Wearable sensing type multi-component sweat sensing patch, preparation method thereof and intelligent detection system
By designing a wearable multi-component sweat sensor patch and using the synergistic effect of signal probes and thermal stimulation layers, the calibration and signal stability problems in sweat analysis are solved, and high-sensitivity real-time monitoring is achieved, which is suitable for metabolic and chronic disease management.
Patent Information
- Application Number
- CN202511259151.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-04
- Publication Date
- 2025-10-03
- Estimated Expiration
- 2045-09-04
AI Technical Summary
Existing wearable devices face problems in sweat analysis, such as calibration and signal stability that are difficult to adapt to real-time monitoring needs, low sensitivity, and a contradiction between device miniaturization and comfort, which affects the continuous acquisition of multi-channel detection.
A wearable multi-component sweat sensor patch is designed, including an epidermal contact layer, a thermal stimulation layer, a microfluidic channel and a sensing layer. Different signal probes are used to selectively bind calcium ions, potassium ions, uric acid and glucose. The molecular binding is converted into a color signal through nanoparticle aggregation or indicator displacement. The thermal stimulation layer is used to optimize sweat generation and collection. Signal acquisition, data amplification and machine learning are combined to achieve electronic component-free detection.
It achieves synchronous detection of targets in sweat, improves calibration and signal stability, adapts to real-time monitoring needs, has high sensitivity, and is suitable for metabolic monitoring, sports medicine, and chronic disease management.
Smart Images

Figure CN120732407A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of sensing detection technology, and in particular to a wearable sensing multi-component sweat sensor patch and a preparation method thereof, and an intelligent detection system. Background Art
[0002] Currently, commercial wearable devices (such as smartwatches and fitness trackers) integrate high-precision microsensors to continuously and dynamically monitor physiological parameters such as body temperature, heart rate, and blood oxygen saturation. Using algorithms and models, these physical signals are transformed into visual representations of health status. Using non-invasive detection methods, these devices have successfully established a real-time monitoring network for basic human physiological indicators, providing important technical support for scenarios such as cardiovascular health assessment and motor function analysis.
[0003] Due to the complexity and multidimensionality of various diseases, deeper, multifaceted information at the molecular level is required before wearable sensors can be used for disease monitoring. As a biofluid rich in multidimensional molecular information, including electrolytes, metabolites, hormones, and proteins, sweat provides a unique window for noninvasive and continuous monitoring of human biochemical dynamics. However, current wearable sensing technologies for sweat analysis still face multiple bottlenecks. First, sweat molecular signals exhibit high individual variability and dynamic fluctuations (e.g., pH and ion concentration gradients), making sensor calibration and signal stability difficult to adapt to real-time monitoring needs. Second, the precise capture of low-abundance target molecules (e.g., picomolar cortisol and micromolar glucose) places extremely high demands on sensor sensitivity and selectivity. Existing electrochemical and optical sensing materials are susceptible to interference from the complex sweat matrix. Third, the contradiction between device miniaturization and comfort is prominent. The integration of high-precision multi-channel detection modules often sacrifices wearable breathability and long-term fit, limiting the continuous acquisition of clinical-grade data.
[0004] Therefore, the existing technology still needs to be improved and developed. Summary of the Invention
[0005] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a wearable sensing multi-component sweat sensor patch and its preparation method and intelligent detection system, aiming to solve the problems that the calibration and signal stability of the existing sweat sensor patch are difficult to adapt to real-time monitoring needs and have low sensitivity.
[0006] The technical solutions of the present invention are as follows: A wearable multi-component sweat sensing patch, comprising: Epidermal contact layer, for contact with the skin surface; a thermal stimulation layer, disposed on one side of the epidermal contact layer; a microfluidic channel disposed on one side of the epidermal contact layer and in the same layer as the thermal stimulation layer; A sensing layer is provided at one end of the microfluidic channel; the sensing layer comprises four independent chambers, each of which is loaded with a different signal probe for performing a colorimetric reaction with a target in sweat; The breathable packaging layer is adhered to the epidermal contact layer; the thermal stimulation layer, the microfluidic channel and the sensing layer are sandwiched between the epidermal contact layer and the breathable packaging layer.
[0007] The wearable multi-component sweat sensor patch, wherein the target substances include calcium ions, potassium ions, uric acid, and glucose.
[0008] The wearable multi-component sweat sensor patch, wherein the signal probes include a calcium ion recognition probe, a potassium ion recognition probe, a uric acid recognition probe, and a glucose recognition probe; the calcium ion recognition probe is a naphthalene diimide modified with an azacrown ether; the potassium ion recognition probe is a gold nanoparticle modified with 4'-aminodibenzo-18-crown-6; the uric acid recognition probe is a complex of a water-soluble naphthyl tetralactam macrocyclic compound and the phenolic dye resorufin; and the glucose recognition probe is a chitosan composite material loaded with silver nanoparticles.
