+

CN116688209B - Medical dressing, preparation method and application - Google Patents

Medical dressing, preparation method and application Download PDF

Info

Publication number
CN116688209B
CN116688209B CN202310661260.2A CN202310661260A CN116688209B CN 116688209 B CN116688209 B CN 116688209B CN 202310661260 A CN202310661260 A CN 202310661260A CN 116688209 B CN116688209 B CN 116688209B
Authority
CN
China
Prior art keywords
parts
weight
polyurethane
dressing
medical dressing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310661260.2A
Other languages
Chinese (zh)
Other versions
CN116688209A (en
Inventor
东为富
杨铄冰
黄晶
李婷
汪洋
王世波
张旭辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangnan University
Original Assignee
Jiangnan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Priority to CN202310661260.2A priority Critical patent/CN116688209B/en
Publication of CN116688209A publication Critical patent/CN116688209A/en
Application granted granted Critical
Publication of CN116688209B publication Critical patent/CN116688209B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/20Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/32Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/44Medicaments
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00Electrotherapy; Circuits therefor
    • A61N1/18Applying electric currents by contact electrodes
    • A61N1/32Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/326Applying electric currents by contact electrodes alternating or intermittent currents for promoting growth of cells, e.g. bone cells
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00Electrotherapy; Circuits therefor
    • A61N1/18Applying electric currents by contact electrodes
    • A61N1/32Applying electric currents by contact electrodes alternating or intermittent currents
    • A61N1/36Applying electric currents by contact electrodes alternating or intermittent currents for stimulation
    • A61N1/36014External stimulators, e.g. with patch electrodes
    • 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
    • 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
    • A61L2300/252Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
    • 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Hematology (AREA)
  • Biomedical Technology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Radiology & Medical Imaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Biophysics (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Cell Biology (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Materials For Medical Uses (AREA)

Abstract

A medical dressing, a preparation method and application belong to the field of functional composite materials. The dressing is prepared by blending liquid metal, a multifunctional additive and polyurethane, wherein the addition amount of each substance is 10-55 parts by weight of the multifunctional additive, 800-1500 parts by weight of the liquid metal is urea-containing polyurea polyurethane, the liquid metal is gallium-indium alloy with the melting point of 3-30 ℃, and the multifunctional additive is glutathione and derivatives thereof, based on 100 parts by weight of the polyurethane. The medical dressing has excellent biocompatibility, has the functions of self-repairing and promoting wound healing, can be widely applied to the field of medical materials, plays a positive role in wound repair under the assistance of electric stimulation, and can be used as a wound dressing or a medical material for promoting tissue regeneration.

