CN116478425A - Double-layer conductive adhesive hydrogel for electrocardiograph patch sensing and electrocardiograph patch - Google Patents
Double-layer conductive adhesive hydrogel for electrocardiograph patch sensing and electrocardiograph patch Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims abstract description 27
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000000499 gel Substances 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 235000011187 glycerol Nutrition 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 24
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- 239000008273 gelatin Substances 0.000 claims description 16
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000010382 chemical cross-linking Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- YXMISKNUHHOXFT-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) prop-2-enoate Chemical group C=CC(=O)ON1C(=O)CCC1=O YXMISKNUHHOXFT-UHFFFAOYSA-N 0.000 claims description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 5
- KLGDRWGOXDJNPH-UHFFFAOYSA-N P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical group P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C KLGDRWGOXDJNPH-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
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- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
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- 239000004332 silver Substances 0.000 claims description 2
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- 238000012544 monitoring process Methods 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000010062 adhesion mechanism Effects 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 229960002317 succinimide Drugs 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/251—Means for maintaining electrode contact with the body
- A61B5/257—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes
- A61B5/259—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes using conductive adhesive means, e.g. gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
- A61B5/28—Bioelectric electrodes therefor specially adapted for particular uses for electrocardiography [ECG]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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Abstract
The invention relates to the technical field of conductive hydrogel materials, in particular to a double-layer conductive adhesive hydrogel for electrocardiograph patch sensing and an electrocardiograph patch. The double-layer conductive adhesive hydrogel comprises a first layer of hydrogel and a second layer of hydrogel, wherein the raw materials of the first layer of hydrogel comprise a gel forming monomer, a first adhesive monomer, a cross-linking agent, conductive molecules and a photoinitiator; the raw materials of the second layer of hydrogel comprise a gel forming monomer, a second adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator; the electrocardio paste comprises double layers of conductive adhesive hydrogel and a metal electrode, wherein the metal electrode is adhered on the second layer of hydrogel. According to the invention, different adhesion monomers are added into the components of the two layers of hydrogel, so that the two layers of hydrogel can be firmly adhered to the skin and the electrode respectively; conductive polymers are added, so that the real-time transmission of electrocardiosignals is facilitated; and glycerin is added into the solvent, so that the moisture retention and freezing resistance of the hydrogel are improved, the electric signal transmission in a severe environment is realized, and meanwhile, the hydrogel can be stored for a long time.
Description
Technical Field
The invention relates to the technical field of conductive hydrogel materials, in particular to a double-layer conductive adhesive hydrogel for electrocardiograph patch sensing and an electrocardiograph patch.
Background
In clinic, heart health monitoring by Electrocardiogram (ECG) is an important health monitoring and disease diagnosis mode, and can be used for monitoring heart rate variability (HR), which is an important index of heart disease; meanwhile, the information obtained from the shape change of the electrocardiogram waveform can be used for assisting in diagnosing myocardial ischemia, injury, malignant arrhythmia and other diseases. The traditional detecting instrument is inconvenient to use and carry in daily life due to large volume of equipment and electrodes, and the intelligent dynamic electrocardiograph is a wearable electrocardiograph detecting instrument, can continuously record the heart running condition of a user, realizes dynamic detection within 24 hours, solves the problem that a conventional electrocardiograph cannot monitor for a long time, can be used as a medical screening means matched with the conventional electrocardiograph, and improves the cardiovascular-like disease detection rate.
In the intelligent dynamic electrocardiograph, the electrocardiograph electrode which is in contact with the human body and receives signals needs to meet the conditions of lightness, thinness, softness, skin friendliness and the like, and meanwhile needs to be firmly fixed at the corresponding position of the human body, so that the flexible wearable sensor is an ideal choice for manufacturing the electrocardiograph electrode.
