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CN111617309B - Antibacterial hemostatic sponge and preparation method thereof - Google Patents

Antibacterial hemostatic sponge and preparation method thereof Download PDF

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CN111617309B
CN111617309B CN202010381521.1A CN202010381521A CN111617309B CN 111617309 B CN111617309 B CN 111617309B CN 202010381521 A CN202010381521 A CN 202010381521A CN 111617309 B CN111617309 B CN 111617309B
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mxene
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drying
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CN111617309A (en
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马贵平
王良玉
宋季轩
聂俊
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Beijing University of Chemical Technology
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28Polysaccharides or their derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/425Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/46Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001Use of materials characterised by their function or physical properties
    • A61L24/0036Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/02Surgical adhesives or cements; Adhesives for colostomy devices containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/04Materials for stopping bleeding

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Abstract

The invention relates to the technical field of medical dressings, in particular to an antibacterial hemostatic sponge and a preparation method thereof. In order to prepare a medical dressing with good mechanical property and excellent antibacterial property by taking chitosan derivative and MXene as main raw materials, the invention provides an antibacterial hemostatic sponge, which comprises the following components in percentage by mass: 12-42% of O-carboxymethyl chitosan, 11-28% of sodium carboxymethyl cellulose, 0.1-2% of MXene, 0.5-1.2% of softener and 27-66% of cross-linking agent.