Description

Medical dressing, preparation method and application
Technical Field
The invention belongs to the field of functional composite materials, and particularly relates to a medical dressing, a preparation method and application.
Background
The skin is the largest organ of the human body, not only protects the internal tissue and organs of the human body from being affected by external harmful factors, but also plays a role in perception and metabolism. However, skin or tissue injury is difficult to heal for a long time due to diabetes, aging, burn and the like, which not only causes inconvenience in daily life, but also reduces immunity and even endangers life. Therefore, research on promoting wound healing is an important subject for life sciences and improving human life quality.
The proliferation and differentiation of cells can be promoted by applying Electrical Stimulation (ES) to the wound site of the patient, thereby promoting tissue repair. Researchers have found that skin damage can lead to endogenous currents at the wound site that help to accelerate key cell migration, playing a positive role in wound healing. On this basis, the simulation and enhancement of wound potential will contribute to tissue repair by (1) facilitating DNA and collagen synthesis, (2) migration of wound healing-related cells, and (3) in vitro and in vivo antibacterial effects. Therefore, the method for promoting wound healing by external electrical stimulation has a great application prospect. However, the traditional electrode material has overlarge rigidity and poor plasticity, so that the problem of interface discomfort with skin is caused, good skin compliance is difficult to realize, the traditional electrode material has poor self-healing property and is difficult to cope with complex daily use requirements, and meanwhile, the power supply part of the traditional electrode material is too concentrated, so that stable and uniform electric stimulation is difficult to form, and the treatment effect and the use feeling are influenced. The use of flexible conductive dressings instead of conventional rigid electrodes is an effective way to solve the above-mentioned problems. Paper CHEMICAL ENGINEERING Journal 406 (2021) 126741 prepares a conductive foam dressing by dispersing silver nanowires in porous polyurethane, which can uniformly and effectively promote wound healing under external electrical stimulation, but the silver nanowire conductive filler and polyurethane foam used in the dressing do not have self-repairing property.
The Liquid Metal (LM) is a novel alloy with good biocompatibility and conductivity, has the same fluidity as liquid under the condition of approaching environment, has high deformability and high plasticity, and provides possibility for the novel alloy to be used as conductive filler to realize the skin compliance and self-repairing of wound dressing. Paper adv.funct.mate.2022, 32,2200444 encapsulation of liquid metal into polyethylene glycol (PEG) blended Polydimethylsiloxane (PDMS) to make epidermal electronics, physiological detection experiments were performed and wound healing was significantly promoted by external electrical stimulation, but the liquid metal in this study was encapsulated into matrix material in a fixed thickness and shape, making it difficult to achieve uniform electrical stimulation for wounds of different shapes. And because of the normal temperature and liquid state characteristics of the liquid metal, the preparation method is easy to cause the problem of massive leakage of the liquid metal after the dressing is damaged, so that the use is unchanged. The paper ACS Nano 2019,13,9122-9130 synthesizes the liquid metal composite hydrogel for the stretchable electronic product by ultraviolet irradiation, and the material can realize circuit reconstruction by friction induction, but the composite hydrogel prepared by the research has lower mechanical property due to poor compatibility of liquid metal and a matrix. At present, no report on a liquid metal-based self-repairing dressing for promoting wound healing exists. Therefore, a medical material with good self-repairing property, skin compliance, biocompatibility and uniform electrical response, which can promote wound healing, needs to be developed.
Disclosure of Invention
The invention provides a medical dressing, a preparation method and application thereof for solving the problems in the prior art. The composite material obtained by the invention has excellent self-healing property, uniform conductivity, good biocompatibility, safety and no toxicity, and can play a remarkable promoting effect on the repair of wound surfaces through the auxiliary effect of external electrical stimulation.
The technical scheme of the invention is as follows:
