A chitosan glycerol gel simulating the adhesion mechanism of barnacles and its preparation method and application

By simulating the electrostatic and hydrophobic interactions of barnacle cement glue and combining it with a glycerol/water solvent exchange strategy, chitosan glycerol gel was prepared, which solved the problems of poor adhesion and stability of traditional hydrogels in harsh environments and achieved skin protection and wound healing in marine, cold and dry environments.

CN119060254BActive Publication Date: 2025-10-10OCEAN UNIV OF CHINA
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Patent Information

Application Number
CN202411112508.0
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-08-14
Publication Date
2025-10-10
Estimated Expiration
2044-08-14

AI Technical Summary

Technical Problem

Traditional hydrogels have poor adhesion and stability in harsh environments, and cannot effectively protect the skin and promote wound healing, especially in seawater, cold and dry environments.

Method used

Chitosan and butyl acrylate were used to form a pregel through photocrosslinking, and a multifunctional chitosan glycerol gel was constructed through glycerol/water solvent exchange to simulate the electrostatic and hydrophobic interactions of barnacle cement glue, giving the gel wet adhesion and antifreeze water retention properties.

Benefits of technology

It achieves stable underwater adhesion, antifreeze and water retention in a variety of harsh environments, promotes skin protection and wound healing, and is suitable for skin protection and wound repair in marine operations, winter training, polar scientific expeditions and desert environments.

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Abstract

The application discloses a chitosan glycerol gel simulating the adhesion mechanism of barnacles, and a preparation method and application thereof. The chitosan glycerol gel is prepared by simulating the adhesion mechanism of marine barnacle cement glue and combining a glycerol / water solvent exchange strategy. The chitosan glycerol gel has strong underwater adhesion capacity, can resist joint torsion and water flow scouring, and can promote the healing of a rat seawater immersion wound. The chitosan glycerol gel also has good anti-freezing and water-retaining properties, can protect the skin from frostbite and scald in an extreme temperature range of-196 DEG C to 120 DEG C, and has excellent water-retaining capacity under dry conditions, and still exhibits good water-retaining property and flexibility after being stored for 30 days at 25% relative humidity. Therefore, the chitosan glycerol gel has wide application prospects in skin protection and wound repair in harsh working environments such as marine and underwater operations, winter training and patrol, polar scientific exploration, desert management and exploration.
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Description

Technical Field

[0001] The invention belongs to the field of biomedical materials, and particularly relates to a chitosan glycerol gel simulating the adhesion mechanism of barnacles, and a preparation method and application thereof. Background Art

[0002] Skin protection and wound healing face significant challenges in harsh environmental conditions such as seawater, cold, and aridity. Hydrogels are widely used in wound care. However, the structure and properties of traditional hydrogels are unstable in these harsh environments, making them inadequate for skin protection and wound healing. For example, the adhesion of traditional hydrogels in water is severely reduced, leading to easy detachment and loss of wound protection. Underwater workers are vulnerable to open wounds during marine production or military activities. The erosion of hypertonic, alkaline, and pathogenic seawater can exacerbate wounds, leading to high rates of disability and mortality. Furthermore, traditional hydrogels are prone to freezing at low temperatures and dehydration in dry environments, limiting their application in extreme environments. Athletes training in winter, soldiers patrolling in cold environments, and scientists conducting polar expeditions all require antifreeze protection. Workers working in dry environments such as deserts need to prevent skin dehydration and cracking. Therefore, the development of new biomaterials for use in harsh environments such as seawater, cold, and aridity is of great significance.

[0003] Some marine organisms, such as mussels and barnacles, can secrete bioadhesives with strong adhesion properties in complex seawater environments. For example, barnacles achieve strong underwater adhesion by secreting barnacle cement glue. Unlike the oxidized structure of catechol groups in mussels, barnacle cement glue relies on a large number of cationic and hydrophobic amino acids for adhesion. The hydrophobic amino acids in barnacle cement glue enhance wet adhesion by eliminating the interfacial hydration layer, while the cationic amino acids in barnacle cement glue achieve tight adhesion through electrostatic interactions with the interface.