Description

Antibacterial hemostatic sponge and preparation method thereof
Technical Field
The invention relates to the technical field of medical dressings, in particular to an antibacterial hemostatic sponge and a preparation method thereof.
Background
The medical dressing can temporarily play a part of the barrier function of the skin, absorb wound exudate, prevent the invasion of bacteria and can relieve a series of negative effects caused by skin damage and blood vessel rupture.
A chitosan-based medical dressing is a medical dressing which takes chitosan and derivatives thereof as main components. The chitosan-based medical dressing has the advantages of relatively low cost, simple preparation process, safety, no toxicity, good biocompatibility, moisture retention, antibiosis, hemostasis and the like, and promotes the wide application of the chitosan-based medical dressing. However, chitosan-based dressings still have many problems in actual wound care: (1) although a single chitosan dressing has certain hygroscopicity, the absorption capacity for wound exudates is limited, and an optimal moist environment cannot be provided for wound healing for a long time, so that the wound healing is slow; (2) the chitosan dressing has weak antibacterial activity; (3) the chitosan is easily affected by the environment, and the degradation of the chitosan can be caused by the light, heat and peracid environments, so that the performances of antibiosis, hemostasis and the like of the chitosan are reduced; (4) limited by natural polymer structure, the chitosan-based dressing has low mechanical strength and poor elasticity (Hepeng. research on mechanical and adsorption properties of chitosan and its composite material [ D ] Qingdao university, 2019.).
MXene is a novel two-dimensional inorganic material comprising three forms of transition metal carbide, transition metal nitride and transition metal carbonitride, with a thickness of only a few atomic layers. MXene has many excellent properties, which makes MXene a very wide range of interests in various fields. MXene has been shown to have good antimicrobial properties. Relevant researches show that compared with a precursor MAX, MXene after stripping and delamination shows excellent antibacterial activity, can simultaneously play a role in inhibiting the growth of gram-positive bacteria and gram-negative bacteria, and has higher inhibition strength than that of a graphene material under the same experimental conditions. The antibacterial activity of MXene shows extremely wide potential application value, and researchers have made good progress in water treatment, air filtration and the like by utilizing the characteristic of MXene, but researches on MXene in the field of dressing are rarely reported.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: how to prepare the antibacterial hemostatic sponge with high mechanical strength, good water absorption and moisture retention and excellent antibacterial performance by taking the chitosan derivative and MXene as main raw materials.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of an antibacterial hemostatic sponge comprises the following steps:
(1) preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain the MXene aqueous solution with the concentration of 0.1-2 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 1% -3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 1% -3%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 6-10mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.2-1g of cross-linking agent, stirring for 24 hours to form a gel, transferring the solution into an ice-water bath, aging for 24 hours, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, transferring the frozen gel into a freeze-drying machine, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying into a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial hemostatic sponge;
the cross-linking agent is KH 560.
Specifically, the deacetylation degree of the O-carboxymethyl chitosan is more than or equal to 80%, and the carboxylation degree is more than or equal to 60%.
Specifically, MXene is Ti3C2、V2C、Nb2C、V3C2、Ti3CN or Ta4C3
Specifically, the softener is glycerol.
Specifically, the MAX powder is Ti3AlC2、V2SiC、Nb2SiC、V3AlC2、Ti3AlCN or Ta4AlC3
An antibacterial hemostatic sponge, which is prepared according to the preparation method of the antibacterial hemostatic sponge.
The invention has the beneficial effects that:
(1) the novel nano two-dimensional material MXene is added into the antibacterial hemostatic sponge prepared by the invention, and the MXene can be stably fixed on a polymer by adjusting the proportion of the MXene and the cross-linking agent, so that the antibacterial performance of the natural high-molecular-weight dressing is greatly enhanced while the good compatibility of the material is ensured, the antibacterial effect on escherichia coli and staphylococcus aureus is good, and the antibacterial effect can reach more than 99%;
(2) the antibacterial hemostatic sponge prepared by the invention has good mechanical strength and elasticity, the mechanical strength can reach 65KPa, the deformation recovery rate can reach 100%, and medical auxiliary materials play good roles in damping and buffering in the process of human body movement, so that the wound surface can be better protected;
(3) the antibacterial hemostatic sponge prepared by the invention has good water absorption, moisture retention and hemostatic performances and good commercial application prospect.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 0.1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 2
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 0.5 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 3
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 4
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1.5 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 5
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 2 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 6
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 2%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 7
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 1%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 8
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 1%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 9
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 3%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial sponge hemostatic sponge.
Example 10
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.2g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath for aging for 24 hours after the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze drier, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Example 11
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.8g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath for aging for 24 hours after the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze drier, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Example 12
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 1g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice-water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze drier, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Comparative example 1
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 2g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice-water bath to age for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze drier, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Comparative example 2
(1) Preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(2) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(3) mixing 10mL of aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethyl cellulose solution, stirring for 4h at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.5g of cross-linking agent, stirring for 24h, transferring the solution to an ice-water bath to age for 24h until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48h at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2h at 110 ℃, then washing by using acetone and deionized water in sequence, sterilizing by ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Comparative example 3
