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CN111007124B - Sensor for sweat detection and preparation method thereof - Google Patents

Sensor for sweat detection and preparation method thereof Download PDF

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CN111007124B
CN111007124B CN201911231345.7A CN201911231345A CN111007124B CN 111007124 B CN111007124 B CN 111007124B CN 201911231345 A CN201911231345 A CN 201911231345A CN 111007124 B CN111007124 B CN 111007124B
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sweat
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CN111007124A (en
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刘春秀
薛宁
蔡浩原
孙建海
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    • A61B5/14517Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue specially adapted for measuring characteristics of body fluids other than blood for sweat
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    • A61B5/14546Measuring characteristics of blood in vivo, e.g. gas concentration or pH-value ; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid or cerebral tissue for measuring analytes not otherwise provided for, e.g. ions, cytochromes
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    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
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Abstract

本公开提供了一种用于汗液检测的传感器。所述传感器包括:双电极体系(1),包括工作电极(11)和对/参比电极(12);电渗凝胶层(2),设置在对/参比电极(12)上,电渗凝胶层(2)中包含促排剂,促排剂用于促进排出汗液,电渗凝胶层(2)中设置有沟槽(4),沟槽(4)用于对排出的汗液进行收集及存放;活性选择凝胶层(3),设置在工作电极(11)上,活性选择凝胶层(3)用于从沟槽(4)溢出的汗液中选择相应的离子,使得工作电极(11)检测汗液中包含的离子的浓度。本公开还提供了一种用于汗液检测的传感器的制备方法。

Figure 201911231345

The present disclosure provides a sensor for sweat detection. The sensor comprises: a two-electrode system (1) including a working electrode (11) and a counter/reference electrode (12); an electroosmotic gel layer (2) arranged on the counter/reference electrode (12), The permeable gel layer (2) contains a drainage promoting agent, and the drainage promoting agent is used for promoting the discharge of sweat, and the electroosmotic gel layer (2) is provided with a groove (4), and the groove (4) is used for the discharge of sweat. Collect and store; the active selection gel layer (3) is arranged on the working electrode (11), and the active selection gel layer (3) is used to select corresponding ions from the sweat overflowing from the groove (4), so that the work Electrodes (11) detect the concentration of ions contained in sweat. The present disclosure also provides a preparation method of a sensor for sweat detection.

Figure 201911231345

Description

Sensor for sweat detection and preparation method thereof
Technical Field
The disclosure relates to the technical field of sensors, in particular to a sensor for sweat detection and a preparation method thereof.
Background
Sweat originates from eccrine sweat glands and is conveyed to the surface of the skin through the epidermis by a dermal canal, and the sweat contains various ions, amino acids, hormones, polypeptides and other secretions, and can be used for judging the health degree of a human body by detecting the various secretions in the sweat. The correlation technique shows that sweat detection can replace blood/urine detection to a certain extent, and the physiological indexes of the sweat detection and the urine detection have high correlation. For example, the functional status of the human body can be judged according to the metabolic trends of potassium ions and sodium ions in sweat, the sign information such as muscle spasm early warning and dehydration trend of the user can be obtained, and the electrolyte level and the health state of the human body can be obtained.
Wearable electrochemical detection sensors in the related art can monitor physiological parameters of a human body in real time by measuring ions (e.g., sodium ions, potassium ions, etc.). However, the amount of sweat secreted is not constant, and ion detection in sweat is subject to sampling and detection consistency.
Disclosure of Invention
Technical problem to be solved
In view of the above, the present disclosure provides a sensor for sweat detection that can facilitate sweat discharge, collect sweat, and form a sweat chamber for analysis, and a method of manufacturing the same.
