CN111110222A - Biological protein flexible skin patch type electrode and preparation method thereof - Google Patents
Biological protein flexible skin patch type electrode and preparation method thereof Download PDFInfo
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- CN111110222A CN111110222A CN201911366751.4A CN201911366751A CN111110222A CN 111110222 A CN111110222 A CN 111110222A CN 201911366751 A CN201911366751 A CN 201911366751A CN 111110222 A CN111110222 A CN 111110222A
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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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
- A61B2562/12—Manufacturing methods specially adapted for producing sensors for in-vivo measurements
- A61B2562/125—Manufacturing methods specially adapted for producing sensors for in-vivo measurements characterised by the manufacture of electrodes
Abstract
The invention relates to a biological protein flexible skin patch type electrode and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing a plasticized biological protein solution; s2, coating a plasticized biological protein solution on the surface of the preset template, and preparing a first plasticized biological protein film through curing and drying; s3, preparing a mask plate, and attaching the mask plate to the first plasticized biological protein film; s4, coating conductor slurry on the surface of the mask plate attached with the first plasticized biological protein film, and preparing a second plasticized biological protein film through curing and drying, wherein the second plasticized biological protein film has an electrode structure; s5, separating the second plasticized biological protein film, and preparing the biological protein flexible skin-attached type electrode through cutting and packaging; the electrode is made of human body biocompatible materials, does not cause immune reaction, can be firmly attached to the surface of a human body to collect electrophysiological and chemical signals on the surface of the human body, and further monitors the real-time change condition of the physiological state of the human body.
Description
Technical Field
The invention relates to the technical field of implantable medical generators, in particular to a bioprotein flexible skin patch type electrode and a preparation method thereof.
Background
At present, the electrode slice that appears in the market is mostly skin adhesion formula electrode slice, and its main effect is used for flesh electricity and electrocardio to gather, and skin adhesion formula electrode slice's major structure and principle are: the metal solid electrode (about 5 mm-1 cm thick) is directly pasted on the skin through conductive ion gel, and the periphery of the electrode is fixed with the surrounding skin through sticky gauze similar to plaster; the skin electrophysiological signals form a local micro-electric field between the skin surface layer and the electrodes, so that they can be collected and measured by external electronic devices.
However, the existing skin-adhesive electrode sheet has certain disadvantages or shortcomings: the diameter of one electrode patch is about 5-10cm, the electrode patch can only be used as one electrode, 2 to 3 electrodes are needed for measuring skin physiological electric signals to form a loop, namely 2 to 3 patches are needed, and the whole coverage area is overlarge; because the metal solid electrode is too thick, a single electrode needs to be fixed by adhesive gauze after being pasted on the skin, the motion range and the use comfort of a human body are seriously limited, and the electrode is very easy to cause pain and even injury when being taken off, so that the electrode cannot be applied to wounds or sensitive skin tissues, overweight hair areas and sweat-prone skin surfaces. The electrode is made of materials with limited biocompatibility and is not a green environment-friendly biodegradable material, so potential environmental pollution can be caused after the electrode is used once.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a bioprotein flexible skin patch electrode and a method for manufacturing the same, wherein the electrode is made of a biocompatible material for human body, does not cause immune reaction after contacting human skin, has the same mechanical properties as skin, can be firmly attached to the surface of human body to collect electrophysiological and chemical signals on the surface of human body, and further monitors the real-time change of the physiological state of human body.
In order to solve the problems, the invention provides a preparation method of a bioprotein flexible skin patch type electrode, which comprises the following steps:
s1, preparing a plasticized biological protein solution;
s2, coating the plasticized biological protein solution on the surface of a preset template, and preparing a first plasticized biological protein film through curing and drying;
s3, preparing a mask plate, and attaching the mask plate to the first plasticized biological protein film;
s4, coating conductor slurry on the surface of the mask plate which is attached with the first plasticized biological protein film, and preparing a second plasticized biological protein film through curing and drying, wherein the second plasticized biological protein film has an electrode structure;
and S5, separating the second plasticized biological protein film, and preparing the biological protein flexible skin-attached electrode through cutting and packaging.
Further, in the step S1, the plasticized biological protein solution is prepared by preparing fibroin, spider silk protein, arthritic elastin, glycerol, calcium chloride and deionized water according to a preset ratio, wherein the glycerol accounts for 5% -25% of the mass of the plasticized biological protein solution, the calcium chloride accounts for 0.5% -3% of the mass of the protein solution, the deionized water is used for adjusting the concentration, and the volume of the deionized water accounts for 0% -50% of the volume of the protein solution.
