CN115998299A - Breathable high-substrate-adhesion flexible stretchable nerve electrode and preparation method and application thereof - Google Patents

Breathable high-substrate-adhesion flexible stretchable nerve electrode and preparation method and application thereof Download PDF

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CN115998299A
CN115998299A CN202211624242.9A CN202211624242A CN115998299A CN 115998299 A CN115998299 A CN 115998299A CN 202211624242 A CN202211624242 A CN 202211624242A CN 115998299 A CN115998299 A CN 115998299A
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nerve electrode
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sebs
pdms
dimensional porous
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CN115998299B (en
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齐殿鹏
梁翠媛
刘妍
樊文倩
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention discloses a flexible stretchable nerve electrode with ventilation and high substrate adhesion, and a preparation method and application thereof, and belongs to the technical field of nerve electrode composite materials and preparation thereof. The invention solves the problems of poor air permeability, poor adhesion between the conductive layer and the flexible substrate and poor stability caused by electrode deformation for adapting to tissue movement of the existing nerve electrode. According to the invention, a thermoplastic elastomer styrene-ethylene-butylene-styrene block copolymer (SEBS), polydimethylsiloxane (PDMS) and a conductive polymer polypyrrole (PPy) material are adopted, and an SEBS/PDMS/PPy nerve electrode which is regular in appearance and has three-dimensional folds is obtained by using an electrostatic spinning process, a pre-stretching technology, plasma pretreatment, spraying and a vapor deposition method, and has the performances of ventilation, stretching conductive stability and high substrate adhesion, so that stable and accurate monitoring of bioelectricity physiological signals (such as electrocardio, myoelectricity and the like) is realized.