The medical dressing is prepared by blending liquid metal, a multifunctional additive and polyurethane, wherein the polyurethane is urea-containing polyurea polyurethane, the liquid metal is one or more than two of gallium-indium alloy with a melting point of 3-30 ℃, and the multifunctional additive is one or more than two of glutathione and derivatives thereof.
Further, the addition amount of each substance is 10-55 parts by weight of the multifunctional additive and 800-1500 parts by weight of the liquid metal based on 100 parts by weight of the polyurea polyurethane.
Furthermore, in the medical dressing, the polyurea polyurethane has self-repairing property, the liquid metal has a structure remodelling function, the multifunctional additive improves system compatibility, and the medical dressing has the function of promoting wound healing.
Further, the polyurea polyurethane is prepared by solution reaction of 100 parts by weight of isocyanate, 50-500 parts by weight of polyol mixture, 10-50 parts by weight of chain extender, 1-8 parts by weight of catalyst and 500-1000 parts by weight of solvent.
Further, the isocyanate is one or more than two of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and diphenylmethane diisocyanate, the polyol mixture is two or more than two of polyether glycol 200-3000 or polyester glycol 200-2000, the chain extender is one of m-phthalhydrazide, maleic dihydrazide, succinic dihydrazide and furan-2, 5-diformylhydrazine, the catalyst is an organotin catalyst, and the solvent is one of dimethylformamide and dimethylacetamide.
The preparation process of the polyurea polyurethane comprises the steps of dissolving a polyol mixture, a catalyst and isocyanate in a solvent according to a proportion, heating to 60-80 ℃, stirring and reacting for 2-3 hours, cooling to normal temperature, adding a chain extender, stirring and reacting for 2-4 hours at normal temperature, removing the solvent, and drying and preserving or dissolving in an ethanol solution for later use.
A method of preparing a medical dressing comprising the steps of:
Dispersing liquid metal in an alcohol-water solution of the dissolved multifunctional additive by utilizing ultrasonic waves for 10-120min, adding an alcohol solution of polyurea polyurethane according to a proportion, carrying out ultrasonic waves for 1-5min, pouring or knife coating the dispersion liquid, and drying to obtain the dressing.
The medical dressing has excellent biocompatibility, has the functions of self-repairing and promoting wound healing, and can be widely applied to the field of medical materials.
Further, the electric stimulation auxiliary material plays a positive role in wound repair, and can be used as a wound dressing or a medical material for promoting tissue regeneration.
The invention has the following beneficial effects:
(1) The dressing has excellent biocompatibility, can be self-repaired, is safe and nontoxic, and can promote the rapid healing of wound surfaces.
(2) The multifunctional additive disclosed by the invention is beneficial to good dispersion of liquid metal in a polymer matrix, greatly improves the conductive uniformity, and is also beneficial to improving the skin immunity, so that wound skin repair is assisted.
(3) In the invention, the urea-group-containing polyurea polyurethane structure contains multiple hydrogen bonds, so that the matrix material is endowed with excellent self-repairing property, and the urea-group-containing polyurea polyurethane structure and the multifunctional additive are synergistic to further improve the stable dispersion of liquid metal.
(4) The liquid metal has low melting point, strong deformability, favorable structural remodeling, excellent biocompatibility, good skin compliance, high plasticity and self-healing property even under the conditions of high filling and large thickness, and is favorable for promoting the future development of more individuation and differentiation of tissue healing by electric stimulation.
Drawings
FIG. 1 is a projection electron micrograph of a liquid metal-glutathione dispersion of example 1;
FIG. 2 is a scanning electron micrograph of a cross section of the dressing of example 1;
FIG. 3 is a photograph of 24-hour and 48-hour stained live cells of the dressing of example 1.
Detailed description of the preferred embodiments
The sources of reagents used in the examples of the present invention may be commercially available, except where otherwise specified.
It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention. The raw material components which are equivalent to or contain the same structural units as the functional groups contained in the raw materials used in the examples except the raw materials used in the examples are included in the protection scope of the invention. The invention is further illustrated below with reference to specific examples.
The present invention provides a drawing of detection results of some embodiments, other embodiments and comparative examples employ the same detection method, and those skilled in the art can directly and unambiguously determine the content of the embodiments of the present invention through the detection method provided by the present invention.
