A kind of wound care dressing after thyroid surgery and preparation method thereof

Abstract

The invention discloses a thyroid postoperative wound care dressing in the technical field of care dressings and a preparation method thereof, comprising the following components in parts by weight: 3.5-5 parts of phenylboronic acid modified polysiloxane, 1.8-2.7 parts of caffeic acid, 2.0-3.0 parts of dopamine hydrochloride, 2.5-6 parts of iodine, 3.5-5.5 parts of vinyl pyrrolidone, and 0.4-0.6 parts of polyethylene glycol diacrylate. The invention uses polysiloxane and polyacrylamide to form a composite material to prepare a wound care dressing, and forms a boron ester bond by using the boric acid group in phenylboronic acid and the catechol hydroxyl matrix on caffeic acid / dopamine, thereby improving the compatibility between polysiloxane and polyacrylamide, and through the adsorption and release of iodine by vinyl pyrrolidone, the antibacterial property of the wound care dressing is improved, and the irritation to the wound is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of nursing dressings, and specifically refers to a wound nursing dressing after thyroid surgery and a preparation method thereof. Background Art

[0002] Thyroid surgery is a common surgical method for treating thyroid diseases, and postoperative wound care is crucial to the patient's recovery. Although thyroid surgery is usually a minimally invasive surgery, the postoperative wound may still face problems such as infection, bleeding, and scar hyperplasia. These problems will not only delay the patient's recovery process, but may also lead to long-term health complications. Therefore, how to effectively prevent wound infection, accelerate wound healing, and reduce scar formation have become important goals of postoperative care for thyroid surgery. Traditional wound care dressings mainly prevent external bacterial invasion through physical barriers and promote wound healing through a moist environment. However, a simple physical barrier and a moist environment cannot fully meet the needs of postoperative wounds for thyroid surgery. In order to improve the wound healing effect, modern medicine has begun to pay attention to the integration of multiple functions such as drug sustained release, antibacterial, and biocompatibility, and develop multifunctional wound care dressings that can effectively promote wound healing.

[0003] Most of the existing wound care dressings are made of traditional natural materials (such as gauze, tape) or synthetic materials (such as polyethylene, polyurethane, etc.). Although these dressings can cover the wound and keep it moist to a certain extent, their functionality is relatively simple. Their main function is physical barrier, and they lack functions such as antibacterial, healing promotion, and controlled drug release. For example, many dressings can only provide temporary antibacterial protection, but cannot continuously and effectively inhibit bacterial infection, resulting in the continued risk of postoperative infection. In addition, traditional dressings usually do not have active biological repair capabilities and cannot promote wound regeneration and healing. With the gradual increase in the demand for wound care, there is an urgent need for new multifunctional dressings that can play a positive role in antibacterial, healing promotion, and avoiding scar hyperplasia.

[0004] With the continuous development of materials science, pharmacy and biomedicine, smart wound dressings have emerged and become an important research direction to improve wound healing effects. Smart dressings usually integrate multiple functions such as drug sustained release, antibacterial, anti-inflammatory, and healing promotion, and can be adjusted according to the specific conditions of the wound to achieve precise treatment. At present, smart dressings based on a variety of materials such as polymers, nanomaterials, and bioactive molecules have gradually been widely studied. Some researchers have adopted technologies such as nano-antimicrobial agents (such as silver nanoparticles), bioactive molecules (such as growth factors, antioxidants), and controlled release systems (such as hydrogels and microparticle drug delivery systems) and have made certain research progress. For example, by loading antibiotics or antibacterial molecules into dressings and continuously releasing them for a certain period of time through a controllable release mechanism, better antibacterial effects can be achieved. However, these technologies usually face problems such as drug resistance and unstable release rate, and they urgently need to be further optimized. Summary of the invention

[0005] In view of the above situation, in order to overcome the defects of the prior art, the present invention provides a wound care dressing after thyroid surgery and a preparation method thereof. The present invention uses polysiloxane and acrylate to form a composite material to make a wound care dressing, and uses the boric acid group in phenylboronic acid and the catechol hydroxyl matrix on caffeic acid / dopamine to form a boron ester bond to improve the compatibility between polysiloxane and acrylate. Through the adsorption and release of iodine by vinyl pyrrolidone, the antibacterial property of the wound care dressing is improved, thereby reducing the irritation to the wound.

[0006] In order to achieve the above-mentioned object, the technical scheme adopted by the present invention is as follows: The present invention provides a wound care dressing after thyroid surgery, wherein the raw materials for preparing the care dressing include the following components in parts by weight: 3.5-5 parts of phenylboronic acid modified polysiloxane, 1.8-2.7 parts of caffeic acid, 2.0-3.0 parts of dopamine hydrochloride, 2.5-6 parts of iodine, 3.5-5.5 parts of vinyl pyrrolidone, and 0.4-0.6 parts of polyethylene glycol diacrylate;

[0007] Preferably, the raw materials for preparing the phenylboronic acid modified polysiloxane include the following components in parts by weight: 14-24 parts of methylcyclosiloxane, 1.5-3.5 parts of vinylcyclosiloxane, 0.08-0.2 parts of hexamethyldisiloxane, and 0.5-0.7 parts of 4-bromophenylboric acid;

[0008] Preferably, the methylcyclosiloxane includes at least one of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, methylhydrogencyclotrisiloxane and methylhydrogencyclotetrasiloxane;

[0009] Preferably, the vinyl cyclosiloxane includes at least one of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane;

[0010] Preferably, the preparation method of the phenylboronic acid modified polysiloxane specifically comprises the following steps:

