Wearable sensor based on supramolecular modification and preparation method and application thereof
Patent Information
- Application Number
- CN202311154515.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-07
- Publication Date
- 2026-10-27
- Estimated Expiration
- 2043-09-07
Smart Images
Figure CN117434134B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of sensor technology, and in particular to a wearable sensor based on supramolecular modification, its preparation method, and its application. Background Technology
[0002] With the rapid development of technology, wearable sensing devices can continuously and closely monitor an individual's vital activities by being worn or closely integrated with the skin. However, most wearable sensing devices at present can only track some physical parameters related to an individual's physical activities or vital signs, and cannot reflect an individual's physiological state at the molecular level in a timely manner.
[0003] Sweat is not only a biofluid secreted by sweat glands within the body, but it can also reflect metabolic information about bodily functions. Metabolites in sweat, such as glucose, lactic acid, urea, ethanol, and inorganic salt ions, are potential analytes for non-invasive monitoring of human physiological conditions. Glucose is the primary source of energy for the human body and is associated with diabetes, Alzheimer's disease, and kidney complications. Glucose is recognized as an important health indicator, and studies have shown a correlation between glucose levels in sweat and their concentration in the blood. Therefore, there is an urgent need for a wearable sensing device based on sweat to monitor various physiologically relevant signals in real time. Summary of the Invention
[0004] To address the aforementioned issues, this invention aims to provide a wearable sensor based on supramolecular modification, its preparation method, and its application.
[0005] The technical solution of the present invention is as follows:
[0006] On the one hand, a wearable sensor based on supramolecular modification is provided, including a sensor substrate and a wearable device for wearing the sensor substrate on human skin;
[0007] The sensor substrate is provided with a glucose detection working electrode, a reference electrode and a counter electrode. The glucose detection working electrode is provided with a modification layer, which is a supramolecular modified inorganic / organic material.
[0008] Preferably, the supramolecular modified inorganic / organic material is any one of supramolecular modified carbides, oxides, sulfides, nitrides, graphene, and organometallic frameworks.
[0009] Preferably, the supramolecular modified inorganic / organic material is a metal-polyphenol supramolecular layer modified metal oxide.
[0010] Preferably, the metal salt used in the metal-polyphenol supramolecular layer modified metal oxide is a metal chloride salt, a metal nitrate salt, or a metal sulfate salt;
[0011] The metal salt used is cerium, iron, cobalt, manganese, zinc, aluminum, copper, molybdenum, zirconium, ruthenium, rhodium, gallium, magnesium, or vanadium;
[0012] The polyphenols used in the metal-polyphenol supramolecular layer modified metal oxide are tannic acid, gallic acid, catechin, anthocyanin, pyrogallol, amino acids, polyphenol amides, or phenol.
[0013] Preferably, the mass-to-volume ratio of the metal oxide to the metal salt solution in the metal-polyphenol supramolecular layer modified metal oxide is 1-10 mg: 40-400 μL, and the mass-to-volume ratio of the metal oxide to the polyphenol solution is 1-10 mg: 400-4000 μL.
[0014] Preferably, the sensor substrate is made of polyimide, polydimethylsiloxane, polyacrylamide, polyethylene naphthalate, or polyethylene terephthalate.
[0015] Preferably, the reference electrode is an Ag / AgCl reference electrode, and the counter electrode is a Pt counter electrode.
[0016] Preferably, the width of the glucose detection working electrode, reference electrode, and counter electrode is 2-3.2 mm, and the electrode spacing is 2-3.2 mm.
[0017] On the other hand, a method for preparing a wearable sensor based on supramolecular modification as described in any one of the above claims is also provided, comprising the following steps: cutting the sensor substrate to the target size, cleaning it sequentially with ultrapure water, ethanol, and ultrapure water, and drying and fixing it on a glass plate; transferring the glucose detection working electrode, reference electrode, and counter electrode onto the sensor substrate to obtain the wearable sensor based on supramolecular modification.
[0018] On the other hand, an application of the supramolecular modified wearable sensor described in any one of the above claims in analyzing glucose concentration in sweat is also provided.