Further, in the step S1, the plasticized bioprotein solution needs to be surface-bubble-removed and stored at a first preset temperature, which is 4 ℃.
Further, in the step S2, the preset template is one of a polydimethylsiloxane template, a glass template, a teflon template, a polyethylene template, and a silica gel template.
Further, in the step S2, the first plasticized bio-protein film is prepared by performing curing and drying in a constant temperature and humidity chamber, wherein the ambient temperature is 25 ℃, the ambient humidity is 30% and the drying and curing time is 12 hours in the curing and drying process.
Further, in the step S3, the mask is prepared according to a preset electrode pattern.
Further, in the step S4, the mask is divided into a mask prepared based on a metal and a mask prepared based on a silicon wafer, wherein the mask prepared based on a metal includes: the mask plate prepared based on the silicon wafer comprises one of a silicon plate, a silicon oxide plate, a glass plate and a silicon nitride plate.
Further, in the step S4, the curing and drying are divided into fast curing and slow curing;
the rapid curing needs to be carried out on a heating plate, and the heating temperature is 80 ℃ in the curing and drying process, and the drying and curing time is 5 minutes;
the slow curing needs to be carried out in a constant temperature and humidity box, the ambient temperature is 25 ℃, the ambient humidity is 30% and the drying and curing time is 12 hours in the curing and drying process.
Further, in the S4 step, the conductor slurry includes one of graphene, carbon nanotubes, or silver nanowires.
The invention also provides a bioprotein flexible skin patch electrode which is prepared by adopting the preparation method of the bioprotein flexible skin patch electrode, and the bioprotein flexible skin patch electrode has the length of not more than 4 cm, the width of not more than 3 cm and the thickness of not more than 50 microns.
The invention provides a biological protein flexible skin patch type electrode and a preparation method thereof, and the biological protein flexible skin patch type electrode has the following beneficial effects:
1) the electrode of the invention is made of human body biocompatible materials, and does not cause immune reaction after contacting human skin.
2) The electrode has the advantages that the whole thickness is less than 50 micrometers, the thickness is consistent with the mechanical property of skin, the electrode has viscosity, and the electrode can be firmly attached to the surface of a human body to collect electrophysiological signals and chemical signals on the surface of the human body and monitor the real-time change condition of the physiological state of the human body.
3) After the electrode is used, the electrode can be washed by a large amount of water, and can fall off automatically after being dried, so that the skin cannot be damaged, and the electrode can be environmentally-friendly and degradable and is free from waste pollution.
4) The electrode can be stored for a long time under the condition of room temperature sealing, generally more than 6 months, and has high temperature resistance generally more than 140 ℃ and resistance to the interference of bending deformation.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiment or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a flow chart of a method for preparing a bioprotein flexible skin-patch electrode provided by an embodiment of the invention;
FIG. 2 is a schematic structural diagram of a bioprotein flexible skin-patch type electrode provided by an embodiment of the invention;
FIG. 3 is a graph showing the results of experiment one provided by the present invention;
FIG. 4 is a graph showing the results of experiment two provided by the present invention;
FIG. 5 is a graphical representation of the results of experiment three provided by the present example;
in the figure: 1-plasticized protein substrate, 2-conductive member, 21-first conductive member, 22-second conductive member, 23-third conductive member.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", and the like, indicate orientations or positional relationships based on those shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Moreover, the terms "first," "second," and the like are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein.
Example one
The embodiment provides a preparation method of a bioprotein flexible skin patch electrode, as shown in fig. 1, which includes the following steps:
s1, preparing a plasticized biological protein solution;
s2, coating the plasticized biological protein solution on the surface of a preset template, and preparing a first plasticized biological protein film through curing and drying;
s3, preparing a mask plate, and attaching the mask plate to the first plasticized biological protein film;
s4, coating conductor slurry on the surface of the mask plate which is attached with the first plasticized biological protein film, and preparing a second plasticized biological protein film through curing and drying, wherein the second plasticized biological protein film has an electrode structure;
and S5, separating the second plasticized biological protein film, and preparing the biological protein flexible skin-attached electrode through cutting and packaging.
Further, in the step S1, the plasticized biological protein solution is prepared by preparing fibroin, spider silk protein, arthritic elastin, glycerol, calcium chloride and deionized water according to a preset ratio, wherein the glycerol accounts for 5% -25% of the mass of the plasticized biological protein solution, the calcium chloride accounts for 0.5% -3% of the mass of the protein solution, the deionized water is used for adjusting the concentration, and the volume of the deionized water accounts for 0% -50% of the volume of the protein solution.
Further, in the step S1, the plasticized bioprotein solution needs to be surface-bubble-removed and stored at a first preset temperature, which is 4 ℃.
