技术领域technical field
本发明属于功能复合材料领域，具体涉及一种医用敷料、制备方法及应用。The invention belongs to the field of functional composite materials, and in particular relates to a medical dressing, a preparation method and an application.
背景技术Background technique
皮肤是人体最大的器官，不仅保护人体内部组织器官免受外界有害因素的侵袭，还起到感知功能和代谢功能。但是，由于糖尿病、衰老、烧伤等原因，皮肤或组织损伤存在长期难以愈合的现象，这不仅会造成日常生活不便，降低免疫力，甚至会危害生命。为此，对于促进创面愈合的研究是面向生命科学、提高人类生命质量的重要课题。The skin is the largest organ of the human body. It not only protects the internal tissues and organs of the human body from the invasion of harmful external factors, but also performs sensory and metabolic functions. However, due to diabetes, aging, burns and other reasons, skin or tissue damage is difficult to heal for a long time, which will not only cause inconvenience in daily life, reduce immunity, and even endanger life. For this reason, the research on promoting wound healing is an important topic facing life science and improving the quality of human life.
通过向患者创伤部位施加电刺激(ES)可以促进细胞的增值和分化，从而促进组织修复。研究人员检测发现，皮肤损伤会导致伤口处的内源电流有助于加速关键细胞迁移，对伤口愈合起到积极作用。在此基础上，模拟和增强创伤电位会从以下方面有助于组织的修复：(1)有利于DNA和胶原合成；(2)伤口愈合相关细胞的迁移；(3)体外和体内抗菌效果。为此，通过外加电刺激促进创面愈合具有较大的应用前景。然而，传统电极材料刚性过大且可塑性差，导致与皮肤界面不适配问题，难以实现良好的皮肤顺应性；并且，传统电极材料自愈合性较差，难以应对复杂的日常使用要求；同时，传统电极材料供电部位过于集中，难以形成稳定均匀的电刺激，影响治疗效果以及使用感受。采用柔性导电敷料代替传统刚性电极为解决上述问题的有效方法。论文Chemical Engineering Journal 406(2021)126741通过将银纳米线分散在多孔聚氨酯制备了导电泡沫敷料，该敷料在外加电刺激下可均匀有效促进伤口愈合，但该敷料所用银纳米线导电填料及聚氨酯泡沫不具备自修复性。Applying electrical stimulation (ES) to a patient's trauma site can promote cell proliferation and differentiation, thereby promoting tissue repair. The researchers detected that skin damage causes endogenous electrical currents at the wound site to help accelerate the migration of key cells that play a positive role in wound healing. On this basis, simulating and enhancing wound potential will contribute to tissue repair in the following aspects: (1) DNA and collagen synthesis; (2) cell migration related to wound healing; (3) antibacterial effects in vitro and in vivo. Therefore, promoting wound healing through external electrical stimulation has a great application prospect. However, traditional electrode materials are too rigid and have poor plasticity, resulting in incompatibility with the skin interface, making it difficult to achieve good skin compliance; moreover, traditional electrode materials have poor self-healing properties, making it difficult to cope with complex daily use requirements; at the same time , The power supply parts of traditional electrode materials are too concentrated, it is difficult to form a stable and uniform electrical stimulation, which affects the therapeutic effect and user experience. Using flexible conductive dressings to replace traditional rigid electrodes is an effective way to solve the above problems. Paper Chemical Engineering Journal 406(2021) 126741 prepared a conductive foam dressing by dispersing silver nanowires in porous polyurethane. Not self-healing.
液态金属(LM)是一种具有良好生物相容性和导电性的新型合金，在接近环境条件下液体一样的流动性，具有高形变能力和可重塑性，为其做为导电填料实现伤口敷料的皮肤顺应性及自修复性提供了可能性。论文Adv.Funct.Mater.2022,32,2200444将液态金属封装进聚乙二醇(PEG)共混的聚二甲基硅氧烷(PDMS)制备表皮电子器件，进行了生理检测实验并通过外加电刺激显著促进了伤口愈合，但该研究中的液态金属以固定厚度和形状封装入基体材料，难以对不同形状的伤口实现均匀电刺激。并且由于液态金属常温液态特性，该制备方式易造成敷料损伤后液态金属大量泄露问题，造成使用不变。论文ACS Nano2019,13,9122-9130通过紫外辐射法合成了用于可拉伸电子产品的液态金属复合水凝胶，该材料可通过摩擦诱导实现电路重构，但由于液态金属与基体的相容性较差，本研究制备的复合水凝胶呈现较低的力学性能。目前，基于液态金属的可自修复型促进创面愈合敷料还未见相关报道。所以，一种具有良好自修复性、皮肤顺应性、生物相容性、均匀电响应性的可促进伤口愈合的医用材料亟待开发。Liquid metal (LM) is a new type of alloy with good biocompatibility and electrical conductivity. It has liquid-like fluidity under close to environmental conditions, has high deformability and remodelability, and can be used as a conductive filler to realize wound healing. The skin compliance and self-healing properties of dressings offer possibilities. Paper Adv.Funct.Mater.2022, 32, 2200444 encapsulated liquid metal into polyethylene glycol (PEG) blended polydimethylsiloxane (PDMS) to prepare epidermal electronic devices, carried out physiological detection experiments and passed external Electrical stimulation significantly promoted wound healing, but the liquid metal in this study was encapsulated into a matrix material with a fixed thickness and shape, making it difficult to achieve uniform electrical stimulation for wounds of different shapes. Moreover, due to the liquid properties of liquid metal at room temperature, this preparation method is likely to cause a large amount of leakage of liquid metal after the dressing is damaged, resulting in no change in use. The paper ACS Nano2019,13,9122-9130 synthesized a liquid metal composite hydrogel for stretchable electronic products by ultraviolet radiation. The composite hydrogels prepared in this study exhibited low mechanical properties. At present, there are no relevant reports on liquid metal-based self-healing dressings for promoting wound healing. Therefore, a medical material that can promote wound healing with good self-healing properties, skin compliance, biocompatibility, and uniform electrical responsiveness needs to be developed urgently.