(II) technical scheme
The present disclosure provides a sensor for sweat detection, comprising: a two-electrode system comprising a working electrode and a counter/reference electrode; the electro-osmosis gel layer is arranged on the counter/reference electrode, the electro-osmosis gel layer contains a discharge promoting agent, the discharge promoting agent is used for promoting the discharge of sweat, and a groove is formed in the electro-osmosis gel layer and used for collecting and storing the discharged sweat; an active selection gel layer disposed on the working electrode, the active selection gel layer for selecting corresponding ions from sweat that overflows the channels such that the working electrode detects a concentration of the ions contained in the sweat.
Optionally, the number of the working electrodes is one or more, the working electrodes correspond to the activity selection gel layers one to one, and the one or more activity selection gel layers are used for respectively selecting ions of corresponding types from sweat overflowing from the grooves, so that the one or more working electrodes respectively detect the concentration of the one or more ions contained in the sweat.
Optionally, the activity-selective gel layer comprises at least one or more of an activity-selective gel layer for selecting sodium ions, an activity-selective gel layer for selecting potassium ions, and an activity-selective gel layer for selecting calcium ions.
Optionally, the active substance in the activity selection gel layer for selecting sodium ions is valinomycin, the active substance in the activity selection gel layer for selecting potassium ions is dicoroyl ether, and the active substance in the activity selection gel layer for selecting calcium ions is isooctylphenyl calcium phosphate.
Optionally, the support substrate of the two-electrode system is a flexible material, and the flexibility of the flexible material is greater than a preset value.
Optionally, the amount of drainage enhancer in the electro-osmotic gel layer is no greater than 0.1% w/w.
Optionally, when the sensor is used for sweat detection in motion monitoring, the expulsion enhancer is not included in the electro-osmotic gel layer.
The present disclosure also provides a method of making a sensor for sweat detection, comprising: preparing a two-electrode system comprising a working electrode and a counter/reference electrode; preparing an electroosmotic gel layer on the counter/reference electrode, adding an excretion promoter into the electroosmotic gel layer to promote sweat excretion, and arranging grooves in the electroosmotic gel layer to collect and store the excreted sweat; preparing an active selection gel layer on the working electrode for selecting corresponding ions from sweat that spills over the channel such that the working electrode detects a concentration of the ions contained in the sweat.
Optionally, the preparing a two-electrode system comprises: and preparing the double-electrode system on a supporting base material by taking a flexible material as the supporting base material, wherein the flexibility of the flexible material is greater than a preset value.
Optionally, the preparing an active selective gel layer on the working electrode comprises: preparing a selective sensitive film on a substrate made of a flexible material to form the active selective gel layer; placing the active selective gel layer on the working electrode.
(III) advantageous effects
The sensor for sweat detection and the preparation method thereof have the following beneficial effects:
(1) by adding the excretion promoter into the gel layer on the counter/reference electrode, the continuous excretion of sweat is promoted, and the stable excretion of the sweat is ensured;
(2) the grooves are formed in the gel layer on the counter/reference electrode to collect and store the discharged sweat, and a sealing structure is formed between the grooves and the skin when the electrode is worn, so that sweat volatilization is reduced, and long-term continuous monitoring is facilitated;
(3) a plurality of working electrodes are integrated in the sensor, and different activity selection gel layers are arranged on each working electrode so as to simultaneously detect a plurality of different ions in sweat, thereby being beneficial to the integral judgment of human body information;
(4) the sensor is made of flexible materials, can be directly worn and is easy to store and carry.
Drawings
Fig. 1 schematically illustrates a top view of a schematic structural view of a sensor for sweat detection provided by an embodiment of the present disclosure;
fig. 2 schematically illustrates a schematic structural view of an electro-osmotic gel layer in a sensor for sweat detection provided by an embodiment of the present disclosure;
fig. 3 schematically illustrates a flow chart of a method of manufacturing a sensor for sweat detection provided by an embodiment of the present disclosure.
Description of reference numerals:
1-two-electrode system; 2-an electro-osmotic gel layer; 3-reactive selection of gel layer; 4-a groove; 11-a working electrode; 12-counter/reference electrode.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
Fig. 1 schematically illustrates a top view of a schematic structural diagram of a sensor for sweat detection provided by an embodiment of the present disclosure.