[0011] S1. Put methylcyclosiloxane and vinylcyclosiloxane in a flask, add toluene, add hexamethyldisiloxane, introduce nitrogen, add potassium trifluoromethanesulfonate, stir and react at a speed of 200-300 rpm under a nitrogen atmosphere, react for 3-6 hours, add DCM (dichloromethane) to dissolve the polymer, add anhydrous methanol for sedimentation treatment, concentrate under reduced pressure, and dry to obtain polysiloxane;

[0012] Preferably, in step S1, the volume fraction of the methylcyclosiloxane in toluene is 25-35%;

[0013] Preferably, in step S1, the potassium trifluoromethanesulfonate is added to the methylcyclosiloxane at a concentration of 3-4 mg / mL;

[0014] S2, the polysiloxane prepared in step S1 is placed in dioxane, flowing nitrogen is introduced, and after uniform mixing at a speed of 150-200 rpm, Karstedt catalyst is added, stirring is continued, and the reaction temperature is increased to 80-90°C, 4-bromophenylboric acid is dissolved in dioxane and added dropwise to the reaction system, and the reaction is continued for 18-24 hours, and then vacuum distillation is performed, and 2wt% NaCO is used. 3 Extract with aqueous solution, collect the organic phase, wash the organic phase with saturated NaCl aqueous solution, add anhydrous sodium sulfate to dry the organic phase, and vacuum dry to obtain phenylboronic acid modified polysiloxane;

[0015] Preferably, in step S2, the mass concentration of the polysiloxane in dioxane is 0.15-0.2 g / mL;

[0016] Preferably, in step S2, the added mass of the Karstedt catalyst is 0.14%-0.19% of the mass of 4-bromophenylboric acid.

[0017] The present invention also provides a method for preparing a wound care dressing after thyroid surgery, which specifically comprises the following steps:

[0018] S3, add caffeic acid to anhydrous DMF (N,N-dimethylformamide), stir until fully dissolved, add HOBt (1-hydroxybenzotriazole) and continue stirring, slowly add EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide), stir at 120-150 rpm for 1-2 hours to obtain an activated caffeic acid solution;

[0019] Preferably, in step S3, the mass concentration of caffeic acid in anhydrous DMF is 36-54 mg / mL;

[0020] Preferably, in step S3, the mass ratio of caffeic acid, HOBt and EDC is 1.2-1.35:1:1.2-1.4;

[0021] S4, dissolving dopamine hydrochloride in anhydrous DMF, adding DIPEA (diisopropylethylamine) to adjust the pH to 8-9 to obtain a dopamine solution, adding the dopamine solution dropwise to the activated caffeic acid solution prepared in step S3, maintaining the reaction temperature between 25-35°C, reacting at a speed of 180-200 rpm for 4-8 hours, transferring the reaction system to ice water, extracting with ethyl acetate, collecting the organic phase, washing the organic phase with a saturated sodium chloride solution and deionized water in sequence, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, purifying and drying to obtain caffeic acid dopamine;

[0022] Preferably, in step S4, the mass concentration of dopamine hydrochloride in anhydrous DMF is 40-60 mg / mL;

[0023] S5, dissolving the caffeic acid dopamine prepared in step S5 in an ethanol aqueous solution, introducing flowing nitrogen, adding vinyl pyrrolidone and polyethylene glycol diacrylate and mixing thoroughly, adding p-hydroxybenzoic acid, stirring at a speed of 300-400 rpm, adding AIBN (azobisisobutyronitrile) under anaerobic sealing conditions, raising the reaction temperature to 60-70°C, stirring and reacting for 4-6 hours, adding anhydrous ether for precipitation, filtering, collecting the precipitate, washing the precipitate with anhydrous ethanol and deionized water, and vacuum drying to obtain a copolymer;

[0024] Preferably, in step S5, the mass concentration of the caffeic acid dopamine in the ethanol aqueous solution is 13-20 g / L;

[0025] Preferably, in step S5, the added mass of the p-hydroxybenzoic acid is 3.0%-4.5% of the mass of the caffeic acid dopamine;

[0026] Preferably, in step S5, the added mass of AIBN is 1.3%-2.3% of the mass of caffeic acid dopamine;

[0027] S6, dissolving potassium iodide in an ethanol aqueous solution, adding iodine, and continuing to mix until the solution becomes dark brown and no longer changes color, placing in a light-proof environment, adding the copolymer prepared in step S5, stirring at a speed of 120-180 rpm, reacting for 18-24 hours, filtering, collecting the solid, washing with deionized water, and vacuum drying to obtain a PVP-I-multi-copolymer;

[0028] Preferably, in step S6, the mass concentration of potassium iodide in the ethanol aqueous solution is 0.05-0.13 g / mL;

[0029] Preferably, in step S6, the mass ratio between iodine and potassium iodide is 1:2-3;

[0030] S7. Dissolve the phenylboronic acid modified polysiloxane prepared in step S2 in DMSO (dimethyl sulfoxide), adjust the pH to 8-9, add the PVP-I-multipolymer prepared in step S6, stir at a speed of 500-600 rpm, react for 1-3 hours, concentrate under reduced pressure to remove DMSO, apply with a doctor coater, and solidify at room temperature to obtain a wound care dressing.