[0009] The wearable sensing multi-component sweat sensor patch, wherein the material of the epidermal contact layer and the breathable packaging layer is selected from one of polyethylene terephthalate, thermoplastic polyurethane, and polydimethylsiloxane; the epidermal contact layer and the breathable packaging layer are provided with through holes with a pore size of 1.0 mm to 1.4 mm.
[0010] The wearable sensing multi-component sweat sensor patch, wherein the thermal stimulation layer includes a first arc-shaped thermal stimulation chamber and a second arc-shaped thermal stimulation chamber that are symmetrically arranged; the microfluidic channel and the sensing layer are located between the first arc-shaped thermal stimulation chamber and the second arc-shaped thermal stimulation chamber.
[0011] The wearable sensing multi-component sweat sensor patch, wherein the cross-section of the microfluidic channel in the thickness direction of the wearable sensing multi-component sweat sensor patch is trapezoidal.
[0012] A method for preparing a wearable multi-component sweat sensor patch comprises the following steps: performing plasma treatment on the epidermal contact film to obtain an epidermal contact layer; injecting a thermal stimulation material into the mold on one side of the epidermis contact layer to obtain a thermal stimulation layer; forming a tree-like fractal channel network on the epidermal contact layer by using a printing and demoulding process to obtain a microfluidic channel; In situ synthesizing a signal probe at one end of the microfluidic channel to form a sensing layer with four independent chambers; The thermal stimulation layer, the microfluidic channel and the sensing layer are covered with a breathable packaging film, and laminated with the epidermal contact layer to prepare a wearable sensing multi-component sweat sensing patch.
[0013] The preparation method of the wearable sensing multi-component sweat sensor patch, wherein the signal probes include a calcium ion recognition probe, a potassium ion recognition probe, a uric acid recognition probe, and a glucose recognition probe; The preparation steps of the calcium ion recognition probe include: mixing and grinding dibromo-substituted naphthalene diimide and azacrown ether under the catalysis of anhydrous potassium carbonate and copper sulfate, and heating the mixture in the absence of solvent to obtain the calcium ion recognition probe; The preparation steps of the potassium ion recognition probe include: preparing gold nanoparticles by using a sodium citrate reduction method, and then modifying the gold nanoparticles by using 4'-aminodibenzo-18-crown-6 to obtain the potassium ion recognition probe.
[0014] The preparation method of the wearable multi-component sweat sensor patch, wherein the uric acid recognition probe is a complex of a water-soluble naphthyl tetralactam macrocyclic compound and a phenolazine dye resorufin; the preparation method of the complex of the water-soluble naphthyl tetralactam macrocyclic compound and a phenolazine dye resorufin comprises the steps of: 2,6-dihydroxynaphthalene and trimesic acid were mixed, and the intermediate was constructed through ethyl bromide substitution, paraformaldehyde bridging and amination reaction; The intermediate is used to achieve a ring-closing reaction between a diester and a diamine in dichloromethane by a pseudo-high dilution method to form a rigid skeleton with 2,6-diethoxynaphthalene as a hydrophobic side wall and four lactam bonds as polar sites; The rigid skeleton is hydrolyzed with trifluoroacetic acid to form an ester group and alkalized to introduce a sodium carboxylate hydrophilic group to obtain a water-soluble naphthyl tetralactam macrocyclic compound; The water-soluble naphthyl tetralactam macrocyclic compound and the phenolazine dye resorufin are subjected to an indicator displacement reaction to obtain a complex.
[0015] A wearable sensor-based multi-component sweat intelligent detection system, comprising: Wearable sensing multi-component sweat sensing patch; a signal acquisition unit, configured to acquire a color spectrum of the sensing layer on the wearable multi-component sweat sensor patch to form a basic data set; a data amplification unit, configured to amplify the basic data set to form an amplified data set; The machine learning analysis unit is used to perform training using the amplified data set and output a sweat detection result based on the color spectrum collected by the signal collection unit.