Referring to fig. 1, the structure shown in fig. 1 will be described in detail with reference to fig. 2. The sensor for sweat detection is composed of a two-electrode system 1, an electro-osmotic gel layer 2, an activity selection gel layer 3, and a groove 4.
The two-electrode system 1 includes a working electrode 11 and a counter/reference electrode 12. The support substrate of the two-electrode system 1 is a flexible material, which should have a compliance greater than a preset value, so that the sensor formed on the basis of the flexible material is a wearable sensor.
The electroosmotic gel layer 2 is provided on the counter/reference electrode 12, and the electroosmotic gel layer 2 contains therein an excretion promoter (for example, pilocarpine or the like) for promoting the excretion of sweat. According to an embodiment of the present disclosure, the amount of the expulsion enhancer added to the electro-osmotic gel layer 2 is not more than 0.1% w/w to avoid harm to the human body. Before sweat detection, the counter/reference electrode 12 can be used as an electroosmosis electrode, a trace of excretion promoting agent is introduced into the skin surface layer through pores on the skin by the low-voltage electroosmosis action of the electroosmosis electrode to promote sweat excretion, and then the electroosmosis electrode stops the electroosmosis action and is used as the counter/reference electrode to carry out sweat detection.
Referring to fig. 2, the electro-osmotic gel layer 2 is further provided with a groove 4, and the groove 4 is used for collecting and storing the discharged sweat. In the embodiment of the present disclosure, the groove 4 is a micrometer groove structure, for example, the depth and the opening width of the groove 4 are both micrometer levels, etc., so as to ensure that the amount of sweat collected in the groove 4 meets the detection requirement, and avoid increasing the difficulty of the sweat overflowing to the working electrode 11 due to the overlarge storage space of the groove 4.
According to the embodiment of the disclosure, when the sensor is used for sweat detection in motion monitoring, the electro-osmotic gel layer 2 does not contain a discharge promoting agent, and naturally discharged sweat can meet the requirement of ion detection in sweat.
And an active selection gel layer 3 disposed on the working electrode 11, the active selection gel layer 3 being used to select corresponding ions from sweat overflowing from the channel 4, so that the working electrode 11 detects the concentration of ions contained in the sweat.
According to the embodiment of the present disclosure, the number of the working electrodes 11 in the two-electrode system 1 is one or more, the working electrodes 11 correspond to the activity selection gel layers 3 one by one, and the one or more activity selection gel layers 3 are used for respectively selecting ions of corresponding types from sweat overflowing from the grooves 4, so that the one or more working electrodes 11 respectively detect the concentration of one or more ions contained in the sweat. Specifically, each working electrode 11 may accomplish the detection of one ion in sweat. For example, the number of the working electrodes 11 is three, and the active selection gel layer 3 on the three working electrodes 11 is used for selecting sodium ions, potassium ions and calcium ions from sweat, so that the three working electrodes 11 can respectively complete the detection of the sodium ions, potassium ions and calcium ions in the sweat. Other values for the number of working electrodes 11 can be derived as described by one skilled in the art in light of the embodiments of the present disclosure.
According to an embodiment of the present disclosure, the activity-selecting gel layer 3 includes at least one or more of an activity-selecting gel layer for selecting sodium ions, an activity-selecting gel layer for selecting potassium ions, and an activity-selecting gel layer for selecting calcium ions. The active substance in the activity selection gel layer for selecting sodium ions is valinomycin, the active substance in the activity selection gel layer for selecting potassium ions is dicoroyl ether, and the active substance in the activity selection gel layer for selecting calcium ions is isooctylphenyl calcium phosphate.