The external electric stimulation mode adopted by the invention is to connect a 3.6V button cell on the dressing for promoting wound healing
The invention will be further illustrated with reference to the following examples.
Example 1
(1) The preparation method of the polyurea polyurethane comprises the steps of weighing 100 parts by weight of isophorone diisocyanate, 280 parts of polyethylene glycol 2000,20 parts of polyethylene glycol 400 and 5 parts of dibutyl tin dilaurate, adding 600 parts of N, N-dimethylformamide into a three-neck flask for dissolution, heating to 60 ℃, stirring for 3 hours, stopping heating, naturally cooling to normal temperature, adding 40 parts of m-phthalhydrazide, stirring for 2 hours at normal temperature, and drying the N, N-dimethylformamide to obtain the polyurea polyurethane 1.
(2) The preparation of the medical dressing comprises the steps of dispersing 1500 parts by weight of gallium-indium alloy (with the melting point of 3 ℃) into 20ml of alcohol-water solution in which 55 parts of glutathione are dissolved by utilizing ultrasonic grinding, carrying out ultrasonic treatment for 60min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 1min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 1. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 2
(1) The preparation of the polyurea polyurethane comprises the steps of weighing 100 parts by weight of dicyclohexylmethane-4, 4' -diisocyanate, 280 parts of polyethylene glycol 2000,20 parts of polyethylene glycol 400 and 3 parts of dibutyl tin dilaurate, adding 800 parts of N, N-dimethylacetamide into a three-neck flask to dissolve, heating to 75 ℃, stirring and reacting for 2.5 hours, stopping heating, naturally cooling to normal temperature, adding 40 parts of maleic dihydrazide, stirring and reacting for 3 hours at normal temperature, and drying the N, N-dimethylacetamide to obtain the polyurea polyurethane 2.
(2) The preparation of the medical dressing comprises the steps of dispersing 1200 parts by weight of gallium indium alloy (with the melting point of 11 ℃) into 20ml of alcohol water solution in which 45 parts of glutathione is dissolved by utilizing ultrasonic grinding, carrying out ultrasonic treatment for 60min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 2min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 2. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 3
(1) The preparation method of the polyurea polyurethane comprises the steps of weighing 100 parts by weight of isophorone diisocyanate, 200 parts by weight of polyethylene glycol 2000,40 parts by weight of polyethylene glycol 400,2 parts by weight of dibutyl tin dilaurate, adding 500 parts by weight of N, N-dimethylformamide into a three-neck flask for dissolution, heating to 80 ℃, stirring for 2 hours, stopping heating, naturally cooling to normal temperature, adding 30 parts by weight of isophthaloyl dihydrazide, stirring for 3 hours at normal temperature, and drying the N, N-dimethylformamide to obtain the polyurea polyurethane 3.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 1200 parts by weight of gallium-indium alloy (with the melting point of 11 ℃) into 20ml of alcohol-water solution in which 40 parts of glutathione are dissolved by utilizing ultrasonic crushing, carrying out ultrasonic treatment for 100min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 1min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 3. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 4
(1) The preparation of the polyurea polyurethane comprises the steps of weighing 100 parts by weight of diphenylmethane diisocyanate, 200 parts by weight of polyethylene glycol 2000,40 parts by weight of polyethylene glycol 400,1 parts by weight of dibutyl tin dilaurate, adding 600 parts by weight of N, N-dimethylacetamide into a three-neck flask for dissolution, heating to 80 ℃, stirring for 3 hours, stopping heating, naturally cooling to normal temperature, adding 30 parts by weight of succinic acid dihydrazide, stirring for 4 hours at normal temperature, and drying the N, N-dimethylacetamide to obtain the polyurea polyurethane 4.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 1000 parts by weight of gallium-indium alloy (with the melting point of 11 ℃) into 20ml of alcohol-water solution in which 40 parts of glutathione are dissolved by utilizing ultrasonic crushing, carrying out ultrasonic treatment for 100min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 1min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 4. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 5
