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CN114618006B - Intelligent wound dressing, preparation method and application thereof, and flexible sensor - Google Patents

Intelligent wound dressing, preparation method and application thereof, and flexible sensor Download PDF

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CN114618006B
CN114618006B CN202210371111.8A CN202210371111A CN114618006B CN 114618006 B CN114618006 B CN 114618006B CN 202210371111 A CN202210371111 A CN 202210371111A CN 114618006 B CN114618006 B CN 114618006B
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wound dressing
flexible sensor
functional layer
thermoplastic elastomer
citric acid
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CN114618006A (en
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汪滨
丁姗姗
牛泽浩
王杰
金旭
马佳瑜
张延萍
李秀艳
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Beijing Institute Fashion Technology
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28Polysaccharides or their derivatives
    • AHUMAN NECESSITIES
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    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/00051Accessories for dressings
    • A61F13/00063Accessories for dressings comprising medicaments or additives, e.g. odor control, PH control, debriding, antimicrobic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/01Non-adhesive bandages or dressings
    • A61F13/01008Non-adhesive bandages or dressings characterised by the material
    • A61F13/01012Non-adhesive bandages or dressings characterised by the material being made of natural material, e.g. cellulose-, protein-, collagen-based
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/01Non-adhesive bandages or dressings
    • A61F13/01008Non-adhesive bandages or dressings characterised by the material
    • A61F13/01017Non-adhesive bandages or dressings characterised by the material synthetic, e.g. polymer based
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/01Non-adhesive bandages or dressings
    • A61F13/01021Non-adhesive bandages or dressings characterised by the structure of the dressing
    • A61F13/01029Non-adhesive bandages or dressings characterised by the structure of the dressing made of multiple layers
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    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/01Non-adhesive bandages or dressings
    • A61F13/01034Non-adhesive bandages or dressings characterised by a property
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    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/01Non-adhesive bandages or dressings
    • A61F13/01034Non-adhesive bandages or dressings characterised by a property
    • A61F13/01046Air-vapor permeability
    • AHUMAN NECESSITIES
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    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
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    • A61F13/02Adhesive bandages or dressings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/02Adhesive bandages or dressings
    • A61F13/0203Adhesive bandages or dressings with fluid retention members
    • A61F13/0206Adhesive bandages or dressings with fluid retention members with absorbent fibrous layers, e.g. woven or non-woven absorbent pads or island dressings
    • AHUMAN NECESSITIES
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    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F13/02Adhesive bandages or dressings
    • A61F13/0276Apparatus or processes for manufacturing adhesive dressings or bandages
    • A61F13/0286Apparatus or processes for manufacturing adhesive dressings or bandages manufacturing of non adhesive dressings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/425Porous materials, e.g. foams or sponges
    • AHUMAN NECESSITIES
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    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/44Medicaments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/56Wetness-indicators or colourants
    • AHUMAN NECESSITIES
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    • A61F13/00Bandages or dressings; Absorbent pads
    • A61F2013/00089Wound bandages
    • A61F2013/00238Wound bandages characterised by way of knitting or weaving
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/23Carbohydrates
    • A61L2300/236Glycosaminoglycans, e.g. heparin, hyaluronic acid, chondroitin
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract

本发明涉及伤口敷料技术领域,尤其涉及一种智能伤口敷料及其制备方法和应用、柔性传感器。本发明提供了一种智能伤口敷料,包括基底和设置在所述基底表面的功能层;所述基底为壳聚糖止血海绵;所述功能层为柠檬酸‑热塑性弹性体聚氨酯复合纳米纤维膜。所述智能伤口敷料对湿度和压力均具有较好的响应性。

Figure 202210371111

The invention relates to the technical field of wound dressings, in particular to an intelligent wound dressing, its preparation method and application, and a flexible sensor. The invention provides an intelligent wound dressing, which comprises a substrate and a functional layer arranged on the surface of the substrate; the substrate is a chitosan hemostatic sponge; and the functional layer is a citric acid-thermoplastic elastomer polyurethane composite nanofiber film. The smart wound dressing has better responsiveness to humidity and pressure.

Figure 202210371111

Description

一种智能伤口敷料及其制备方法和应用、柔性传感器A kind of intelligent wound dressing and its preparation method and application, flexible sensor

技术领域technical field

本发明涉及伤口敷料技术领域,尤其涉及一种智能伤口敷料及其制备方法和应用、柔性传感器。The invention relates to the technical field of wound dressings, in particular to an intelligent wound dressing, its preparation method and application, and a flexible sensor.

背景技术Background technique

目前致病性感染作为慢性伤口最常见的并发症已成为全球性的医疗保健挑战,伤口愈合过程的检测也变得尤为重要。目前,以薄膜、海绵和水凝胶形式的敷料是临床伤口处理的主要选择。然而,当前伤口敷料基本上都是被动治疗,难以同时实现实际伤口治疗并满足慢性伤口的动态愈合情况监测的需求。因此,非常需要一种智能伤口敷料系统,以实现实时监控伤口愈合状态和按需治疗。随着物联网和智能可穿戴设备的出现,由智能可穿戴传感器为核心的新一代智能伤口敷料通过检测与伤口愈合过程有关的理化信号,可以解决当前伤口敷料面临的上述问题。其中,与伤口部位的验证和感染状态密切相关的伤口处湿度以及伤口愈合过程中周围皮肤的压力值变化被认为是最重要和最有希望的监测指标。Pathogenic infection, as the most common complication of chronic wounds, has become a global healthcare challenge, and the detection of wound healing process has become particularly important. Currently, dressings in the form of films, sponges, and hydrogels are the main options for clinical wound management. However, the current wound dressings are basically passive treatments, and it is difficult to achieve actual wound treatment and meet the needs of dynamic healing monitoring of chronic wounds at the same time. Therefore, there is a great need for an intelligent wound dressing system for real-time monitoring of wound healing status and on-demand treatment. With the emergence of the Internet of Things and smart wearable devices, a new generation of smart wound dressings with smart wearable sensors as the core can solve the above-mentioned problems faced by current wound dressings by detecting physical and chemical signals related to the wound healing process. Among them, the humidity at the wound, which is closely related to the verification and infection status of the wound site, and the pressure value change of the surrounding skin during the wound healing process are considered to be the most important and promising monitoring indicators.