[0031] The beneficial effects achieved by the present invention are as follows:

[0032] The invention provides a wound care dressing after thyroid surgery and a preparation method thereof. The wound care dressing is prepared by forming a composite material of polysiloxane and acrylate, and a boron ester bond is formed by using a boric acid group in phenylboronic acid and a catechol hydroxyl matrix on caffeic acid / dopamine to improve the compatibility between polysiloxane and acrylate. The antibacterial property of the wound care dressing is improved by the adsorption and release of iodine by vinyl pyrrolidone, and the irritation to the wound is reduced. In the invention, a phenylboronic acid group (4-bromophenylboronic acid) is introduced into a polysiloxane chain to form a stable silicone-based dressing. The phenylboronic acid group has the ability to combine with some bacterial cell wall components in aqueous solution, thereby showing antibacterial properties. In the present invention, caffeic acid undergoes a coupling reaction with dopamine hydrochloride under the activation of EDC (N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide) and HOBt (1-hydroxy-4-methyl-2-thiazolinone) to generate caffeic acid-dopamine, form a covalent bond between caffeic acid and dopamine, and produce a compound with strong affinity. Dopamine molecules contain amino and phenolic hydroxyl groups, which can form strong non-covalent interactions (such as hydrogen bonds, electrostatic effects, etc.) with biological macromolecules such as collagen in wound tissue, thereby promoting cell attachment and growth. The synthesis of the PVP-I (polyvinyl pyrrolidone-iodine) multipolymer in the present invention is based on a polymerization reaction. Through the synthesis of the copolymer, iodine is slowly released through the PVP carrier, and can be released stably for a long time, maintain a continuous antibacterial effect, and reduce the risk of postoperative wound infection; the present invention forms a boron ester bond between the catechol hydroxyl group in the PVP-I-multipolymer and the boric acid group of the phenylboronic acid-modified polysiloxane, which can be reversible through changes in the wound environment and has self-recovery ability, thereby adjusting the structure in the wound care dressing to achieve iodine release performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is an infrared spectrum image of the phenylboronic acid modified polysiloxane prepared in Example 1;

[0034] Figure 2 The infrared spectrum image of the PVP-I-multi-polymer and the wound care dressing prepared in Example 1;

[0035] Figure 3 The tensile strength and elongation at break results of the wound care dressings prepared in Examples 1-3 of the present invention and Comparative Examples 1-3 are shown in FIG.

[0036] Figure 4 This is a graph showing the tissue adhesion performance results of the wound care dressings prepared in Examples 1-3 of the present invention and Comparative Examples 1-3.

[0037] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0039] Unless otherwise defined, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein may be applied to the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only and are not intended to limit the content of this application.

[0040] The experimental methods in the following examples are conventional methods unless otherwise specified; the experimental materials and test strains used in the following examples are purchased from commercial channels unless otherwise specified.

[0041] Polyethylene glycol diacrylate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. with the product number of P131592.

[0042] Example 1

[0043] The present embodiment provides a wound care dressing after thyroid surgery, wherein the raw materials for preparing the care dressing include the following components in parts by weight: 3.5 parts of phenylboronic acid-modified polysiloxane, 1.8 parts of caffeic acid, 2.0 parts of dopamine hydrochloride, 2.5 parts of iodine, 3.5 parts of vinyl pyrrolidone, and 0.4 parts of polyethylene glycol diacrylate;

[0044] The raw materials for preparing phenylboronic acid modified polysiloxane include the following components in parts by weight: 14 parts of octamethylcyclotetrasiloxane, 3.5 parts of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 0.08 parts of hexamethyldisiloxane, and 0.65 parts of 4-bromophenylboric acid;

[0045] The preparation method of phenylboronic acid modified polysiloxane specifically comprises the following steps:

[0046] S1. Accurately weigh 14 mL of octamethylcyclotetrasiloxane and 3.5 mL of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and place them in a reaction flask. Add 50 mL of dry toluene and mix well. Then add 0.1 mL of hexamethyldisiloxane, introduce nitrogen, exclude oxygen in the reaction system, raise the temperature to 110° C., dissolve potassium trifluoromethylsulfonate in toluene to prepare a 10 g / L potassium trifluoromethylsulfonate solution, take 5 mL and add it to the reaction flask. Stir and react at a speed of 300 rpm. After reacting for 4 hours, the reaction is completed. After the reaction system is cooled to room temperature, add 100 mL of DCM to dissolve the reaction product, add 100 mL of anhydrous methanol for sedimentation treatment, concentrate under reduced pressure to remove the reaction solvent, and place it under vacuum drying at 40° C. for 6 hours to obtain polysiloxane.

[0047] S2, dissolving the polysiloxane prepared in step S1 in 100 mL of dioxane, introducing flowing nitrogen, turning on the stirrer, adjusting the speed to 180 rpm for stirring, preparing a 1 mg / L catalyst solution of Karstedt catalyst with dioxane, taking 1 mL of the catalyst solution and adding it to the reaction system, continuing to stir and mix evenly, raising the reaction temperature to 80°C, adding 4-bromophenylboric acid to dioxane to prepare a 10 mg / mL 4-bromophenylboric acid solution, taking 65 mL of the 4-bromophenylboric acid solution and dropping it into the reaction system at a speed of 1 mL / min, after the dropwise addition is completed, continuing the reaction for 18 h, removing the solvent by reduced pressure distillation, and adding 2 wt% of NaCO 3 The organic phase was extracted with an aqueous solution, and the organic phase was collected and washed with a saturated NaCl aqueous solution. After repeated extraction and washing three times, the organic phases were combined, dried with anhydrous sodium sulfate to remove water, placed in a vacuum drying oven, and dried at 40°C for 12 hours to obtain phenylboronic acid modified polysiloxane.