[0004] Glycerol is a non-toxic antifreeze agent that forms strong hydrogen bonds to trap water molecules, disrupting ice crystal formation at low temperatures and preventing water evaporation in dry environments. Glycerol / water solvent exchange can impart antifreeze and water-retention properties to gels. Furthermore, the introduction of hydrophobic components through solvent exchange can construct uniform, anti-swelling gels, which benefits their mechanical properties and stability underwater.

[0005] To address the poor adhesion and stability of gels in harsh environments such as seawater, cold, and dryness, this study employed photocrosslinking of chitosan and butyl acrylate with acrylamide and acrylic acid to form a pregel. This pregel was then constructed through a glycerol / water solvent exchange process to create a multifunctional glycerol gel (CB-G-Gel). By mimicking the electrostatic and hydrophobic interactions of barnacle cement glue, chitosan and butyl acrylate imparted wettability and underwater adhesion to the gel. Combined with the glycerol / water solvent exchange process, the gel was found to possess antifreeze and water-retention properties, enabling it to protect skin and promote wound healing in a variety of harsh environments. Summary of the Invention

[0006] In response to the problem that traditional hydrogel materials are limited in application in harsh environments, the purpose of the present invention is to provide a chitosan glycerol gel that simulates the adhesion mechanism of barnacles. It is constructed by simulating the adhesion mechanism of barnacle cement glue and combining a glycerol / water solvent exchange strategy, and has important practical application value.

[0007] Another object of the present invention is to provide a method for preparing chitosan glycerol gel.

[0008] Another object of the present invention is to provide an application of chitosan glycerol gel.

[0009] To achieve the above object, the present invention adopts the following technical solutions:

[0010] The invention provides a chitosan glycerol gel for simulating the adhesion mechanism of barnacles. The chitosan glycerol gel comprises, by mass percentage, 0% to 2% of chitosan and its derivatives, 0.5% to 10% of a hydrophobic compound, 10% to 27% of a matrix material, 0.01% to 0.2% of a cross-linking agent, 0.01% to 0.1% of an initiator, 40% to 80% of glycerol, and the balance being a solvent.

[0011] Furthermore, the chitosan and its derivatives are any one of chitosan, carboxymethyl chitosan, chitosan quaternary ammonium salt, and hydroxypropyl chitosan.

[0012] Furthermore, the molecular weight of the chitosan and its derivatives is 1 kDa to 10 kDa.

[0013] Furthermore, the hydrophobic compound is any one of butyl acrylate, 2-phenoxymethyl acrylate, 2-phenoxyethyl acrylate, and ethyl acrylate; the matrix material is at least one of acrylamide and acrylic acid; the crosslinking agent is N,N'-methylenebisacrylamide; and the initiator is phenyl (2,4,6-trimethylbenzoyl) phosphate lithium salt.

[0014] The present invention also provides a method for preparing the chitosan glycerol gel, comprising the following steps:

[0015] S1: Weigh 0-2% chitosan or its derivatives by mass and dissolve them in water. Completely dissolve the chitosan by vortexing or ultrasound to obtain a chitosan aqueous solution.

[0016] S2: Weigh 10-27% of the matrix material, 0.01-0.2% of the cross-linking agent, and 0.01-0.1% of the initiator by mass, add them to the chitosan aqueous solution of step S1 and mix evenly to obtain a mixed solution A;

[0017] S3: Weigh 0.5-10% of the hydrophobic compound by mass and dissolve it in anhydrous ethanol, and mix it thoroughly by vortexing or ultrasonication to obtain a mixed solution B;

[0018] S4: fully mixing the mixed solution A of step S2 and the mixed solution B of step S3, and pouring the mixture into a gel mold; performing a photocrosslinking reaction in the mold to prepare a primary gel;

[0019] S5: placing the initial gel from step S4 in glycerol / water for solvent exchange until the initial solvent and unreacted cross-linking monomers are fully removed to obtain chitosan glycerol gel.

[0020] Furthermore, the photocrosslinking reaction conditions in step S4 are: crosslinking under 365 nm ultraviolet light for 20 min to 40 min.

[0021] Furthermore, the chitosan glycerol gel has good underwater adhesion, antifreeze properties, water retention, mechanical properties, biocompatibility, and antibacterial ability.

[0022] Furthermore, the chitosan glycerol gel still exhibits good flexibility after being stored at a relative humidity of 25% for 30 days.

[0023] The present invention also provides application of the chitosan glycerol gel in preparing antibacterial materials.