发明内容Contents of the invention

本发明的目的在于提供一种智能伤口敷料及其制备方法和应用、柔性传感器。所述智能伤口敷料对湿度和压力均具有较好的响应性。The object of the present invention is to provide an intelligent wound dressing, its preparation method and application, and a flexible sensor. The smart wound dressing has better responsiveness to humidity and pressure.

为了实现上述发明目的,本发明提供以下技术方案:In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:

本发明提供了一种智能伤口敷料,包括基底和设置在所述基底表面的功能层;The invention provides an intelligent wound dressing, comprising a substrate and a functional layer arranged on the surface of the substrate;

所述基底为壳聚糖止血海绵;The base is chitosan hemostatic sponge;

所述功能层为柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜。The functional layer is a citric acid-thermoplastic elastomer polyurethane composite nanofiber film.

优选的,所述柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜中柠檬酸和热塑性弹性体聚氨酯的质量比为(0.05~0.15):1。Preferably, the mass ratio of citric acid to thermoplastic elastomer polyurethane in the citric acid-thermoplastic elastomer polyurethane composite nanofiber film is (0.05-0.15):1.

本发明还提供了上述技术方案所述智能伤口敷料的制备方法,包括以下步骤:The present invention also provides a preparation method for the intelligent wound dressing described in the above technical solution, comprising the following steps:

将柠檬酸、热塑性弹性体聚氨酯和溶剂混合,得到复合纺丝溶液;mixing citric acid, thermoplastic elastomer polyurethane and a solvent to obtain a composite spinning solution;

以壳聚糖止血海绵为基底,将所述复合纺丝溶液进行静电纺丝,得到所述智能伤口敷料。Using the chitosan hemostatic sponge as a base, the composite spinning solution is electrospun to obtain the intelligent wound dressing.

优选的,所述复合纺丝溶液中热塑性弹性体聚氨酯的质量浓度为15~30%。Preferably, the mass concentration of thermoplastic elastomer polyurethane in the composite spinning solution is 15-30%.

优选的,所述柠檬酸和热塑性弹性体聚氨酯的质量比为(0.05~0.15):1。Preferably, the mass ratio of the citric acid to the thermoplastic elastomer polyurethane is (0.05-0.15):1.

优选的,所述溶剂包括N,N-二甲基甲酰胺和四氢呋喃;Preferably, the solvent includes N,N-dimethylformamide and tetrahydrofuran;

所述N,N-二甲基甲酰胺和四氢呋喃的体积比为(0.5~2.5):1。The volume ratio of the N,N-dimethylformamide to tetrahydrofuran is (0.5-2.5):1.

优选的,所述静电纺丝采用2~4喷头纺丝;Preferably, the electrospinning uses 2 to 4 nozzles for spinning;

所述静电纺丝的温度为30~50℃,正电压为10~24kV,负电压为-5~-1kV,时间为1~5h,推进速度为1~3mL/h,接收距离为10~18cm。The temperature of the electrospinning is 30-50°C, the positive voltage is 10-24kV, the negative voltage is -5--1kV, the time is 1-5h, the advancing speed is 1-3mL/h, and the receiving distance is 10-18cm .

本发明还提供了上述技术方案所述智能伤口敷料或上述技术方案所述制备方法制备得到的智能伤口敷料在伤口智能监测领域中的应用。The present invention also provides the application of the intelligent wound dressing described in the above technical solution or the intelligent wound dressing prepared by the preparation method described in the above technical solution in the field of intelligent wound monitoring.

本发明还提供了一种用于伤口智能监测的柔性传感器,包括上述技术方案所述智能伤口敷料或上述技术方案所述制备方法制备得到的智能伤口敷料和设置在所述智能伤口敷料中功能层表面的电极层。The present invention also provides a flexible sensor for intelligent monitoring of wounds, comprising the intelligent wound dressing described in the above technical solution or the intelligent wound dressing prepared by the preparation method described in the above technical solution and a functional layer arranged in the intelligent wound dressing surface electrode layer.

优选的,所述电极层的厚度为50~60nm。Preferably, the thickness of the electrode layer is 50-60 nm.

本发明提供了一种智能伤口敷料,包括基底和设置在所述基底表面的功能层;所述基底为壳聚糖止血海绵;所述功能层为柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜。The invention provides an intelligent wound dressing, which comprises a substrate and a functional layer arranged on the surface of the substrate; the substrate is a chitosan hemostatic sponge; and the functional layer is a citric acid-thermoplastic elastomer polyurethane composite nanofiber film.

与现有技术相比,本发明具有以下优势:Compared with the prior art, the present invention has the following advantages:

1)本发明所述柠檬酸中的羟基和羧基容易形成氢键连接的网络结构,柠檬酸表面暴露的羟基可以与外部水分子形成氢键,柠檬酸中所含的三个羧基也可以与水分子形成分子间氢键,将其添加到纳米纤维膜中可以达到超高的湿度响应灵敏度;1) Hydroxyl and carboxyl in the citric acid of the present invention are easy to form the network structure that hydrogen bond connects, and the hydroxyl that citric acid surface exposes can form hydrogen bond with external water molecule, and three carboxyls contained in citric acid also can be with water Molecules form intermolecular hydrogen bonds, which can be added to nanofiber membranes to achieve ultra-high humidity response sensitivity;

2)所述纳米纤维膜结构在微观下的纳米纤维交错排列,且表面凹凸不平的微结构,在功能层中构建上述微结构可以有效的提高其灵敏度和响应时间;同时,所述柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜还具有柔软、可拉伸和透气的特点,并且具有良好的生物相容性,用于人体皮肤上也不会对人体造成伤害,与壳聚糖止血海绵结合,可组合成为智能监测开放性伤口愈合状况的伤口敷料,并且对伤口有止血作用,用于开放性伤口人体健康监测;2) The nanofiber membrane structure has nanofibers staggered at the microscopic level, and the microstructure with uneven surface, constructing the above-mentioned microstructure in the functional layer can effectively improve its sensitivity and response time; at the same time, the citric acid- The thermoplastic elastomer polyurethane composite nanofiber membrane is also soft, stretchable and breathable, and has good biocompatibility. It will not cause harm to the human body when used on human skin. Combined with chitosan hemostatic sponge, It can be combined into a wound dressing that intelligently monitors the healing status of open wounds, and has a hemostatic effect on wounds, and is used for monitoring human health in open wounds;

3)本发明所述智能伤口敷料能够通过实时检测伤口处湿度及压力变化,以作为病理感染的早期预测指标,并判断伤口愈合情况;3) The smart wound dressing of the present invention can detect changes in humidity and pressure at the wound in real time as an early predictor of pathological infection and judge wound healing;

4)所述壳聚糖止血海绵具有吸水膨胀性能,迅速吸收血液中的水分而止血,还能通过壳聚糖的聚阳离子与血红细胞膜表面的阴离子结合使红细胞凝集,同时激活血小板聚集,活化凝血酶,从而达到快速止血的目的;具有可溶解性,在渗血创面形成均匀的壳聚糖凝胶层,起到保护创面并止血的作用。4) The chitosan hemostatic sponge has water-absorbing swelling properties, can quickly absorb moisture in the blood to stop bleeding, and can also agglutinate red blood cells through the combination of polycations of chitosan and anions on the surface of red blood cell membranes, while activating platelet aggregation and activating blood coagulation Enzyme, so as to achieve the purpose of rapid hemostasis; it is soluble, and forms a uniform chitosan gel layer on the oozing wound to protect the wound and stop bleeding.