In the embodiment of the present disclosure, the number of counter/reference electrodes 12 is two, for example, and the counter/reference electrodes 12 are respectively disposed on both sides of the working electrode 11, so that when the sensor is worn, the counter/reference electrodes 12 surround the working electrode 11, when sweat collected in the grooves 4 of the counter/reference electrodes 12 overflows, the overflowed sweat flows into the region formed by the electro-osmotic gel layer 2 along with the grooves 4, and then reaches the region where the working electrode 11 is located, specifically, the region where the active selection gel layer 3 is located on the working electrode 11, and the active selection gel layer 3 selects ions of a corresponding kind from the sweat, so that the working electrode 11 corresponding to the active selection gel layer 3 can detect the concentration of the ions in the sweat.
In the disclosed embodiment, the substrate of the two-electrode system 1 and the active selection gel layer 3 are both flexible materials to ensure that the detector they constitute is a wearable detector.
Fig. 3 schematically illustrates a flow chart of a method of manufacturing a sensor for sweat detection provided by an embodiment of the present disclosure. As shown in fig. 3, the preparation method includes operation S310-operation S330.
In operation S310, a two-electrode system 1 is prepared, the two-electrode system 1 including a working electrode 11 and a counter/reference electrode 12.
According to an embodiment of the present disclosure, a flexible material is used as a supporting substrate on which the two-electrode system 1 is prepared, and the flexibility of the flexible material is greater than a preset value. The flexible material is, for example, Polyethylene terephthalate (PET).
In the embodiment of the present disclosure, for example, a PET substrate is used as a substrate, an array of working electrodes 11 and counter/reference electrodes 12 is prepared on the PET substrate by using a metal evaporation technology, a photolithography technology, a printing technology or a Micro-Electro-Mechanical systems (MEMS) technology, so as to prepare a sensor array, precious metal platinum is used as the working electrodes 11 and the counter/reference electrodes 12, the number of the working electrodes 11 in one sensor is one or more, and the thickness of the working electrodes 11 and the counter/reference electrodes 12 is, for example, 500 nm.
In operation S320, an electroosmotic gel layer 2 is prepared on the counter/reference electrode 12, and an expulsion promoting agent is added to the electroosmotic gel layer 2 to promote the expulsion of sweat, and grooves 4 are provided in the electroosmotic gel layer 2 to collect and store the expelled sweat.
In the disclosed embodiment, for example, a hydrogel layer is prepared using polymethacrylic acid, polyacrylamide, or the like, and an expulsion promoter such as pilocarpine is added to the hydrogel layer in an amount of not more than 0.1% w/w to form an electroosmotic gel layer 2, and the electroosmotic gel layer 2 is fixed to a counter/reference electrode 12. It will be appreciated that in sweat detection such as athletic monitoring where wicking is not required, the wicking agent may not be added to the hydrogel layer and the hydrogel layer may be affixed directly to the counter/reference electrode 12.
In operation S330, an active selection gel layer 3 is prepared on the working electrode 11, and the active selection gel layer 3 is used to select corresponding ions from sweat overflowing from the groove 4, so that the working electrode 11 detects the concentration of ions contained in the sweat.
According to an embodiment of the present disclosure, a selective sensitive film is prepared on a substrate made of a flexible material to form an active selection gel layer 3, and the active selection gel layer 3 is placed on a working electrode 11.
In the embodiment of the present disclosure, for example, a flexible material such as Polydimethylsiloxane (PDMS) is used as a substrate, a selective sensitive film is modified on the PDMS, and the selective sensitive film is placed on the working electrode 11. Specifically, for example, 1% of each of the active substances dicrown ether, valinomycin, and isooctylphenylcalcium phosphate is added to the organic solvent; then, respectively adding 5-40% tetrahydrofuran solution to completely dissolve the active substances, and stirring to obtain uniform transparent liquid; then dripping the solution on a steel sheet with a round hollow structure, placing a smooth silicon wafer below the steel sheet, coating the solution with a scraper to form a thin film with uniform thickness, and drying the thin film overnight at normal temperature to form a smooth and transparent round thin film, wherein the round thin film is an activity selection gel layer 3; finally, the circular thin film is placed on the working electrode 11.