[0048] With air as the background spectrum, the polysiloxane modified with phenylboronic acid prepared in step S2 of Example 1 was prepared by a KBr pellet method, and the wavelength of 4000-500 cm- 1 FTIR spectrum in the range, Figure 1The infrared spectrum image of the phenylboronic acid modified polysiloxane prepared in Example 1, wherein A is the polysiloxane prepared in step S1 of Example 1, and B is the phenylboronic acid modified polysiloxane prepared in step S2 of Example 1. Compared with A, B has a higher infrared spectrum at 2970-2910 cm -1 At 1520-1495cm -1 The characteristic absorption peak of benzene ring appeared at 3580-3510cm -1 The characteristic absorption peak of OH appeared at , while the characteristic peak of C=C bond on A became smaller, indicating that 4-bromophenylboronic acid reacted with polysiloxane and phenylboronic acid-modified polysiloxane was successfully synthesized.

[0049] This embodiment also provides a method for preparing a wound care dressing after thyroid surgery, which specifically comprises the following steps:

[0050] S3. Accurately weigh 1.8 g of caffeic acid and place it in a dry flask. Add 50 mL of anhydrous DMF to fully dissolve the caffeic acid. After mixing evenly, add 1.5 g of HOBt and continue stirring. Add EDC in portions for a total of 1.8 g. Stir at a speed of 150 rpn for 1 h to obtain an activated caffeic acid solution.

[0051] S4, accurately weigh 2.0 g of dopamine hydrochloride and dissolve it in 50 mL of anhydrous DMF, add DIPEA to adjust the pH to 8.0 to obtain a dopamine solution, and add the dissolved dopamine dropwise to the activated caffeic acid solution prepared in step S3 at a rate of 1 mL / min, maintain the reaction temperature at 25°C, and stir the reaction at a speed of 200 rpm. After reacting for 6 hours, transfer the reaction system to ice water, mix, add ethyl acetate for extraction, repeat the extraction three times, collect and combine the organic phases, wash three times with a saturated NaCl aqueous solution and deionized water in sequence, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, purify by chromatography, and vacuum dry at 30°C to obtain caffeic acid dopamine;

[0052] S5, dissolving the caffeic acid dopamine prepared in step S4 in 200 mL of 75 vol% ethanol aqueous solution, mixing evenly, introducing flowing nitrogen, adding 3.5 mL of vinyl pyrrolidone and 0.36 mL of polyethylene glycol diacrylate to mix well, adding 1 mL of Tween 80 to mix the reactants into a uniform system, adding 0.1 g of p-hydroxybenzoic acid under a nitrogen atmosphere, stirring and reacting at a speed of 400 rpm, adding 60 mg of AIBN under anaerobic sealing conditions, raising the reaction temperature to 60°C, stirring and reacting for 4 hours, and after the reaction is cooled to room temperature, adding anhydrous ether for precipitation, filtering, collecting the precipitate, repeatedly washing the precipitate with anhydrous ethanol and deionized water three times, and vacuum drying at 35°C for 8 hours to obtain a copolymer;

[0053] S6, weigh 8g of potassium iodide and put it in a beaker, add 100mL, 75vol% ethanol aqueous solution and mix thoroughly, after the potassium iodide is completely dissolved, accurately weigh 2.5g of iodine, mix until the solution appears dark brown, and the color no longer changes, place it in a light-proof environment, add the copolymer prepared in step S5, stir at a speed of 180rpm, react for 24h, filter, collect the solid, wash with deionized water, and vacuum dry at 40°C to obtain PVP-I-multi-copolymer;

[0054] S7. Take 3.5 g of phenylboronic acid-modified polysiloxane and dissolve it in 500 mL of DMSO, adjust the pH to 9.0, add the PVP-I-multi-polymer prepared in step S6, and stir the mixture at 600 rpm for reaction. After reacting for 3 hours, reduce the pressure and concentrate to remove excess DMSO, apply it with a doctor coater, and solidify it at room temperature to obtain a wound care dressing.

[0055] With air as the background spectrum, the phenylboronic acid-modified polysiloxane prepared in step S2 of Example 1 was prepared by a KBr pellet method to measure the wavelength of 4000-500 cm in a Fourier transform infrared spectrometer. -1 FTIR spectrum in the range, Figure 2 The infrared spectra of the PVP-I-multi-polymer and the wound care dressing prepared in Example 1, wherein A is the PVP-I-multi-polymer prepared in step S6 of Example 1, and B is the wound care dressing prepared in step S7 of Example 1. As shown in the figure, compared with A, B has an infrared spectrum of 1180-970cm -1 The absorption peak of Si-O-Si bond appears at the hydroxyl group (3540-3410cm) due to the formation of boron ester bond between hydroxyl group and boric acid. -1 ) weakened, indicating that the wound care dressing of Example 1 was successfully synthesized.