发明内容Contents of the invention
为解决现有技术中出现的问题，本发明提供了一种医用敷料、制备方法及应用。本发明获得的复合材料具有优异的自愈合性、均匀的导电性、良好的生物相容性、安全无毒，并可通过外加电刺激的辅助作用对创面的修复起到显著促进效果。In order to solve the problems in the prior art, the invention provides a medical dressing, a preparation method and an application. The composite material obtained by the invention has excellent self-healing properties, uniform electrical conductivity, good biocompatibility, safety and non-toxicity, and can significantly promote wound repair through the auxiliary effect of external electrical stimulation.
本发明的技术方案：Technical scheme of the present invention:
一种医用敷料，所述敷料由液态金属、多功能添加剂与聚氨酯共混制备；所述聚氨酯为含脲基的聚脲聚氨酯；所述液态金属为熔点3-30℃的镓铟合金中的一种或两种以上混合；所述多功能添加剂为谷胱甘肽及其衍生物的一种或两种以上混合。A medical dressing, the dressing is prepared by blending liquid metal, multifunctional additives and polyurethane; the polyurethane is polyurea polyurethane containing urea groups; the liquid metal is one of gallium indium alloys with a melting point of 3-30°C One or two or more kinds; the multifunctional additive is one or two or more kinds of glutathione and its derivatives.
进一步的，各物质添加量以聚脲聚氨酯重量为100重量分数计，多功能添加剂为10-55重量份，液态金属为800-1500重量份。Further, the addition amount of each substance is based on 100 parts by weight of the polyurea polyurethane, 10-55 parts by weight of the multifunctional additive, and 800-1500 parts by weight of the liquid metal.
进一步的，所述医用敷料中，聚脲聚氨酯具有自修复性，液态金属具有结构重塑功能，多功能添加剂提高体系相容性，且具有促进创面愈合作用。Further, in the medical dressing, polyurea polyurethane has self-healing properties, liquid metal has structure remodeling function, and multifunctional additives improve system compatibility and promote wound healing.
进一步的，所述聚脲聚氨酯由包括以下组分的原料通过溶液反应制得：以异氰酸酯为100重量份，聚多元醇混合物为50-500重量份，扩链剂为10-50重量份，催化剂为1-8重量份，溶剂为500-1000重量份。Further, the polyurea polyurethane is prepared by solution reaction of raw materials including the following components: 100 parts by weight of isocyanate, 50-500 parts by weight of polypolyol mixture, 10-50 parts by weight of chain extender, catalyst It is 1-8 parts by weight, and the solvent is 500-1000 parts by weight.
进一步的，所述异氰酸酯为异佛尔酮二异氰酸酯、二环己基甲烷-4,4'-二异氰酸酯、二苯基甲烷二异氰酸酯中的一种或两种以上混合；所述聚多元醇混合物为聚醚二元醇200-3000或聚酯二元醇200-2000中的两种以上混合；所述扩链剂为间苯二甲酰肼、马来酸二酰肼、丁二酸二酰肼、呋喃-2,5-二甲酰肼中的一种；；所述催化剂为有机锡类催化剂；所述溶剂为二甲基甲酰胺、二甲基乙酰胺中的一种。Further, the isocyanate is one or more mixtures of isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and diphenylmethane diisocyanate; the polypolyol mixture is Two or more of polyether diol 200-3000 or polyester diol 200-2000 are mixed; the chain extender is isophthalic acid dihydrazide, maleic acid dihydrazide, succinic acid dihydrazide , one of furan-2,5-dicarboxylhydrazide; the catalyst is an organotin catalyst; the solvent is one of dimethylformamide and dimethylacetamide.