[0019] The beneficial effects of this invention are:
[0020] The wearable sensor based on supramolecular modification described in this invention has high sensitivity, wide detection range, and low detection limit; it adopts an enzyme-free detection method, utilizing the enhanced detection sensitivity and accuracy of inorganic / organic materials after supramolecular modification, while ensuring the stability of the structure and catalytic activity of the organic / inorganic materials; this invention can achieve rapid detection of glucose levels in sweat, and the flexible electrode can be bent without damaging the internal circuitry, making it safer to use. Attached Figure Description
[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0022] Figure 1 This is a schematic diagram of the structure of the wearable sensor based on supramolecular modification according to the present invention;
[0023] Figure 2 Here is a SEM image of CoMoO4@Co-GA from Example 1;
[0024] Figure 3 The XRD pattern of CoMoO4@Co-GA in Example 1;
[0025] Figure 4 The electrode of Example 1 is shown as a time-current response curve to a glucose concentration gradient at 0.5V.
[0026] Figure 5 The calibration curve of the electrode in Example 1 responding to a glucose concentration gradient at 0.5V is shown.
[0027] Figure 6 This is a schematic diagram showing the comparison results of the sensitivity and detection limit of wearable sensors in various embodiments and comparative examples.
[0028] The numbers in the diagram are: 1-wearable device, 2-sensor substrate, 3-glucose detection working electrode, 4-reference electrode, 5-pair electrode. Detailed Implementation
[0029] The present invention will be further described below with reference to the accompanying drawings and embodiments. It should be noted that, unless otherwise specified, the embodiments and technical features described in this application can be combined with each other. It should also be pointed out that, unless otherwise indicated, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. The terms "comprising" or "including" and similar words used in this invention refer to elements or objects preceding the word that encompass the elements or objects listed following the word and their equivalents, without excluding other elements or objects.
[0030] On the one hand, such as Figure 1As shown, the present invention provides a wearable sensor based on supramolecular modification, including a sensor substrate 2 and a wearable device 1 for wearing the sensor substrate 2 on human skin; the sensor substrate 2 is provided with a glucose detection working electrode 3, a reference electrode 4 and a counter electrode 5, and the glucose detection working electrode 3 is provided with a modification layer, which is a supramolecular modified inorganic / organic material.
[0031] In one specific embodiment, the wearable device 1 is made of adhesive tape, through which the sensor substrate 2 is worn onto human skin.
[0032] In one specific embodiment, the supramolecular modified inorganic / organic material is any one of supramolecular modified carbides, oxides, sulfides, nitrides, graphene, and organometallic frameworks.
[0033] Optionally, the supramolecular modified inorganic / organic material is a metal-polyphenol supramolecular layer modified metal oxide. The metal salt used in the metal-polyphenol supramolecular layer modified metal oxide is a metal chloride, metal nitrate, or metal sulfate; the metal used in the metal salt is cerium, iron, cobalt, manganese, zinc, aluminum, copper, molybdenum, zirconium, ruthenium, rhodium, gallium, magnesium, or vanadium; the polyphenol used in the metal-polyphenol supramolecular layer modified metal oxide is tannic acid, gallic acid, catechin, anthocyanin, pyrogallol, amino acids, polyphenol amides, or phenol.
[0034] In one specific embodiment, the mass-to-volume ratio of the metal oxide to the metal salt solution in the metal-polyphenol supramolecular layer modified metal oxide is 1-10 mg: 40-400 μL, and the mass-to-volume ratio of the metal oxide to the polyphenol solution is 1-10 mg: 400-4000 μL.
[0035] In one specific embodiment, the sensor substrate is made of polyimide, polydimethylsiloxane, polyacrylamide, polyethylene naphthalate, or polyethylene terephthalate, the reference electrode is an Ag / AgCl reference electrode, and the counter electrode is a Pt counter electrode.
[0036] Optionally, the width of the glucose detection working electrode, reference electrode, and counter electrode is 2-3.2 mm, and the electrode spacing is 2-3.2 mm.
[0037] On the other hand, the present invention also provides a method for preparing a wearable sensor based on supramolecular modification as described in any one of the above claims, comprising the following steps: cutting the sensor substrate to a target size, cleaning it sequentially with ultrapure water, ethanol, and ultrapure water, and drying and fixing it on a glass plate; transferring the glucose detection working electrode, reference electrode, and counter electrode onto the sensor substrate to obtain the wearable sensor based on supramolecular modification.
[0038] On the other hand, the present invention also provides an application of the supramolecular modified wearable sensor described in any one of the above claims in the analysis of glucose concentration in sweat.