[0056] Example 2

[0057] The present embodiment provides a wound care dressing after thyroid surgery, wherein the raw materials for preparing the care dressing include the following components in parts by weight: 5.0 parts of phenylboronic acid-modified polysiloxane, 2.7 parts of caffeic acid, 2.5 parts of dopamine hydrochloride, 5 parts of iodine, 5.5 parts of vinyl pyrrolidone, and 0.5 parts of polyethylene glycol diacrylate;

[0058] The raw materials for preparing phenylboronic acid modified polysiloxane include the following components in parts by weight: 20 parts of octamethylcyclotetrasiloxane, 1.5 parts of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 0.16 parts of hexamethyldisiloxane, and 0.54 parts of 4-bromophenylboric acid;

[0059] The preparation method of phenylboronic acid modified polysiloxane specifically comprises the following steps:

[0060] S1. Accurately weigh 20 mL of octamethylcyclotetrasiloxane and 1.7 mL of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and place them in a reaction flask. Add 80 mL of dry toluene and mix well. Then add 0.2 mL of hexamethyldisiloxane, introduce nitrogen, exclude oxygen in the reaction system, raise the temperature to 120° C., dissolve potassium trifluoromethylsulfonate in toluene to prepare a 10 g / L potassium trifluoromethylsulfonate solution, take 6 mL and add it to the reaction flask. Stir and react at a speed of 200 rpm. After reacting for 6 hours, the reaction is completed. After the reaction system is cooled to room temperature, add 100 mL of DCM to dissolve the reaction product, add 100 mL of anhydrous methanol for sedimentation treatment, concentrate under reduced pressure to remove the reaction solvent, and place it under vacuum drying at 40° C. for 6 hours to obtain polysiloxane.

[0061] S2, dissolving the polysiloxane prepared in step S1 in 100 mL of dioxane, introducing flowing nitrogen, turning on the stirrer, adjusting the speed to 180 rpm for stirring, preparing a 1 mg / L catalyst solution of Karstedt catalyst with dioxane, taking 1 mL of the catalyst solution and adding it to the reaction system, continuing to stir and mix evenly, raising the reaction temperature to 85°C, adding 4-bromophenylboric acid to dioxane to prepare a 10 mg / mL 4-bromophenylboric acid solution, taking 54 mL of the 4-bromophenylboric acid solution and dropping it into the reaction system at a speed of 1 mL / min, after the dropwise addition is completed, continuing the reaction for 22 h, removing the solvent by reduced pressure distillation, and adding 2 wt% of NaCO 3 The organic phase was extracted with an aqueous solution, and the organic phase was collected and washed with a saturated NaCl aqueous solution. After repeated extraction and washing three times, the organic phases were combined, dried with anhydrous sodium sulfate to remove water, placed in a vacuum drying oven, and dried at 40°C for 12 hours to obtain phenylboronic acid modified polysiloxane.

[0062] This embodiment also provides a method for preparing a wound care dressing after thyroid surgery, which specifically comprises the following steps:

[0063] S3. Accurately weigh 2.7 g of caffeic acid and place it in a dry flask. Add 50 mL of anhydrous DMF to fully dissolve the caffeic acid. After mixing evenly, add 2.0 g of HOBt and continue stirring. Add EDC in portions for a total of 2.8 g. Stir at a speed of 150 rpn for 1 h to obtain an activated caffeic acid solution.

[0064] S4, accurately weigh 2.5 g of dopamine hydrochloride and dissolve it in 50 mL of anhydrous DMF, add DIPEA to adjust the pH to 8.5 to obtain a dopamine solution, and add the dissolved dopamine dropwise to the activated caffeic acid solution prepared in step S3 at a rate of 1 mL / min, maintain the reaction temperature at 30°C, and stir the reaction at a speed of 180 rpm. After reacting for 8 hours, transfer the reaction system to ice water, mix, add ethyl acetate for extraction, repeat the extraction three times, collect and combine the organic phases, wash three times with a saturated NaCl aqueous solution and deionized water in sequence, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, purify by chromatography, and vacuum dry at 30°C to obtain caffeic acid dopamine;

[0065] S5, dissolving the caffeic acid dopamine prepared in step S4 in 200 mL of 75 vol% ethanol aqueous solution, mixing evenly, introducing flowing nitrogen, adding 5.3 mL of vinyl pyrrolidone and 0.45 mL of polyethylene glycol diacrylate to mix well, adding 1 mL of Tween 80 to mix the reactants into a uniform system, adding 0.15 g of p-hydroxybenzoic acid under a nitrogen atmosphere, stirring and reacting at a speed of 300 rpm, adding 45 mg of AIBN under anaerobic sealing conditions, raising the reaction temperature to 70°C, stirring and reacting for 5 hours, and after the reaction is cooled to room temperature, adding anhydrous ether for precipitation, filtering, collecting the precipitate, repeatedly washing the precipitate with anhydrous ethanol and deionized water three times, and vacuum drying at 35°C for 8 hours to obtain a copolymer;

[0066] S6, weigh 10.0 g of potassium iodide and put it in a beaker, add 100 mL of 75 vol% ethanol aqueous solution and mix thoroughly, after the potassium iodide is completely dissolved, accurately weigh 5.0 g of iodine, mix until the solution appears dark brown and the color no longer changes, place in a light-proof environment, add the copolymer prepared in step S5, stir at a speed of 120 rpm, react for 18 hours, filter, collect the solid, wash with deionized water, and vacuum dry at 40°C to obtain PVP-I multi-polymer;

[0067] S7, dissolving 5.0 g of phenylboronic acid-modified polysiloxane in 500 mL of DMSO, adjusting the pH to 8.0, adding the PVP-I-multi-polymer prepared in step S6, stirring and reacting at a speed of 550 rpm, reacting for 3 h, concentrating under reduced pressure to remove excess DMSO, applying with a doctor coater, and curing at room temperature to obtain a wound care dressing.