Among them, the conductive hydrogel has the advantages of high water content, low modulus, and the like, and has good biocompatibility, flexibility, and high stretchability, so the conductive hydrogel is widely focused as an excellent soft conductor material of the flexible wearable sensor. However, conventional conductive hydrogels have poor adhesion, particularly because of the high water content and hydrophilic network of the conductive hydrogels, and the adhesion to wet surfaces is particularly low, and they are prone to falling off when perspiration occurs on the skin of the user during use. Therefore, in the prior art, the electrocardiographic patch electrode covered with the conductive hydrogel is adhered to the skin of a user by using an adhesive or an adhesive tape for monitoring. Although the fixing effect is good by using the adhesive or the adhesive tape, the conductive hydrogel cannot form close contact with the skin, and the monitoring capability on weak signals is poor; in long-term use, the adhesive or the adhesive tape can continuously stimulate the skin of a user, and cause the problems of discomfort, skin allergy and the like; the adhesive or the adhesive tape is easy to show excessive adhesion after being used, and is not easy to be removed from the skin; meanwhile, the conductive hydrogel is affected by environmental conditions such as temperature and humidity, water loss caused by high temperature or drying and condensation caused by low temperature occur, and the signal transmission quality is seriously affected, so that monitoring data cannot be fed back correctly in time.
Disclosure of Invention
Aiming at the technical problems that the existing conductive hydrogel for electrocardiograph patch sensing has insufficient adhesion and poor resistance to severe environment, and weak signal detection capability and skin irritation are poor due to the fact that an adhesive and an adhesive tape are used for fixation, the invention provides a double-layer conductive adhesion hydrogel for electrocardiograph patch sensing and an electrocardiograph patch, wherein different adhesion monomers are added into components of the two layers of hydrogels, so that the two layers of hydrogels are firmly adhered to skin and an electrode respectively; conductive molecules are added, so that the real-time transmission of electrocardiosignals is facilitated; and glycerin is added into the solvent, so that the moisture retention and freezing resistance of the hydrogel are improved, the electric signal transmission in a severe environment is realized, and meanwhile, the hydrogel can be stored for a long time.
In a first aspect, the invention provides a double-layer conductive adhesion hydrogel for electrocardiographic patch sensing, which comprises a first layer of hydrogel and a second layer of hydrogel, wherein the raw materials of the first layer of hydrogel comprise a gel forming monomer, a first adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator, and the first adhesion monomer is N-succinimidyl acrylate; the raw materials of the second layer of hydrogel comprise a gel forming monomer, a second adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator, wherein the second adhesion monomer is 3-methacrylic dopamine.
Further, the preparation method comprises the following steps:
(1) Preparing a first precursor liquid: adding a gel forming monomer, a first adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator into a solvent to obtain a uniformly dispersed first precursor solution;
(2) Preparing a second precursor liquid: adding a gel forming monomer, a second adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator into a solvent to obtain a uniformly dispersed second precursor solution;
(3) Preparation of a first layer of hydrogel: pouring the first precursor liquid into a mould, and preparing a first layer of hydrogel by photoinitiating chemical crosslinking;
(4) Preparing a second layer of hydrogel: after the first layer of hydrogel is formed, pouring the second precursor liquid into a mould to cover the first layer of hydrogel, and then preparing the second layer of hydrogel covered on the first layer of hydrogel by using a photoinitiated chemical crosslinking mode to obtain the double-layer conductive adhesion hydrogel.
Further, the gel forming monomer is acrylic acid, the cross-linking agent is methacrylic acid acylated gelatin, the conductive molecule is poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, the photoinitiator is phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate, and the solvent is a mixed solvent of deionized water and glycerin which are mutually soluble in any proportion.
Further, the preparation method of the methacryloylated gelatin comprises the following steps:
dripping glycidyl methacrylate into gelatin water solution, stirring at 50-80deg.C, adding deionized water to terminate reaction, dialyzing with dialysis bag with molecular weight of 12000-14000, and lyophilizing to obtain light yellow or white sponge-like methacryloylated gelatin.