[0039] Example 1: A wearable sensor based on supramolecular modification
[0040] 5 mg CoMoO4 was dispersed in 200 μL of deionized water to form a suspension. 1500 μL of 24 mM gallic acid (GA) solution and 200 μL of 24 mM cobalt chloride solution were added, and the mixture was vortexed for 120 s each time. The vortexed suspension was then washed twice alternately with ethanol and deionized water, and centrifuged at 3000 rpm. The washed and centrifuged material was freeze-dried at -20 °C for 48 h to obtain the supramolecularly modified working electrode material, denoted as CoMoO4@Co-GA. Figure 2 The image shows a SEM image of CoMoO4@Co-GA, which reveals that CoMoO4@Co-GA consists of nanoparticles with a rough surface. This roughness is due to the presence of a Co-GA coating structure on the surface. Figure 3 The XRD pattern of CoMoO4@Co-GA is shown. By comparing it with the standard card, it can be concluded that the Co-GA coating has an amorphous supramolecular structure.
[0041] 10 mg of CoMoO4@Co-GA was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto the sensor substrate to obtain the supramolecular modified wearable sensor, which was then used for glucose detection in sweat.
[0042] Figure 4 The time-current response curves are shown for adding glucose solutions of different concentrations to the electrolyte at 0.5V. Figure 5 The calibration curve is shown for the glucose concentration gradient response at 0.5V. Experimental results indicate that the sensitivity of the supramolecular modified wearable sensor CoMoO4@Co-GA described in this invention for glucose detection is 5058.25 μM. -1 cm -2 The detection range is 0.05–7030 μM, and the detection limit is 0.02 μM when the signal / noise ratio is 3 (S / N = 3).
[0043] Example 2: A wearable sensor based on supramolecular modification
[0044] 5 mg Cr3C2 was dispersed in 200 μL of deionized water to form a suspension. 1800 μL of 24 mM catechin (CT) solution and 100 μL of 24 mM manganese chloride solution were added, and the mixture was vortexed for 120 s. The vortexed suspension was then washed twice alternately with ethanol and deionized water, and centrifuged at 4000 rpm. The washed and centrifuged material was freeze-dried at -20 °C for 48 h to obtain the supramolecularly modified working electrode material, denoted as Cr3C2@Mn-CT.
[0045] The sensor preparation and testing process were the same as in Example 1. Experimental results showed that the sensitivity of the supramolecular modified wearable sensor Cr3C2@Mn-CT described in this invention for glucose detection was 4900.13 μM. -1 cm -2 The detection range is 0.07–6550 μM, and the detection limit is 0.03 μM when the signal / noise ratio is 3 (S / N = 3).
[0046] Example 3: A wearable sensor based on supramolecular modification
[0047] 5 mg of MoS2 was dispersed in 200 μL of deionized water to form a suspension. 1000 μL of 24 mM pyrogallol (PG) solution and 200 μL of 24 mM chromium chloride solution were added, and the mixture was vortexed for 120 s each time. The vortexed suspension was then washed twice alternately with ethanol and deionized water, and centrifuged at 6000 rpm. The washed and centrifuged material was freeze-dried at -20 °C for 48 h to obtain the supramolecularly modified working electrode material, denoted as MoS2@Cr-PG.
[0048] The sensor preparation and testing process were the same as in Example 1. Experimental results showed that the sensitivity of the supramolecular modified wearable sensor MoS2@Cr-PG described in this invention for glucose detection was 4350.29 μA mM. -1 cm -2 The detection range is 0.08–6900 μM, and the detection limit is 0.06 μM when the signal / noise ratio is 3 (S / N = 3).
[0049] Example 4: A wearable sensor based on supramolecular modification
[0050] 5 mg TiN was dispersed in 200 μL of deionized water to form a suspension. 1500 μL of 24 mM anthocyanin (APC) solution and 150 μL of 24 mM zinc chloride solution were added, and the mixture was vortexed for 120 s each time. The vortexed suspension was then washed twice alternately with ethanol and deionized water, and centrifuged at 5000 rpm. The washed and centrifuged material was freeze-dried at -20 °C for 48 h to obtain the supramolecularly modified working electrode material, denoted as TiN@Zn-APC.
[0051] The sensor fabrication and testing processes were the same as in Example 1. Experimental results showed that the wearable sensor TiN@Zn-APC based on supramolecular modification described in this invention has a sensitivity of 4190.28 μA mM for glucose detection. -1 cm -2 The detection range is 0.1–6100 μM, and the detection limit is 0.085 μM when the signal / noise ratio is 3 (S / N = 3).
[0052] Example 5: A wearable sensor based on supramolecular modification
[0053] 5 mg ZnO / GO was dispersed in 200 μL of deionized water to form a suspension. 2200 μL of 24 mM tannic acid (TA) solution and 200 μL of 24 mM copper chloride solution were added, and the mixture was vortexed for 120 s each time. The vortexed suspension was then washed twice alternately with ethanol and deionized water, and centrifuged at 5500 rpm. The washed and centrifuged material was freeze-dried at -20 °C for 48 h to obtain the supramolecularly modified working electrode material, denoted as ZnO / GO@Cu-TA.