[0024] Furthermore, the antibacterial material can inhibit Escherichia coli and Staphylococcus aureus.

[0025] The present invention also provides the use of the chitosan glycerol gel in preparing a wound care product for promoting wound healing.

[0026] Furthermore, the wound care is to use the chitosan glycerol gel to perform antibacterial, hemostatic and / or sealing on water-contacted wounds to promote wound healing.

[0027] The present invention also provides application of the chitosan glycerol gel in preparing skin protection products for use in harsh environments.

[0028] Furthermore, the harsh environment includes seawater, cold, high temperature, and dryness.

[0029] Furthermore, the chitosan glycerol gel protects the skin from frostbite and burns in an extreme temperature range of -196 to 120°C.

[0030] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0031] (1) The application scenarios of traditional hydrogels are limited. The chitosan glycerol gel described in the present invention can be used for skin protection and wound repair in harsh environments such as marine operations, winter training and patrols, polar scientific research or desert control and exploration, and is suitable for a variety of harsh environments.

[0032] (2) Traditional hydrogels tend to lose their adhesion when exposed to water. The chitosan glycerol gel described in the present invention simulates the adhesion mechanism of barnacle cement glue in the ocean, utilizes hydrophobic and electrostatic interactions to achieve stable underwater adhesion, and can promote the healing of wounds immersed in seawater.

[0033] (3) Traditional hydrogels are prone to freezing in cold environments and losing water in dry environments. However, the chitosan glycerol gel of the present invention has good antifreeze and water retention properties. It can still show good flexibility when stored at 25% relative humidity for 30 days and protect the skin from frostbite and burns in the temperature range of -196 to 120°C.

[0034] (4) The gel of the present invention also exhibits strong mechanical properties, good biocompatibility, antibacterial ability and the ability to promote wound healing, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the infrared spectrum of CB-G-Gel of Example 1.

[0036] Figure 2 These are images characterizing the adhesion performance of CB-G-Gel in Example 1; among them, a is an image of adhesion to metal, glass, polypropylene plastic, rubber and pig skin surfaces, b is an image of adhesion to clams, razor clams, conchs, scallops and shrimp surfaces, c is an image of blocking pig large intestine, d is an image of resistance to water impact, e is a distorted image, and f is a curved image.

[0037] Figure 3 These are the lap shear strength results of CB-G-Gel of Example 1 on wet surfaces and in different water environments.

[0038] Figure 4 These are the rheological temperature scan results of the CB-G-Gel of Example 1 and the CB-W-Gel of Comparative Example 4.

[0039] Figure 5These are pictures of the morphology of the gels of Example 1 and Comparative Example 4 after being cooled (-20°C), dried (60°C 20% RH), and freeze-dried for 1 day.

[0040] Figure 6 The weight change results of Example 1 and Comparative Example 4 after long-term storage for 30 days under normal conditions (25°C 25% RH); wherein a is a weight change curve graph, and b is a morphology picture.

[0041] Figure 7 The antifreeze (a) and anti-scalding (b) results of the rat back skin in Example 1 and Comparative Example 4 are shown.

[0042] Figure 8 The safety evaluation results of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 are shown in Figures a and b, respectively, are images of live and dead cell staining and fluorescence quantification results of L929 cells, c is the cell viability test result, and d is the hemolysis test result.

[0043] Figure 9 These are the antibacterial evaluation results of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4; wherein a is the plate count result, and b is the transmission electron microscopy result.

[0044] Figure 10 The CB-G-Gel of Example 1 and the commercial hydrogel Hydrosorb ® Promoting wound healing effect in a seawater immersion wound model. DETAILED DESCRIPTION

[0045] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the technical solutions of the present invention are further described below in conjunction with the accompanying drawings and specific embodiments. In the following embodiments, unless otherwise specified, the experimental methods used are all conventional methods, and the materials and reagents used can be purchased from biological or chemical reagent companies.