5. Further, the first precursor liquid comprises 10-30% of gel forming monomer, 0.5-2% of first adhesion monomer, 0.5-1% of cross-linking agent, 0.1-0.2% of conductive molecule, 0.05-0.5% of photoinitiator and the balance of solvent by mass percent; the second precursor liquid comprises 10% -30% of a gel forming monomer, 0.05% -0.5% of a second adhesion monomer, 0.5% -1% of a cross-linking agent, 0.1% -0.2% of a conductive molecule, 0.05% -0.5% of a photoinitiator and the balance of a solvent.
Further, the double-layer conductive adhesion hydrogel prepared in the step (4) is of a double-layer structure, and the thickness of each layer of gel is 100m-5mm; the double-layer conductive adhesive hydrogel has the geometric shapes of a circle, a rectangle, a square, a triangle and the like.
Further, the light source used in the photoinitiation chemical crosslinking process in the steps (3) - (4) is selected from ultraviolet light, purple light and blue light, and the reaction time is 0.5min-1h.
Further, in the step (4), the second precursor solution is poured into the top of the first layer of hydrogel and then is kept stand for 5-30 min, and then the photoinitiated chemical crosslinking process is carried out.
Further, the thickness of the first layer hydrogel and the second layer hydrogel is 100 μm-5mm.
In a second aspect, the present invention provides an electrocardiograph patch comprising a bilayer conductive adhesive hydrogel and a metal electrode, the metal electrode being adhered to a second layer of hydrogel.
Further, after the double-layer conductive adhesion hydrogel is placed on the skin surface of a human body and the surface of the metal electrode, firm adhesion is realized by pressing for a certain time, and the pressing time is 5s-5min.
Further, the metal electrode is one or more of gold, silver, copper, platinum, titanium, palladium and iridium.
The invention has the beneficial effects that:
(1) According to the invention, different adhesion monomers are added into the components of the two layers of hydrogel, so that the two layers of hydrogel can be firmly adhered to the skin and the metal electrode respectively, wherein the carboxyl of acrylic acid in the first layer of hydrogel and the amino on the surface of the skin form a hydrogen bond effect, and the N-succinimide acrylate reacts with the amino on the surface of the skin to form a covalent bond, so that the first layer of hydrogel has better adhesion on the surface of the skin, and meanwhile, the gel falling caused by sweat wetting the skin is prevented; the 3-methacrylic dopamine in the second layer of hydrogel can form coordination action with metal, so that the adhesion of the second layer of hydrogel to the metal electrode is enhanced.
(2) The invention uses the methacryloylated gelatin as the biopolymer cross-linking agent, the prepared gel has better tensile property and biocompatibility, high adhesion with skin tissues, no irritation, no adhesive adhesion after tearing, and no skin pain.
(3) According to the invention, conductive molecules are added into raw material components, so that bioelectric signals generated by a heart can be rapidly and accurately transmitted to an electrode plate, and real-time acquisition of the bioelectric signals can be realized through an external signal acquisition and data module; meanwhile, the gel can be directly contacted with skin tissues to realize weak signal sensing, and the sensitivity is high.
(4) According to the invention, the glycerol is added into the solvent, so that the moisture retention and freezing resistance of the hydrogel can be improved, the hydrogel is not easy to lose water or freeze, the transmission of electric signals in a severe environment can be realized, and the hydrogel can be stored for a long time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of steps (3) - (4) in example 1.
Fig. 2 is a schematic application diagram of example 2.
FIG. 3 is a schematic view of the adhesion mechanism of example 2.
In the figure, 1-skin, 2-bilayer conductive adhesive hydrogel, 2.1-first layer hydrogel, 2.2-second layer hydrogel, 3-metal electrode.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The methacryloylated gelatin used in the following examples was prepared as follows:
10g of gelatin (Type A, sigma,300 g/Bloom) was dissolved in 100mL of deionized water with stirring at 60℃for 30min to obtain a uniform aqueous gelatin solution, 10mL of glycidyl methacrylate was added dropwise to the aqueous gelatin solution at a rate of 0.5mL/min, the reaction was terminated by adding 5 times of deionized water after vigorously stirring at 60℃for 12 hours, and the mixture was dialyzed for 7 days using a dialysis bag having a molecular weight of 12000-14000, and light yellow or white sponge-like methacryloylated gelatin (GelMA) was obtained by freeze-drying for 5 days and stored at-20 ℃.