[0016] Beneficial effects: The present invention provides a wearable sensing multi-component sweat sensor patch and a preparation method thereof, and an intelligent detection system. The wearable sensing multi-component sweat sensor patch includes: an epidermal contact layer, which is used to contact the skin surface; a thermal stimulation layer, which is arranged on one side of the epidermal contact layer; a microfluidic channel, which is arranged on one side of the epidermal contact layer and is in the same layer as the thermal stimulation layer; a sensing layer, which is arranged at one end of the microfluidic channel; the sensing layer includes four independent chambers, and the four independent chambers are respectively loaded with different signal probes for color reaction with target substances in sweat; a breathable packaging layer, which is attached to the epidermal contact layer; the thermal stimulation layer, the microfluidic channel and the sensing layer are sandwiched between the epidermal contact layer and the breathable packaging layer. This invention uses capillary action to drive the directional transport of sweat and achieve simultaneous detection of four target compounds in sweat. The sensing layer uses different signal probes to selectively bind calcium ions, potassium ions, uric acid, and glucose. Nanoparticle aggregation or indicator displacement converts these molecular bindings into color signals. A thermal stimulation layer simultaneously optimizes sweat generation and collection, improving the sweat sensor patch's calibration and signal stability, making it suitable for real-time monitoring and exhibiting high sensitivity. Furthermore, the sweat sensor patch combines signal acquisition, data amplification, and machine learning to achieve highly selective, multi-index sweat analysis without electronic components. This sweat sensor patch is suitable for metabolic monitoring, sports medicine, and chronic disease management. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Figure 1 This is a schematic diagram of the overall structure of a wearable multi-component sweat sensor patch of the present invention; Figure 2 This is a schematic diagram of the exploded structure of a wearable multi-component sweat sensor patch of the present invention; Figure 3 This is a schematic diagram of the principle of the calcium ion recognition probe; Figure 4 This is a schematic diagram of the principle of the potassium ion recognition probe; Figure 5 Schematic diagram of the principle of uric acid recognition probe; Figure 6 This is a diagram showing the sensing effects of the calcium ion sensor, potassium ion sensor, and uric acid sensor in Example 1; Figure 7 The scanning electron micrographs of the analyte before and after binding to the main body 1, main body 2 and main body 3 in Example 1 are shown; Figure 8 Schematic diagram for calculating the non-covalent interaction force between host and guest using DFT; Figure 9 This is a diagram showing the effect of a wearable multi-component sweat sensing patch in sweat biomarker detection; Figure 10This is the confusion matrix result diagram integrated with the K-NN classification algorithm; Figure 11 The synthetic route diagram of water-soluble naphthyl tetralactam macrocyclic compounds; Figure 12 This is the selective verification result diagram; Explanation of reference numerals: epidermal contact layer 10 , thermal stimulation layer 20 , microfluidic channel 30 , sensing layer 40 , breathable packaging layer 50 , skin surface 100 . DETAILED DESCRIPTION
[0018] The present invention provides a wearable multi-component sweat sensor patch, a preparation method thereof, and an intelligent detection system. To clarify the objectives, technical solutions, and effects of the present invention, the present invention is described in further detail below. It should be understood that the specific embodiments described herein are intended only to illustrate the present invention and are not intended to limit the present invention.
[0019] It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art in the art to which the present invention belongs. It should also be understood that terms such as those defined in common dictionaries should be understood to have meanings consistent with their meanings in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless specifically defined as herein.
[0020] like Figure 1 and Figure 2 As shown, the present invention provides a wearable sensing multi-component sweat sensing patch, comprising: Epidermal contact layer 10, for contacting with skin surface 100; The thermal stimulation layer 20 is provided on one side of the epidermal contact layer 10; The microfluidic channel 30 is provided on one side of the epidermal contact layer 10 and is in the same layer as the thermal stimulation layer 20; The sensing layer 40 is disposed at one end of the microfluidic channel 30; the sensing layer 40 includes four independent chambers, each of which carries a different signal probe for performing a colorimetric reaction with a target substance in sweat; The breathable packaging layer 50 is attached to the epidermal contact layer; the thermal stimulation layer, the microfluidic channel and the sensing layer are sandwiched between the epidermal contact layer and the breathable packaging layer.
[0021] In this embodiment, capillary action drives the directional transport of sweat and enables the simultaneous detection of four target substances in sweat. The sensing layer uses different signal probes to selectively bind calcium ions, potassium ions, uric acid (UA), and glucose (Glu). Nanoparticle aggregation or indicator displacement converts molecular binding into color signals. A thermal stimulation layer simultaneously optimizes sweat generation and collection, improving the calibration and signal stability of the sweat sensor patch, making it suitable for real-time monitoring needs and exhibiting high sensitivity. Furthermore, the sweat sensor patch can combine signal acquisition, data amplification, and machine learning to achieve highly selective, multi-index sweat analysis without electronic components. This sweat sensor patch is suitable for metabolic monitoring, sports medicine, and chronic disease management.
[0022] Specifically, the wearable sensing multi-component sweat sensing patch achieves a color reaction of the target in sweat through the synergistic effect of microfluidic design, thermal stimulation of sweating and supramolecular precise recognition. By utilizing the color signals produced by the reaction between different signal probes loaded in the four independent chambers on the sensing layer and the target, the concentration of the target in sweat can be monitored in real time with high sensitivity. It exhibits the advantages of high sensitivity, strong anti-interference and multi-mode detection compatibility in the fields of environmental pollutant monitoring and biomarker sensing.
[0023] In some embodiments, the target substances include calcium ions, potassium ions, uric acid, and glucose. Calcium ions, potassium ions, uric acid, and glucose are important indicators of metabolites. Real-time monitoring of calcium ions, potassium ions, uric acid, and glucose in sweat using a sweat sensor patch can improve monitoring of the target substances.
[0024] In some embodiments, the signal probes include a calcium ion recognition probe, a potassium ion recognition probe, a uric acid recognition probe, and a glucose recognition probe; the calcium ion recognition probe is a naphthalene diimide modified with an azacrown ether; the potassium ion recognition probe is a gold nanoparticle modified with 4'-aminodibenzo-18-crown-6; the uric acid recognition probe is a mixture of a water-soluble naphthyl tetralactam macrocyclic compound and a phenolic dye resorufin; and the glucose recognition probe is a chitosan composite material loaded with silver nanoparticles.