[0068] Example 3

[0069] The present embodiment provides a wound care dressing after thyroid surgery, wherein the raw materials for preparing the care dressing include the following components in parts by weight: 4.2 parts of phenylboronic acid-modified polysiloxane, 2.2 parts of caffeic acid, 3.0 parts of dopamine hydrochloride, 6 parts of iodine, 4.23 parts of vinyl pyrrolidone, and 0.6 parts of polyethylene glycol diacrylate;

[0070] The raw materials for preparing phenylboronic acid modified polysiloxane include the following components in parts by weight: 24 parts of octamethylcyclotetrasiloxane, 3.5 parts of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 0.2 parts of hexamethyldisiloxane, and 0.7 parts of 4-bromophenylboric acid;

[0071] The preparation method of phenylboronic acid modified polysiloxane specifically comprises the following steps:

[0072] S1. Accurately weigh 25 mL of octamethylcyclotetrasiloxane and 1.7 mL of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and place them in a reaction flask. Add 70 mL of dry toluene and mix well. Then add 0.25 mL of hexamethyldisiloxane, introduce nitrogen, exclude oxygen in the reaction system, raise the temperature to 130° C., dissolve potassium trifluoromethylsulfonate in toluene to prepare a 10 g / L potassium trifluoromethylsulfonate solution, take 7 mL and add it to the reaction flask. Stir and react at a speed of 250 rpm. After reacting for 3 hours, the reaction is completed. After the reaction system is cooled to room temperature, add 100 mL of DCM to dissolve the reaction product, add 100 mL of anhydrous methanol for sedimentation treatment, concentrate under reduced pressure to remove the reaction solvent, and place it under vacuum drying at 40° C. for 6 hours to obtain polysiloxane.

[0073] S2, dissolving the polysiloxane prepared in step S1 in 100 mL of dioxane, introducing flowing nitrogen, turning on the stirrer, adjusting the speed to 180 rpm for stirring, preparing a 1 mg / L catalyst solution of Karstedt catalyst with dioxane, taking 1 mL of the catalyst solution and adding it to the reaction system, continuing to stir and mix evenly, raising the reaction temperature to 90°C, adding 4-bromophenylboric acid to dioxane to prepare a 10 mg / mL 4-bromophenylboric acid solution, taking 70 mL of the 4-bromophenylboric acid solution and dropping it into the reaction system at a speed of 1 mL / min, after the dropwise addition is completed, continuing the reaction for 24 h, removing the solvent by reduced pressure distillation, and adding 2 wt% of NaCO 3 The organic phase was extracted with an aqueous solution, and the organic phase was collected and washed with a saturated NaCl aqueous solution. After repeated extraction and washing three times, the organic phases were combined, dried with anhydrous sodium sulfate to remove water, placed in a vacuum drying oven, and dried at 40°C for 12 hours to obtain phenylboronic acid modified polysiloxane.

[0074] This embodiment also provides a method for preparing a wound care dressing after thyroid surgery, which specifically comprises the following steps:

[0075] S3. Accurately weigh 2.2 g of caffeic acid and place it in a dry flask. Add 50 mL of anhydrous DMF to fully dissolve the caffeic acid. After mixing evenly, add 1.75 g of HOBt and continue stirring. Add EDC in portions for a total of 2.4 g. Stir at a speed of 150 rpn for 1 h to obtain an activated caffeic acid solution.

[0076] S4, accurately weigh 3.0 g of dopamine hydrochloride and dissolve it in 50 mL of anhydrous DMF, add DIPEA to adjust the pH to 9.0 to obtain a dopamine solution, and add the dissolved dopamine dropwise to the activated caffeic acid solution prepared in step S3 at a rate of 1 mL / min, maintain the reaction temperature at 35°C, and stir the reaction at a speed of 200 rpm. After reacting for 4 hours, transfer the reaction system to ice water, mix, add ethyl acetate for extraction, repeat the extraction three times, collect and combine the organic phases, wash three times with a saturated NaCl aqueous solution and deionized water in sequence, dry the organic phase with anhydrous sodium sulfate, concentrate under reduced pressure, purify by chromatography, and vacuum dry at 30°C to obtain caffeic acid dopamine;

[0077] S5, dissolving the caffeic acid dopamine prepared in step S4 in 200 mL of 75 vol% ethanol aqueous solution, mixing evenly, introducing flowing nitrogen, adding 4.0 mL of vinyl pyrrolidone and 0.54 mL of polyethylene glycol diacrylate to mix well, adding 1 mL of Tween 80 to mix the reactants into a uniform system, adding 0.12 g of p-hydroxybenzoic acid under a nitrogen atmosphere, stirring and reacting at a speed of 350 rpm, adding 80 mg of AIBN under anaerobic sealing conditions, raising the reaction temperature to 65°C, stirring and reacting for 6 hours, and after the reaction is cooled to room temperature, adding anhydrous ether for precipitation, filtering, collecting the precipitate, repeatedly washing the precipitate with anhydrous ethanol and deionized water three times, and vacuum drying at 35°C for 8 hours to obtain a copolymer;

[0078] S6, weigh 13.0 g of potassium iodide and put it in a beaker, add 100 mL of 75 vol% ethanol aqueous solution and mix thoroughly, after the potassium iodide is completely dissolved, accurately weigh 6.0 g of iodine, mix until the solution appears dark brown and the color no longer changes, place in a light-proof environment, add the copolymer prepared in step S5, stir at a speed of 150 rpm, react for 22 hours, filter, collect the solid, wash with deionized water, and vacuum dry at 40°C to obtain PVP-I multi-polymer;

[0079] S7. Take 4.2 g of phenylboronic acid-modified polysiloxane and dissolve it in 500 mL of DMSO, adjust the pH to 8.5, add the PVP-I-multi-polymer prepared in step S6, and stir the mixture at 500 rpm for reaction. After reacting for 3 hours, reduce the pressure and concentrate to remove excess DMSO, apply it with a doctor coater, and solidify it at room temperature to obtain a wound care dressing.