Example 1
The double-layer conductive adhesion hydrogel for electrocardiograph patch sensing comprises a first layer of hydrogel and a second layer of hydrogel, wherein the raw materials of the first layer of hydrogel comprise a gel forming monomer, a first adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator, and the first adhesion monomer is N-succinimidyl acrylate; the raw materials of the second layer of hydrogel comprise a gel forming monomer, a second adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator, wherein the second adhesion monomer is 3-methacrylic dopamine.
The preparation method comprises the following steps:
(1) Preparing a first precursor liquid: 300mg of acrylic acid is taken, 10mg of methacryloylated gelatin, 10mg of N-succinimidyl acrylate, 200 mg of glycerol and 500mg of deionized water are added, the mixture is stirred by a magnetic stirrer to be completely dissolved, 10 mu L of ethanol-assisted 1mg of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid and 0.1mg of phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate are added, and the mixture is subjected to light-proof ultrasonic treatment for 30min to be uniformly dispersed, so that a first precursor liquid is obtained.
(2) Preparing a second precursor liquid: taking 300mg of acrylic acid, adjusting the pH to 7 by using 10mol/L sodium hydroxide solution, adding 10mg of methacryloylated gelatin, 1mg of 3-methacryloyl dopamine, adding 200 glycerol and 500mg of deionized water, stirring by using a magnetic stirrer to completely dissolve the solution, adding 10 mu L of ethanol-assisted 1mg of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, 0.1mg of phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate, and carrying out light-shielding ultrasonic treatment for 30min to uniformly disperse the solution, thereby obtaining a second precursor solution.
(3) Preparation of a first layer of hydrogel: pouring the first precursor solution into a mold, and using a wavelength of 365nm and an illumination intensity of 4.5mW/cm at room temperature (25deg.C) 2 The ultraviolet lamp of (2) is irradiated and reacts for 10min to prepare a first layer of hydrogel;
(4) Preparing a second layer of hydrogel: after the first layer of hydrogel is formed, pouring the second precursor solution into a mold, covering the first layer of hydrogel, standing for 10min, and using 365nm wavelength and 4.5mW/cm illumination intensity at room temperature (25deg.C) 2 The ultraviolet lamp of (2) is irradiated and reacted for 10min to prepare a second layer of hydrogel tightly combined with the first layer of hydrogel, and the two layers of hydrogel are removed from the die to obtain the double-layer conductive adhesion hydrogel.
Example 2
As shown in fig. 2, the first layer of hydrogel 2.1 in the double-layer conductive adhesive hydrogel 2 prepared in example 1 is used for adhering to the skin 1, and the second layer of hydrogel 2.2 is used for adhering to the metal electrode 3, and the adhesion method is as follows: after the double-layer conductive adhesion hydrogel 2 is placed at a designated position of skin (such as the position of the left edge of the sternum, the position of the first rib is parallel to the sternum), the metal electrode 3 is attached to the surface of the double-layer conductive adhesion hydrogel 2, and the double-layer conductive adhesion hydrogel is pressed for 1min to realize firm adhesion.
Fig. 3 is a schematic diagram of the adhesion mechanism of the double-layer conductive adhesion hydrogel 2, wherein the part a is before adhesion and the part b is after adhesion. As shown in fig. 3, the adhesion mechanism of the double-layer conductive adhesion hydrogel 2 is:
(1) The first layer of hydrogel 2.1 forms hydrogen bonds through carboxyl of acrylic acid and amino on the skin surface respectively, and N-succinimidyl acrylate and amino on the skin surface react with each other to form covalent bonds to realize adhesion with the skin surface.
(2) The 3-methyl acrylamide in the second layer of hydrogel 2.2 can form coordination with metal to adhere to the metal electrode.