附图说明Description of drawings

图1为实施例1~3和对比例1制备得到的智能伤口敷料中的功能层的SEM图;Fig. 1 is the SEM picture of the functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1;

图2为实施例1~3和对比例1制备得到的智能伤口敷料中的功能层的XRD图;Fig. 2 is the XRD diagram of the functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1;

图3为实施例1~3和对比例1制备得到的智能伤口敷料中的功能层和纯CA的FT-TR图;Fig. 3 is the FT-TR diagram of the functional layer and pure CA in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1;

图4为实施例1~3和对比例1制备得到的智能伤口敷料中的功能层的TG曲线;Fig. 4 is the TG curve of the functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1;

图5为实施例1~3和对比例1制备得到的智能伤口敷料中的功能层的力学性能测试结果;Fig. 5 is the mechanical performance test result of the functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1;

图6为实施例1~3和对比例1制备得到的智能伤口敷料中的功能层的水接触角测试结果;Fig. 6 is the water contact angle test result of the functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1;

图7为实施例3制备得到的智能伤口敷料中的功能层的生物相容性测试结果;Fig. 7 is the biocompatibility test result of the functional layer in the smart wound dressing prepared in Example 3;

图8为实施例4~6所述柔性传感器的湿度响应性能测试结果;Fig. 8 is the humidity response performance test result of the flexible sensor described in embodiments 4-6;

图9为实施例6所述柔性传感器的压力响应性能测试结果;Fig. 9 is the pressure response performance test result of the flexible sensor described in embodiment 6;

图10为实施例6所述柔性传感器的透气性测试结果。Fig. 10 is the gas permeability test result of the flexible sensor described in Example 6.

具体实施方式Detailed ways

本发明提供了一种智能伤口敷料,包括基底和设置在所述基底表面的功能层;The invention provides an intelligent wound dressing, comprising a substrate and a functional layer arranged on the surface of the substrate;

所述基底为壳聚糖止血海绵;The base is chitosan hemostatic sponge;

所述功能层为柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜。The functional layer is a citric acid-thermoplastic elastomer polyurethane composite nanofiber film.

在本发明中,所述壳聚糖止血海绵的厚度优选为0.5~3mm,更优选为1~2mm,最优选为1.8mm。In the present invention, the thickness of the chitosan hemostatic sponge is preferably 0.5-3 mm, more preferably 1-2 mm, most preferably 1.8 mm.

在本发明中,所述功能层的厚度优选为30~60μm,更优选为35~50μm,最优选为44μm。In the present invention, the thickness of the functional layer is preferably 30-60 μm, more preferably 35-50 μm, most preferably 44 μm.

在本发明中,所述柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜中柠檬酸和热塑性弹性体聚氨酯的质量比优选为(0.05~0.15):1,更优选为(0.10~0.15):1。In the present invention, the mass ratio of citric acid to thermoplastic elastomer polyurethane in the citric acid-thermoplastic elastomer polyurethane composite nanofiber film is preferably (0.05-0.15):1, more preferably (0.10-0.15):1.

本发明还提供了上述技术方案所述智能伤口敷料的制备方法,包括以下步骤:The present invention also provides a preparation method for the intelligent wound dressing described in the above technical solution, comprising the following steps:

将柠檬酸(CA)、热塑性弹性体聚氨酯(TPU)和溶剂混合,得到复合纺丝溶液;Mixing citric acid (CA), thermoplastic elastomer polyurethane (TPU) and a solvent to obtain a composite spinning solution;

以壳聚糖止血海绵为基底,将所述复合纺丝溶液进行静电纺丝,得到所述智能伤口敷料。Using the chitosan hemostatic sponge as a base, the composite spinning solution is electrospun to obtain the smart wound dressing.

在本发明中,若无特殊说明,所有制备原料均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, all preparation materials are commercially available products well known to those skilled in the art.

本发明将柠檬酸、热塑性弹性体聚氨酯和溶剂混合,得到复合纺丝溶液。The invention mixes citric acid, thermoplastic elastomer polyurethane and solvent to obtain composite spinning solution.

在本发明中,所述溶剂优选包括N,N-二甲基甲酰胺和四氢呋喃;所述N,N-二甲基甲酰胺和四氢呋喃的体积比优选为(0.5~2.5):1,更优选为1:1。In the present invention, the solvent preferably includes N,N-dimethylformamide and tetrahydrofuran; the volume ratio of N,N-dimethylformamide and tetrahydrofuran is preferably (0.5-2.5):1, more preferably 1:1.

在本发明中,所述复合纺丝溶液中热塑性弹性体聚氨酯的质量浓度优选为15~30%,更优选为18~26%,最优选为20~23%。In the present invention, the mass concentration of thermoplastic elastomer polyurethane in the composite spinning solution is preferably 15-30%, more preferably 18-26%, most preferably 20-23%.

在本发明中,所述柠檬酸和热塑性弹性体聚氨酯的质量比优选为(0.05~0.15):1,更优选为(0.10~0.15):1。In the present invention, the mass ratio of the citric acid to the thermoplastic elastomer polyurethane is preferably (0.05-0.15):1, more preferably (0.10-0.15):1.