[0046] Example 1

[0047] A chitosan-butyl acrylate glycerol gel (CB-G-Gel) was prepared by mimicking the electrostatic and hydrophobic interactions of barnacle cement and combining a glycerol / water solvent exchange strategy. 1 mL of water was added to 40 mg of chitosan and stirred until completely dissolved. 405 mg of acrylamide, 135 mg of acrylic acid, 2.2 mg of N'N-methylenebisacrylamide, and 1.8 mg of lithium phenyl (2,4,6-trimethylbenzoyl) phosphate were added to the chitosan aqueous solution and mixed thoroughly to obtain mixed solution A. 200 mg of butyl acrylate was mixed with 1 mL of anhydrous ethanol to obtain mixed solution B. After mixing, mixed solutions A and B were poured into a gel mold. Crosslinking was performed under 365 nm UV light for 20 min to prepare a primary gel. The primary gel was then placed in a 60% glycerol aqueous solution for solvent exchange for 3 days, with the solvent changed every 8 hours, to produce the CB-G-Gel.

[0048] Comparative Example 1

[0049] A glycerol gel (G-Gel) was prepared using only a glycerol / water solvent exchange strategy, without mimicking the adhesion mechanism of barnacle cement glue. 405 mg of acrylamide, 135 mg of acrylic acid, 2.2 mg of N'N-methylenebisacrylamide, and 1.8 mg of lithium phenyl (2,4,6-trimethylbenzoyl) phosphate were added to 1 mL of water and mixed thoroughly to obtain mixed solution A. 1 mL of anhydrous ethanol was added to form solution B. After mixing, mixed solutions A and B were poured into a gel mold. Cross-linking under 365 nm UV light for 20 minutes produced a primary gel. The primary gel was then placed in a 60% glycerol / water solution for solvent exchange for 3 days, with the solvent changed every 8 hours, to produce the G-Gel.

[0050] Comparative Example 2

[0051] A chitosan-glycerol gel (CG-Gel) was prepared by mimicking the electrostatic interactions of barnacle cement glue and combining a glycerol / water solvent exchange strategy: 1 mL of water was added to 40 mg of chitosan and stirred until completely dissolved. Then, 405 mg of acrylamide, 135 mg of acrylic acid, 2.2 mg of N'N-methylenebisacrylamide, and 1.8 mg of lithium phenyl (2,4,6-trimethylbenzoyl) phosphate were added to the chitosan aqueous solution and mixed thoroughly to obtain mixed solution A. 1 mL of anhydrous ethanol was added to obtain solution B. After mixing, mixed solutions A and B were poured into a gel mold. Crosslinking under 365 nm UV light for 20 minutes produced a primary gel. The primary gel was then placed in a 60% glycerol aqueous solution for solvent exchange for 3 days, with the solvent changed every 8 hours, to produce the CG-Gel.

[0052] Comparative Example 3

[0053] Preparation of a butyl acrylate glycerol gel (B-G-Gel) which only simulates the hydrophobic interaction of barnacle cement and combines with glycerol / water solvent exchange strategy: 405 mg of acrylamide, 135 mg of acrylic acid, 2.2 mg of N’N-methylene bisacrylamide, 1.8 mg of lithium phenyl (2,4,6-trimethylbenzoyl) phosphate salt were added to 1 mL of water, and the solution was mixed uniformly to obtain a mixed solution A. 200 mg of butyl acrylate was mixed uniformly with 1 mL of anhydrous ethanol to obtain a mixed solution B. After mixing the mixed solution A and the mixed solution B uniformly, pour into the gel mold. Crosslinking under 365 nm ultraviolet light for 20 min to prepare a preliminary gel. The preliminary gel was placed in a 60% glycerol aqueous solution for solvent exchange for 3 days, and the solvent was replaced every 8 h to prepare the B-G-Gel.

[0054] Comparative Example 4

[0055] Preparation of a chitosan-butyl acrylate hydrogel (CB-W-Gel) which simulates the electrostatic and hydrophobic interaction of barnacle cement but does not combine with glycerol / water solvent exchange strategy, only using ordinary water solvent exchange: 40 mg of chitosan was added to 1 mL of water and stirred until completely dissolved. 405 mg of acrylamide, 135 mg of acrylic acid, 2.2 mg of N’N-methylene bisacrylamide, 1.8 mg of lithium phenyl (2,4,6-trimethylbenzoyl) phosphate salt were added to the chitosan aqueous solution, and the solution was mixed uniformly to obtain a mixed solution A. 200 mg of butyl acrylate was mixed uniformly with 1 mL of anhydrous ethanol to obtain a mixed solution B. After mixing the mixed solution A and the mixed solution B uniformly, pour into the gel mold. Crosslinking under 365 nm ultraviolet light for 20 min to prepare a preliminary gel. The preliminary gel was placed in water for solvent exchange for 3 days, and the solvent was replaced every 8 h to prepare the CB-W-Gel.