(1) Preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain an MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethyl cellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min to form a gel, transferring the solution into an ice water bath, aging for 24 hours, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then washing by using acetone and deionized water in sequence, sterilizing by using ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Comparative example 4
(1) Preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(2) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(3) mixing 10mL of aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethyl cellulose solution, stirring for 4h at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, transferring the mixed solution into an ice-water bath to age for 24h after the solution forms a gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze dryer, freeze-drying for 48h at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2h at 110 ℃, then washing by using acetone and deionized water in sequence, sterilizing by using ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Comparative example 5
(1) Preparing MXene, dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution, adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain MXene aqueous solution with the concentration of 1 mg/mL;
(3) preparing an O-carboxymethyl chitosan solution, adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 3%;
(4) preparing a sodium carboxymethyl cellulose solution, adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain the sodium carboxymethyl cellulose solution with the mass concentration of 2%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 8mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.05g of cross-linking agent, stirring for 24 hours, transferring the solution to an ice water bath for aging for 24 hours until the solution forms gel, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, then transferring the frozen gel to a freeze drier, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying to a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, then sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the medical organic-inorganic nano composite antibacterial hemostatic sponge.
Evaluation of material properties:
(1) measurement of Water absorption (see GB/T18944.1-2003): weighing the mass of the sponge before water absorption, soaking the obtained sponge sample (with the height of 10mm and the diameter of 12 mm) in deionized water, weighing the weight of the sponge sample again after the sponge sample is saturated, and calculating the water absorption of the sponge by using the following formula: water absorption (g/g): (mass after water saturation-mass before water saturation)/mass before water saturation X100%;
measurement of Water Retention (see GB/T18944.1-2003): weighing the mass of the sponge before water absorption, soaking the obtained sponge sample in deionized water, weighing the sponge sample again after the sponge sample is saturated, transferring the sponge into a centrifugal machine, centrifuging for 10min at the rotating speed of 2500 rpm, and measuring the mass of the centrifuged sponge. The water retention of the sponge is calculated by the following formula: water retention (%) = (mass of sponge after centrifugation-mass of sponge before water saturation)/(mass of sponge after water saturation-mass of sponge before water saturation) × 100%.
(2) Measurement of compressive strength and elastic recovery:
the test of the compressive strength was carried out on an E44.104 electromechanical universal tester, the sponge having a gauge of 10mm in height, 12mm in diameter, a compression rate of 2mm/min and a deformation rate set at 60%. The compressive strength is the maximum compressive stress value at 60% strain, and the elastic recovery rate can be expressed as: elastic recovery (%) = (100-final strain) × 100%.
(3) Antibacterial experiments(see FZ/T73023-2006): adopting colony counting method, respectively using gram-positive bacteria Staphylococcus aureus and gram-negative bacteria Escherichia coli as experimental objects, wherein the concentration of the used bacteria is 107 CFU/mL, grinding the experimental material sponge of each group into powder, preparing into 0.01g/mL suspension solution, culturing for 5h, adding no sponge suspension to the control group, and making the product have antibacterial effect according to the standard that the antibacterial rate is more than or equal to 50-90%; the bacteriostatic rate is more than or equal to 90 percent, and the product has stronger bacteriostatic action and the bacteriostatic rate is as follows: (control-experimental)/control × 100%.
(4) Testing the hemostatic ability:
a dynamic whole blood coagulation model is adopted to evaluate the in-vitro hemostatic capacity of the sponge, and the specific experimental method comprises the following steps: the prepared sponge (thickness 14 mm)) was preheated at 37 ℃ for 10min in advance before the start of the experiment; 100 μ L of fresh blood drawn from the rat was added dropwise to the surface of the sponge sample, followed by 10 μ L of LCaCI2(0.2mol/L) solution, placing the sample in a shaking table with 37 ℃ and 30rpm for heat preservation for 5min to ensure that the blood is fully contacted with the material, then slowly dripping 5 mL of deionized water, placing the sample in a constant-temperature shaking table with 37 ℃ for heat preservation for 5min, collecting supernatant, measuring the absorbance of the supernatant, directly dripping the blood on the surface of a container in a negative control group, keeping the rest content unchanged, and obtaining the blood coagulation index through the following calculation formula: blood coagulation index (%) = (absorbance of experimental group/absorbance of negative control group) × 100%, and the lower the blood coagulation index, the stronger the in vitro hemostatic ability of the material is.
A rat femoral artery blood loss model is adopted to evaluate the in-vivo hemostatic capacity of the sponge, and the specific experimental method comprises the following steps: rats were anesthetized with 10% chloral hydrate (0.3 mL/100 g) before the start of surgery, after the rats were fixed on an operating table, the femoral artery of the rats was separated from the surrounding tissues with a scalpel, the femoral artery of the rats was separated from the veins with a triangular plastic sheet, 50% of the femoral artery was cut around the circumference thereof to induce blood loss, and after 10s, the sponge was covered on the wound to measure the hemostatic time, the shorter the hemostatic time, the better the hemostatic effect of the material in vivo.
(5) Cytotoxicity experiments: by MTT methodEvaluation of cytotoxicity test was performed. Before the experiment, all samples were ground into powder and soaked in DMEM culture solution, incubated at 37 deg.C for 24h to obtain the extractive solution of sponge sample, and the density was 5 × 103NIH-3T3 mouse embryo fibroblast cells in the well are placed at 37 deg.C, sterilized, and CO2After 24h of incubation in 5% environment, the original culture medium of the cultured cells was replaced with sponge extract, 10% bovine fetal serum was added, the negative control group directly replaced the original culture medium with DMEM, incubation was continued for 48h, the culture solution was aspirated with a dropper, 50 μ L MTT (5mg/mL) was added, reaction was performed for 4h in dark environment, absorbance at 490nm was measured, and cell activity was expressed as: cell activity = (absorbance of experimental group/absorbance of negative control group) × 100%.
The performance tests of the medical dressings prepared in examples 1 to 12 and comparative examples 1 to 5 are shown in table 1:
TABLE 1
Figure 902562DEST_PATH_IMAGE002
TABLE 1
Figure 235455DEST_PATH_IMAGE004
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (6)