(1) The preparation of the polyurea polyurethane comprises the steps of weighing 100 parts by weight of dicyclohexylmethane-4, 4' -diisocyanate, 120 parts by weight of polyethylene glycol 2000,57 parts by weight of polyethylene glycol 400,2 parts by weight of dibutyl tin dilaurate, adding 500 parts by weight of N, N-dimethylformamide into a three-neck flask for dissolution, heating to 75 ℃, stirring for 2.5 hours, stopping heating, naturally cooling to normal temperature, adding 40 parts by weight of m-phthalhydrazide, stirring for 3 hours at normal temperature, and drying the N, N-dimethylformamide to obtain the polyurea polyurethane 5.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 800 parts by weight of gallium-indium alloy (with the melting point of 16 ℃) into 20ml of alcohol water solution in which 30 parts of glutathione are dissolved by utilizing ultrasonic crushing, carrying out ultrasonic treatment for 80min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 3min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 5. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, as shown in table 5.
Example 6
(1) The preparation of polyurea polyurethane comprises the steps of weighing 100 parts by weight of dicyclohexylmethane-4, 4' -diisocyanate, 120 parts by weight of polyethylene glycol 2000,30 parts by weight of polyethylene glycol 400,2 parts by weight of dibutyl tin dilaurate, adding 200 parts by weight of N, N-dimethylformamide into a three-neck flask for dissolution, heating to 70 ℃, stirring for 3 hours, stopping heating, naturally cooling to normal temperature, adding 50 parts by weight of furan-2, 5-dicarboxylic acid hydrazide, stirring for 3 hours at normal temperature, and drying the N, N-dimethylformamide to obtain polyurea polyurethane 6.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 1000 parts by weight of gallium-indium alloy (with the melting point of 30 ℃) into 20ml of alcohol water solution in which 30 parts of glutathione are dissolved by utilizing ultrasonic crushing, carrying out ultrasonic treatment for 120min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 5min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 6. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 7
(1) The preparation of polyurea polyurethane comprises the steps of weighing 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 of dibutyl tin dilaurate, adding 500 parts of N, N-dimethylformamide into a three-neck flask for dissolving, heating to 70 ℃, stirring for 3 hours, stopping heating, naturally cooling to normal temperature, adding 40 parts of m-phthalhydrazide, stirring for 3 hours at normal temperature, and drying N, N-dimethylformamide to obtain the polyurea polyurethane 7.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 1000 parts by weight of gallium-indium alloy (with the melting point of 11 ℃) into 20ml of alcohol water solution in which 15 parts of S-acetyl-L-glutathione are dissolved by ultrasonic grinding, carrying out ultrasonic treatment for 40min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 2min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 7. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 8
(1) The preparation of polyurea polyurethane comprises the steps of weighing 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 of dibutyl tin dilaurate, adding 1000 parts of N, N-dimethylformamide into a three-neck flask for dissolving, heating to 70 ℃, stirring for 3 hours, stopping heating, naturally cooling to normal temperature, adding 10 parts of m-phthalhydrazide, stirring for 2 hours at normal temperature, and drying N, N-dimethylformamide to obtain polyurea polyurethane 8.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 1000 parts by weight of gallium-indium alloy (with the melting point of 11 ℃) into 20ml of alcohol-water solution in which 10 parts of glutathione are dissolved by utilizing ultrasonic crushing, carrying out ultrasonic treatment for 40min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 2min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 8. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Example 9
(1) The preparation of the polyurea polyurethane comprises the steps of weighing 100 parts by weight of isophorone diisocyanate, 360 parts of polyethylene glycol 1000,8 parts of polyethylene glycol 400 and 8 parts of dibutyl tin dilaurate, adding 1000 parts of N, N-dimethylformamide into a three-neck flask for dissolution, heating to 60 ℃, stirring for 3 hours, stopping heating, naturally cooling to normal temperature, adding 40 parts of m-phthalhydrazide, stirring for 3 hours at normal temperature, and drying the N, N-dimethylformamide to obtain the polyurea polyurethane 9.
(2) The preparation of the self-repairing dressing comprises the steps of dispersing 1000 parts by weight of gallium-indium alloy (with the melting point of 11 ℃) into 20ml of alcohol water solution in which 40 parts of S-acetyl-L-glutathione are dissolved by ultrasonic grinding, carrying out ultrasonic treatment for 40min, adding the polyurethane-ethanol (100 parts by weight) solution prepared in the step (1) according to the proportion, carrying out ultrasonic treatment for 5min, pouring the dispersion liquid into a mould, and drying to obtain the self-repairing dressing 9. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Comparative example 1