Further, in the step S2, the preset template is one of a polydimethylsiloxane template, a glass template, a teflon template, a polyethylene template, and a silica gel template.
Further, in the step S2, the first plasticized bio-protein film is prepared by performing curing and drying in a constant temperature and humidity chamber, wherein the ambient temperature is 25 ℃, the ambient humidity is 30% and the drying and curing time is 12 hours in the curing and drying process.
Further, in the step S3, the mask is prepared according to a preset electrode pattern.
Further, in the step S4, the mask is divided into a mask prepared based on a metal and a mask prepared based on a silicon wafer, wherein the mask prepared based on a metal includes: the mask plate prepared based on the silicon wafer comprises one of a silicon plate, a silicon oxide plate, a glass plate and a silicon nitride plate.
Further, in the step S4, the curing and drying are divided into fast curing and slow curing;
the rapid curing needs to be carried out on a heating plate, and the heating temperature is 80 ℃ in the curing and drying process, and the drying and curing time is 5 minutes;
the slow curing needs to be carried out in a constant temperature and humidity box, the ambient temperature is 25 ℃, the ambient humidity is 30% and the drying and curing time is 12 hours in the curing and drying process.
Further, in the S4 step, the conductor slurry includes one of graphene, carbon nanotubes, or silver nanowires.
Further, the step S5 further includes:
taking down the prefabricated film plate and the mask plate to separate the second plasticized biological protein film;
and cutting and hermetically storing the separated second plasticized biological protein film, wherein the hermetically storing condition is that the second plasticized biological protein film is stored in a constant temperature and humidity box, and the environmental temperature is 25 ℃ and the environmental humidity is 30% in the storing process.
The embodiment also provides a bioprotein flexible skin conformable electrode which is prepared by adopting the preparation method of the bioprotein flexible skin conformable electrode, the bioprotein flexible skin conformable electrode comprises a plasticized protein substrate 1 and a conductive piece 2 arranged on the plasticized protein substrate 1, the bioprotein flexible skin conformable electrode has the advantages of length not more than 4 cm, width not more than 3 cm and thickness not more than 50 microns, can be consistent with the mechanical property of skin, has viscosity, can be firmly attached to the surface of a human body to collect electrophysiological signals and chemical signals on the surface of the human body, and can monitor the real-time change condition of the physiological state of the human body.
Further, the pattern of the conductive member 2 may be changed according to the design electrode pattern.
As shown in fig. 2, the conductive member 2 is made of three different electrode materials, the conductive member 2 includes a first conductive member 21, a second conductive member 22 and a third conductive member 23, the first conductive member 21, the second conductive member 22 and the third conductive member 23 respectively correspond to one electrode material, the electrode materials among the first conductive member 21, the second conductive member 22 and the third conductive member 23 are different from each other, the three electrode materials may be made of different human body bio-compatible materials, the human body bio-compatible material includes one of graphene, carbon nanotube or silver nanowire, and immune reaction is not caused after contacting human skin.
Further, plastify biological protein base 1 is prepared by plastify biological protein solution and forms, plastify biological protein solution is through preparing fibroin, spider silk protein, joint branch elastin, glycerine, calcium chloride and deionized water according to preset proportion and forms, wherein, glycerine occupies 5% ~ 25% of plastify biological protein solution quality, the calcium chloride occupies 0.5% ~ 3% of protein solution quality, deionized water is used for adjusting the concentration, the deionized water volume accounts for protein solution volume 0% ~ 50%.
Specifically, the first experiment is carried out on the bioprotein flexible skin patch type electrode, skin electrodes made of different materials are adhered to a pigskin upper die to simulate the human body surface environment, and a tensile force and displacement curve required for removing the electrodes is measured through a mechanical tester; as shown in fig. 3, the experimental results show that the bioprotein flexible skin patch electrode of the present invention has very high skin surface adhesion in both dry and wet (sweat) states, far exceeding that of a common protein film.
Specifically, the second experiment is carried out on the biological protein flexible skin patch type electrode, the biological protein flexible skin patch type electrode is adhered to different parts of the body surface of a human body, such as the chest, the arms, the eyelids and the like, and various electrophysiological signals of the human body can be measured through an oscilloscope; as shown in FIG. 4, experimental results show that the bioprotein flexible skin patch type electrode can accurately acquire a plurality of electric signals; mainly due to good skin surface adhesiveness and extremely low contact resistance, a plurality of key human body physiological indexes such as heartbeat, muscle strain, human drowsiness degree and the like can be obtained.
