 1mL syringe, the syringe cap was closed, and placed in an oven at 70 ℃.
(4) After 4h, the syringe was removed, the gel was pushed out, soaked in excess deionized water, and swollen to give a chitosan-based transparent hydrogel (CSG hydrogel).
In the reaction system, the feeding mass concentration of chitosan is 3.16%, the feeding mass concentration of glyoxylic acid is 1.90%, the amount ratio of the feeding substances of chitosan and glyoxylic acid is 1:1.05 (the chitosan is calculated according to a single chain knot), and the obtained gel is named as CSG-HH.
Example 2
(1) 0.09g of glyoxylic acid monohydrate was dissolved in 3mL of deionized water at room temperature to obtain a solution A.
(2) Dispersing 0.2g of high-viscosity chitosan (>400 mPas) in 3mL of deionized water, adding the solution A in the whole volume under the conditions of heating at 50 ℃ and magnetic stirring, and continuously heating and stirring for 20min to obtain a clear yellowish and viscous solution B.
(3) The solution B was sonicated for one minute to remove small bubbles, pipetted into a 1mL syringe, the syringe cap was closed, and placed in an oven at 70 ℃.
(4) And after 4h, taking out the injector, pushing out the gel, soaking in excessive deionized water, and swelling to obtain the CSG hydrogel.
In the reaction system, the feeding mass concentration of chitosan is 3.17%, the feeding mass concentration of glyoxylic acid is 1.43%, the amount ratio of the feeding substances of chitosan and glyoxylic acid is 1:0.78 (the chitosan is calculated according to a single chain knot), and the obtained gel is named as CSG-HL.
Example 3
(1) 0.12g glyoxylic acid monohydrate was dissolved in 3mL deionized water at room temperature to give solution A.
(2) Dispersing 0.15g of high-viscosity chitosan (>400 mPas) in 3mL of deionized water, adding the solution A in the whole volume under the conditions of heating at 50 ℃ and magnetic stirring, and continuously heating and stirring for 20min to obtain a clear yellowish and viscous solution B.
(3) The solution B was sonicated for one minute to remove small bubbles, pipetted into a 1mL syringe, the syringe cap was closed, and placed in an oven at 70 ℃.
(4) And after 4h, taking out the injector, pushing out the gel, soaking in excessive deionized water, and swelling to obtain the CSG hydrogel.
In the reaction system, the feeding mass concentration of chitosan is 2.39%, the feeding mass concentration of glyoxylic acid is 1.91%, the amount ratio of the feeding substances of chitosan and glyoxylic acid is 1:1.40 (the chitosan is calculated according to a single chain knot), and the obtained gel is named as CSG-LH.
Example 4
(1) 0.09g of glyoxylic acid monohydrate was dissolved in 3mL of deionized water at room temperature to obtain a solution A.
(2) Dispersing 0.15g of high-viscosity chitosan (>400 mPas) in 3mL of deionized water, adding the solution A in the whole volume under the conditions of heating at 50 ℃ and magnetic stirring, and continuously heating and stirring for 20min to obtain a clear yellowish and viscous solution B.
(3) The solution B was sonicated for one minute to remove small bubbles, pipetted into a 1mL syringe, the syringe cap was closed, and placed in an oven at 70 ℃.
(4) And after 4h, taking out the injector, pushing out the gel, soaking in excessive deionized water, and swelling to obtain the CSG hydrogel.
In the reaction system, the feeding mass concentration of chitosan is 2.40%, the feeding mass concentration of glyoxylic acid is 1.44%, the amount ratio of the feeding substances of chitosan and glyoxylic acid is 1:1.05 (the chitosan is calculated according to a single chain knot), and the obtained gel is named as CSG-LL.
FIG. 1 is a photograph showing a process for preparing a chitosan-based transparent hydrogel and a finished product in example 1, wherein FIG. 1a is chitosan dispersed in deionized water; FIG. 1B is a view showing a mixed solution B after addition of an aqueous glyoxylic acid solution as a viscous liquid having a yellowish color; FIG. 1c shows that after cross-linking, a hydrogel is formed, and the gel does not flow when the reaction flask is inverted; figures 1d and 1e show the swollen CSG gel, which has a high water content, is transparent in colour and can be bent to some extent.
After freeze-drying the chitosan-based transparent hydrogel obtained in example 1 (freezing at-20 ℃ C. for 24 hours, and then putting the gel into a freeze-dryer, and freeze-drying under a pressure as low as 1Pa and a cold trap temperature as low as-55 ℃ C. for 8 hours), the hydrogel after freeze-drying was analyzed by a scanning electron microscope, and a scanning electron micrograph thereof is shown in FIG. 2. It can be seen from FIG. 2 that the cross-linked chitosan molecular chains form subunits. As can be seen from the inner graph of FIG. 2a, after the water molecules are removed, the gel is spongy; FIGS. 2a and 2b show lamellar subunits composed of chitosan molecular chains; in fig. 2c and 2d, the sheets are hundreds of nanometers thick and stacked together to make up the CSG hydrogel. There are voids between sheets and therefore a large number of water molecules can be contained when the CSG hydrogel swells.
The mechanical properties of the CSG hydrogels obtained in examples 1 to 4 were tested. And taking the CSG hydrogel out of the distilled water, wiping off water on the surface, taking a CSG hydrogel cylinder with the height of 9-11 mm and the diameter of the bottom surface of 10mm, and measuring the mechanical property by using a compressor to obtain the compression curve of the CSG hydrogel with different components as shown in figure 3. As can be seen from FIG. 3, the CSG hydrogel can be compressed to 30% of its original length at maximum before breaking, and can bear a maximum stress of about 45 kPa.
The compressive stress at break, compressive strain at break and water content of the different components are tabulated as in table 1. As can be seen from Table 1, the fracture compressive stress is partially decreased and the fracture compressive strain is also decreased when the water content is increased, but the fracture compressive stress reaches the maximum value and the fracture compressive strain is maintained at a preferable level when the water content is 99.7%, i.e., CSG-HH, under the condition that the best results are obtained in examples 1 to 4.
TABLE 1 compressive stress at break, compressive strain at break and Water content of hydrogels of different compositions
Figure BDA0002936963120000081
FIG. 4 is a UV-VIS spectrum of the CSG hydrogel obtained in example 1. As can be seen from FIG. 4, the absorption of the CSG hydrogel is almost 0 in the range of 400 to 800nm, and thus is nearly 100% transparent.
Fig. 5 is a photograph of the CSG hydrogel obtained in example 1, and fig. 5 actually shows that the high transparency of the CSG hydrogel can be explained. In fig. 5a and 5b, the CSG hydrogel is laid up on top of the pattern, respectively, and the red numeral "1958" is clearly visible through the CSG hydrogel. FIGS. 5c and 5d show the process of the investigator scooping the hydrogel out of the water. The existence of gel cannot be seen in the water of FIG. 5c, but the gel can be seen by the researcher in FIG. 5d after being scooped up, which shows that the CSG hydrogel has very good transparency, which is very beneficial for the application of the CSG hydrogel in cell culture and tissue engineering.