进一步的，所述聚脲聚氨酯的制备过程为：聚多元醇混合物、催化剂、异氰酸酯按比例溶解于溶剂中，升温至60℃-80℃，搅拌反应2-3h；降温至常温后，加入扩链剂，常温搅拌反应2h-4h；去除溶剂后，干燥保存或溶解于乙醇溶液中备用。Further, the preparation process of the polyurea polyurethane is as follows: the polypolyol mixture, the catalyst, and the isocyanate are dissolved in the solvent in proportion, the temperature is raised to 60°C-80°C, and the reaction is stirred for 2-3 hours; agent, stirring at room temperature for 2h-4h; after removing the solvent, store it dry or dissolve it in ethanol solution for later use.
一种医用敷料的制备方法，包括以下步骤：A preparation method of medical dressing, comprising the following steps:
利用超声将液态金属分散在已溶解多功能添加剂的醇水溶液中，超声10-120min；按配比加入聚脲聚氨酯的乙醇溶液，超声1-5min；将分散液浇筑或刮涂，干燥后得到敷料。Disperse the liquid metal in the alcohol aqueous solution in which the multifunctional additive has been dissolved by ultrasonication, ultrasonication for 10-120 minutes; add the ethanol solution of polyurea polyurethane according to the proportion, and ultrasonication for 1-5 minutes; cast or scrape the dispersion liquid, and obtain a dressing after drying.
一种医用敷料的应用，所述医用敷料生物相容性优异，具有自修复、促进创面愈合功能，可广泛应用于医用材料领域。An application of a medical dressing, the medical dressing has excellent biocompatibility, has the functions of self-repairing and promoting wound healing, and can be widely used in the field of medical materials.
进一步的，在电刺激的辅助下，对伤口修复起到积极作用，可用于创面敷料或促进组织再生的医用材料。Further, with the assistance of electrical stimulation, it has a positive effect on wound repair, and can be used as a medical material for wound dressing or tissue regeneration.
本发明包含以下有益效果：The present invention comprises following beneficial effect:
(1)本发明的敷料具有优异的生物相容性、可自修复性，安全无毒，同时可促进创面快速愈合。(1) The dressing of the present invention has excellent biocompatibility, self-repairability, safety and non-toxicity, and can promote rapid wound healing.
(2)本发明的多功能添加剂，不仅有利于液态金属在聚合物基体中的良好分散，大幅度提升导电均匀性，还有助于提高皮肤免疫力，从而辅助创口皮肤修复。(2) The multifunctional additive of the present invention is not only conducive to the good dispersion of liquid metal in the polymer matrix, greatly improving the uniformity of conductivity, but also helping to improve skin immunity, thereby assisting wound skin repair.
(3)本发明中，含脲基的聚脲聚氨酯结构中含有多重氢键，赋予基体材料优异的自修复性，与多功能添加剂协同作用，进一步提高液态金属的稳定分散。(3) In the present invention, the urea group-containing polyurea polyurethane structure contains multiple hydrogen bonds, endows the base material with excellent self-healing properties, and works synergistically with multifunctional additives to further improve the stable dispersion of liquid metal.
(4)本发明中的液态金属，熔点低，形变能力强，利于实现结构重塑；生物相容性优异，即使在高填充和厚度较大的情况下，敷料仍具有良好的皮肤顺应性、重塑性及自愈合性，有助于电刺激促进组织愈合更个性化、差异化的未来发展。(4) The liquid metal in the present invention has a low melting point and strong deformability, which is beneficial to realize structural remodeling; it has excellent biocompatibility, and even in the case of high filling and large thickness, the dressing still has good skin compliance, The remodeling and self-healing properties will help electrical stimulation promote more personalized and differentiated future development of tissue healing.
附图说明Description of drawings
图1为实施例1中液态金属-谷胱甘肽分散液的投射电子显微镜照片；Fig. 1 is the transmission electron micrograph of liquid metal-glutathione dispersion liquid in embodiment 1;
图2为实施例1中敷料截面的扫描电子显微镜照片；Fig. 2 is the scanning electron micrograph of dressing section in embodiment 1;
图3为实施例1中敷料24小时及48小时活死细胞染色照片。Fig. 3 is the staining photos of living and dead cells in the dressing in Example 1 at 24 hours and 48 hours.
具体实施方法Specific implementation method
本发明实施例中所采用的试剂来源除了另有特殊规定的以外，均可以通过市售方式购买得到。The sources of reagents used in the examples of the present invention can be purchased commercially unless otherwise specified.