[0080] Comparative Example 1

[0081] This comparative example provides a wound care dressing and a preparation method thereof, which is different from Example 1 only in that all components do not contain phenylboric acid-modified polysiloxane, and the remaining components and component contents are the same as those in Example 1.

[0082] Comparative Example 2

[0083] This comparative example provides a wound care dressing and a preparation method thereof, which is different from Example 1 only in that the phenylboronic acid-modified polysiloxane is replaced with polysiloxane of the same weight fraction, and the remaining components and component contents are the same as those in Example 1.

[0084] Comparative Example 3

[0085] This comparative example provides a wound care dressing and a preparation method thereof, which is different from Example 1 only in that all components do not contain dopamine hydrochloride, and the remaining components and component contents are the same as those in Example 1.

[0086] Experimental Example 1

[0087] In this experimental example, the mechanical properties of the wound care dressings prepared in Examples 1-3 and Comparative Examples 1-3 were tested: an electronic tensile testing machine was used to perform a tensile test on the wound care dressings prepared in Examples 1-3 and Comparative Examples 1-3, the wound care dressings were cut into sheet-shaped dumbbell-shaped samples, the experimental temperature was set to 25°C, and the speed was set to 100 mm / min;

[0088] Figure 3The tensile strength and elongation at break of the wound care dressings prepared by Examples 1-3 of the present invention and Comparative Examples 1-3 are shown in the figure. As shown in the figure, the tensile strength and elongation at break of the wound care dressings prepared by Examples 1-3 are significantly higher than those of Comparative Example 1. The polysiloxane modified with phenylboronic acid can improve the mechanical properties of the three-dimensional network structure of the wound care dressing through Si-O-Si. The wound care dressing prepared by Comparative Example 1 does not contain any polysiloxane components. Specifically, with acrylate and polyethylene glycol, the elongation at break of the copolymer of the matrix is ​​low, while the tensile strength is high, indicating that the wound care dressing has a more obvious pulling sensation on the wound during use, and is easily damaged when the wound moves relative to the wound. The polysiloxane used in the wound care dressing prepared by Comparative Example 2 has not been modified with phenylboronic acid, which affects the compatibility between the polysiloxane and the acrylate material, resulting in poor material stability. Comparative Example 3 uses a wound care dressing without dopamine, which has little effect on the tensile properties of the wound care dressing.

[0089] Experimental Example 2

[0090] In this experimental example, the tissue adhesion performance of the wound care dressings prepared in Examples 1-3 and Comparative Examples 1-3 was tested: the tissue adhesion performance of the wound care dressings prepared in Examples 1-3 and Comparative Examples 1-3 was tested by the overlap shear method, the pigskin was dehaired and cleaned, and then cut into 10cm×2cm strips, the wound care dressings prepared in Examples 1-3 and Comparative Examples 1-3 were coated in the middle of the surfaces of two pigskin strips to prepare samples, and the overlapping area was 2cm×3cm. Under room temperature conditions, the samples were subjected to a uniaxial tensile test using an electronic universal material experimental testing machine, and the rate was set to 5mm / min. When the two pigskin strips were separated, the experiment was terminated, and the maximum tensile force during the stretching process was recorded;

[0091] Figure 4 The results of tissue adhesion performance of wound care dressings prepared by Examples 1-3 and Comparative Examples 1-3 of the present invention are shown in the figure. As shown in the figure, the wound care dressings prepared by Examples 1-3 have higher tissue adhesion performance. A large number of catechol groups are introduced into the molecular structure of the wound care dressings described in the examples. The catechol groups are derived from caffeic acid and dopamine. The compound caffeic acid dopamine forms catechol groups at both ends of C=C. During the polymerization reaction of caffeic acid dopamine, vinyl pyrrolidone and polyethylene glycol diacrylate, both ends of the polymer molecular chain have catechol groups. While forming a boron ester bond with phenylboronic acid-modified polysiloxane, a large number of phenolic hydroxyl groups can be retained at the other end, thereby improving adhesion to tissues. The wound care dressings prepared by Comparative Examples 1 and 2 have poor adhesion, because the cross-linking degree of the structure is low, which easily causes the disintegration of the dressing structure, resulting in poor tissue adhesion.

[0092] While the embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that many changes, modifications, substitutions and variations can be made to the embodiments without departing from the principles and spirit of the invention.