在本发明中,所述混合优选为将柠檬酸和溶剂在超声条件下混合后,加入热塑性弹性体聚氨酯进行搅拌混合。在本发明中,所述超声的功率优选为400W,时间优选为15min;本发明对所述搅拌混合的条件没有任何特殊的限定,采用本领域技术人员熟知的条件进行并使得到的复合纺丝溶液混合均匀即可。In the present invention, the mixing is preferably mixing the citric acid and the solvent under ultrasonic conditions, and then adding the thermoplastic elastomer polyurethane for stirring and mixing. In the present invention, the power of the ultrasonic wave is preferably 400W, and the time is preferably 15min; the present invention does not have any special restrictions on the conditions of the stirring and mixing, and the conditions known to those skilled in the art are used to carry out and make the resulting composite spinning The solution is mixed evenly.

得到复合纺丝溶液后,本发明以壳聚糖止血海绵为基底,将所述复合纺丝溶液进行静电纺丝,得到所述智能伤口敷料。After the composite spinning solution is obtained, the invention uses the chitosan hemostatic sponge as a base, and carries out electrostatic spinning on the composite spinning solution to obtain the intelligent wound dressing.

在本发明中,所述静电纺丝优选采用2~4喷头纺丝。所述静电纺丝的温度优选为30~50℃,更优选为35~45℃,最优选为38~42℃;正电压优选为10~24kV,更优选为13~20kV,最优选为15~18kV;负电压优选为-5~-1kV,更优选为-4~-2kV;时间优选为1~5h,更优选为2~4h,最优选为2.5~3.5h;推进速度优选为1~3mL/h,更优选为1.5~2.5mL/h,最优选为1.8~2.2mL/h;接收距离优选为10~18cm,更优选为12~16cm,最优选为13~15cm。In the present invention, the electrospinning preferably adopts 2-4 nozzles for spinning. The temperature of the electrospinning is preferably 30-50°C, more preferably 35-45°C, most preferably 38-42°C; the positive voltage is preferably 10-24kV, more preferably 13-20kV, most preferably 15-20kV 18kV; the negative voltage is preferably -5~-1kV, more preferably -4~-2kV; the time is preferably 1~5h, more preferably 2~4h, most preferably 2.5~3.5h; the propulsion speed is preferably 1~3mL /h, more preferably 1.5-2.5mL/h, most preferably 1.8-2.2mL/h; receiving distance is preferably 10-18cm, more preferably 12-16cm, most preferably 13-15cm.

本发明还提供了上述技术方案所述智能伤口敷料或上述技术方案所述制备方法制备得到的智能伤口敷料在伤口智能监测领域中的应用。The present invention also provides the application of the intelligent wound dressing described in the above technical solution or the intelligent wound dressing prepared by the preparation method described in the above technical solution in the field of intelligent wound monitoring.

本发明还提供了一种用于伤口智能监测的柔性传感器,包括上述技术方案所述智能伤口敷料或上述技术方案所述制备方法制备得到的智能伤口敷料和设置在所述智能伤口敷料中功能层表面的电极层。The present invention also provides a flexible sensor for intelligent monitoring of wounds, comprising the intelligent wound dressing described in the above technical solution or the intelligent wound dressing prepared by the preparation method described in the above technical solution and a functional layer arranged in the intelligent wound dressing surface electrode layer.

在本发明中,所述电极层为网状结构。In the present invention, the electrode layer has a mesh structure.

在本发明中,所述电极层的厚度优选为50~60nm,更优选为53~56nm。In the present invention, the thickness of the electrode layer is preferably 50-60 nm, more preferably 53-56 nm.

在本发明中,所述电极层的材料优选包括银、碳纳米管和石墨烯中的一种或几种。In the present invention, the material of the electrode layer preferably includes one or more of silver, carbon nanotubes and graphene.

在本发明中,所述电极层优选替换为导电贴。In the present invention, the electrode layer is preferably replaced by a conductive paste.

在本发明中,所述柔性传感器还优选包括导线;所述导线与所述电极层的相对两侧进行连接;所述导线优选为铜线。In the present invention, the flexible sensor further preferably includes wires; the wires are connected to opposite sides of the electrode layer; the wires are preferably copper wires.

在本发明中,所述柔性传感器在使用时优选与监测设备电连接。In the present invention, the flexible sensor is preferably electrically connected with a monitoring device when in use.

在本发明中,所述柔性传感器的制备方法优选包括以下步骤:In the present invention, the preparation method of the flexible sensor preferably includes the following steps:

制备智能伤口敷料;Preparation of smart wound dressings;

采用丝网印刷的方式,在所述智能伤口敷料中功能层表面制备电极层后,在所述电极层的相对两侧连接导线,得到所述柔性传感器;Using screen printing, after preparing an electrode layer on the surface of the functional layer in the intelligent wound dressing, connecting wires on opposite sides of the electrode layer to obtain the flexible sensor;

或在所述智能伤口敷料中功能层表面贴上一层导电贴后,在所述电极层的相对两侧连接导线,得到所述柔性传感器。Or after pasting a layer of conductive paste on the surface of the functional layer in the intelligent wound dressing, connecting wires on opposite sides of the electrode layer to obtain the flexible sensor.

在本发明中,所述制备智能伤口敷料的方法优选采用上述技术方案所述的制备方法进行,在此不再进行赘述。In the present invention, the method for preparing the smart wound dressing is preferably carried out by using the preparation method described in the above technical solution, which will not be repeated here.

得到智能伤口敷料后,本发明采用丝网印刷的方式,在所述智能伤口敷料中功能层表面制备电极层,得到所述柔性传感器。After the smart wound dressing is obtained, the present invention uses screen printing to prepare an electrode layer on the surface of the functional layer in the smart wound dressing to obtain the flexible sensor.

在本发明中,所述电极层的制备过程优选包括:In the present invention, the preparation process of the electrode layer preferably includes:

提供导电油墨;Provide conductive ink;

将丝网印刷板覆在所述功能层上,将所述导电油墨倒在丝网印刷板上,利用刮板将所述导电油墨推开平铺,晾干,得到所述电极层。A screen printing plate is covered on the functional layer, the conductive ink is poured on the screen printing plate, the conductive ink is pushed away by a scraper, and dried to obtain the electrode layer.

在本发明中,所述导电油墨优选为导电银浆、含碳纳米管的油墨和含石墨烯的油墨中的一种或几种,本发明对所述导电银浆、碳纳米管油墨和石墨烯油墨的组成均没有任何特殊的限定,采用本领域技术人员熟知的市售产品即可。In the present invention, the conductive ink is preferably one or more of conductive silver paste, ink containing carbon nanotubes, and ink containing graphene. The composition of the vinyl ink is not particularly limited, and commercially available products well known to those skilled in the art can be used.