The conduction mechanism of the double-layer conductive adhesion hydrogel 2 is as follows: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid in the double-layer conductive adhesive hydrogel 2 can transmit bioelectric signals generated by the heart to the electrode plate, and the real-time acquisition of the electrocardiosignals can be realized through an external signal acquisition and data module.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (10)
1. The double-layer conductive adhesion hydrogel for electrocardiographic patch sensing is characterized by comprising a first layer of hydrogel and a second layer of hydrogel, wherein the raw materials of the first layer of hydrogel comprise a gel forming monomer, a first adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator, and the first adhesion monomer is N-succinimidyl acrylate; the raw materials of the second layer of hydrogel comprise a gel forming monomer, a second adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator, wherein the second adhesion monomer is 3-methacrylic dopamine.
2. The double-layer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 1, wherein the preparation method comprises the following steps:
(1) Preparing a first precursor liquid: adding a gel forming monomer, a first adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator into a solvent to obtain a uniformly dispersed first precursor solution;
(2) Preparing a second precursor liquid: adding a gel forming monomer, a second adhesion monomer, a cross-linking agent, conductive molecules and a photoinitiator into a solvent to obtain a uniformly dispersed second precursor solution;
(3) Preparation of a first layer of hydrogel: pouring the first precursor liquid into a mould, and preparing a first layer of hydrogel by photoinitiating chemical crosslinking;
(4) Preparing a second layer of hydrogel: after the first layer of hydrogel is formed, pouring the second precursor liquid into a mould to cover the first layer of hydrogel, and then preparing the second layer of hydrogel covered on the first layer of hydrogel by using a photoinitiated chemical crosslinking mode to obtain the double-layer conductive adhesion hydrogel.
3. The double-layer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 2, wherein the gel-forming monomer is acrylic acid, the crosslinking agent is methacrylic acid gelatin, the conductive molecule is poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, the photoinitiator is phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate, and the solvent is a mixed solvent of deionized water and glycerin which are mutually soluble in any proportion.
4. The double-layer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 1, wherein the preparation method of the methacryloylated gelatin comprises the following steps:
dripping glycidyl methacrylate into gelatin water solution, stirring at 50-80deg.C, adding deionized water to terminate reaction, dialyzing with dialysis bag with molecular weight of 12000-14000, and lyophilizing to obtain light yellow or white sponge-like methacryloylated gelatin.
5. The double-layer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 2, wherein the first precursor liquid comprises, by mass, 10% -30% of a gel forming monomer, 0.5% -2% of a first adhesive monomer, 0.5% -1% of a cross-linking agent, 0.1% -0.2% of a conductive molecule, 0.05% -0.5% of a photoinitiator, and the balance of a solvent; the second precursor liquid comprises 10% -30% of a gel forming monomer, 0.05% -0.5% of a second adhesion monomer, 0.5% -1% of a cross-linking agent, 0.1% -0.2% of a conductive molecule, 0.05% -0.5% of a photoinitiator and the balance of a solvent.
6. The double-layer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 2, wherein the light source used in the photoinitiation chemical crosslinking process in the steps (3) - (4) is selected from ultraviolet light, purple light and blue light, and the reaction time is 0.5min-1h.
7. The double-layer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 2, wherein the second precursor solution is poured into the top of the first layer of hydrogel in the step (4) and then is left for 5-30 min, and then a photoinitiated chemical crosslinking process is performed.
8. A bilayer conductive adhesive hydrogel for electrocardiographic patch sensing according to claim 1 wherein the first layer of hydrogel and the second layer of hydrogel have a thickness of 100 μm to 5mm.
9. An electrocardiograph patch is characterized by comprising double layers of conductive adhesive hydrogel and a metal electrode, wherein the metal electrode is adhered on a second layer of hydrogel.
10. The electrocardiographic patch of claim 9 wherein the metal electrode is one or more of gold, silver, copper, platinum, titanium, palladium, iridium.
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