[0025] Specifically, the four independent chambers each hold a different macrocyclic host. Leveraging its pre-organized cavity structure and multiple non-covalent synergistic interactions (including hydrogen bonding, hydrophobic effects, and ion-dipole interactions), the supramolecular macrocyclic host achieves highly selective recognition and binding of target ions / molecules. Furthermore, through the entropy-enthalpy synergy of host-guest complexation, it enriches the target in sweat, significantly increasing its local concentration and thus overcoming the sensitivity bottleneck of traditional detection methods. Furthermore, modular modification of the molecular backbone with functional nanomaterials (such as gold nanoparticles) and signal probe molecules (such as fluorescent dyes and electroactive molecules) creates a composite system that can be used to manipulate the coupling efficiency of molecular recognition and signal transduction, triggering visual / spectral detection signal outputs based on colorimetric reactions, fluorescence quenching / enhancement, or localized surface plasmon resonance.
[0026] In some embodiments, the target may also include but is not limited to cortisol and creatinine. In this case, the signal probe is replaced by a cortisol recognition probe and a creatinine recognition probe; the cortisol recognition probe and the creatinine recognition probe are cucurbituril or sulfonated calixarene, respectively.
[0027] In some embodiments, the skin contact layer and the breathable encapsulation layer are made of a material selected from polyethylene terephthalate (PET), thermoplastic polyurethane (TPU), and polydimethylsiloxane (PDMS). Through-holes with a pore size of 1.0 mm to 1.4 mm are provided in the skin contact layer and the breathable encapsulation layer. The material selection for the skin contact layer and the breathable encapsulation layer takes into account biocompatibility, flexibility, breathability, and compatibility with microfluidic structures. Similar materials include hydrogel composites and modified polylactic acid (PLA) materials. Preferably, the pore size of the through-holes is 1.2 mm ± 10%.
[0028] In some embodiments, the thermal stimulation layer includes a first curved thermal stimulation chamber and a second curved thermal stimulation chamber that are symmetrically arranged; the microfluidic channel and the sensing layer are located between the first curved thermal stimulation chamber and the second curved thermal stimulation chamber.
[0029] Specifically, the concave parts of the first arc-shaped thermal stimulation chamber and the second arc-shaped thermal stimulation chamber are arranged relative to each other, and an asymmetric thermal field (40-45°C gradient) is formed through the difference in curvature, which both directionally activates the sweat glands and inhibits edge heat diffusion.
[0030] In some embodiments, the thermal stimulation layer is formed from an iron-based composite composed of 60-85% by weight of iron powder, 10-30% by weight of activated carbon, and 2-15% by weight of sodium chloride. Preferably, the iron powder has a particle size of 200-400 mesh. The resulting iron-based composite, when subjected to continuous oxidation in an air environment (RH = 60%), reaches a temperature of 38±2°C within 30 minutes and is maintained for more than 6 hours.
[0031] Specifically, the thermal stimulation layer adjusts the reaction rate by adjusting the NaCl content and controls the temperature at 30-45°C; moreover, the double-arc layout of the thermal stimulation layer can make the heat flow evenly distributed (the temperature difference of the epidermis is less than 1.5°C), avoiding local burns.
[0032] In some embodiments, in the construction of a self-heating material system, a variety of inorganic composite materials based on redox exothermic reactions can be used as alternative heat sources for the iron-based micropowder mixture; specifically, calcium compounds (such as calcium oxide, calcium hydroxide), magnesium-iron composite metal powders, aluminum-activated quicklime mixtures, and transition metal oxide composite systems (such as the MnO2-CuO-Fe3O4 ternary system) can be selected.
[0033] In some embodiments, the cross-section of the microfluidic channel in the thickness direction of the wearable multi-component sweat sensor patch is trapezoidal. Using a microfluidic channel with a trapezoidal cross-section can optimize capillary flow rate.
[0034] In a preferred embodiment, the trapezoidal cross-section of the microfluidic channel has a top width of 0.1 mm, a bottom width of 0.15 mm, and a depth of 0.6 mm. A microfluidic channel of this size has a faster capillary flow rate, driving sweat to be directional transported to the sensing layer within 6 minutes.
[0035] In some embodiments, the epidermal contact layer 10 is provided with a sweat inlet 11 corresponding to the independent chamber, which is used to transport sweat on the skin surface into each independent chamber; the breathable packaging layer 50 is provided with a sweat outlet 51, which is used to discharge the sweat remaining after the independent chamber is detected; specifically, the sweat on the skin surface enters the independent chamber through the sweat inlet 11, and the remaining sweat is discharged from the sweat outlet 51 through the microfluidic channel.