下面结合实施例对本发明提供的智能伤口敷料及其制备方法和应用、柔性传感器进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。The smart wound dressing provided by the present invention, its preparation method and application, and the flexible sensor will be described in detail below in conjunction with the examples, but they should not be construed as limiting the protection scope of the present invention.

实施例1Example 1

将0.25g CA与20mL体积比为1:1的N,N-二甲基甲酰胺和四氢呋喃的混合液混合,400W超声15min后,加入5g TPU搅拌至TPU完全溶解后,得到复合纺丝溶液;Mix 0.25g of CA with 20mL of a mixture of N,N-dimethylformamide and tetrahydrofuran at a volume ratio of 1:1, and after ultrasonication at 400W for 15 minutes, add 5g of TPU and stir until the TPU is completely dissolved to obtain a composite spinning solution;

将所述复合纺丝溶液转移到两只10mL注射器中,安装在纺丝机上,以壳聚糖止血海绵为基底,贴合在纺丝机接收滚筒上,调整纺丝条件(温度为30℃,正电压为18kV,负电压为2kV,时间为3h,推进速度为1mL/h,接收距离为10cm),得到智能伤口敷料(功能层中柠檬酸和热塑性弹性体聚氨酯的质量比0.05:1,记为CA/TPU-5%)。The composite spinning solution is transferred to two 10mL syringes, installed on the spinning machine, with the chitosan hemostatic sponge as the base, attached to the receiving drum of the spinning machine, and adjusting the spinning conditions (the temperature is 30 ° C, The positive voltage is 18kV, the negative voltage is 2kV, the time is 3h, the propulsion speed is 1mL/h, and the receiving distance is 10cm), to obtain a smart wound dressing (the mass ratio of citric acid and thermoplastic elastomer polyurethane in the functional layer is 0.05:1, record is CA/TPU-5%).

实施例2Example 2

参考实施例1,区别仅在于CA的用量为0.5g,制备得到智能伤口敷料(功能层中柠檬酸和热塑性弹性体聚氨酯的质量比0.1:1,记为CA/TPU-10%)。Referring to Example 1, the only difference is that the amount of CA is 0.5g, and a smart wound dressing is prepared (the mass ratio of citric acid and thermoplastic elastomer polyurethane in the functional layer is 0.1:1, denoted as CA/TPU-10%).

实施例3Example 3

参考实施例1,区别仅在于CA的用量为0.75g,制备得到智能伤口敷料(功能层中柠檬酸和热塑性弹性体聚氨酯的质量比0.15:1,记为CA/TPU-15%)。Referring to Example 1, the only difference is that the amount of CA is 0.75g, and a smart wound dressing is prepared (the mass ratio of citric acid and thermoplastic elastomer polyurethane in the functional layer is 0.15:1, denoted as CA/TPU-15%).

实施例4Example 4

将丝网印刷板覆在实施例1所述的功能层表面上,将碳纳米管油墨倒在所述丝网印刷板上,利用刮板将所述导电油墨推开平铺,自然晾干,得到所述电极层;Cover the screen printing plate on the surface of the functional layer described in Example 1, pour the carbon nanotube ink on the screen printing plate, push the conductive ink away and spread it with a scraper, and let it dry naturally. obtaining the electrode layer;

将导电铜线粘在所述电极层的相对两端,得到柔性传感器(记为CTHPS-5%)。Conductive copper wires were glued to the opposite ends of the electrode layer to obtain a flexible sensor (denoted as CTHPS-5%).

实施例5Example 5

参考实施例4,区别仅在于在实施例2所述的功能层表面上制备电极层,得到柔性传感器(记为CTHPS-10%)。Referring to Example 4, the only difference is that an electrode layer is prepared on the surface of the functional layer described in Example 2 to obtain a flexible sensor (referred to as CTHPS-10%).

实施例6Example 6

参考实施例4,区别仅在于在实施例3所述的功能层表面上制备电极层,得到柔性传感器(记为CTHPS-15%)。Referring to Example 4, the only difference is that an electrode layer is prepared on the surface of the functional layer described in Example 3 to obtain a flexible sensor (denoted as CTHPS-15%).

对比例1Comparative example 1

参考实施例1,区别仅在于未添加CA。Referring to Example 1, the only difference is that no CA is added.

测试例test case

将实施例1~3和对比例1制备得到的智能伤口敷料中的功能层进行SEM测试,测试结果如图1所示,其中(a)对应对比例1,(b)对应实施例1,(c)对应实施例2,(d)对应实施例3;由图1可知,对比例1中没有添加CA的功能层纤维光滑连续且直径分布均匀(平均直径约为582±7.2nm),形成三维排列的网格结构;实施例1中纤维表面负载少量的CA颗粒,随着CA添加量的增加,CA颗粒在柠檬酸/热塑性弹性体聚氨酯(CA/TPU)复合纳米纤维表面的负载量也随之增加,且分布十分均匀,此外,由于CA添加量的增加,静电纺丝过程中需要克服的表面张力降低,因此纤维直径减少至525±6.5nm,从而在膜中形成更多的微观结构,有利于提升纤维膜的湿度和压力传感性能;The functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1 was subjected to SEM testing, and the test results are shown in Figure 1, wherein (a) corresponds to Comparative Example 1, (b) corresponds to Example 1, ( c) corresponds to Example 2, and (d) corresponds to Example 3; as can be seen from Figure 1, the fibers of the functional layer without adding CA in Comparative Example 1 are smooth and continuous with uniform diameter distribution (the average diameter is about 582±7.2nm), forming a three-dimensional Arranged grid structure; a small amount of CA particles loaded on the fiber surface in Example 1, along with the increase of CA addition, the load of CA particles on the surface of citric acid/thermoplastic elastomer polyurethane (CA/TPU) composite nanofibers also increases with In addition, due to the increase of CA addition, the surface tension to be overcome in the electrospinning process is reduced, so the fiber diameter is reduced to 525±6.5nm, thereby forming more microstructures in the film, It is beneficial to improve the humidity and pressure sensing performance of the fiber membrane;