Polyurethane and dressing were prepared using isophthalamide instead of the intermediate phthalhydrazide of example 1 (1), leaving the other conditions unchanged in example 1. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Comparative example 2
Keeping the other conditions of the embodiment 1 (1) unchanged, directly ultrasonically treating liquid metal in polyurethane ethanol solution for 62min without adding glutathione in the step 2, pouring the dispersion liquid in a mould, and drying to obtain the product. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
Comparative example 3
And (3) replacing the intermediate phthalhydrazide in the embodiment 1 (1) with isophthalamide, directly carrying out ultrasonic treatment on liquid metal in a polyurethane ethanol solution for 62min without adding glutathione in the step (2), pouring the dispersion liquid in a mould, and drying to obtain the product. Test bars were prepared, center cut vertically, re-spliced at 35 ℃ air dryer and tested for mechanical strength recovery of the dressing at different times, and conductivity recovery as in tables 1-2. The wound healing was promoted by applying electrical stimulation to the wound of the mice in addition to the 3.6V button cell, and the wound healing conditions are shown in table 3.
TABLE 1 recovery rate of mechanical strength
TABLE 2 conductivity recovery
30min 1h 2h 3h 4h 5h 6h
Example 1 100% - - - - - -
Example 2 100% - - - - - -
Example 3 100% - - - - - -
Example 4 100% - - - - - -
Example 5 96% 100% - - - - -
Example 6 96% 100% - - - - -
Example 7 90% 100% - - - - -
Example 8 88% 100% - - - - -
Example 9 100% - - - - - -
Comparative example 1 0 0 0 0 0 0 0
Comparative example 2 40% 62% 83% 83% 83% 83% 83%
Comparative example 3 0 0 0 0 0 0 0
TABLE 3 wound healing Rate
Comparative tables 1 and 2 show that the mechanical properties of the dressing of the example recovered well within 4-5 hours at 35 ℃, the conductivity was recovered instantaneously, but the mechanical properties and electrical properties of comparative examples 1 and 3, which did not introduce urea bonds into the structure, were not recovered, and the dispersibility of the internal gallium indium alloy was poor in comparative example 2, due to the non-addition of the multifunctional additive, the mechanical properties self-repairing rate was reduced and the electrical properties were difficult to recover completely.
Compared with the table 3, the dressing of the comparative examples 1 and 3 has poor self-repairing capability, and can not always maintain uniform and stable electric stimulation through self-repairing in the treatment process, so that the wound healing speed is slower than that of the example, and meanwhile, compared with the example 2 without the multifunctional additive, the wound healing speed is slower, and the addition of the additive is proved to be beneficial to achieving better healing effect by promoting dispersion and improving skin immunity.
In fig. 1, the projection electron microscope can see that the multifunctional additive (glutathione) in example 1 is coated on the surface of the liquid metal, and has good interaction with the liquid metal, so that good dispersion of the multifunctional additive (glutathione) can be promoted. The scanning electron microscope photograph of the section of the figure 2 further proves that the liquid metal is uniformly dispersed in the dressing, no obvious agglomeration phenomenon exists, and uniform and stable electric response can be formed. FIG. 3 shows in vitro live dead cell experiments (CalceinAM stained as live cells and PI stained as dead cells), the presence of a large number of CalceinAM stained green cells and the minimal PI stained red cells indicate that large area death does not occur in 48h of fibroblasts proliferated in dressing leachate, and the cell morphology remains good, demonstrating that the dressing of example 1 has good biocompatibility and can be applied in medical fields.
The composite dressing provided by the invention can promote wound healing, has good flexibility, self-repairing property, biocompatibility and plasticity, overcomes the problem that the traditional dressing is difficult to self-repair, has potential to realize wider, more convenient and more effective medical application, and has good development prospect.
It should be understood by those skilled in the art that the foregoing description is only illustrative of the present invention and is not intended to limit the invention, and that any modifications, equivalents, improvements or modifications are intended to be included within the spirit and scope of the present invention.