[0054] The sensor preparation and testing process were the same as in Example 1. Experimental results showed that the sensitivity of the supramolecular modified wearable sensor ZnO / GO@Cu-TA described in this invention for glucose detection was 4200.36 μA mM. -1 cm -2 The detection range is 0.15–5300 μM, and the detection limit is 0.04 μM when the signal / noise ratio is 3 (S / N = 3).
[0055] Example 6: A wearable sensor based on supramolecular modification
[0056] 5 mg Zr-MOF was dispersed in 200 μL of deionized water to form a suspension. 1500 μL of 24 mM phenol (Ph) solution and 150 μL of 24 mM ferric chloride solution were added, and the mixture was vortexed for 120 s each time. The vortexed suspension was then washed twice alternately with ethanol and deionized water, and centrifuged at 5000 rpm. The washed and centrifuged material was freeze-dried at -20 °C for 48 h to obtain the supramolecularly modified working electrode material, denoted as Zr-MOF@Fe-Ph.
[0057] The sensor fabrication and testing processes were the same as in Example 1. Experimental results showed that the sensitivity of the supramolecular modified wearable sensor Zr-MOF@Fe-Ph described in this invention for glucose detection was 4755.20 μA mM. -1 cm -2 The detection range is 0.05–5800 μM, and the detection limit is 0.02 μM when the signal / noise ratio is 3 (S / N = 3).
[0058] Comparative Example 1: A Wearable Sensor
[0059] 10 mg of CoMoO4 electrode material was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto a sensor substrate to obtain a wearable sensor, which was used for glucose detection in sweat.
[0060] The testing procedure was the same as in Example 1. Experimental results showed that the sensitivity of the wearable CoMoO4 sensor for glucose detection was 2915.7 μAmM. -1 cm -2 The detection range is 0.3–7000 μM, and the detection limit is 0.2 μM when the signal / noise ratio is 3 (S / N = 3).
[0061] According to the test results of Example 1 and Comparative Example 1, the wearable sensor based on supramolecular modification described in this invention has improved the sensitivity of glucose detection by 73.48%; the detection range has also been expanded, and it can detect glucose in the range of 0.05-0.3 μM and 7000-7030 μM, while the detection limit has been reduced from 0.2 μM to 0.02 μM.
[0062] Comparative Example 2: A Wearable Sensor
[0063] 10 mg of Cr3C2 electrode material was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto a sensor substrate to obtain a wearable sensor, which was used for glucose detection in sweat.
[0064] The testing procedure was the same as in Example 1. Experimental results showed that the sensitivity of the wearable Cr3C2 sensor for glucose detection was 2100.9 μM. -1 cm -2 The detection range is 0.7–5900 μM, and the detection limit is 0.5 μM when the signal / noise ratio is 3 (S / N = 3).
[0065] According to the test results of Example 2 and Comparative Example 2, the wearable sensor based on supramolecular modification described in this invention has improved the sensitivity of glucose detection by 133.24% and expanded the detection range to 0.07-0.7 μM and 5900-6550 μM, while the detection limit has decreased from 0.5 μM to 0.03 μM.
[0066] Comparative Example 3: A Wearable Sensor
[0067] 10 mg of MoS2 electrode material was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto a sensor substrate to obtain a wearable sensor, which was used for glucose detection in sweat.
[0068] The testing procedure was the same as in Example 1. Experimental results showed that the wearable MoS2 sensor had a sensitivity of 1846.3 μA mM for glucose detection. -1 cm -2 The detection range is 0.9–6080 μM, and the detection limit is 0.65 μM when the signal / noise ratio is 3 (S / N = 3).
[0069] According to the test results of Example 3 and Comparative Example 3, the wearable sensor based on supramolecular modification described in this invention has improved the sensitivity of glucose detection by 135.62% and expanded the detection range to 0.08-0.9 μM and 6080-6900 μM, while the detection limit has decreased from 0.65 μM to 0.06 μM.
[0070] Comparative Example 4: A Wearable Sensor
[0071] 10 mg of TiN electrode material was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto a sensor substrate to obtain a wearable sensor, which was used for glucose detection in sweat.
[0072] The testing procedure was the same as in Example 1. Experimental results showed that the wearable TiN sensor had a sensitivity of 2239.5 μAmM for glucose detection. -1 cm -2 The detection range is 0.2–4900 μM, and the detection limit is 0.12 μM when the signal / noise ratio is 3 (S / N = 3).