[0036] In addition, the present invention also provides a method for preparing a wearable sensing multi-component sweat sensor patch, comprising the steps of: Step S10: performing plasma treatment on the epidermis contact film to obtain an epidermis contact layer; Step S20: injecting a thermal stimulation material into the mold on one side of the epidermal contact layer to obtain a thermal stimulation layer; Step S30: forming a tree-like fractal channel network on the epidermal contact layer by using a printing and demoulding process to obtain a microfluidic channel; Step S40: in situ synthesizing a signal probe at one end of the microfluidic channel to form a sensing layer with four independent chambers; Step S50: Covering the thermal stimulation layer, the microfluidic channel, and the sensing layer with a breathable packaging film, and laminating the film to the epidermal contact layer to prepare a wearable sensing multi-component sweat sensor patch.
[0037] In this embodiment, the wearable sensing multi-component sweat sensor patch prepared using this preparation method can drive the directional transmission of sweat through capillary action and realize the simultaneous detection of four target substances in sweat; wherein, the sensing layer uses different signal probes to selectively bind calcium ions, potassium ions, uric acid and glucose, and converts molecular binding into color signals through nanoparticle aggregation or indicator replacement. At the same time, the thermal stimulation layer is used to optimize sweat generation and collection, improve the calibration and signal stability of the sweat sensor patch, so that it is adapted to real-time monitoring needs and has high sensitivity.
[0038] In some embodiments, the power of the plasma treatment is 30 W and the time is 30 s; after the plasma treatment, the contact angle of the epidermal contact film can be reduced from 110° to less than 10°, thereby promoting capillary absorption of sweat.
[0039] In some embodiments, in step S30, a tree-like fractal channel network is formed by 3D printing a resin mold, then pouring PDMS and demolding the mold to obtain a microfluidic channel.
[0040] This method uses precision projection microstereolithography (PμSL) 3D printing technology to create a high-resolution resin master mold, combined with a polydimethylsiloxane (PDMS) molding process to construct microfluidic channels with precise microstructures. The specific steps include: preparing the master mold using biocompatible polymethacrylate (PMA) resin via 3D printing; mixing the PDMS matrix and curing agent in appropriate proportions, vacuum degassing, and then pouring it onto the master mold surface. Curing the PDMS layer by heating, the mold is then removed to create a clearly defined microfluidic channel structure. This method offers a simple, low-cost, and highly reproducible preparation process, making it suitable for the rapid manufacturing and personalized design of flexible wearable devices.
[0041] In some embodiments, the signal probes include calcium ion recognition probes, potassium ion recognition probes, uric acid recognition probes, and glucose recognition probes.
[0042] In some embodiments, the preparation step of the calcium ion recognition probe includes: mixing and grinding dibromo-substituted naphthalene diimide and azacrown ether under the catalysis of anhydrous potassium carbonate and copper sulfate, and then heating the mixture under solvent-free conditions to obtain the calcium ion recognition probe.
[0043] Specifically, the schematic diagram of the principle of the calcium ion recognition probe is as follows Figure 3 As shown, its effect on Ca 2+ The selectively recognized macrocyclic host is an azacrown ether (host 1), which reacts with Ca 2+ The binding constant K a 9.1×10 6 M -1 The macrocyclic main body can be purchased directly, CAS number 33941-15-0, purchased from Aladdin, product number A151566. The macrocyclic main body alone is colorless, and the addition of Ca 2+ The present invention synthesizes Ca by copper-catalyzed nucleophilic aromatic substitution (SNAr) reaction. 2+ The sensing system specifically includes the following steps: heating bisbrominated naphthalene diimide (Br2-cNDI), 1-aza-18-crown-6-ether, anhydrous K2CO3 and CuSO4 powder at 100-120°C for 6 hours without solvent, and using Cu + The nucleophilicity of the crown ether amine group was activated to selectively replace the dibromo site of naphthalene diimide. K2CO3 was used as a base to capture HBr to drive the reaction equilibrium. The crude product was purified by silica gel column chromatography (dichloromethane:methanol volume ratio of 98:2) to obtain a blue solid (yield 31.9%). 2+ Specific "turn-on" fluorescence response: Addition of Ca 2+ After that, the UV absorption peak shifted 60nm from 580nm to 520nm, and the color changed from purple to reddish brown.
[0044] In some embodiments, the preparation step of the potassium ion recognition probe includes: preparing gold nanoparticles by sodium citrate reduction method, and then modifying the gold nanoparticles with 4'-aminodibenzo-18-crown-6 to obtain the potassium ion recognition probe.