Description

Breathable high-substrate-adhesion flexible stretchable nerve electrode and preparation method and application thereof
Technical Field
The invention relates to a breathable high-substrate-adhesion flexible stretchable nerve electrode and a preparation method and application thereof, and belongs to the technical field of nerve electrode composite materials and preparation thereof.
Background
Since the discovery of bioelectricity by Luigi Galvani, we have better understood the communication of information between living beings and electrons, so-called bioelectricity interfaces or bioelectronics. Bioelectronics is an emerging discipline formed by interdigitating permeation of biology and electronic information science. Almost every physiological process in the human body is associated with bioelectricity, such as heart beating, muscle contraction, brain thought, etc. The nerve electrode in bioelectronics carries out information communication (stimulation and recording) with biological tissues in a bidirectional mode, and has great potential in guiding treatment of various nervous system diseases (such as nerve paralysis, epilepsy, alzheimer's disease, blindness, spinal cord injury and the like).
Although neural electrodes have achieved significant advances in the diagnosis, treatment and prevention of neurological diseases, neural electrodes require some more sophisticated properties for practical use, such as: (1) The poor air permeability of the nerve electrode not only can reduce the quality of the electrode collection and transmission signals, but also can cause inflammation, which can have negative influence on organisms; (2) Poor adhesion between the conductive layer of the neural electrode and the flexible substrate can lead to unstable signal acquisition; (3) The inextensibility of the neural electrode results in instability of the electrode to signal tissue movement. Therefore, the nerve electrode is also required to have air permeability, high substrate adhesiveness, and good tensile conductivity in practical application, which is of great importance for recording and transmitting signals.
Disclosure of Invention
The invention provides a flexible stretchable nerve electrode with ventilation and high substrate adhesion, a preparation method and application thereof, and aims to solve the problems that the nerve electrode in the prior art is poor in ventilation performance and poor in adhesion between a conductive layer and a flexible substrate, and the stability is poor due to electrode deformation is avoided in order to adapt to tissue movement.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a preparation method of a breathable high-substrate-adhesion flexible stretchable nerve electrode, which comprises the following steps:
s1, preparing an electrospinning solution by using SEBS and PDMS raw materials, and carrying out electrostatic spinning to obtain a three-dimensional porous elastomer fiber membrane;
s2, sequentially pre-stretching, plasma pretreatment, spraying and vapor deposition treatment are carried out on the three-dimensional porous elastomer fiber membrane to obtain a conductive three-dimensional porous fiber membrane;
and S3, connecting the conductive three-dimensional porous fiber membrane with a lead, and packaging by ultraviolet irradiation of hydrogel to obtain the nerve electrode.
Further defined, the electrospinning liquid in S1 is configured to: SEBS is dissolved in tetrahydrofuran to obtain solution A with the concentration of 11-30 wt%; dissolving PDMS in n-hexane to obtain a solution B with the concentration of 11-30 wt%; and mixing the solution A and the solution B to obtain the electrospinning liquid.
Further defined, the mass ratio of SEBS and PDMS in the electrospinning liquid is (1-6): 1.
further defined, the mass ratio of SEBS to PDMS in the electrospinning liquid is 2:1.
further defined, the concentration of the electrospinning liquid is 0.1 to 10g/mL.
Further defined, the electrospinning conditions in S1 are: the voltage is 7-20 KV, the propelling speed is 0.01-10 mL/h, and the collecting temperature is 80-130 ℃.
Further defined, the plasma pretreatment conditions in S2 are: the pressure is less than 20Pa, the oxygen atmosphere, the power is 20W, and the time is 1-3 min.
Further defined, the front and back sides of the three-dimensional porous elastomeric fibrous membrane were each subjected to 1 plasma pretreatment.
Further limiting, wherein the pre-stretching strain in S2 is 400-900%; the spraying solution is ferric chloride hexahydrate solution; and after the spraying is finished, placing the film in a vacuum drying reactor containing pyrrole for vapor deposition, and then washing and drying the film to obtain the conductive three-dimensional porous fiber film.
Further defined, the concentration of ferric chloride hexahydrate solution is 1mol/L.
Further defined, the vapor deposition temperature is room temperature for 1-2 hours.
Further defined, distilled water and ethanol are used for washing.
Further defined, the drying is performed in air.
Further defined, the operation of S3 is: cutting the conductive fiber membrane into a size with the length of 2-8 mm and the width of 2-8 mm, connecting the conductive fiber membrane into an electrode by using a wire, and packaging the electrode by using breathable hydrogel to obtain the nerve electrode.
Further defined, the specific process of encapsulation is: and uniformly dripping the prepared hydrogel solution on a cover slip, covering the cover slip on the conductive three-dimensional porous fiber film, and irradiating for 1-6 min by ultraviolet to perform subsequent tests.
The second purpose of the invention is to provide an application of the breathable high-substrate-adhesion flexible stretchable nerve electrode, which is particularly used for electrophysiological signal detection.
The application has the following beneficial effects:
(1) The invention adopts a thermoplastic elastomer styrene-ethylene-butylene-styrene segmented copolymer (SEBS), polydimethylsiloxane (PDMS) and conductive polymer polypyrrole (PPy), and utilizes an electrostatic spinning process, a prestretching technology, spraying and a vapor deposition method to obtain the SEBS/PDMS/PPy nerve electrode which is regular in appearance and has three-dimensional folds, and the nerve electrode has the performances of ventilation, stretching conductive stability and high substrate adhesion.
(2) The conductive fiber lap joint formed by utilizing technologies such as electrostatic spinning and the like has a three-dimensional network porous structure, realizes high flexibility, avoids the phenomenon of fracture along with the movement of organism soft tissues, and realizes conformal capability with skin.
Drawings
FIG. 1 is a scanning electron microscope picture of SEBS/PDMS/PPy neural electrode obtained in example 1;
FIG. 2 is the data of the epidermis myoelectricity monitored by SEBS/PDMS/PPy nerve electrode obtained in example 1;