In the embodiment of the present disclosure, the working electrode 11 and the counter/reference electrode 12 in the two-electrode system 1 should be further encapsulated with an insulating film to obtain a complete flexible solid-state ion sensor.
In summary, the sensor for sweat detection and the preparation method thereof in the embodiment of the disclosure add the excretion promoter into the gel layer on the counter/reference electrode to promote the continuous excretion of sweat, and the grooves are arranged in the gel layer on the counter/reference electrode to collect and store the excreted sweat, and form a sealing structure with the skin when being worn, so as to reduce the volatilization of sweat, facilitate the long-term continuous monitoring, and can detect various ions simultaneously, and can be worn directly, thus having wide application prospects in the aspects of monitoring the reasonable degree of exercise of fitness people, monitoring the health of chronic patients, and the like.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (10)

1.一种用于汗液检测的传感器,包括:1. A sensor for sweat detection, comprising: 双电极体系(1),包括工作电极(11)和对/参比电极(12),其中,所述对/参比电极(12)包围所述工作电极(11);A two-electrode system (1) comprising a working electrode (11) and a counter/reference electrode (12), wherein the counter/reference electrode (12) surrounds the working electrode (11); 电渗凝胶层(2),设置在所述对/参比电极(12)上,所述电渗凝胶层(2)中包含促排剂,所述促排剂用于促进排出汗液,所述电渗凝胶层(2)中设置有沟槽(4),所述沟槽(4)用于对排出的汗液进行收集及存放,其中,所述沟槽(4)为微米量级沟槽;an electroosmotic gel layer (2), disposed on the counter/reference electrode (12), the electroosmotic gel layer (2) comprising an excretion-promoting agent for promoting the excretion of sweat, The electroosmotic gel layer (2) is provided with a groove (4), and the groove (4) is used for collecting and storing the discharged sweat, wherein the groove (4) is of the order of microns groove; 活性选择凝胶层(3),设置在所述工作电极(11)上,所述活性选择凝胶层(3)用于从所述沟槽(4)溢出的汗液中选择相应的离子,使得所述工作电极(11)检测所述汗液中包含的所述离子的浓度。An active selection gel layer (3) is arranged on the working electrode (11), and the active selection gel layer (3) is used to select corresponding ions from the sweat overflowing from the groove (4), so that The working electrode (11) detects the concentration of the ions contained in the sweat. 2.根据权利要求1所述的传感器,其中,所述工作电极(11)的数量为一个及以上,所述工作电极(11)与所述活性选择凝胶层(3)一对应,所述一个及以上的活性选择凝胶层(3)用于分别从所述沟槽(4)溢出的汗液中选择相应种类的离子,使得所述一个及以上的工作电极(11)分别检测所述汗液中包含的一种及以上的离子的浓度。2. The sensor according to claim 1, wherein the number of the working electrodes (11) is one or more, the working electrodes (11) correspond to the active selective gel layer (3), the One or more active selection gel layers (3) are used to select corresponding types of ions from the sweat overflowing from the grooves (4), so that the one and more working electrodes (11) detect the sweat respectively The concentration of one or more ions contained in . 3.根据权利要求1所述的传感器,其中,所述活性选择凝胶层(3)至少包括用于选择钠离子的活性选择凝胶层、用于选择钾离子的活性选择凝胶层以及用于选择钙离子的活性选择凝胶层中的一种及以上。3. The sensor according to claim 1, wherein the active selective gel layer (3) comprises at least an active selective gel layer for selecting sodium ions, an active selective gel layer for selecting potassium ions, and an active selective gel layer for selecting potassium ions. One or more of the gel layers are selected for the activity of selecting calcium ions. 4.