应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。除了本发明实施例中所用原料以外，与实施例中所用原料含有的官能团相同或者包含本发明所涉及的相同结构单元，采用等同替换的原料组分，都应包含在本发明的保护范围内。以下结合具体实施例对本发明作进一步说明。It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention. In addition to the raw materials used in the examples of the present invention, the raw materials used in the examples have the same functional groups or contain the same structural units involved in the present invention, and the raw material components that are equivalently replaced should be included in the protection scope of the present invention. The present invention will be further described below in conjunction with specific examples.
本发明提供了部分实施例的检测结果附图，其他实施例和对比例采用同样的检测方法，本领域技术人员可以通过本发明提供的检测方法，直接地毫无疑义地确定本发明实施例的内容。The present invention provides the accompanying drawings of the detection results of some embodiments, and other embodiments and comparative examples adopt the same detection method, and those skilled in the art can directly and unambiguously determine the detection method of the embodiment of the present invention through the detection method provided by the present invention. content.
本发明所采用的外界电刺激方式为在促进创面愈合敷料上接入3.6V纽扣电池The external electrical stimulation mode adopted in the present invention is to insert a 3.6V button battery on the dressing for promoting wound healing
下面结合实施例，进一步说明本发明。Below in conjunction with embodiment, further illustrate the present invention.
实施例1Example 1
(1)聚脲聚氨酯的制备：称取100重量份异佛尔酮二异氰酸酯，280份聚乙二醇2000，20份聚乙二醇400，5份二月硅酸二丁基锡，至于三口烧瓶中加入600份N，N-二甲基甲酰胺溶解，升温至60℃，搅拌反应3h；停止加热，自然冷却至常温后，加入40份间苯二甲酰肼，常温搅拌反应2h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯1。(1) Preparation of polyurea polyurethane: take 100 parts by weight of isophorone diisocyanate, 280 parts of polyethylene glycol 2000, 20 parts of polyethylene glycol 400, and 5 parts of dibutyltin silicate in two parts of a three-necked flask Add 600 parts of N,N-dimethylformamide to dissolve, raise the temperature to 60°C, and stir for 3 hours; stop heating, cool to room temperature naturally, add 40 parts of isophthalic hydrazide, and stir for 2 hours at room temperature; Polyurea polyurethane 1 was obtained after drying N-dimethylformamide.
(2)医用敷料的制备：利用超声粉碎将1500重量份镓铟合金(熔点为3℃)为分散在已溶解55份谷胱甘肽的20ml醇水溶液中，超声60min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声1min；将分散液浇筑在模具中，干燥后得到可自修复敷料1。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of medical dressing: Utilize ultrasonic pulverization to disperse 1500 parts by weight of gallium-indium alloy (melting point is 3° C.) in 20 ml of alcoholic aqueous solution in which 55 parts of glutathione has been dissolved, and ultrasonicate for 60 minutes; add step (1 ) standby polyurethane-ethanol (100 parts by weight) solution, ultrasonicated for 1 min; the dispersion was poured into a mold, and the self-healing dressing 1 was obtained after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例2Example 2
(1)聚脲聚氨酯的制备：称取100重量份二环己基甲烷-4,4'-二异氰酸酯，280份聚乙二醇2000，20份聚乙二醇400，3份二月硅酸二丁基锡，至于三口烧瓶中加入800份N，N-二甲基乙酰胺溶解，升温至75℃，搅拌反应2.5h；停止加热，自然冷却至常温后，加入40份马来酸二酰肼，常温搅拌反应3h；将N，N-二甲基乙酰胺烘干后得到聚脲聚氨酯2。(1) Preparation of polyurea polyurethane: Weigh 100 parts by weight of dicyclohexylmethane-4,4'-diisocyanate, 280 parts of polyethylene glycol 2000, 20 parts of polyethylene glycol 400, 3 parts of dilauric acid diisocyanate Butyltin, add 800 parts of N,N-dimethylacetamide to the three-necked flask to dissolve, heat up to 75°C, stir for 2.5 hours; stop heating, cool to room temperature naturally, add 40 parts of maleic acid dihydrazide, Stirring and reacting for 3 hours; drying N,N-dimethylacetamide to obtain polyurea polyurethane 2.