Claims (10)

1. A medical dressing is characterized by being prepared by blending liquid metal, a multifunctional additive and polyurethane, wherein the polyurethane is urea-group-containing polyurea polyurethane, the liquid metal is one or more than two of gallium-indium alloy with a melting point of 3-30 ℃, and the multifunctional additive is one or more than two of glutathione and derivatives thereof.
2. A medical dressing according to claim 1, wherein the amount of each substance added is 10-55 parts by weight of the multifunctional additive and 800-1500 parts by weight of the liquid metal based on 100 parts by weight of the polyurea polyurethane.
3. The medical dressing according to claim 1, wherein the polyurea polyurethane has self-repairing property, the liquid metal has a structure remodelling function, and the multifunctional additive improves system compatibility and has a function of promoting wound healing.
4. The medical dressing according to claim 1, wherein the polyurea polyurethane is prepared by solution reaction of 100 parts by weight of isocyanate, 50-500 parts by weight of a polyol mixture, 10-50 parts by weight of a chain extender, 1-8 parts by weight of a catalyst and 500-1000 parts by weight of a solvent.
5. The medical dressing according to claim 4, wherein the isocyanate is one or a mixture of two or more of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and diphenylmethane diisocyanate.
6. The medical dressing according to claim 4, wherein the polyol mixture is a mixture of two or more of polyether glycol 200-3000 or polyester glycol 200-2000, the chain extender is one of isophthaloyl dihydrazide, maleic dihydrazide, succinic dihydrazide and furan-2, 5-dicarboxylic hydrazide, the catalyst is an organotin catalyst, and the solvent is one of dimethylformamide and dimethylacetamide.
7. The medical dressing according to claim 4, wherein the polyurea polyurethane is prepared by dissolving the mixture of the polyatomic alcohol, the catalyst and the isocyanate in the solvent according to a certain proportion, heating to 60-80 ℃, stirring and reacting for 2-3 hours, cooling to normal temperature, adding the chain extender, stirring and reacting for 2-4 hours at normal temperature, removing the solvent, and drying and preserving or dissolving in ethanol solution for standby.
8. A method of preparing a medical dressing according to any one of claims 1 to 7, comprising the steps of:
Dispersing liquid metal in an alcohol-water solution of the dissolved multifunctional additive by utilizing ultrasonic waves for 10-120min, adding an alcohol solution of polyurea polyurethane according to a proportion, carrying out ultrasonic waves for 1-5min, pouring or knife coating the dispersion liquid, and drying to obtain the dressing.
9. The application of the medical dressing obtained by the preparation method of any one of claims 1-7 or 8 is characterized in that the medical dressing has excellent biocompatibility, has the functions of self-repairing and promoting wound healing, and can be widely applied to the field of preparing medical materials.
10. The use of a medical dressing according to claim 9, wherein the dressing has a positive effect on wound repair with the aid of electrical stimulation, and can be used for the preparation of wound dressings or medical materials for promoting tissue regeneration.
CN202310661260.2A 2023-06-06 2023-06-06 Medical dressing, preparation method and application Active CN116688209B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310661260.2A CN116688209B (en) 2023-06-06 2023-06-06 Medical dressing, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310661260.2A CN116688209B (en) 2023-06-06 2023-06-06 Medical dressing, preparation method and application