[0045] Specifically, the schematic diagram of the principle of the potassium ion recognition probe is as follows Figure 4 As shown, its effect on K + The selectively recognized macrocyclic host is 4'-aminodibenzo-18-crown-6 (host 2), which is K + The binding constant K a 5.1×10 3 M -1The macrocyclic main body can be purchased directly, CAS number 126531-26-8, purchased from Shanghai Myril, product number M62601. The potassium ion recognition probe was synthesized by sodium citrate reduction method to synthesize gold nanoparticles (AuNPs) of about 18nm. The single AuNPs were added with K + The color does not change and the color remains wine red. However, the amino group of 4-aminobenzo-18-crown-6 is modified with the Au-N bond on the surface of AuNPs. + When present, the crown ether cavity of 4'-aminodibenzo-18-crown-6 interacts with K + Specific binding formed a 2:1 sandwich complex, which triggered the aggregation of AuNPs, causing the solution color to change from wine red to gray-blue, accompanied by a red shift of the surface plasmon resonance absorption peak from 520 nm to 630 nm.
[0046] In some embodiments, the uric acid recognition probe is a mixture of a water-soluble naphthyl tetralactam macrocyclic compound and a phenolic dye resorufin; and the preparation method of the water-soluble naphthyl tetralactam macrocyclic compound comprises the steps of: Step S1: 2,6-dihydroxynaphthalene and trimesic acid are mixed, and an intermediate is constructed through ethyl bromide substitution, paraformaldehyde bridging, and amination reactions; Step S2: using the intermediate to carry out a ring-closing reaction between the diester and the diamine in dichloromethane by a pseudo-high dilution method to form a rigid skeleton with 2,6-diethoxynaphthalene as a hydrophobic side wall and four lactam bonds as polar sites; Step S3: hydrolyzing the ester group of the rigid skeleton with trifluoroacetic acid and alkalizing to introduce a sodium carboxylate hydrophilic group to obtain a water-soluble naphthyl tetralactam macrocyclic compound; Step S4: performing an indicator displacement reaction on the water-soluble naphthyl tetralactam macrocyclic compound and the phenolazine dye resorufin to obtain a complex.
[0047] Specifically, the schematic diagram of the principle of uric acid recognition probe is as follows Figure 5 As shown, the macrocyclic main body that selectively recognizes uric acid (UA) is a water-soluble naphthyl tetralactam macrocyclic compound (main body 3), and its binding constant with UA is K a 1.7×10 5 M -1The synthesis of water-soluble naphthyl tetralactam macrocyclic compounds uses 2,6-dihydroxynaphthalene and trimesic acid as starting materials. Intermediates are constructed through bromoethane substitution, polyformaldehyde bridging and amination reactions. The [2+2] ring-closure reaction of diesters and diamines is achieved in dichloromethane using a pseudo-height dilution method to form a rigid skeleton with 2,6-dihydroxynaphthalene as the hydrophobic side wall and four lactam bond polar sites; the ester group is then hydrolyzed by trifluoroacetic acid and alkalized to introduce a sodium carboxylate hydrophilic group, finally obtaining a biomimetic macrocycle with both a deep hydrophobic cavity and water solubility, namely a water-soluble naphthyl tetralactam macrocyclic compound.
[0048] In this embodiment, the water-soluble naphthyl tetralactam macrocyclic compound realizes the detection of UA through supramolecular non-covalent interaction. The water-soluble naphthyl tetralactam macrocyclic compound can selectively bind to uric acid and form a complex with the phenolic dye resorufin (RF) based on the indicator displacement mechanism (K a 4.6×10 4 M -1 ), causing the solution color to change from pink to blue; when uric acid is present, it competitively displaces RF, causing the solution color to return to pink (40nm red shift).
[0049] In some embodiments, the chitosan composite material loaded with silver nanoparticles (CS / Ag NCs) is synthesized by a chemical reduction method, using chitosan as both a reducing agent and a stabilizer, reducing silver nitrate to silver nanoparticles at 90°C and uniformly loading them on a chitosan matrix to obtain a chitosan composite material loaded with silver nanoparticles (CS / Ag NCs).
[0050] Specifically, the composite CS / Ag NCs exhibits a typical silver nanoparticle surface plasmon resonance peak (429 nm). Its colorimetric sensing mechanism is based on the interaction between glucose molecules and silver nanoparticles: glucose adsorption leads to aggregation of silver nanoparticles, triggering a decrease in SPR peak intensity and a concomitant change in solution color from yellow to gray-purple. This sensor enables visual detection of glucose without the need for enzyme catalysis, demonstrating the advantages of low cost, ease of operation, and enzyme independence, providing a viable solution for the development of novel enzyme-free glucose sensors.
[0051] In addition, the present invention also provides a wearable sensor-type multi-component sweat intelligent detection system, comprising: Wearable sensing multi-component sweat sensing patch; a signal acquisition unit, configured to acquire a color spectrum of the sensing layer on the wearable multi-component sweat sensor patch to form a basic data set; a data amplification unit, configured to amplify the basic data set to form an amplified data set; The machine learning analysis unit is used to perform training using the amplified data set and output a sweat detection result based on the color spectrum collected by the signal collection unit.