(2)医用敷料的制备：利用超声粉碎将1200重量份镓铟合金(熔点为11℃)为分散在已溶解45份谷胱甘肽的20ml醇水溶液中，超声60min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声2min；将分散液浇筑在模具中，干燥后得到可自修复敷料2。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of medical dressing: Utilize ultrasonic pulverization to disperse 1200 parts by weight of gallium-indium alloy (melting point is 11° C.) in 20 ml of alcoholic aqueous solution in which 45 parts of glutathione has been dissolved, and ultrasonicate for 60 minutes; add step (1 ) a spare polyurethane-ethanol (100 parts by weight) solution, ultrasonicated for 2 minutes; the dispersion was poured into a mold, and the self-healing dressing 2 was obtained after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the recovery of mechanical strength and electrical conductivity of the dressing at different times, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice and applied electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例3Example 3
(1)聚脲聚氨酯的制备：称取100重量份异佛尔酮二异氰酸酯，200份聚乙二醇2000，40份聚乙二醇400，2份二月硅酸二丁基锡，至于三口烧瓶中加入500份N，N-二甲基甲酰胺溶解，升温至80℃，搅拌反应2h；停止加热，自然冷却至常温后，加入30份间苯二甲酰肼，常温搅拌反应3h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯3。(1) Preparation of polyurea polyurethane: take 100 parts by weight of isophorone diisocyanate, 200 parts of polyethylene glycol 2000, 40 parts of polyethylene glycol 400, and 2 parts of dibutyltin silicate in two parts of a three-necked flask Add 500 parts of N,N-dimethylformamide to dissolve, raise the temperature to 80°C, and stir for 2 hours; stop heating, cool to room temperature naturally, add 30 parts of isophthalic hydrazide, and stir for 3 hours at room temperature; Polyurea polyurethane 3 was obtained after drying N-dimethylformamide.
(2)可自修复敷料的制备：利用超声粉碎将1200重量份镓铟合金(熔点为11℃)分散在已溶解40份谷胱甘肽的20ml醇水溶液中，超声100min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声1min；将分散液浇筑在模具中，干燥后得到可自修复敷料3。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of self-healing dressing: use ultrasonic pulverization to disperse 1200 parts by weight of gallium-indium alloy (melting point is 11 ° C) in 20 ml of alcoholic aqueous solution in which 40 parts of glutathione has been dissolved, and ultrasonically for 100 minutes; add the step according to the proportion ( 1) A spare polyurethane-ethanol (100 parts by weight) solution, ultrasonicated for 1 min; pour the dispersion into a mold, and obtain a self-healing dressing 3 after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例4Example 4
(1)聚脲聚氨酯的制备：称取100重量份二苯基甲烷二异氰酸酯，200份聚乙二醇2000，40份聚乙二醇400，1份二月硅酸二丁基锡，至于三口烧瓶中加入600份N，N-二甲基乙酰胺溶解，升温至80℃，搅拌反应3h；停止加热，自然冷却至常温后，加入30份丁二酸二酰肼，常温搅拌反应4h；将N，N-二甲基乙酰胺烘干后得到聚脲聚氨酯4。(1) Preparation of polyurea polyurethane: Weigh 100 parts by weight of diphenylmethane diisocyanate, 200 parts of polyethylene glycol 2000, 40 parts of polyethylene glycol 400, and 1 part of dibutyltin silicate in a three-necked flask Add 600 parts of N, N-dimethylacetamide to dissolve, raise the temperature to 80°C, and stir for 3 hours; stop heating, cool to room temperature naturally, add 30 parts of succinic acid dihydrazide, and stir for 4 hours at room temperature; Polyurea polyurethane 4 was obtained after drying N-dimethylacetamide.
(2)可自修复敷料的制备：利用超声粉碎将1000重量份镓铟合金(熔点为11℃)分散在已溶解40份谷胱甘肽的20ml醇水溶液中，超声100min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声1min；将分散液浇筑在模具中，干燥后得到可自修复敷料4。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of self-healing dressing: use ultrasonic pulverization to disperse 1000 parts by weight of gallium-indium alloy (melting point is 11 ° C) in 20 ml of alcoholic aqueous solution in which 40 parts of glutathione has been dissolved, and ultrasonically for 100 minutes; add the step according to the proportion ( 1) A spare polyurethane-ethanol (100 parts by weight) solution, ultrasonicated for 1 min; pour the dispersion into a mold, and obtain a self-healing dressing 4 after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例5Example 5
(1)聚脲聚氨酯的制备：称取100重量份二环己基甲烷-4,4'-二异氰酸酯，120份聚乙二醇2000，57份聚乙二醇400，2份二月硅酸二丁基锡，至于三口烧瓶中加入500份N，N-二甲基甲酰胺溶解，升温至75℃，搅拌反应2.5h；停止加热，自然冷却至常温后，加入40份间苯二甲酰肼，常温搅拌反应3h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯5。(1) Preparation of polyurea polyurethane: Weigh 100 parts by weight of dicyclohexylmethane-4,4'-diisocyanate, 120 parts of polyethylene glycol 2000, 57 parts of polyethylene glycol 400, 2 parts of dilaurate Butyltin, add 500 parts of N,N-dimethylformamide to the three-necked flask to dissolve, heat up to 75°C, stir for 2.5 hours; stop heating, cool to room temperature naturally, add 40 parts of isophthalic hydrazide, Stirring and reacting for 3 hours; drying N,N-dimethylformamide to obtain polyurea polyurethane 5.