[0056] Example 2

[0057] (1) Infrared characterization of CB-G-Gel

[0058] The gel CB-G-Gel of Example 1 was characterized by Fourier transform infrared spectroscopy. The infrared spectra of CB-G-Gel and its constituent components are shown in Figure 1 : CB-G-Gel appears the characteristic absorption of chitosan, butyl acrylate, acrylamide, acrylic acid; the absorption peaks of C=O of butyl acrylate and acrylic acid at 1734 cm -1 and 1725 cm -1 , and the absorption peak of OH at 3422 cm -1 shift to low wavenumber; it shows that the gel CB-G-Gel of Example 1 is successfully prepared and forms intermolecular hydrogen bonds.

[0059] (2) Characterization of underwater adhesion performance of CB-G-Gel

[0060] The adhesive properties of the CB-G-Gel of Example 1 were characterized. CB-G-Gel not only remained adherent to the surfaces of metal, glass, polypropylene plastic, rubber, and pigskin in water, but also remained adherent to the surfaces of metal, glass, polypropylene plastic, rubber, and pigskin in water. Figure 2 a), and can also firmly adhere to the surface of clams, razor clams, conch, scallops and shrimp and remain adhered in water ( Figure 2 b), indicating its potential application in underwater operations and marine fishing. CB-G-Gel can seal leaking pig large intestine ( Figure 2 c), is expected to be used for organ closure during surgery and to plug fluid leaks in the ocean. CB-G-Gel can adhere firmly to pig skin and resist water impact ( Figure 2 d), can also firmly adhere to the surface of pig skin or fingers and twist or bend with the skin ( Figure 2 e, f), which is expected to be used for underwater motion monitoring.

[0061] The water contact adhesion strength of the CB-G-Gel of Example 1 was quantified using a universal testing machine ( Figure 3 ). Wet pigskin soaked for 1 hour was used as the adhesion medium. After applying a preload strength of 5 kPa, it was fixed to both ends of the shear fixture of the universal testing machine. The force and displacement during the movement of the fixture were recorded. The adhesion results of CB-G-Gel in different environments are shown in Figure 2. Figure 3 As shown, CB-G-Gel exhibits the highest adhesion strength to dry tissue and also exhibits an adhesion strength of approximately 20 kPa to wet tissue. Furthermore, CB-G-Gel exhibits strong adhesion both underwater and in phosphate buffered solution. Although the gel's adhesion strength decreases slightly in seawater, it still exhibits an adhesion strength of approximately 10 kPa.

[0062] (3) Characterization of CB-G-Gel's antifreeze and water retention properties

[0063] The rheological properties of the gel at different temperatures were evaluated using a rheometer. Figure 4 As shown, as the temperature decreases, the G' and G' of the CB-W-Gel of Comparative Example 4 increase significantly at -15°C, indicating that freezing has occurred. However, the storage modulus (G') and loss modulus (G'') of the CB-G-Gel of Example 1 increase slowly, with G' always higher than G'', indicating that the CB-G-Gel exhibits stable elastic behavior in a low-temperature environment.

[0064] The morphology of the gel was observed after 1 day of freezing (-20°C), drying (60°C 20%RH) or even freeze drying. Figure 5As shown, CB-W-Gel of Comparative Example 4 was frozen after 1 day at -20 °C, and completely lost water after 1 day of drying at 60 °C or after 1 day of freeze-drying, all of which were broken in the twisting process. CB-G-Gel of Example 1 maintained good flexibility in both low temperature and dry environment.

[0065] After long-term storage for 30 days under normal conditions (25 °C, 25% RH), CB-G-Gel of Example 1 showed the least weight loss Figure 6 a), and still could be twisted and stretched. However, CB-W-Gel of Comparative Example 4 showed rapid weight loss within 3 days, lost a large amount of water, and finally broke due to water loss Figure 6 b). The results showed that CB-G-Gel had good water retention performance, which was beneficial to its long-term preservation in dry environment.