FIG. 3 is electrocardiographic data obtained in example 1 and monitored by SEBS/PDMS/PPy neural electrodes.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The SEBS used in the following examples was purchased from Asahi Karaku chemical under the model number H1221; PDMS was purchased from us doucorning under the model Sylgard 184.
Example 1:
the embodiment provides a preparation method of a breathable high-substrate-adhesion flexible stretchable nerve electrode, which comprises the following steps:
step one, weighing 6g of SEBS, adding the SEBS into 26.61g of tetrahydrofuran, stirring the mixture at 60 ℃ until the SEBS is completely dissolved, cooling the mixture to room temperature, adding 3g of PDMS and 5g of n-hexane into the solution, and continuously stirring the mixture until the mixture is uniform.
And step two, removing bubbles from the uniform solution obtained in the step one by a vacuum dryer, transferring the uniform solution into an electrostatic spinning device, and carrying out electrostatic spinning under the following technological parameter conditions to obtain the three-dimensional porous elastomer fiber membrane.
The electrostatic spinning process parameters are as follows: the advancing speed was maintained at 0.01mL/h using a 21G syringe needle, the collection temperature was 120 ℃, the applied spinning voltage was 15kV, the distance from the orifice to the drum receiver was 15cm, the constant rotational speed of the drum was maintained at 100rpm, and the entire electrospinning process was performed in a closed chamber at a constant temperature of 25℃and a relative humidity of 60%.
Step three, firstly, the three-dimensional porous elastomer fiber film is prestretched by a prestretching method by using a stretching table instrument, and the prestretching strain is 500%. Then, plasma pretreatment is carried out on the front side and the back side of the film to enable the surface of the film to be immersed, and specific plasma pretreatment conditions are as follows: the pressure is less than 20Pa, the oxygen atmosphere, the power is 20W, and the time is 2min. Then spraying ferric chloride hexahydrate solution with the concentration of 1mol/L on the surface of the membrane, then placing the membrane in a vacuum drying reactor containing pyrrole, performing vapor deposition for 1h at room temperature, taking out and washing the membrane by using a large amount of distilled water and ethanol, and drying the membrane in air for standby, thus obtaining the conductive three-dimensional porous fibrous membrane with the properties of ventilation, high substrate adhesion, flexibility and stretchability, namely SEBS/PDMS/PPy nerve electrode for short.
Step four, an electrospun membrane prepared by adopting an electrostatic spinning technology is used as a substrate material of a flexible electrode, and an SEBS/PDMS/PPy nerve electrode is used as a conductive part of the flexible electrode, so that the interface adhesion strength of the flexible electrode and the stability of the flexible electrode in the use process are effectively improved, the flexible electrode is packaged by adopting hydrogel with adhesion characteristics, and the specific hydrogel preparation method comprises the following steps: choline chloride and ethylene glycol were mixed in a ratio of 1:2, stirring for 2 hours at 100 ℃ to form a uniform transparent solution, then taking 3.5g of the transparent solution, adding 1.45g of acrylic acid, 0.1g of 2-ketoglutaric acid and 0.01g of polyethylene glycol diacrylate, stirring at room temperature until the solution is dissolved to obtain hydrogel, dripping the hydrogel on a cover slip, covering an SEBS/PDMS/PPy nerve electrode on the cover slip, connecting a wire, and irradiating for 3 minutes by ultraviolet to obtain the flexible electrode capable of achieving the film adhesion effect.
The SEBS/PDMS/PPy nerve electrode and the flexible electrode obtained above were subjected to structural characterization and performance testing:
(1) The obtained SEBS/PDMS/PPy nerve electrode is subjected to microscopic morphology characterization, the result is shown in figure 1, the fiber morphology of the electrospun membrane is uniform, holes are formed by the three-dimensional structure of the lap joint of the fibers, and the breathability of the electrode fiber is verified. More notably, the conductive layer of the nerve electrode is tightly wrapped on the surface of the spinning fiber, so that the conductive layer of the nerve electrode and the substrate material have better adhesion performance and tensile stability, which are of great significance for the tensile conductive stability of the flexible electrode.
(2) The air permeability test is carried out on the obtained SEBS/PDMS/PPy nerve electrode connection copper wire, the specific test process is that the prepared conductive electrospun film is stuck on the needle seat with an air injector by using an airtight transparent adhesive tape, and then the injector is inserted into a beaker filled with water. When the syringe is pushed, air in the syringe is discharged outwards due to the pressure and bubbles are generated in water, so that the film has air permeability. This not only demonstrates the good breathability of the film, but also suggests that the conductive polymer does not have an impact on breathability. The good air permeability can be attributed to the three-dimensional porous structure of the film, so that the electrospun film provides a good platform for the production of commercial wearable electronic products.
(3) The obtained SEBS/PDMS/PPy nerve electrode connection copper wire is subjected to a cyclic stretching test, the prepared film is cut into a size of 2cm multiplied by 2cm, the film is placed into a clamp of a stretching machine, the film is circulated for 100 times under the condition of stretching by 50%, and the change of a current signal is recorded in real time. The result shows that the tensile deformation does not have great influence on the current signal, and the conductive fiber prepared by the invention has good tensile stability, thereby providing important guarantee for the acquisition and transmission of the adaptive dynamic signal.
(4) The obtained flexible electrode is used for monitoring the surface electromyographic signals, and the result is shown in fig. 2, and the acquired signals are stable and uniform, so that the nerve electrode has better stretchability, reliability and stability, and the accurate measurement of the surface electromyographic signals cannot be influenced due to the change of resistance caused by the movement of arm muscles, so that the nerve electrode is also proved to have feasibility in entering clinical application.
(5) The obtained flexible electrode is used for monitoring fine electrocardiosignals, and specifically, three prepared flexible electrodes are respectively placed on a left chest, a right chest and a left abdomen to obtain ECG signals of a subject shown in figure 3, and the result shows that the tested electrocardiosignals have better peak morphology, and the signals play an important role in diagnosing myocardial ischemia, myocardial infarction and various cardiac arrhythmias.
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.

Claims (10)

1. A method for preparing a neural electrode, comprising the steps of:
s1, preparing an electrospinning solution by taking SEBS and PDMS as raw materials, and carrying out electrostatic spinning to obtain a three-dimensional porous elastomer fiber membrane;
s2, sequentially pre-stretching, plasma pretreatment, spraying and vapor deposition treatment are carried out on the three-dimensional porous elastomer fiber membrane to obtain a conductive three-dimensional porous fiber membrane;
and S3, connecting the conductive three-dimensional porous fiber membrane with a lead, and packaging by ultraviolet irradiation of hydrogel to obtain the nerve electrode.
2. The method of claim 1, wherein the electrospinning liquid in S1 is configured to: SEBS is dissolved in tetrahydrofuran to obtain solution A with the concentration of 11-30 wt%; dissolving PDMS in n-hexane to obtain a solution B with the concentration of 11-30 wt%; and mixing the solution A and the solution B to obtain the electrospinning liquid.
3. The method for preparing the nerve electrode according to claim 1 or 2, wherein the mass ratio of SEBS and PDMS in the electrospinning liquid is (1-6): 1.
4. the method for producing a nerve electrode according to claim 1 or 2, wherein the concentration of the electrospinning liquid is 0.1 to 10g/mL.
5. The method for preparing a neural electrode according to claim 1, wherein the electrospinning conditions in S1 are: the voltage is 7-20 KV, the propelling speed is 0.01-10 mL/h, and the collecting temperature is 80-130 ℃.
6. The method for preparing a neural electrode according to claim 1, wherein the plasma pretreatment conditions in S2 are: the pressure is less than 20Pa, the oxygen atmosphere, the power is 20W, the time is 1-3 min, and the front and the back of the three-dimensional porous elastomer fiber membrane are respectively treated for 1 time.
7. The method for preparing a nerve electrode according to claim 1, wherein the pre-stretching strain in S2 is 400-900%; the spraying solution is ferric chloride hexahydrate solution; and after the spraying is finished, placing the film in a vacuum drying reactor containing pyrrole for vapor deposition, and then washing and drying the film to obtain the conductive three-dimensional porous fiber film.
8. The method for producing a nerve electrode according to claim 7, wherein the vapor deposition time is 1 to 2 hours.
9. A breathable, high substrate adhesion flexible stretchable neural electrode obtained by the method of claim 1.
10. Use of a breathable, high substrate adhesion flexible stretchable neural electrode according to claim 9 for electrophysiological signal detection.
CN202211624242.9A 2022-12-15 2022-12-15 Breathable high-substrate-adhesion flexible stretchable nerve electrode and preparation method and application thereof Active CN115998299B (en)

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