(2)可自修复敷料的制备：利用超声粉碎将800重量份镓铟合金(熔点为16℃)分散在已溶解30份谷胱甘肽的20ml醇水溶液中，超声80min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声3min；将分散液浇筑在模具中，干燥后得到可自修复敷料5。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表5。(2) Preparation of self-healing dressing: use ultrasonic pulverization to disperse 800 parts by weight of gallium-indium alloy (melting point is 16 ° C) in 20 ml of alcoholic aqueous solution in which 30 parts of glutathione has been dissolved, and ultrasonicate for 80 minutes; add the step according to the proportion ( 1) A spare polyurethane-ethanol (100 parts by weight) solution was ultrasonicated for 3 minutes; the dispersion was poured into a mold and dried to obtain a self-healing dressing 5 . Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 5.
实施例6Example 6
(1)聚脲聚氨酯的制备：称取100重量份二环己基甲烷-4,4'-二异氰酸酯，120份聚乙二醇2000，30份聚乙二醇400，2份二月硅酸二丁基锡，至于三口烧瓶中加入200份N，N-二甲基甲酰胺溶解，升温至70℃，搅拌反应3h；停止加热，自然冷却至常温后，加入50份呋喃-2,5-二甲酰肼，常温搅拌反应3h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯6。(1) Preparation of polyurea polyurethane: Weigh 100 parts by weight of dicyclohexylmethane-4,4'-diisocyanate, 120 parts of polyethylene glycol 2000, 30 parts of polyethylene glycol 400, 2 parts of dilaurate Butyl tin, add 200 parts of N,N-dimethylformamide to the three-necked flask to dissolve, heat up to 70°C, stir for 3 hours; stop heating, cool to room temperature naturally, add 50 parts of furan-2,5-diformyl Hydrazine, stirred at room temperature for 3 hours; N,N-dimethylformamide was dried to obtain polyurea polyurethane 6.
(2)可自修复敷料的制备：利用超声粉碎将1000重量份镓铟合金(熔点为30℃)分散在已溶解30份谷胱甘肽的20ml醇水溶液中，超声120min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声5min；将分散液浇筑在模具中，干燥后得到可自修复敷料6。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of self-healing dressing: use ultrasonic pulverization to disperse 1000 parts by weight of gallium-indium alloy (melting point is 30 ° C) in 20 ml of alcoholic aqueous solution in which 30 parts of glutathione has been dissolved, and ultrasonically for 120 minutes; add the step according to the proportion ( 1) A spare polyurethane-ethanol (100 parts by weight) solution, ultrasonicated for 5 minutes; pour the dispersion into a mold, and obtain a self-healing dressing 6 after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例7Example 7
(1)聚脲聚氨酯的制备：称取100重量份二环己基甲烷-4,4'-二异氰酸酯，20份聚碳酸酯二醇2000(PCDL 2000)，70份聚乙二醇400，2份二月硅酸二丁基锡，至于三口烧瓶中加入500份N，N-二甲基甲酰胺溶解，升温至70℃，搅拌反应3h；停止加热，自然冷却至常温后，加入40份间苯二甲酰肼，常温搅拌反应3h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯7。(1) Preparation of polyurea polyurethane: Weigh 100 parts by weight of dicyclohexylmethane-4,4'-diisocyanate, 20 parts of polycarbonate diol 2000 (PCDL 2000), 70 parts of polyethylene glycol 400, 2 parts February dibutyltin silicate, add 500 parts of N,N-dimethylformamide to the three-necked flask to dissolve, heat up to 70°C, stir for 3 hours; stop heating, cool to room temperature naturally, add 40 parts of m-phthalamide Hydrazide, stirred at room temperature for 3 hours; N, N-dimethylformamide was dried to obtain polyurea polyurethane 7.
(2)可自修复敷料的制备：利用超声粉碎将1000重量份镓铟合金(熔点为11℃)分散在已溶解15份S-乙酰基-L-谷胱甘肽的20ml醇水溶液中，超声40min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声2min；将分散液浇筑在模具中，干燥后得到可自修复敷料7。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of self-healing dressing: 1000 parts by weight of gallium-indium alloy (melting point: 11°C) was dispersed in 20 ml of alcoholic aqueous solution in which 15 parts of S-acetyl-L-glutathione had been dissolved by ultrasonic pulverization. 40 minutes; add the spare polyurethane-ethanol (100 parts by weight) solution in step (1) according to the proportion, and ultrasonicate for 2 minutes; pour the dispersion into a mold, and obtain a self-healing dressing 7 after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the recovery of mechanical strength and electrical conductivity of the dressing at different times, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice and applied electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例8Example 8
(1)聚脲聚氨酯的制备：称取100重量份二环己基甲烷-4,4'-二异氰酸酯，140份聚碳酸酯二醇2000(PCDL 2000)，50份聚乙二醇400，2份二月硅酸二丁基锡，至于三口烧瓶中加入1000份N，N-二甲基甲酰胺溶解，升温至70℃，搅拌反应3h；停止加热，自然冷却至常温后，加入10份间苯二甲酰肼，常温搅拌反应2h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯8。(1) Preparation of polyurea polyurethane: Weigh 100 parts by weight of dicyclohexylmethane-4,4'-diisocyanate, 140 parts of polycarbonate diol 2000 (PCDL 2000), 50 parts of polyethylene glycol 400, 2 parts In February, dibutyltin silicate, add 1000 parts of N,N-dimethylformamide to the three-necked flask to dissolve, heat up to 70°C, stir for 3 hours; stop heating, cool to room temperature naturally, add 10 parts of m-phthalamide Hydrazide, stirred at room temperature for 2 hours; N,N-dimethylformamide was dried to obtain polyurea polyurethane 8.