[0073] According to the test results of Example 4 and Comparative Example 4, the wearable sensor based on supramolecular modification described in this invention has improved the sensitivity of glucose detection by 87.11% and expanded the detection range to 0.1-0.2 μM and 4900-6100 μM, and the detection limit has been reduced from 0.12 μM to 0.085 μM.
[0074] Comparative Example 5: A Wearable Sensor
[0075] 10 mg of ZnO / GO electrode material was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto a sensor substrate to obtain a wearable sensor, which was used for glucose detection in sweat.
[0076] The testing procedure was the same as in Example 1. Experimental results showed that the wearable ZnO / GO sensor had a sensitivity of 1637.1 μAmM for glucose detection. -1 cm -2 The detection range is 0.2–3850 μM, and the detection limit is 0.16 μM when the signal / noise ratio is 3 (S / N = 3).
[0077] According to the test results of Example 5 and Comparative Example 5, the wearable sensor based on supramolecular modification described in this invention has improved the sensitivity of glucose detection by 156.57% and expanded the detection range to 0.15-0.2 μM and 3850-5300 μM, while the detection limit has decreased from 0.16 μM to 0.04 μM.
[0078] Comparative Example 6: A Wearable Sensor
[0079] 10 mg of Zr-MOF electrode material was weighed and dispersed in deionized water and Nafion solution to obtain ink. The uniformly dispersed ink was then evenly drop-coated onto the glucose detection working electrode. The glucose detection working electrode, reference electrode, and counter electrode were then transferred onto a sensor substrate to obtain a wearable sensor, which was used for glucose detection in sweat.
[0080] The testing procedure was the same as in Example 1. Experimental results showed that the sensitivity of the wearable Zr-MOF sensor for glucose detection was 1559.2 μAmM. -1 cm -2 The detection range is 0.5–5300 μM, and the detection limit is 0.39 μM when the signal / noise ratio is 3 (S / N = 3).
[0081] According to the test results of Example 6 and Comparative Example 6, the wearable sensor based on supramolecular modification described in this invention has improved the sensitivity of glucose detection by 204.98%, and the detection range has also been expanded. It can detect glucose in the range of 0.05-0.5 μM and 5300-5800 μM, and the detection limit has been reduced from 0.39 μM to 0.02 μM.
[0082] The comparison results of sensitivity and detection limit of wearable sensors in each embodiment and comparative example are as follows: Figure 6 As shown.
[0083] In summary, this invention enables rapid detection of glucose levels in sweat, and compared to unmodified wearable sensors, it offers a 73.48%-204.98% increase in sensitivity, a wider detection range, and a lower detection limit. This invention represents a significant advancement over existing technologies.
[0084] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.
Claims
1. A wearable sensor based on supramolecular modification, characterized in that, Includes a sensor substrate and a wearable device for wearing the sensor substrate onto human skin; The sensor substrate is provided with a glucose detection working electrode, a reference electrode, and a counter electrode. The glucose detection working electrode is provided with a modification layer, which is CoMoO4@Co-gallic acid, Cr3C2@Mn-catechin, MoS2@Cr-pyrogallol, TiN@Zn-anthocyanin, ZnO / GO@Cu-tannic acid, or Zr-MOF@Fe-phenol.
2. The wearable sensor based on supramolecular modification according to claim 1, characterized in that, The sensor substrate is made of polyimide, polydimethylsiloxane, polyethylene naphthalate, or polyethylene terephthalate.
3. The wearable sensor based on supramolecular modification according to claim 1 or 2, characterized in that, The reference electrode is an Ag / AgCl reference electrode, and the counter electrode is a Pt counter electrode.
4. The wearable sensor based on supramolecular modification according to any one of claims 1-3, characterized in that, The width of the glucose detection working electrode, reference electrode, and counter electrode is 2-3.2 mm, and the electrode spacing is 2-3.2 mm.
5. The method for preparing a wearable sensor based on supramolecular modification as described in any one of claims 1-4, characterized in that, Includes the following steps: The sensor substrate is cut to the target size, cleaned sequentially with ultrapure water, ethanol, and ultrapure water, and then dried and fixed onto a glass plate. The glucose detection working electrode, reference electrode, and counter electrode are transferred onto the sensor substrate to obtain the wearable sensor based on supramolecular modification.
6. The application of the supramolecular modified wearable sensor as described in any one of claims 1-4 in the analysis of glucose concentration in sweat.