[0066] (4) Anti-freezing and anti-scalding performance characterization of CB-G-Gel

[0067] Skin injury models under ultra-low temperature (-196 °C) and ultra-high temperature (120 °C) were established on the back of rats. The frostbite model was constructed by applying a very cold coin pre-soaked in liquid nitrogen (-196 °C) to the skin of the back of rats, and the scalding model was constructed by applying a coin burned on the flame (120 °C) to the skin of the back of rats. In the frostbite model, the exposed skin formed a hard white eschar after exposure to the very cold coin. Under the protection of CB-W-Gel of Comparative Example 4, the damage to the skin was reduced, but still showed a small area of white eschar. In contrast, no significant changes were observed on the skin surface protected by CB-G-Gel of Example 1, which still showed an intact epidermis Figure 7 a). In the scalding model, the surface of the exposed skin was severely scalded. CB-W-Gel slightly reduced the degree of scalding, but there were still some scald marks on the skin surface. However, the skin protected by CB-G-Gel showed a normal surface structure Figure 7 b). The above results confirmed that CB-G-Gel overcame the shortcomings of CB-W-Gel, maintained moisture and flexibility in low and high temperature environments, and protected the skin from frostbite and scalding.

[0068] (5) Biocompatibility characterization of CB-G-Gel

[0069] The cell compatibility of the gels of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 was evaluated by cell viability assay using a cell viability detection kit (CCK-8). The gel was soaked in a culture medium at 37°C for 24 h to prepare an extract (60 mg / mL). L929 cells were seeded into a 96-well plate at a density of 5,000 cells per well and incubated with gel extracts at concentrations of 10, 20, 40, and 60 mg / mL for 1 day. An appropriate amount of CCK-8 solution was then added and detected at 450 nm to calculate the cell viability. The L929 cells co-incubated with the sample were subjected to live / dead staining, and after staining with calcein (AM) / propidium iodide (PI) dye for 15 minutes, the green (492 nm) and red (545 nm) fluorescence of the cells were observed under a fluorescence microscope, and photographed and recorded. The results showed that the survival rate of L929 cells in each group was above 80% ( Figure 8 c), the cells in each group showed fluorescence intensity and growth status comparable to those in the control group ( Figure 8 a and 8b). It is proved that the gels of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 all have good cell compatibility.

[0070] The blood compatibility of the gels of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 was evaluated by hemolysis test. Rat whole blood was centrifuged at 2000 rpm for 3 min to obtain red blood cells, which were washed and diluted to a final concentration of 5% (v / v). The red blood cells were incubated with the extract at a 1 / 1 (v / v) ratio at 37°C for 1 h. 1% Triton X-100 and phosphate buffered saline (PBS) were used as positive and blank controls. After centrifugation, the optical density of the supernatant was measured at 540 nm to calculate the hemolysis rate. The results of the hemolysis test showed that the hemolysis rate of all gels did not exceed 2% ( Figure 8 d), indicating that they have good blood compatibility.

[0071] (6) Characterization of antibacterial properties of CB-G-Gel

[0072] The antibacterial properties of the gels of Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were evaluated by plate counting. 100 μL of bacterial suspension (10 7 CFU / mL) were placed on the samples and incubated at 37°C for 2 hours. Then, 900 μL of sterile water was added to each group to resuspend the surviving bacteria on the gel. The bacterial suspension was diluted 100-fold and spread on a culture dish. The single colonies were counted and compared with the control group after incubation at 37°C for 18-24 hours. The results are shown in Figure 2. Figure 9a shows that the antibacterial effect of CB-G-Gel in Example 1 is the best, which is better than CG-Gel in Comparative Example 2 containing only chitosan and BG-Gel in Comparative Example 3 containing only butyl acrylate, and is even better than G-Gel in Comparative Example 1. We also studied the antibacterial mechanism of CB-G-Gel by transmission electron microscopy. The results are shown in Figure 1. Figure 9 Figure b shows that the bacteria in the control group were morphologically intact, while E. coli and S. aureus treated with CB-G-Gel exhibited cell fragmentation and outflow of their contents. This is likely due to the interaction between the positive charge of chitosan and the negative charge on the bacterial surface. These results demonstrate that CB-G-Gel has significant antibacterial activity.