Claims (10)

1. A transparent hydrogel based on chitosan is characterized in that the transparent hydrogel is formed by chitosan and an aldehyde micromolecule cross-linking agent; the aldehyde small molecule cross-linking agent comprises a carboxyl group.
2. The transparent hydrogel according to claim 1, wherein the aldehyde small molecule cross-linking agent is selected from glyoxylic acid; the viscosity of the chitosan is more than or equal to 400 mPas.
3. The transparent hydrogel according to claim 1, wherein the mass ratio of chitosan to aldehyde small molecule cross-linking agent is 1: (0.5 to 1.5).
4. The transparent hydrogel of claim 1, wherein the transparent hydrogel has a water content of greater than 99% after swelling.
5. The transparent hydrogel according to claim 1, wherein the transparent hydrogel has a compressive stress at break after swelling of 19 to 45 kPa; the fracture compression strain is 16-30%.
6. A method for preparing a transparent hydrogel based on chitosan, which is characterized by comprising the following steps:
s) mixing chitosan and an aldehyde micromolecule cross-linking agent in water, and heating for reaction to obtain the transparent hydrogel based on chitosan.
7. The preparation method according to claim 6, wherein the mass concentration of chitosan in the mixed system is 2-4%; the mass concentration of the aldehyde micromolecule cross-linking agent in the mixed system is 1.4-2%.
8. The preparation method according to claim 6, wherein the step S) is specifically:
dispersing chitosan in water, adding an aqueous solution of an aldehyde micromolecule cross-linking agent under a heating condition, and stirring and mixing to obtain a viscous solution;
and heating the viscous solution for reaction to obtain the transparent chitosan-based hydrogel.
9. The method according to claim 8, wherein the ratio of chitosan to water is (0.15-0.2) g: 3 ml; the concentration of the aldehyde micromolecule cross-linking agent in the aqueous solution of the aldehyde micromolecule cross-linking agent is 0.03-0.04 g/mL; the heating temperature is 45-50 ℃; the stirring and mixing time is more than or equal to 10-60 min.
10. The preparation method according to claim 8, wherein the viscous solution is subjected to defoaming treatment and then to heating reaction to obtain a transparent chitosan-based hydrogel; the temperature of the heating reaction is 70-80 ℃; the heating reaction time is 4-6 h.
CN202110161784.6A 2021-02-05 2021-02-05 Transparent hydrogel based on chitosan and preparation method thereof Active CN112940291B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110161784.6A CN112940291B (en) 2021-02-05 2021-02-05 Transparent hydrogel based on chitosan and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110161784.6A CN112940291B (en) 2021-02-05 2021-02-05 Transparent hydrogel based on chitosan and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112940291A true CN112940291A (en) 2021-06-11
CN112940291B CN112940291B (en) 2024-02-09