1. The preparation method of the antibacterial hemostatic sponge is characterized by comprising the following steps:
(1) preparation of MXene
Dissolving 1g of lithium fluoride in 20mL of hydrochloric acid solution with the concentration of 6mol/L to obtain LiF/HCl mixed solution, adding 1g of MAX powder into the LiF/HCl mixed solution at room temperature, stirring and etching for 24 hours, washing with water, and drying to obtain MXene;
(2) preparing MXene aqueous solution
Adding MXene into the aqueous solution, and uniformly dispersing by ultrasonic to obtain the MXene aqueous solution with the concentration of 0.1-2 mg/mL;
(3) preparing O-carboxymethyl chitosan solution
Adding O-carboxymethyl chitosan into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain an O-carboxymethyl chitosan solution with the mass concentration of 1% -3%;
(4) preparing sodium carboxymethylcellulose solution
Adding carboxymethyl cellulose into a sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution with the pH =8 to obtain a sodium carboxymethyl cellulose solution with the mass concentration of 1% -3%;
(5) mixing 10mL of MXene aqueous solution, 10g O-carboxymethyl chitosan solution and 10g of sodium carboxymethylcellulose solution, stirring for 4 hours at 50 ℃ to obtain a mixed solution, then dropwise adding 6-10mg of softener into the mixed solution, stirring for 30min, continuously dropwise adding 0.2-1g of cross-linking agent, stirring for 24 hours to form a gel, transferring the solution into an ice-water bath, aging for 24 hours, then pouring the gel into a mold, freezing the gel by using liquid nitrogen, transferring the frozen gel into a freeze-drying machine, freeze-drying for 48 hours at-50 ℃, transferring the sponge obtained after freeze-drying into a vacuum drying oven, vacuum-drying for 2 hours at 110 ℃, sequentially washing by using acetone and deionized water, sterilizing by ultraviolet irradiation, and cutting to obtain the antibacterial hemostatic sponge;
the cross-linking agent is KH 560.
2. The method for preparing an antibacterial hemostatic sponge according to claim 1, wherein the method comprises the following steps: the deacetylation degree of the O-carboxymethyl chitosan is more than or equal to 80 percent, and the carboxylation degree is more than or equal to 60 percent.
3. The method for preparing an antibacterial hemostatic sponge according to claim 1, wherein the method comprises the following steps: the MXene is Ti3C2、V2C、Nb2C、V3C2、Ti3CN or Ta4C3
4. The method for preparing an antibacterial hemostatic sponge according to claim 1, wherein the method comprises the following steps: the softener is glycerol.
5. The method for preparing an antibacterial hemostatic sponge according to claim 1, wherein the method comprises the following steps: the MAX powder is Ti3AlC2、V2SiC、Nb2SiC、V3AlC2、Ti3AlCN or Ta4AlC3
6. An antibacterial hemostatic sponge, prepared by the method of any one of claims 1-5.
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