Technical background:
wound infection can inhibit wound healing and cause sepsis and other diseases in severe cases. Photothermal therapy (PTT) achieves indiscriminate sterilization without causing bacterial resistance, and is an effective method for combating microbial infections. Examples of the photo-thermal agent that is commonly used include inorganic nanosheets such as MXene, organic photo-thermal molecules such as cyanines, catechols, and the like. The photothermal properties of catechol photothermal agents may be enhanced by the addition of metal ions to form metal coordination interactions with charge transfer transitions therebetween.
The hydrophobic alkyl chain can further interfere with the normal physiological metabolic activity of the bacteria while capturing the bacteria through hydrophobic interaction, so that the antibacterial ability of the molecule can be improved while bacterial resistance is not induced by grafting the hydrophobic alkyl chain. In addition, hydrophobic alkyl chains may enhance the hemostatic ability of the molecule. Therefore, the introduction of the hydrophobic alkyl chain can realize the simultaneous promotion of the antibacterial and hemostatic dual functions of the material.
The natural polymer has the advantages of wide sources, good biocompatibility, capability of functional modification according to the needs, and the like. Chitosan (CS) is the only basic polysaccharide in natural polymers, has certain antibacterial capacity, and is one of the most commonly used raw materials for preparing antibacterial dressing. Gelatin can be formed into gel through various supermolecular interactions, on one hand, gelatin can be formed into gel through hydrogen bonds among three helices, on the other hand, a large amount of amino carboxyl groups contained in the gelatin can be coordinated with metal ions to form the gel, and the gelatin has good biocompatibility and low immunogenicity, so that the gelatin is often used as a base frame material of a wet gel material.
In addition to water, glycerol is also one of the common solvents used to prepare wet gel materials. The addition of glycerin can improve the freezing resistance, water retention capacity and mechanical property of the material. In addition, since the specific heat capacity of glycerin is lower than that of water, the gel material doped with glycerin as a solvent has higher photo-thermal conversion capability when the surface of the gel material of the same mass is irradiated with light intensity of the same intensity for the same time. Therefore, the incorporation of glycerol as a second solvent in hydrogels is a convenient way to improve the overall properties of the gel material.
The invention comprises the following steps:
aiming at the problems in the prior art, the invention aims to solve the technical problems that: how to quickly prepare the wet antibacterial dressing with controllable adhesion, infrared light response, antioxidation and antibacterial effects by taking CS, lauric acid (DA) dihydrocaffeic acid (HCA) and gelatin as raw materials.
The technical scheme adopted for solving the technical problems is as follows: the invention provides a wet antibacterial dressing which comprises the following components in percentage by mass:
water: 25 to 75 weight percent
Glycerol: 10 to 60 percent by weight
FeCl 3 :0.01wt~1wt%
hmCSC:0.1wt~4wt%
Gelatin: 5 to 15 percent by weight
Specifically, the preparation method of the wet antibacterial dressing specifically comprises the following steps:
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution, 50mL of ethanol solution was added, followed by dropwise addition of 10mL of DA (0.027M to 0.081M) ethanol solution and 20mL of NaCNBH 3 (0.816M-2.448M) solution; (2) adjusting the pH value of the solution to 5, and reacting for 12 hours at 40 ℃; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous solution of hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M-0.66M) and 12EDC (0.258M-0.774M) in ethanol water (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) Preparing 10mL of an aqueous solution of hmCSC glycerol with the pH=5 and the concentration of 1 to 4 weight percent at room temperature; (2) heating the solution to 55 ℃ to prepare gelatin glycerol water solution with the concentration of 5-15 wt%; (3) after it is dissolved, 24 mu L to 1200 mu L FeCl with concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
The specific embodiment is as follows:
example 1
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) will beThe pH value of the solution is adjusted to 5, and the solution is placed at 40 ℃ for reaction for 12 hours; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 1wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 7wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 2
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) adjusting the pH value of the solution to 5, and reacting for 12 hours at 40 ℃; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 1wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 9wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 3
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) adjusting the pH value of the solution to 5, and reacting for 12 hours at 40 ℃; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 1wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 11 wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 4
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) will be put onThe pH value of the solution is adjusted to 5, and the solution is placed at 40 ℃ for reaction for 12 hours; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 1wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 13 wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 5
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) adjusting the pH value of the solution to 5, and reacting for 12 hours at 40 ℃; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 1wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 15wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 6
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) adjusting the pH value of the solution to 5, and reacting for 12 hours at 40 ℃; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 2wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 11 wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 7
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) the above-mentioned materials are mixedThe pH value of the solution is adjusted to 5, and the solution is placed at 40 ℃ for reaction for 12 hours; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 3wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 11 wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.
Example 8
(1) Preparation of hmCS
(1) To 100mL of 1wt% CS acetic acid aqueous solution was added 50mL of ethanol solution, followed by dropwise addition of 10mL of DA (0.027M) ethanol solution and 20mL of NaCNBH 3 (0.816M) solution; (2) adjusting the pH value of the solution to 5, and reacting for 12 hours at 40 ℃; (3) the pH value of the solution after the reaction is adjusted to 7, and the small molecules DA and NaCNBH which do not participate in the reaction are repeatedly washed by ethanol and water 3 The method comprises the steps of carrying out a first treatment on the surface of the (4) The obtained product was stored by freeze drying.
(2) Preparation of hmCSC
(1) To 100mL of 1wt% aqueous hmCS hydrochloric acid, 50mL of ethanol solution was added followed by 12 HCA (0.220M) and 12EDC (0.258M) aqueous ethanol solution (ethanol: water=1:1, v/v); (2) the pH value is adjusted to 5, and the mixture is placed at room temperature for reaction for 12 hours; (3) after the reaction is finished, the product is purified by a membrane dialysis method. (4) The obtained product was stored by freeze drying.
(3) Preparation of GCFe n-gly Gel
(1) 10mL of an aqueous solution of hmCSC glycerol at a concentration of 4wt% was prepared at room temperature at ph=5; (2) heating the solution to 55deg.C to obtain gelatin glycerol water solution with concentration of 11 wt%; (3) after it is dissolved, 480. Mu.L of FeCl with a concentration of 1mol/L 3. 6H 2 Dropwise adding the O solution into the prepared hmCSC/gelatin glycerin water solution, and stirring to form gel; (4) the gel obtained was cooled at room temperature and used.