将实施例1~3和对比例1(纯TPU)制备得到的智能伤口敷料中的功能层进行XRD测试,测试结果如图2所示,CA/TPU-5%和CA/TPU-10%的XRD谱线与纯TPU基本一致,由此推断CA的掺杂不会显著改变TPU的晶体结构。并且随着掺杂量的增加,CA颗粒在XRD中的特征衍射峰更加明显,表明CA颗粒成功掺入TPU纳米纤维膜;The functional layer in the smart wound dressing prepared in Examples 1 to 3 and Comparative Example 1 (pure TPU) is subjected to XRD testing, and the test results are as shown in Figure 2, CA/TPU-5% and CA/TPU-10% The XRD spectrum is basically consistent with that of pure TPU, so it can be inferred that the doping of CA will not significantly change the crystal structure of TPU. And as the doping amount increases, the characteristic diffraction peaks of CA particles in XRD are more obvious, indicating that CA particles are successfully incorporated into the TPU nanofiber film;

将实施例1~3和对比例1制备得到的智能伤口敷料中的功能层和纯CA进行FT-TR测试,测试结果如图3所示,由图3可知,纯TPU 3000cm-1和1750cm-1处的峰值分别为-N-H-伸缩振动吸收峰和C≡O伸缩振动吸收峰,这在CA/TPU复合纳米纤维膜的FT-IR中是非常明显的,表明TPU与CA共混静电纺丝不会破坏TPU的基本结构。此外,在1736~1720cm-1处,CA/TPU复合纳米纤维膜中出现了一个新的吸收带,为C=O拉伸振动峰,属于CA的特征峰,证明TPU膜已成功负载CA;The functional layer and pure CA in the smart wound dressings prepared in Examples 1-3 and Comparative Example 1 were tested by FT-TR. The test results are shown in Figure 3. It can be seen from Figure 3 that the pure TPU 3000cm The peaks at 1 are -NH- stretching vibration absorption peak and C≡O stretching vibration absorption peak, which are very obvious in FT-IR of CA/TPU composite nanofibrous membrane, indicating that TPU and CA blended electrospinning Will not destroy the basic structure of TPU. In addition, at 1736-1720 cm -1 , a new absorption band appeared in the CA/TPU composite nanofiber membrane, which is the C=O stretching vibration peak, which belongs to the characteristic peak of CA, which proves that the TPU membrane has successfully loaded CA;

将实施例1~3和对比例1(纯TPU)制备得到的智能伤口敷料中的功能层进行TG测试,测试结果如图4所示,由图4可知,当温度低于200℃时,纯TPU和所有CA/TPU复合纳米纤维膜由于吸附水的损失而有少量的重量损失。在200~450℃之间,由于聚合物的分解,纯TPU和CA/TPU复合纳米纤维膜表现出严重的质量损失。随着CA掺杂量的增加,CA/TPU复合纳米纤维膜的剩余质量百分比呈增加趋势,CA/TPU-15%的剩余重量为10.5%,表明CA已成功掺杂到TPU中;The functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1 (pure TPU) was tested by TG, and the test results are shown in Figure 4. It can be seen from Figure 4 that when the temperature is lower than 200°C, the pure TPU TPU and all CA/TPU composite nanofibrous membranes had a small weight loss due to the loss of adsorbed water. Between 200 and 450 °C, pure TPU and CA/TPU composite nanofibrous membranes exhibit severe mass loss due to the decomposition of the polymer. With the increase of CA doping amount, the remaining mass percentage of CA/TPU composite nanofibrous membrane showed an increasing trend, and the remaining weight of CA/TPU-15% was 10.5%, indicating that CA had been successfully doped into TPU;

将实施例1~3和对比例1(纯TPU)制备得到的智能伤口敷料中的功能层进行力学性能测试,应力应变曲线如图5所示,由图5可知,随着CA含量从0增加到10wt%,极限应力从0.7MPa单调增加到1.3MPa。当CA掺杂量为15%时,CA/TPU复合纳米纤维膜的拉伸应变在350%左右,断裂伸长率约为450%。CA/TPU复合纳米纤维膜的拉伸应变始终保持在350%以上,断裂伸长率也保持在较高水平(约470%),表明CA/TPU纳米纤维膜具有良好的柔性和可拉伸性,在贴附于皮肤时不易断裂;The functional layer in the smart wound dressing prepared in Examples 1-3 and Comparative Example 1 (pure TPU) was tested for mechanical properties. The stress-strain curve is shown in Figure 5. It can be seen from Figure 5 that as the CA content increases from 0 Up to 10wt%, the ultimate stress increases monotonically from 0.7MPa to 1.3MPa. When the CA doping amount is 15%, the tensile strain of the CA/TPU composite nanofiber membrane is about 350%, and the elongation at break is about 450%. The tensile strain of the CA/TPU composite nanofibrous membrane was always maintained above 350%, and the elongation at break was also maintained at a high level (about 470%), indicating that the CA/TPU nanofibrous membrane has good flexibility and stretchability , not easy to break when attached to the skin;

将实施例1~3和对比例1(纯TPU)制备得到的智能伤口敷料中的功能层进行水接触角测试,测试结果如图6所示,由图6可知,对比例1的水接触角为132°,实施例1~3的水接触角分别为72°、57°和46°,由此可见掺杂CA后的复合纳米纤维膜的水接触角减小,表明CA的加入改善了复合纳米纤维膜的浸润性,增强了复合纳米纤维膜的亲水性能。这是由于CA分子中含有多个羧基和羟基,而羧基和羟基可以与空气中的水分子形成分子间氢键,将水分子以物理吸附的形式吸附在纳米纤维膜表面,是湿度响应的基础;The functional layer in the smart wound dressing prepared in Examples 1 to 3 and Comparative Example 1 (pure TPU) was tested for water contact angle, and the test results are shown in Figure 6. As can be seen from Figure 6, the water contact angle of Comparative Example 1 is 132°, and the water contact angles of Examples 1 to 3 are 72°, 57° and 46° respectively. It can be seen that the water contact angle of the composite nanofibrous membrane doped with CA decreases, indicating that the addition of CA improves the composite nanofiber membrane. The wettability of the nanofibrous membrane enhances the hydrophilic property of the composite nanofibrous membrane. This is because CA molecules contain multiple carboxyl groups and hydroxyl groups, and carboxyl groups and hydroxyl groups can form intermolecular hydrogen bonds with water molecules in the air, and adsorb water molecules on the surface of nanofiber membranes in the form of physical adsorption, which is the basis of humidity response. ;