(2)可自修复敷料的制备：利用超声粉碎将1000重量份镓铟合金(熔点为11℃)分散在已溶解10份谷胱甘肽的20ml醇水溶液中，超声40min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声2min；将分散液浇筑在模具中，干燥后得到可自修复敷料8。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of self-healing dressing: use ultrasonic pulverization to disperse 1000 parts by weight of gallium-indium alloy (melting point is 11° C.) in 20 ml of alcoholic aqueous solution in which 10 parts of glutathione has been dissolved, and ultrasonicate for 40 minutes; add the step according to the proportion ( 1) A spare polyurethane-ethanol (100 parts by weight) solution, ultrasonicated for 2 minutes; pour the dispersion into a mold, and obtain a self-healing dressing 8 after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
实施例9Example 9
(1)聚脲聚氨酯的制备：称取100重量份异佛尔酮二异氰酸酯，360份聚乙二醇1000，8份聚乙二醇400，8份二月硅酸二丁基锡，至于三口烧瓶中加入1000份N，N-二甲基甲酰胺溶解，升温至60℃，搅拌反应3h；停止加热，自然冷却至常温后，加入40份间苯二甲酰肼，常温搅拌反应3h；将N，N-二甲基甲酰胺烘干后得到聚脲聚氨酯9。(1) Preparation of polyurea polyurethane: take 100 parts by weight of isophorone diisocyanate, 360 parts of polyethylene glycol 1000, 8 parts of polyethylene glycol 400, and 8 parts of dibutyltin silicate in a three-necked flask Add 1000 parts of N,N-dimethylformamide to dissolve, raise the temperature to 60°C, and stir for 3 hours; stop heating, cool to room temperature naturally, add 40 parts of isophthalic hydrazide, and stir for 3 hours at room temperature; mix N, Polyurea polyurethane 9 was obtained after drying N-dimethylformamide.
(2)可自修复敷料的制备：利用超声粉碎将1000重量份镓铟合金(熔点为11℃)分散在已溶解40份S-乙酰基-L-谷胱甘肽的20ml醇水溶液中，超声40min；按配比加入步骤(1)备用聚氨酯-乙醇(100重量份)溶液，超声5min；将分散液浇筑在模具中，干燥后得到可自修复敷料9。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。(2) Preparation of self-healing dressing: 1000 parts by weight of gallium-indium alloy (melting point: 11°C) was dispersed in 20 ml of alcoholic aqueous solution in which 40 parts of S-acetyl-L-glutathione had been dissolved by ultrasonic pulverization. 40 minutes; add the spare polyurethane-ethanol (100 parts by weight) solution in step (1) according to the proportion, and ultrasonicate for 5 minutes; pour the dispersion into a mold, and obtain a self-healing dressing 9 after drying. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
对比例1Comparative example 1
用间苯二甲酰胺代替实施例1(1)中间苯二甲酰肼，保持实施例1中其他条件不变，制备聚氨酯及敷料。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。Using isophthalamide instead of isophthalohydrazide in Example 1 (1), and keeping other conditions in Example 1 unchanged, polyurethane and dressings were prepared. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
对比例2Comparative example 2
保持实施例1(1)其他不变，步骤(2)不添加谷胱甘肽，直接将液态金属超声在聚氨酯乙醇溶液中62min，将分散液浇筑在模具中，干燥得到产品。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。Keep the other things unchanged in Example 1 (1), step (2) without adding glutathione, directly ultrasonically put the liquid metal in the polyurethane ethanol solution for 62 minutes, pour the dispersion into a mold, and dry to obtain the product. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
对比例3Comparative example 3
用间苯二甲酰胺代替实施例1(1)中间苯二甲酰肼，且步骤(2)不添加谷胱甘肽，直接将液态金属超声在聚氨酯乙醇溶液中62min，将分散液浇筑在模具中，干燥得到产品。制备测试样条，中间垂直截断，在35℃鼓风干燥机重新拼接并测试不同时间敷料机械强度恢复情况，以及电导率恢复情况，如表1-2。另辅助3.6V纽扣电池固定于小鼠伤口处施以电刺激促进愈合，其伤口愈合情况如表3。Use isophthalamide to replace Example 1 (1) isophthalohydrazide, and step (2) does not add glutathione, directly ultrasonically liquid metal in polyurethane ethanol solution for 62min, pour the dispersion on the mold , dry to obtain the product. Prepare the test sample, cut it vertically in the middle, resplice it in a blast dryer at 35°C and test the mechanical strength recovery of the dressing at different times, as well as the electrical conductivity recovery, as shown in Table 1-2. In addition, an auxiliary 3.6V button battery was fixed on the wound of the mice to provide electrical stimulation to promote healing. The wound healing conditions are shown in Table 3.