[0052] In this embodiment, a signal acquisition unit acquires color spectra from the reactions of calcium ions, potassium ions, uric acid (UA), and glucose (Glu) with the sensing layer to form a basic dataset for machine learning. Furthermore, to mitigate the inherent overfitting risk associated with limited sample sizes, a data amplification unit amplifies the basic dataset to create an augmented dataset. This avoids the randomness inherent in traditional noise injection and overcomes the limitations of the Synthetic Minority Over-sampling Technique (SMOTE) for high-dimensional data, making it suitable for machine learning optimization of multi-channel optical signals in wearable devices. Finally, a machine learning analysis unit trains the augmented dataset to form a machine learning model, which is then used to output sweat detection results based on the color spectra acquired by the signal acquisition unit. This intelligent detection system enables highly selective, multi-index sweat analysis without electronic components and is suitable for metabolic monitoring, sports medicine, and chronic disease management.
[0053] In some embodiments, after obtaining the color spectrum of the sensing layer on the wearable multi-component sweat sensor patch using a signal acquisition unit, the R / G / B values of the color spectrum are extracted, and the RGB channel intensities of the color spectrum are normalized into percentage values (R%, G%, B%) to construct a feature vector, thereby forming a basic data set.
[0054] In some embodiments, to mitigate the inherent overfitting risk of a limited sample size, the base dataset is amplified 6-8 times by generating data through data variance to obtain an amplified dataset.
[0055] In some embodiments, after training the machine learning analysis unit using the amplified dataset, a KNN algorithm (k=10, Euclidean distance) was used for 5-fold cross-validation to optimize classification accuracy. Ultimately, the classification accuracy for calcium ions reached 100% (0-10mM, 6 concentration gradients), potassium ions reached 97.2% (0-15mM), uric acid reached 87.2% (0-250μM), and glucose reached 100% (0-250μM). Combined with the K-nearest neighbor algorithm to process smartphone RGB signals (87-98% classification accuracy), this system enables electronic-free, highly selective multi-marker sweat analysis. This intelligent test is suitable for metabolic monitoring, sports medicine, and chronic disease management.
[0056] The present invention will be described in detail with reference to the following examples. It should also be understood that the following examples are only intended to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above disclosure of the present invention fall within the scope of protection of the present invention.
[0057] Example 1 This embodiment provides a wearable sensor-type multi-component sweat intelligent detection system, the preparation of which includes the following steps: 1. Preparation of wearable multi-component sweat sensing patch Epidermal contact layer: A PET film with a thickness of 0.5 mm and a pore size of 1.2 mm ± 10% was used. After plasma treatment (50 W, 30 s), the contact angle was reduced from 110° to <10°, promoting the capillary absorption of sweat.
[0058] Thermal stimulation layer: Iron powder (200-400 mesh, 70wt%), activated carbon (20wt%) and NaCl (10wt%) were mixed by mass percentage to form an iron-based composite, which was injected into a mold to form a double-arc thermal stimulation layer.
[0059] Microfluidic channels: A resin mold was 3D printed on the side of the epidermal contact layer close to the thermal stimulation layer, located between the two arcs of the double-arc thermal stimulation layer. PDMS was then poured into the resin mold and demolded to form a tree-like fractal channel network with a trapezoidal cross-section (top width 0.1 mm, bottom width 0.15 mm, depth 0.6 mm).
[0060] The sensing layer includes the following: 1) Synthesis of the calcium ion sensor (a chamber containing a calcium ion recognition probe): Dibromo-substituted naphthalene diimide (Br2-cNDI) was mixed and ground with an excess of 1-aza-18-crown-6 ether in the presence of anhydrous potassium carbonate (K2CO3) and copper sulfate (CuSO4). The mixture was heated at 120°C under solvent-free conditions for 6 hours. After completion of the reaction, the product was purified by column chromatography (CH2Cl2:MeOH = 98:2) to obtain a purple solid product in approximately 30% yield. This reaction introduced two azacrown ether groups into the naphthalene diimide core via nucleophilic substitution, forming a disubstituted structure, namely, an azacrown ether-modified naphthalene diimide, in which the macrocyclic main body is the azacrown ether (main body 1).
[0061] Signaling mechanism: Azacrown ether-modified naphthalene diimide reacts with Ca 2+ The sensing mechanism is based on the inhibition of the photoinduced electron transfer (PET) effect. 2+ When the azacrown ether receptor in the probe is bound, the lone pair of electrons of the crown ether is replaced by Ca 2+The coordination binding blocks the electron transfer process from the crown ether to the naphthalene diimide (NDI) fluorophore, thereby relieving the fluorescence quenching (PET-OFF) and triggering a significant fluorescence enhancement ("turn-on" effect). DFT calculation results show that Ca 2+ It forms a 1:2 complex with azacrown ether, and cyclic voltammetry shows that Ca 2+ The combination shifts the NDI reduction potential positively, confirming the change in electronic structure. This process is highly selective and reversible, enabling naked-eye ratiometric detection of calcium ions through synergistic crown ether coordination and the optical response of the NDI fluorophore.
[0062] Selective verification results such as Figure 12 As shown: In the presence of 10-fold concentration of interfering ions or other small molecules in sweat, Ca 2+ The response signal deviation is <5%.