将实施例3制备得到的智能伤口敷料中的功能层进行生物相容性实验,测试结果如图7所示,其中(a)是在Roswell Park Memorial Institute-1640标准培养基上培养4天后的HaCaT细胞的荧光图像,(b)是在实施例3制备得到的智能伤口敷料中的功能层上培养HaCaT细胞的荧光图像,(c)为空白细胞培养基上培养的HaCaT细胞的荧光图像,(d)为分别在Roswell Park Memorial Institute-1640标准培养基、实施例3制备得到的智能伤口敷料中的功能层和空白细胞培养基上培养不同时间的HaCaT细胞的OD值,由图7可知,实施例3制备得到的智能伤口敷料中的功能层对HaCaT细胞没有明显的细胞毒性作用,与标准细胞培养基非常接近,在实施例3制备得到的智能伤口敷料中的功能层上培养4天后,在特定波长450nm下测量吸光度,HaCaT细胞的存活率没有显著降低。表明实施例3制备得到的智能伤口敷料中的功能层具有生物相容性,可直接在皮肤上或开放性伤口处使用;The functional layer in the smart wound dressing prepared in Example 3 was subjected to a biocompatibility experiment, and the test results are shown in Figure 7, wherein (a) is HaCaT cultured on Roswell Park Memorial Institute-1640 standard medium for 4 days. Fluorescent image of cells, (b) is a fluorescent image of HaCaT cells cultured on the functional layer in the smart wound dressing prepared in Example 3, (c) is a fluorescent image of HaCaT cells cultured on blank cell culture medium, (d ) is the OD value of the HaCaT cells cultured at different times on the Roswell Park Memorial Institute-1640 standard medium, the functional layer in the smart wound dressing prepared in Example 3, and the blank cell medium, as can be seen from Figure 7. 3 The functional layer in the smart wound dressing prepared in Example 3 has no obvious cytotoxic effect on HaCaT cells, which is very close to the standard cell culture medium. After culturing for 4 days on the functional layer in the smart wound dressing prepared in Example 3, the specific The absorbance was measured at a wavelength of 450nm, and the survival rate of HaCaT cells was not significantly reduced. It shows that the functional layer in the smart wound dressing prepared in Example 3 has biocompatibility and can be used directly on the skin or on an open wound;

将实施例4~6所述柔性传感器进行湿度响应性能测试,测试结果如图8所示,其中(a)为所述实施例4~6所述柔性传感器在20~90%RH下的湿度-相对阻值变化曲线,(b)为实施例6所述柔性传感器在20~90%RH下的湿度下的湿滞曲线,由(a)可知,柔性传感器的相对阻值随湿度的增加而变大的,在低湿度范围内(20~50%RH),柔性传感器的感湿灵敏度大致相同,越为0.6%RH,在高湿度范围内(50%~90%RH),CTHPS-15%感湿灵敏度最大,约为2.15%RH,而CTHPS-5%和CTHPS-10%分别为1.32/%RH和1.88/%RH。由此可见,随着CA掺杂量的增加,柔性传感器的感湿性能在增强,因此CA的最佳掺杂量为15%;由(b)可知,在20%~90%RH的湿度范围内,CTHPS-15%的湿度滞后为10%,证明传感器在较宽湿度范围内都具有良好的稳定性;The flexible sensor described in Examples 4-6 was tested for humidity response performance, and the test results are shown in Figure 8, wherein (a) is the humidity of the flexible sensor described in Examples 4-6 at 20-90% RH- The relative resistance change curve, (b) is the hysteresis curve of the flexible sensor described in embodiment 6 at a humidity of 20 to 90% RH, as can be seen from (a), the relative resistance of the flexible sensor changes with the increase of humidity Larger, in the low humidity range (20-50% RH), the humidity sensitivity of the flexible sensor is roughly the same, the higher the 0.6% RH, in the high humidity range (50%-90% RH), the CTHPS-15% sensitivity The wet sensitivity is the largest at about 2.15%RH, while CTHPS-5% and CTHPS-10% are 1.32/%RH and 1.88/%RH, respectively. It can be seen that with the increase of the doping amount of CA, the moisture-sensing performance of the flexible sensor is enhanced, so the optimal doping amount of CA is 15%; it can be seen from (b) that in the humidity range of 20% to 90% RH Within, the humidity hysteresis of CTHPS-15% is 10%, which proves that the sensor has good stability in a wide range of humidity;

将实施例6所述柔性传感器进行压力响应性能测试,测试结果如图9所示,其中(a)为压力灵敏度曲线,(b)为时间响应曲线,(c)为响应恢复曲线;由(a)可知,压力灵敏度分为三个线性区域:低压范围(0~2.25kPa)的SP1、中压范围(2.25~11.25kPa)的SP2和高压范围(11.25~26.25kPa)的SP3。CTHPS-15%对SP1、SP2和SP3的灵敏度分别为10.53、2.56和0.3kPa-1,由于静电纺丝纳米纤维膜内部存在大量的孔隙和缝隙。孔隙和间隙的存在导致导电CNT之间接触不良,导致在不施加压力的情况下CTHPS的原始电阻较大,一旦压力施加到传感器上,就会发生压缩变形,纳米纤维之间的孔隙和间隙会减少,纤维与导电碳纳米管之间的接触会大大增加,当施加较小的压力(0~2.25kPa)时,碳纳米管电极与纳米纤维膜接触更紧密,导致导电性急剧增加,此时灵敏度比较高。当施加压力增加(2.25~11.25kPa)时,多层纳米纤维紧密地压缩在一起,导致电导率进一步增加,电阻降低。根据临床数据,人体腹部开放性伤口的压力值通常低于10kPa,因此,CTHPS可用于开放性智能伤口敷料,根据伤口愈合过程中的周围皮肤所受压力值变化来监测伤口愈合程度。随着压力的增加(11.25~26.25kPa),传感器的灵敏度下降到0.3kPa-1。这是因为导电碳纳米管的相互接触无法改善,输出电阻几乎没有变化;由(b)可知,CTHPS-15%表现出快速响应(88ms)和恢复时间(90ms),说明传感器具有快速响应性;由(c)可知,CTHPS-15%在200次循环测试下的响应恢复曲线,说明传感器具有良好的循环稳定性;The flexible sensor described in Example 6 is tested for pressure response performance, and the test results are as shown in Figure 9, wherein (a) is a pressure sensitivity curve, (b) is a time response curve, and (c) is a response recovery curve; by (a ) shows that the pressure sensitivity is divided into three linear regions: SP1 in the low pressure range (0-2.25kPa), SP2 in the medium-pressure range (2.25-11.25kPa) and SP3 in the high-pressure range (11.25-26.25kPa). The sensitivities of CTHPS-15% to SP1 , SP2 and SP3 are 10.53, 2.56 and 0.3kPa -1 respectively, because there are a lot of pores and gaps inside the electrospun nanofibrous membrane. The existence of pores and gaps leads to poor contact between conductive CNTs, resulting in a large original resistance of CTHPS without applying pressure, once the pressure is applied to the sensor, compression deformation occurs, and the pores and gaps between nanofibers will be Reduced, the contact between the fiber and the conductive carbon nanotube will be greatly increased. When a small pressure (0 ~ 2.25kPa) is applied, the carbon nanotube electrode is in closer contact with the nanofiber film, resulting in a sharp increase in conductivity. At this time The sensitivity is relatively high. When the applied pressure increases (2.25–11.25 kPa), the multilayer nanofibers are tightly compressed together, resulting in a further increase in electrical conductivity and a decrease in electrical resistance. According to clinical data, the pressure value of open wounds in the human abdomen is usually lower than 10kPa. Therefore, CTHPS can be used in open smart wound dressings to monitor the degree of wound healing according to the changes in the pressure value of the surrounding skin during the wound healing process. As the pressure increases (11.25 ~ 26.25kPa), the sensitivity of the sensor drops to 0.3kPa -1 . This is because the mutual contact of conductive carbon nanotubes cannot be improved, and the output resistance has almost no change; as can be seen from (b), CTHPS-15% shows a fast response (88ms) and recovery time (90ms), indicating that the sensor has a fast response; It can be seen from (c) that the response recovery curve of CTHPS-15% under 200 cycle tests shows that the sensor has good cycle stability;