[0073] (7) Characterization of CB-G-Gel's ability to promote wound healing after seawater immersion

[0074] Full-thickness wounds were created in rats and treated with different gels after immersion in seawater for 1 h. The wound healing was monitored at different time points. Figure 10 The results showed that the CB-G-Gel of Example 1 has a significant ability to promote the healing of seawater-immersion wounds, which is better than the commercial hydrogel Hydrosorb. ® .

[0075] The present invention prepares a series of gels by simulating the electrostatic and hydrophobic interactions of barnacle cement glue and combining a glycerol / water solvent exchange strategy. Compared with commercial gels, the chitosan glycerol gel of the present invention has the following advantages: (1) Unlike ordinary commercial gels that easily lose adhesion when in contact with water, CB-G-Gel achieves strong underwater adhesion by simulating the hydrophobic and electrostatic interactions of barnacle bone cement protein, can resist joint torsion and water erosion, and can promote the healing of rat seawater immersion wounds. (2) Ordinary commercial gels are easy to freeze at low temperatures and easy to evaporate water at high temperatures. The chitosan glycerol gel of the present invention can protect the skin from frostbite and burns in the extreme temperature range of -196 to 120°C. (3) Ordinary commercial gels tend to dehydrate and crack in dry environments. However, CB-G-Gel has excellent water retention capacity under dry conditions of 25% relative humidity and still exhibits good flexibility after storage for 30 days. (4) The chitosan glycerol gel described in the present invention has obvious advantages in underwater adhesion, antifreeze, water retention, etc. It has the potential to be used for skin protection and wound healing in various harsh environments such as marine operations, winter training, polar scientific research, desert management, etc., and has broad application transformation prospects.

[0076] The above embodiments are intended to illustrate rather than limit the technical solutions described in the present invention. Although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the present invention, and all technical solutions and improvements thereof that do not depart from the spirit and scope of the present invention should be included within the scope of the claims of the present invention.

Claims

1. A chitosan glycerol gel simulating the adhesion mechanism of barnacles, characterized in that: The components of the chitosan glycerol gel include, by mass percentage, 0% to 2% of chitosan and its derivatives, 0.5% to 10% of a hydrophobic compound, 10% to 27% of a matrix material, 0.01% to 0.2% of a cross-linking agent, 0.01% to 0.1% of an initiator, 40% to 80% of glycerol, and the remainder being a solvent; the hydrophobic compound is any one of butyl acrylate, 2-phenoxymethyl acrylate, and 2-phenoxyethyl acrylate; and the matrix material is at least one of acrylamide and acrylic acid. The preparation method of the chitosan glycerol gel comprises the following steps: S1: dissolving chitosan or its derivatives in water to obtain a chitosan aqueous solution; S2: adding a matrix material, a cross-linking agent, and an initiator to the chitosan aqueous solution of step S1, and mixing them uniformly to obtain a mixed solution A; S3: dissolving the hydrophobic compound in anhydrous ethanol and mixing uniformly to obtain a mixed solution B; S4: fully mixing the mixed solution A of step S2 and the mixed solution B of step S3, and performing a photocrosslinking reaction to prepare a primary gel; S5: placing the initial gel from step S4 in glycerol / water for solvent exchange until the initial solvent and unreacted cross-linking monomers are fully removed to obtain chitosan glycerol gel.

2. The chitosan glycerol gel according to claim 1, characterized in that The chitosan and its derivatives are any one of chitosan, carboxymethyl chitosan, chitosan quaternary ammonium salt and hydroxypropyl chitosan.

3. The chitosan glycerol gel according to claim 1, characterized in that The cross-linking agent is N,N'-methylenebisacrylamide; and the initiator is phenyl (2,4,6-trimethylbenzoyl) lithium phosphate.

4. The chitosan glycerol gel according to claim 1, characterized in that The photocrosslinking reaction conditions in step S4 are: crosslinking under 365 nm ultraviolet light for 20 min to 40 min.

5. Use of the chitosan glycerol gel according to claim 1 in the preparation of antibacterial materials.

6. The use according to claim 5, characterized in that The antibacterial material can inhibit Escherichia coli and Staphylococcus aureus.

7. Use of the chitosan glycerol gel according to claim 1 in preparing a wound care product for promoting wound healing.

8. Use of the chitosan glycerol gel according to claim 1 in preparing skin protection products for use in harsh environments.

9. The use according to claim 8, characterized in that The harsh environment includes seawater, cold, high temperature and dryness.

Citation Information

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