Publications (2)

Publication Number Publication Date
CN116688209A CN116688209A (en) 2023-09-05
CN116688209B true CN116688209B (en) 2025-06-24

Family

ID=87842725

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310661260.2A Active CN116688209B (en) 2023-06-06 2023-06-06 Medical dressing, preparation method and application

Country Status (1)

Country Link
CN (1) CN116688209B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119955061A (en) * 2025-04-10 2025-05-09 中国科学技术大学 Preparation method and application of bio-based high-strength and high-toughness polyurethane

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8057530B2 (en) * 2006-06-30 2011-11-15 Tyco Healthcare Group Lp Medical devices with amorphous metals, and methods therefor
CN102695528B (en) * 2009-08-21 2016-07-13 诺万公司 Wound dressing, its using method and forming method thereof
ES2468740B1 (en) * 2012-11-13 2015-04-01 Consejo Superior De Investigaciones Científicas (Csic) COMMITMENT FOR CICATRIZATION OF COMMITTED WOUNDS
CN109453423B (en) * 2018-11-20 2021-06-25 中国科学院理化技术研究所 A kind of antibacterial spray based on nanomaterials and preparation method and application thereof
CN112076352B (en) * 2020-08-25 2022-03-29 云南迈特力医疗技术有限公司 Medical liquid metal thermoplastic functional composite material and preparation method and application thereof
CA3203967A1 (en) * 2021-01-04 2022-07-07 Lars Stigsson A versatile method to valorize cellulosic waste textiles
CN112957522B (en) * 2021-02-22 2022-10-25 重庆大学 A kind of porous liquid metal bone tissue engineering scaffold with adjustable stiffness and preparation method thereof
CN113136017B (en) * 2021-04-02 2022-08-09 中国科学院合肥物质科学研究院 Polyurethane with pH response and self-healing performance and preparation method thereof
CN116036348A (en) * 2022-12-22 2023-05-02 合肥启灏医疗科技有限公司 Composite sponge and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Rapid and Scar Free Wound Repair by Using a Biologically Flexible and Conductive Dressing Under Electrical Stimulation;Shuo-Bing Yang et al;advanced science news;20240603;1-12 *

Also Published As

Publication number Publication date
CN116688209A (en) 2023-09-05

Similar Documents

Publication Publication Date Title
CN116688209B (en) Medical dressing, preparation method and application
CN107440934B (en) Composition for resisting skin aging, soluble microneedle patch and preparation method thereof
CN102886063B (en) Preparation and application of cellulose nanocrystals (CNCs)-reinforced collagen compound substrate
CN114058014B (en) Lipoic acid-based hydrogel and preparation method and application thereof
CN111825859A (en) A kind of bionic electronic skin medical stent material with self-healing function and preparation method thereof
CN108452375B (en) 3D printed graphene oxide conductive hydrogel and preparation method and application thereof
CN105885436A (en) Biological ink material for 3D printing and preparation method and application thereof
CN113174074A (en) Conductive silk fibroin film and preparation method and application thereof
CN115260545B (en) A kind of small particle size agarose gel, preparation method and application thereof
CN114713150A (en) Novel crosslinking method and application of sodium alginate hydrogel containing graphene oxide
CN109158058B (en) Attapulgite-chitosan composite gel and preparation method thereof
Chen et al. Tissue-like electrophysiological electrode interface construction by multiple crosslinked polysaccharide-based hydrogel
CN111671973A (en) A kind of preparation method of polypyrrole/silk fibroin composite conductive tissue engineering scaffold
CN115227866A (en) Injectable hydrogel wound dressing with functions of tissue adhesion, multiple sterilization and electrical stimulation of tissue regeneration and preparation method thereof
CN118718058A (en) A medical skin repair dressing and its preparation method and use
CN115671388A (en) Performance-adjustable silk protein injectable microsphere gel and preparation method thereof
CN114533763A (en) Novel method for culturing calculus bovis electric calculi in vitro
CN109627460A (en) A kind of preparation method of the degradable conductive hydrogel as tissue repair
CN118028402A (en) G-type brown alginate oligosaccharide and preparation method and application thereof
US20230365760A1 (en) Method for preparing multifunctional hydrogel by yeast fermentation
CN116942562A (en) Skin repair water for high-heat skin barrier damage and preparation method thereof
CN116650714A (en) Tissue engineering scaffold for pressure-controlled drug release and preparation method
CN116162151A (en) Collagen peptide with anti-wrinkle function
CN117085173A (en) Scar-free wound healing promoting material, preparation method and application
CN109880152B (en) Preparation method of orientation-connected porous biomedical scaffold, prepared scaffold and use of the scaffold in preparing medical products

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
点击 这是indexloc提供的php浏览器服务,不要输入任何密码和下载