表1机械强度恢复率Table 1 Mechanical strength recovery rate
表2电导率恢复率Table 2 Conductivity recovery rate
表3伤口愈合率Table 3 wound healing rate
对比表1、表2，在35℃条件下，实施例敷料的机械性能在4-5h内均可良好恢复，其导电性可瞬间恢复，但未引入结构中未引入脲键的对比例1和对比例3机械性能和电性能都未能恢复，对比例2由于未加入多功能添加剂，内部镓铟合金分散性较差，其机械性能自修复速率降低且电性能难以完全恢复。Comparing Table 1 and Table 2, at 35°C, the mechanical properties of the dressings of the examples can be recovered well within 4-5 hours, and the electrical conductivity can be recovered instantly, but no urea bond is introduced into the structure of Comparative Example 1 and In Comparative Example 3, neither the mechanical properties nor the electrical properties were recovered. In Comparative Example 2, since no multifunctional additives were added, the dispersion of the internal gallium-indium alloy was poor, the self-repair rate of the mechanical properties was reduced, and the electrical properties were difficult to fully recover.
由表3对比，由于对比例1、3敷料自修复能力较差，治疗过程中敷料不能通过自修复始终保持均匀稳定电刺激，其伤口愈合速度较实施例缓慢，同时未添加多功能添加剂的对比例2，伤口愈合速度较缓，证明添加剂的加入有利于通过促进分散和提高皮肤免疫，达到更好的愈合效果。Compared with Table 3, due to the poor self-repair ability of the dressings of Comparative Examples 1 and 3, the dressings could not maintain uniform and stable electrical stimulation through self-repair during the treatment process, and the wound healing speed was slower than that of Examples. Ratio 2, the wound healing speed is slow, which proves that the addition of additives is beneficial to achieve better healing effect by promoting dispersion and improving skin immunity.
图1投射电镜可见实施例1中多功能添加剂(谷胱甘肽)包覆在液态金属表面，证明与液态金属具有良好相互作用，可促进其良好分散。图2截面扫面电镜照片进一步证明液态金属在敷料中均匀分散，无明显团聚现象，可形成均匀稳定电响应。图3体外活死细胞实验(CalceinAM染色为活细胞，PI染色为死细胞)，CalceinAM染色绿色细胞大量存在，PI染色红色细胞极少，说明在敷料浸出液中增值的成纤维细胞48h内未出现大面积死亡现象，且细胞形态保持良好，证明实施例1敷料生物相容性良好，可进行医疗方面应用。The transmission electron microscope in Figure 1 shows that the multifunctional additive (glutathione) in Example 1 is coated on the surface of the liquid metal, which proves that it has a good interaction with the liquid metal and can promote its good dispersion. The scanning electron microscope photo of the cross-section in Figure 2 further proves that the liquid metal is uniformly dispersed in the dressing, without obvious agglomeration, and can form a uniform and stable electrical response. Figure 3 In vitro living and dead cell experiment (CalceinAM staining is living cells, PI staining is dead cells), there are a lot of CalceinAM staining green cells, PI staining red cells are very few, indicating that the proliferation of fibroblasts in the dressing leachate did not appear within 48h. The phenomenon of area death and good cell shape maintenance prove that the dressing of Example 1 has good biocompatibility and can be used in medical applications.
本发明提供的复合敷料对伤口愈合可起到促进作用，同时，具有良好的柔顺性、自修复性、生物相容性性及可塑性，克服了传统敷料难以自修复的问题，有潜力实现更广泛、更便捷、更有效的医疗应用，具有良好的发展前景。The composite dressing provided by the invention can promote wound healing. At the same time, it has good flexibility, self-repairability, biocompatibility and plasticity, overcomes the problem that traditional dressings are difficult to self-repair, and has the potential to realize more extensive wound healing. , More convenient and more effective medical application, has a good development prospect.
所属领域的普通技术人员应当理解：以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Those of ordinary skill in the art should understand that: the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention etc., should be included within the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN202310661260.2ACN116688209B (en) | 2023-06-06 | 2023-06-06 | Medical dressing, preparation method and application |
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| CN202310661260.2ACN116688209B (en) | 2023-06-06 | 2023-06-06 | Medical dressing, preparation method and application |
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