[0093] The present invention and its implementation methods are described above, which is not restrictive. The drawings are only one of the implementation methods of the present invention, and the actual application is not limited thereto. In short, if ordinary technicians in the field are inspired by it and design methods and embodiments similar to the technical solution without creativity without departing from the purpose of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A wound care dressing after thyroid surgery, characterized in that: The raw materials for preparing the nursing dressing include the following components in parts by weight: 3.5-5 parts of phenylboronic acid modified polysiloxane, 1.8-2.7 parts of caffeic acid, 2.0-3.0 parts of dopamine hydrochloride, 2.5-6 parts of iodine, 3.5-5.5 parts of vinyl pyrrolidone, and 0.4-0.6 parts of polyethylene glycol diacrylate; The raw materials for preparing the phenylboronic acid modified polysiloxane include the following components in parts by weight: 14-24 parts of methylcyclosiloxane, 1.5-3.5 parts of vinylcyclosiloxane, 0.08-0.2 parts of hexamethyldisiloxane, and 0.5-0.7 parts of 4-bromophenylboric acid; The methylcyclosiloxane includes at least one of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, methylhydrogencyclotrisiloxane and methylhydrogencyclotetrasiloxane; The vinyl cyclosiloxane includes at least one of 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane; The preparation method of the phenylboronic acid modified polysiloxane specifically comprises the following steps: S1. Methylcyclosiloxane and vinylcyclosiloxane were placed in a flask, toluene and hexamethyldisiloxane were added, nitrogen was introduced, potassium trifluoromethanesulfonate was added, and the mixture was stirred at 200-300 rpm under a nitrogen atmosphere. After the reaction time was 3-6 hours, DCM was added to dissolve the polymer, anhydrous methanol was added for sedimentation treatment, the mixture was concentrated under reduced pressure, and polysiloxane was obtained after drying; S2. The polysiloxane prepared in step S1 is placed in dioxane, flowing nitrogen is introduced, and after uniform mixing at a speed of 150-200 rpm, Karstedt catalyst is added, stirring is continued, and the reaction temperature is increased to 80-90° C., 4-bromophenylboric acid is dissolved in dioxane, and added dropwise to the reaction system. After the reaction is continued for 18-24 hours, it is distilled under reduced pressure, extracted with a 2wt% Na2CO3 aqueous solution, the organic phase is collected, the organic phase is washed with a saturated NaCl aqueous solution, anhydrous sodium sulfate is added to dry the organic phase, and after vacuum drying, phenylboric acid-modified polysiloxane is obtained.

2. A thyroid surgery wound care dressing according to claim 1, characterized in that: In step S1, the volume fraction of the methylcyclosiloxane in toluene is 25-35%; The potassium trifluoromethanesulfonate is added to methylcyclosiloxane at a concentration of 3-4 mg / mL.

3. A thyroid surgery wound care dressing according to claim 2, characterized in that: In step S2, the mass concentration of the polysiloxane in dioxane is 0.15-0.2 g / mL; The added mass of the Karstedt catalyst is 0.14%-0.19% of the mass of 4-bromophenylboric acid.

4. A method for preparing a thyroid surgery wound care dressing according to any one of claims 1 to 3, characterized in that: The specific steps include: S3, adding caffeic acid to anhydrous DMF, stirring until fully dissolved, adding HOBt and continuing to stir, slowly adding EDC, stirring at 120-150 rpm for 1-2 hours, and obtaining an activated caffeic acid solution; S4, dissolving dopamine hydrochloride in anhydrous DMF, adding DIPEA to adjust the pH to 8-9 to obtain a dopamine solution, adding the dopamine solution dropwise to the activated caffeic acid solution prepared in step S3, maintaining the reaction temperature between 25-35°C, reacting at a speed of 180-200rpm for 4-8h, transferring the reaction system to ice water, extracting with ethyl acetate, collecting the organic phase, washing the organic phase with saturated sodium chloride solution and deionized water in sequence, drying the organic phase with anhydrous sodium sulfate, concentrating under reduced pressure, purifying and drying to obtain caffeic acid dopamine; S5, dissolving the caffeic acid dopamine prepared in step S5 in an ethanol aqueous solution, introducing flowing nitrogen, adding vinyl pyrrolidone and polyethylene glycol diacrylate to mix thoroughly, adding p-hydroxybenzoic acid, stirring at a speed of 300-400 rpm, adding AIBN under anaerobic sealing conditions, raising the reaction temperature to 60-70° C., stirring and reacting for 4-6 hours, adding anhydrous ether to precipitate, filtering, collecting the precipitate, washing the precipitate with anhydrous ethanol and deionized water, and vacuum drying to obtain a copolymer; S6, dissolving potassium iodide in an ethanol aqueous solution, adding iodine, and continuing to mix until the solution becomes dark brown and no longer changes color, placing in a light-proof environment, adding the copolymer prepared in step S5, stirring at a speed of 120-180 rpm, reacting for 18-24 hours, filtering, collecting the solid, washing with deionized water, and vacuum drying to obtain a PVP-I-multi-copolymer; S7. Dissolve the phenylboronic acid-modified polysiloxane prepared in step S2 in DMSO, adjust the pH to 8-9, add the PVP-I-multipolymer prepared in step S6, stir at a speed of 500-600 rpm, react for 1-3 hours, concentrate under reduced pressure to remove DMSO, apply with a doctor coater, and solidify at room temperature to obtain a wound care dressing.

5. The method for preparing the post-thyroid surgery wound care dressing according to claim 4, characterized in that: In step S3, the mass concentration of caffeic acid in anhydrous DMF is 36-54 mg / mL; The mass ratio of caffeic acid, HOBt and EDC is 1.2-1.35:1:1.2-1.

4.

6. The method for preparing the post-thyroid surgery wound care dressing according to claim 5, characterized in that: In step S4, the mass concentration of dopamine hydrochloride in anhydrous DMF is 40-60 mg / mL.

7. The method for preparing the post-thyroid surgery wound care dressing according to claim 6, characterized in that: In step S5, the mass concentration of the caffeic acid dopamine in the ethanol aqueous solution is 13-20 g / L; The added mass of the p-hydroxybenzoic acid is 3.0%-4.5% of the mass of caffeic acid dopamine; The added mass of the AIBN is 1.3%-2.3% of the mass of caffeic acid dopamine.

8. The method for preparing the post-thyroid surgery wound care dressing according to claim 7, characterized in that: In step S6, the mass concentration of the potassium iodide in the ethanol aqueous solution is 0.05-0.13 g / mL; The mass ratio between the iodine and potassium iodide is 1:2-3.

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