根据权利要求3所述的传感器,其中,所述用于选择钠离子的活性选择凝胶层中的活性物质为缬氨酸霉素,所述用于选择钾离子的活性选择凝胶层中的活性物质为双冠醚,所述用于选择钙离子的活性选择凝胶层中的活性物质为异辛基苯基磷酸钙。4. The sensor according to claim 3, wherein the active substance in the active selective gel layer for selecting sodium ions is valinemycin, and the active selective gel layer for selecting potassium ions The active substance in is double crown ether, and the active substance in the active selective gel layer for selecting calcium ions is isooctylphenyl calcium phosphate. 5.根据权利要求1所述的传感器,其中,所述双电极体系(1)的支撑基材为柔性材料,所述柔性材料的柔度大于预设值。5. The sensor according to claim 1, wherein the supporting substrate of the two-electrode system (1) is a flexible material, and the flexibility of the flexible material is greater than a preset value. 6.根据权利要求1所述的传感器,其中,所述电渗凝胶层(2)中促排剂的含量不大于0.1%w/w。6. The sensor according to claim 1, wherein the content of the expulsion agent in the electroosmotic gel layer (2) is not more than 0.1% w/w. 7.根据权利要求1所述的传感器,其中,当所述传感器用于运动监测中的汗液检测时,所述电渗凝胶层(2)中不包含所述促排剂。7. The sensor according to claim 1, wherein, when the sensor is used for sweat detection in sports monitoring, the electroosmotic gel layer (2) does not contain the expulsion agent. 8.一种用于汗液检测的传感器的制备方法,包括:8. A preparation method of a sensor for sweat detection, comprising: 制备双电极体系(1),所述双电极体系(1)包括工作电极(11)和对/参比电极(12),其中,所述对/参比电极(12)包围所述工作电极(11);A two-electrode system (1) is prepared, the two-electrode system (1) comprising a working electrode (11) and a counter/reference electrode (12), wherein the counter/reference electrode (12) surrounds the working electrode ( 11); 在所述对/参比电极(12)上制备电渗凝胶层(2),并在所述电渗凝胶层(2)中加入促排剂以促进排出汗液,在所述电渗凝胶层(2)中设置微米量级的沟槽(4)以对排出的汗液进行收集及存放;An electroosmotic gel layer (2) is prepared on the counter/reference electrode (12), and an excretion agent is added to the electroosmotic gel layer (2) to promote the excretion of sweat, and the electroosmotic coagulation Micron-level grooves (4) are arranged in the adhesive layer (2) to collect and store the discharged sweat; 在所述工作电极(11)上制备活性选择凝胶层(3),所述活性选择凝胶层(3)用于从所述沟槽(4)溢出的汗液中选择相应的离子,使得所述工作电极(11)检测所述汗液中包含的所述离子的浓度。An active selective gel layer (3) is prepared on the working electrode (11), the active selective gel layer (3) is used to select the corresponding ions from the sweat overflowing from the groove (4), so that all The working electrode (11) detects the concentration of the ions contained in the sweat. 9.根据权利要求8所述的制备方法,其中,所述制备双电极体系(1)包括:9. The preparation method according to claim 8, wherein the preparation of the two-electrode system (1) comprises: 以柔性材料作为支撑基材,在所述支撑基材上制备所述双电极体系(1),所述柔性材料的柔度大于预设值。The two-electrode system (1) is prepared on the supporting substrate by using a flexible material as a supporting substrate, and the flexibility of the flexible material is greater than a preset value. 10.根据权利要求8所述的制备方法,其中,所述在所述工作电极(11)上制备活性选择凝胶层(3)包括:10. The preparation method according to claim 8, wherein the preparation of the active selective gel layer (3) on the working electrode (11) comprises: 以柔性材料作为基底,在所述基底上制备选择性敏感膜,以形成所述活性选择凝胶层(3);Using a flexible material as a substrate, a selective sensitive membrane is prepared on the substrate to form the active selective gel layer (3); 将所述活性选择凝胶层(3)放置于所述工作电极(11)上。The active selective gel layer (3) is placed on the working electrode (11).
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