Specifically, the third experiment is carried out on the bioprotein flexible skin patch type electrode, the bioprotein flexible skin patch type electrode is adhered to the body surface of a human body, various chemical and physiological signals of the human body can be measured through a resistance analyzer, and bacteria are taken as one of the characteristics; as shown in FIG. 5, experimental results show that the bioprotein flexible skin patch electrode can accurately monitor the bacterial growth condition on the skin surface, and bacteria with different concentrations have different electrical responses and are of great significance to the health degree of human skin.
The embodiment provides a biological protein flexible skin patch type electrode and a preparation method thereof, after the electrode is used, the electrode can be washed by a large amount of water, the electrode can fall off automatically after being dried, the skin cannot be damaged, the electrode can be degraded by environment in a green way, no waste pollution exists, meanwhile, the electrode can be stored for a long time under the condition of room temperature sealing, the storage time is generally more than 6 months, and the high temperature resistance is generally more than 140 ℃ and the interference of bending deformation resistance is avoided.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (10)
1. A preparation method of a biological protein flexible skin patch type electrode is characterized by comprising the following steps:
s1, preparing a plasticized biological protein solution;
s2, coating the plasticized biological protein solution on the surface of a preset template, and preparing a first plasticized biological protein film through curing and drying;
s3, preparing a mask plate, and attaching the mask plate to the first plasticized biological protein film;
s4, coating conductor slurry on the surface of the mask plate which is attached with the first plasticized biological protein film, and preparing a second plasticized biological protein film through curing and drying, wherein the second plasticized biological protein film has an electrode structure;
and S5, separating the second plasticized biological protein film, and preparing the biological protein flexible skin-attached electrode through cutting and packaging.
2. The method of claim 1, wherein in the step S1, the plasticized bioprotein solution is prepared by mixing fibroin, spidroin, elastin, glycerol, calcium chloride and deionized water according to a predetermined ratio, wherein the glycerol accounts for 5% -25% of the mass of the plasticized bioprotein solution, the calcium chloride accounts for 0.5% -3% of the mass of the protein solution, the deionized water is used for adjusting the concentration, and the volume of the deionized water accounts for 0% -50% of the volume of the protein solution.
3. The method as claimed in claim 2, wherein in the step S1, the plasticized bioprotein solution is subjected to surface air bubble removal and preservation at a first preset temperature, wherein the first preset temperature is 4 ℃.
4. The method for preparing a bioprotein flexible skin patch electrode according to claim 1, wherein in the step S2, the preset template is one of a polydimethylsiloxane template, a glass template, a teflon template, a polyethylene template or a silica gel template.
5. The method as claimed in claim 4, wherein in the step S2, the first plasticized bioprotein film is prepared by curing and drying in a constant temperature and humidity chamber, wherein the curing and drying process comprises an ambient temperature of 25 ℃, an ambient humidity of 30% and a drying and curing time of 12 hours.
6. The method for preparing a bioprotein flexible skin conformable electrode according to claim 1, wherein in the step of S3, the mask is prepared according to a preset electrode pattern.
7. The method for preparing the bioprotein flexible skin conformable electrode according to claim 1, wherein in the step S4, the masks are divided into masks based on metal preparation and masks based on silicon wafer preparation, wherein the masks based on metal preparation include: the mask plate prepared based on the silicon wafer comprises one of a silicon plate, a silicon oxide plate, a glass plate and a silicon nitride plate.
8. The method for preparing a bioprotein flexible skin patch electrode according to claim 7, wherein in the step S4, the curing and drying are divided into fast curing and slow curing;
the rapid curing needs to be carried out on a heating plate, and the heating temperature is 80 ℃ in the curing and drying process, and the drying and curing time is 5 minutes;
the slow curing needs to be carried out in a constant temperature and humidity box, the ambient temperature is 25 ℃, the ambient humidity is 30% and the drying and curing time is 12 hours in the curing and drying process.
9. The method as claimed in claim 8, wherein in the step S4, the conductive slurry includes one of graphene, carbon nanotubes or silver nanowires.
10. A bioprotein flexible skin patch electrode, which is prepared by the method for preparing the bioprotein flexible skin patch electrode according to any one of claims 1 to 9, and has a length of not more than 4 cm, a width of not more than 3 cm and a thickness of not more than 50 microns.
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| CN111956220A (en) * | 2020-08-24 | 2020-11-20 | 中国科学院上海微系统与信息技术研究所 | Bidirectional cortical brain electrode preparation method and bidirectional cortical brain electrode prepared by same |
| CN114671935A (en) * | 2022-04-25 | 2022-06-28 | 上海脑虎科技有限公司 | Preparation method and structure of flexible probe based on gene recombination spider silk protein solution |
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Application publication date: 20200508 |