Family

ID=76242560

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110161784.6A Active CN112940291B (en) 2021-02-05 2021-02-05 Transparent hydrogel based on chitosan and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112940291B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101595174A (en) * 2007-01-16 2009-12-02 大日精化工业株式会社 Aqueous solution composition
CN102911381A (en) * 2012-11-12 2013-02-06 天津工业大学 Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof
CN104479150A (en) * 2014-10-29 2015-04-01 上海大学 Preparation method of multiple cross-linked polysaccharide injectable hydrogel
CN106046398A (en) * 2016-06-22 2016-10-26 深圳普洛美康材料有限公司 Hydrogel and preparation method thereof
CN106496601A (en) * 2016-10-26 2017-03-15 华南理工大学 A kind of can be from the high intensity hydrogel and preparation method thereof into tubulose or cup-shaped
CN110299251A (en) * 2018-03-23 2019-10-01 中国科学技术大学 The preparation method of electrically conductive polyaniline hydrogel and stretchable supercapacitor
WO2019192628A2 (en) * 2018-04-03 2019-10-10 中国科学院苏州纳米技术与纳米仿生研究所 Thiolated chitosan derivative, chitosan hydrogel, and preparation methods therefor and applications thereof
CN111748106A (en) * 2019-03-29 2020-10-09 武汉大学 Chitosan gel material prepared from chitosan solution with pH value of 6-8 and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101595174A (en) * 2007-01-16 2009-12-02 大日精化工业株式会社 Aqueous solution composition
CN102911381A (en) * 2012-11-12 2013-02-06 天津工业大学 Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof
CN104479150A (en) * 2014-10-29 2015-04-01 上海大学 Preparation method of multiple cross-linked polysaccharide injectable hydrogel
CN106046398A (en) * 2016-06-22 2016-10-26 深圳普洛美康材料有限公司 Hydrogel and preparation method thereof
CN106496601A (en) * 2016-10-26 2017-03-15 华南理工大学 A kind of can be from the high intensity hydrogel and preparation method thereof into tubulose or cup-shaped
CN110299251A (en) * 2018-03-23 2019-10-01 中国科学技术大学 The preparation method of electrically conductive polyaniline hydrogel and stretchable supercapacitor
WO2019192628A2 (en) * 2018-04-03 2019-10-10 中国科学院苏州纳米技术与纳米仿生研究所 Thiolated chitosan derivative, chitosan hydrogel, and preparation methods therefor and applications thereof
CN111748106A (en) * 2019-03-29 2020-10-09 武汉大学 Chitosan gel material prepared from chitosan solution with pH value of 6-8 and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵奎;梁旭华;李星元;: "基于壳聚糖水凝胶的研究进展及其应用" *

Also Published As

Publication number Publication date
CN112940291B (en) 2024-02-09

Similar Documents

Publication Publication Date Title
CN110951096B (en) GelMA-oxidized glucan double-network hydrogel and preparation method thereof
Pourjavadi et al. Injectable chitosan/κ-carrageenan hydrogel designed with au nanoparticles: A conductive scaffold for tissue engineering demands
Chiellini et al. Ulvan: A versatile platform of biomaterials from renewable resources
CN104140630B (en) A kind of chitosan-based double-network hydrogel and preparation method thereof
CN108478867B (en) Injectable polymer hydrogel based on acylhydrazone bond, preparation method thereof and polymer hydrogel injection
CN110157010B (en) Polyelectrolyte complex hydrogel hemostatic based on polysaccharide/polypeptide
CN108727610A (en) A kind of double-network hydrogel and preparation method thereof with high tough, shape memory and self-healing properties
Yang et al. A fluorescent, self-healing and pH sensitive hydrogel rapidly fabricated from HPAMAM and oxidized alginate with injectability
CN113166434A (en) Cross-linked hyaluronic acid, hyaluronic acid hydrogel and preparation method thereof
CN113425890A (en) Bionic hydrogel tissue adhesive and preparation method thereof
CN113185725A (en) Method for rapidly preparing silver nanoparticle/gelatin composite hydrogel in situ
CN113105651A (en) Sprayable hydrogel and preparation method and application thereof
CN110180023B (en) Preparation method of high-strength biomass tissue engineering scaffold material
CN116903884A (en) Hyaluronic acid-polyglutamic acid hydrogel and preparation method thereof
CN104861178A (en) Pullulan-hyaluronic acid hydrogel and preparation method thereof
CN113248743B (en) Biocompatible degradable three-dimensional cellulose gel, and preparation method and application thereof
CN112143410A (en) Injectable biological adhesive and preparation method and application thereof
CN115554462B (en) Anti-swelling injectable hydrogel adhesive and preparation method thereof
CN106999626B (en) Biocompatible compositions and methods of preparation
CN112940291B (en) Transparent hydrogel based on chitosan and preparation method thereof
CN113861447B (en) Modified hydroxypropyl chitosan adhesion self-healing hydrogel and preparation method and application thereof
CN115429935A (en) Injectable cross-linked chondroitin sulfate hydrogel and preparation method thereof
CN112552534B (en) Stretchable self-healing stimulation response biopolymer hydrogel
CN111647110B (en) High-strength anti-swelling chitosan-based physical hydrogel and preparation method thereof
CN113336987A (en) Preparation method of natural high-strength sodium alginate double-crosslinked hydrogel film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant