A wireless wearable self-adhesive sensor utilizing saliva to generate electricity and a method of manufacturing the same

Abstract

This invention relates to the field of flexible wearable energy devices, and particularly to a wireless wearable self-adhesive sensor that generates electricity using saliva and its preparation method. The preparation method includes the following steps: preparing MXene nanosheets and silk fibroin powder; adding MXene nanosheets, pyrrole, and silk fibroin powder to a polyethylene solution and mixing them thoroughly, then adding a borax mixture and glycerin to react and obtain a conductive hydrogel; coating the conductive hydrogel onto both sides of a membrane, sealing it with the membrane, and introducing saliva to obtain the wireless wearable self-adhesive sensor that generates electricity using saliva. This invention utilizes a conductive hydrogel Ti3C2 / PPy / SF / PVA and a membrane to prepare a wireless wearable self-adhesive sensor that generates electricity using saliva. It possesses self-adhesive properties, eliminates the need for additional wearable devices such as teeth protectors, offers high comfort, and minimizes foreign body sensation. This sensor generates electricity using saliva to charge biosensors, detection devices, etc., enabling wireless wearable applications.

Description

Technical Field

[0001] This invention relates to the field of flexible wearable energy devices, and in particular to a wireless wearable self-adhesive sensor that generates electricity using saliva and its preparation method. Background Technology

[0002] Flexible wearable energy devices are widely used in human physiological monitoring, including pulse monitoring, assessment of bodily fluids such as sweat and saliva, and identification of toxic substances in the living environment. To achieve rapid charging, simplify manufacturing processes, and enhance cycle stability, scientists have invented various flexible supercapacitors, enriching the range of wearable electronic products. When designing safe and effective wearable flexible supercapacitors, the biocompatibility of electrodes and electrolytes must first be overcome. Saliva plays a vital role in maintaining oral and overall health. Its main components include water, enzymes, electrolytes, proteins, and urea, and the proportions of these components are closely related to oral and overall health. Therefore, real-time monitoring of the components in saliva can quickly and effectively assess a person's health status and predict the risk of related diseases.

[0003] The saliva sensor disclosed in Chinese invention patent CN202310835743.X is integrated into a mouthguard. The mouthguard is worn on the teeth of fasting patients in the intensive care unit. A sensor array monitors the concentration of biomarkers in the saliva and oral temperature of the fasting patient in real time. A mobile application terminal determines the concentration of biomarkers in the patient's blood based on the real-time monitoring of these biomarker concentrations and oral temperature. This allows for early warning of critical illness based on the concentration of blood biomarkers, achieving real-time detection and early warning of biomarkers in fasting patients in the ICU in a non-invasive manner, avoiding delayed judgment of changes in the patient's condition caused by intermittent blood biochemistry tests. However, the above technical solution has drawbacks: it requires wearing an additional mouthguard, which may affect the patient's chewing and breathing functions, and it causes a strong foreign body sensation. Furthermore, it does not mention the sensor charging method.

[0004] Therefore, there is a need for a small, non-toxic, harmless, biosafety-friendly, wearable, self-adhesive wireless biosensor for saliva monitoring. A wearable flexible supercapacitor for oral cavity that uses saliva as an electrolyte is the best way to solve this problem. Summary of the Invention

[0005] Based on the above, the present invention provides a wireless wearable self-adhesive sensor that utilizes saliva to generate electricity and its preparation method.

[0006] To achieve the above objectives, the present invention provides the following solution: This invention provides a method for fabricating a wireless wearable self-adhesive sensor that utilizes saliva to generate electricity, comprising the following steps: Ti3C2 nanosheets were dispersed in water and ultrasonically treated, followed by centrifugation and drying to obtain MXene nanosheets. Silkworm cocoons were dispersed in a Na2CO3 solution, boiled, washed, and dried to obtain substance A; substance A was dissolved in a mixed solution and dialyzed to obtain a concentrated silk fibroin (SF) solution; the concentrated silk fibroin solution was then vacuum dried to obtain silk fibroin powder; MXene nanosheets, pyrrole and silk fibroin powder were added to a polyethylene solution and mixed well. Then, a borax mixture and glycerol were added and reacted to obtain a conductive hydrogel (Ti3C2 / PPy / SF / PVA). The conductive hydrogel is coated on both sides of the diaphragm, which is then sealed and saliva is introduced to obtain the wireless wearable self-adhesive sensor that generates electricity using saliva.

[0007] In some embodiments of the present invention, Ti3C2 nanosheets are prepared by LiF / HCl etching, and are multilayer Ti3C2 nanosheets; multilayer Ti3C2 nanosheets obtained by other means, such as commercially available ones, are also applicable to the present invention.

[0008] In a preferred embodiment of the present invention, the Na2CO3 solution has a mass fraction of 0.5%.

[0009] In a preferred embodiment of the present invention, the boiling time is 30 minutes.

[0010] In a preferred embodiment of the present invention, the mixed solution is a mixture of CaCl2, CH3CH2OH and H2O in a mass ratio of 1:2:8.

[0011] In a preferred embodiment of the present invention, the polyethylene solution is prepared by adding polyethylene powder to water and stirring vigorously at 95°C for 2 hours; the mass concentration of the polyethylene solution is 10%~15%.

[0012] In a preferred embodiment of the present invention, the volume-to-mass ratio of the polyethylene solution to the MXene nanosheets, pyrrole, and silk fibroin powder is 15 mL: 0.3 g: 0.15 g: 0.8 g.

[0013] In a preferred embodiment of the present invention, the borax mixture is a mixture of borax and water; the mass concentration of the borax mixture is 4%.

[0014] In a preferred embodiment of the present invention, the volume ratio of the polyethylene solution to the borax mixture and glycerin is 15:5:1.

[0015] The second technical solution of the present invention is a wireless wearable self-adhesive sensor that generates electricity using saliva, prepared according to the above-described preparation method.

[0016] The present invention discloses the following technical effects: This invention utilizes a conductive hydrogel Ti3C2 / PPy / SF / PVA and a diaphragm to fabricate a wireless wearable self-adhesive sensor that generates electricity from saliva. It is self-adhesive, eliminating the need for additional wearable devices such as mouthguards, offering high comfort and minimal foreign body sensation. Furthermore, this sensor generates electricity from saliva to charge biosensors, detection devices, etc., enabling wireless wearable applications. Detailed Implementation

[0017] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0018] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0019] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0020] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0021] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0022] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0023] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0024] Example 1 This embodiment provides a method for fabricating a wireless wearable self-adhesive sensor (Ti3C2 / PPy / SF / PVA) that utilizes saliva to generate electricity, the steps of which are as follows: a. Disperse Ti3C2 nanosheets in deionized water, sonicate under argon protection for 40 minutes, centrifuge the supernatant at 3500 rpm for 30 minutes, and finally vacuum filter to obtain MXene nanosheets, and vacuum dry at 70℃.

[0025] b. Disperse silkworm cocoons in a 0.5% (w / w) Na2CO3 solution and boil for 30 minutes to degumme them. After rinsing with deionized water, dry them in a 60℃ oven. Dissolve the dried material in a 75℃ CaCl2 / CH3CH2OH / H2O solution (the mass ratio of CaCl2, CH3CH2OH, and H2O is 1:2:8). Dialyze the obtained solution in deionized water using a MWCO 8000-14000 Da cellulose dialysis membrane for 3 days to obtain a concentrated silk fibroin (SF) solution. Vacuum dry the concentrated solution to obtain silk fibroin powder.

[0026] c. Mix 2.0g of polyethylene (PVA) powder with 15ml of deionized water and stir vigorously at 95°C for 2 hours to form a polyethylene solution.

[0027] d. Add 0.3g of two-dimensional nanomaterial Ti3C2 and 0.15g of pyrrole (PPy) to the above polyethylene solution, and stir the mixture for 1 hour. Then add 0.8g of silk fibroin powder to the mixture and stir vigorously for 1 hour. After that, add 5ml of an aqueous solution containing 0.2g of borax and 1ml of glycerol and stir to react for 30 minutes. A conductive hydrogel is obtained after the reaction.

[0028] e. The conductive hydrogel described above was coated on both sides of a cellulose membrane. Based on the two similar active regions of the Ti3C2 / PPy / SF / PVA electrode, an electrochemical capacitor based on symmetrical Ti3C2 / PPy / SF / PVA was prepared. This electrochemical capacitor was then sealed with a membrane (composed of polyethylene difluoride and polyvinyl fluoride), and saliva was introduced as an electrolyte, successfully constructing a wireless wearable self-adhesive sensor, Ti3C2 / PPy / SF / PVA, that generates electricity using saliva.

[0029] Based on Example 1, a series of conductive hydrogels with different physicochemical properties can be obtained by adjusting the mass ratio of polyethylene, silk fibroin, MXene and pyrrole, thereby controlling the performance of wireless wearable self-adhesive sensors that generate electricity using saliva.

[0030] The sensor prepared by Example 1 of this invention using conductive hydrogel Ti3C2 / PPy / SF / PVA and a diaphragm has self-adhesive properties and can generate electricity using saliva to charge biosensors, detection devices, etc., thus achieving the purpose of wireless wearable use.

[0031] This invention utilizes MXene hydrogel as the capacitor dielectric and designs a layered wearable capacitor structure consisting of a dielectric-septum-saliva-dielectric layer to generate electricity using saliva. This self-adhesive sensor can be directly attached to the surface of teeth or mucous membranes without the need for additional fixation devices. By pre-setting the sensor assembly position, a wireless wearable self-adhesive sensor that generates electricity using saliva is realized.

[0032] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A method for fabricating a wireless wearable self-adhesive sensor that generates electricity using saliva, characterized in that, Includes the following steps: Ti3C2 nanosheets were dispersed in water and ultrasonically treated, followed by centrifugation and drying to obtain MXene nanosheets. Silkworm cocoons were dispersed in a Na2CO3 solution, boiled, washed, and dried to obtain substance A; substance A was dissolved in a mixed solution and dialyzed to obtain a concentrated silk fibroin solution; the concentrated silk fibroin solution was then vacuum dried to obtain silk fibroin powder; MXene nanosheets, pyrrole and silk fibroin powder were added to a polyethylene solution and mixed well. Then, a borax mixture and glycerol were added and reacted to obtain a conductive hydrogel. The conductive hydrogel is coated on both sides of the diaphragm, which is then sealed and saliva is introduced to obtain the wireless wearable self-adhesive sensor that generates electricity using saliva.

2. The preparation method according to claim 1, characterized in that, The Na2CO3 solution has a mass fraction of 0.5%.

3. The preparation method according to claim 1, characterized in that, The boiling time is 30 minutes.

4. The preparation method according to claim 1, characterized in that, The mixed solution is a mixture of CaCl2, CH3CH2OH and H2O in a mass ratio of 1:2:

8.

5. The preparation method according to claim 1, characterized in that, The polyethylene solution is prepared by adding polyethylene powder to water and stirring vigorously at 95°C for 2 hours; the mass concentration of the polyethylene solution is 10%~15%.

6. The preparation method according to claim 1, characterized in that, The volume-to-mass ratio of the polyethylene solution to the MXene nanosheets, pyrrole, and silk fibroin powder is 15 mL: 0.3 g: 0.15 g: 0.8 g.

7. The preparation method according to claim 1, characterized in that, The borax mixture is a mixture of borax and water; the mass concentration of the borax mixture is 4%.

8. The preparation method according to claim 1, characterized in that, The volume ratio of the polyethylene solution to the borax mixture and glycerin is 15:5:

1.

9. A wireless wearable self-adhesive sensor that generates electricity using saliva, prepared by the method according to claim 1.