将实施例6所述柔性传感器、对比例1所述的TPU纳米纤维膜和PDMS膜进行透气性测试,测试结果如图10所示,由图10可知,TPU纳米纤维膜的透气性为192mm/s,优于柔性压力传感器中常用的PDMS膜(0mm/s),与医用防护口罩中用作过滤器的聚丙烯熔喷非织造布(透气性约198mm/s)相似。CTHPS-15%的透气性为171mm/s,透气性较纯TPU略有减弱,但仍表现出良好的透气性,表明CTHPS-15%优越的透气性。The flexible sensor described in Example 6, the TPU nanofiber membrane described in Comparative Example 1, and the PDMS membrane were tested for gas permeability, and the test results are as shown in Figure 10. As can be seen from Figure 10, the gas permeability of the TPU nanofiber membrane is 192mm/ s, better than PDMS membrane (0mm/s) commonly used in flexible pressure sensors, and similar to polypropylene melt-blown nonwovens used as filters in medical protective masks (air permeability about 198mm/s). The air permeability of CTHPS-15% is 171mm/s, which is slightly weaker than that of pure TPU, but still shows good air permeability, indicating the superior air permeability of CTHPS-15%.

以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (8)

1.一种用于伤口智能监测的柔性传感器,其特征在于,包括智能伤口敷料和设置在所述智能伤口敷料中功能层表面的电极层;1. A flexible sensor for intelligent monitoring of wounds, characterized in that it comprises an intelligent wound dressing and an electrode layer arranged on the surface of a functional layer in the intelligent wound dressing; 所述智能伤口敷料包括基底和设置在所述基底表面的功能层;The smart wound dressing includes a substrate and a functional layer arranged on the surface of the substrate; 所述基底为壳聚糖止血海绵;The base is chitosan hemostatic sponge; 所述功能层为柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜。The functional layer is a citric acid-thermoplastic elastomer polyurethane composite nanofiber film. 2.如权利要求1所述的柔性传感器,其特征在于,所述柠檬酸-热塑性弹性体聚氨酯复合纳米纤维膜中柠檬酸和热塑性弹性体聚氨酯的质量比为(0.05~0.15):1。2 . The flexible sensor according to claim 1 , wherein the mass ratio of citric acid to thermoplastic elastomer polyurethane in the citric acid-thermoplastic elastomer polyurethane composite nanofiber film is (0.05-0.15):1. 3.权利要求1或2所述的柔性传感器,其特征在于,所述智能伤口敷料的制备方法包括以下步骤:3. The flexible sensor according to claim 1 or 2, wherein the preparation method of the intelligent wound dressing comprises the following steps: 将柠檬酸、热塑性弹性体聚氨酯和溶剂混合,得到复合纺丝溶液;mixing citric acid, thermoplastic elastomer polyurethane and a solvent to obtain a composite spinning solution; 以壳聚糖止血海绵为基底,将所述复合纺丝溶液进行静电纺丝,得到所述智能伤口敷料。Using the chitosan hemostatic sponge as a base, the composite spinning solution is electrospun to obtain the smart wound dressing. 4.如权利要求3所述的柔性传感器,其特征在于,所述复合纺丝溶液中热塑性弹性体聚氨酯的质量浓度为15~30%。4. The flexible sensor according to claim 3, wherein the mass concentration of thermoplastic elastomer polyurethane in the composite spinning solution is 15-30%. 5.如权利要求3或4所述的柔性传感器,其特征在于,所述柠檬酸和热塑性弹性体聚氨酯的质量比为(0.05~0.15):1。5. The flexible sensor according to claim 3 or 4, wherein the mass ratio of the citric acid to the thermoplastic elastomer polyurethane is (0.05-0.15):1. 6.如权利要求5所述的柔性传感器,其特征在于,所述溶剂包括N,N-二甲基甲酰胺和四氢呋喃;6. The flexible sensor according to claim 5, wherein the solvent comprises N,N-dimethylformamide and tetrahydrofuran; 所述N,N-二甲基甲酰胺和四氢呋喃的体积比为(0.5~2.5):1。The volume ratio of N,N-dimethylformamide to tetrahydrofuran is (0.5-2.5):1. 7.如权利要求3所述的柔性传感器,其特征在于,所述静电纺丝采用2~4喷头纺丝;7. The flexible sensor according to claim 3, wherein the electrospinning adopts 2 to 4 nozzles for spinning; 所述静电纺丝的温度为30~50℃,正电压为10~24kV,负电压为-5~-1kV,时间为1~5h,推进速度为1~3mL/h,接收距离为10~18cm。The temperature of the electrospinning is 30~50°C, the positive voltage is 10~24kV, the negative voltage is -5~-1kV, the time is 1~5h, the advancing speed is 1~3mL/h, and the receiving distance is 10~18cm . 8.如权利要求1所述的柔性传感器,其特征在于,所述电极层的厚度为50~60nm。8. The flexible sensor according to claim 1, wherein the electrode layer has a thickness of 50-60 nm.
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