[0063] 2) Synthesis of potassium ion sensor (chamber containing potassium ion recognition probe): Gold nanoparticles (Au NPs) of approximately 18 nm were prepared by sodium citrate reduction. Subsequently, the amino groups of 4'-aminodibenzo-18-crown-6 (main body 2) were used to modify the gold atoms on the surface of the Au NPs through Au-N bonds to form well-dispersed functionalized nanoprobes. Finally, a solution of 4'-aminodibenzo-18-crown-6 modified Au NPs was obtained for subsequent K + Colorimetric detection (H2 concentration 50 μM, modification time 2 h).
[0064] Signaling mechanism: Based on the interaction between the ABC crown ether cavity in 4'-aminodibenzo-18-crown-6 and K + Size matching characteristics, K + The two ABC molecules can specifically bind to each other through a "sandwich" structure (a 2:1 complex), leading to aggregation of the Au NPs. Aggregation causes a shift in the localized surface plasmon resonance (SPR) absorption peak, manifested by a change in solution color from wine red to bluish-gray and a 120nm red shift in the LSPR peak (520→640nm), enabling naked-eye colorimetric detection of potassium ions.
[0065] Selective verification results such as Figure 12 As shown: In the presence of 10-fold concentration of interfering ions or other small molecules in sweat, K + The response signal deviation is <5%.
[0066] 3) Synthesis of a uric acid sensor (chamber containing a uric acid recognition probe): 2,6-Dihydroxynaphthalene and trimesic acid were mixed, and an intermediate was constructed through bromoethane substitution, paraformaldehyde bridging, and amination reactions. The intermediate was used to achieve a ring-closure reaction between a diester and a diamine in dichloromethane using a pseudo-height dilution method to form a rigid skeleton with 2,6-diethoxynaphthalene as hydrophobic side walls and four lactam bonds as polar sites. The rigid skeleton was hydrolyzed with trifluoroacetic acid for the ester group and alkalized to introduce a sodium carboxylate hydrophilic group to obtain a water-soluble naphthyl tetralactam macrocyclic compound (main body 3). The water-soluble naphthyl tetralactam macrocyclic compound was subjected to an indicator displacement reaction with the phenolazine dye resorufin (RF) to obtain a complex.
[0067] Specifically, the synthesis steps are as follows Figure 11 As shown: (1) Compounds S1, S2, and S3 were prepared according to existing methods.
[0068] (2) Synthesis of compound S4: 2,6-dihydroxynaphthalene (16.0 g, 100 mmol), bromoethane (43.2 g, 400 mmol), potassium carbonate (69.0 g, 500 mmol), and N,N-dimethylformamide (DMF, 600 mL) were added to a 1 L three-necked round-bottom flask. The oil bath temperature was set to 80°C and stirred under argon protection for 10 hours. After the reaction was completed, the mixture was cooled to room temperature and most of the solvent was removed by rotary evaporation. The mixture was then poured into 400 mL of pure water and extracted with dichloromethane solvent several times. The organic phase was retained, dried over anhydrous sodium sulfate, and filtered. The solvent dichloromethane was removed by rotary evaporation to obtain a white solid S4.
[0069] (3) Synthesis of compound S5: S4 (6.9 g, 32 mmol) and paraformaldehyde (5.7 g, 170 mmol) were added to a 250 mL three-necked round-bottom flask. 100 mL of hydrobromic acid / acetic acid solution (33 wt%) was drawn with a syringe and injected into the round-bottom flask. The oil bath temperature was set to 50°C and the mixture was stirred under argon for 5 hours. The reaction was completed by the formation of a large amount of light purple solid. After the reaction system was cooled to room temperature, it was filtered and the filter cake was washed with a large amount of methanol several times to obtain a crude product. The crude product was dissolved in a small amount of dichloromethane and then added dropwise to 50 mL of methanol while ultrasonicating. The resulting precipitate was filtered and dried to obtain a white bisbenzyl bromide compound S5.
[0070] (4) Synthesis of compound S6: S5 (4.1 g, 2.7 mmol), hexamethylenetetramine (HMTA, 4.0 g, 28 mmol), and chloroform (CHCl3, 150 mL) were added to a 250 mL three-necked round-bottom flask and refluxed for 48 hours under argon protection. After the reaction, the reaction system was cooled to room temperature and the precipitate was collected by filtration. The dried filter cake was added to a 1 L round-bottom flask, 500 mL of ethanol solvent and 100 mL of concentrated hydrochloric acid were added, and refluxed for 48 hours under argon protection. After the reaction, the reaction system was cooled to 0°C, filtered, and the filter cake was washed with cold ethanol solvent several times. The solid was added to a sodium bicarbonate solution (2 M, 250 mL) and ultrasonically formed into a suspension, which was extracted with chloroform (600 mL) to obtain benzylamine; a small amount of chloroform was further added to extract the remaining amine in the aqueous phase. The concentrated organic phase was collected and dried with anhydrous sodium sulfate. After filtration, the solvent was removed by rotary evaporation to obtain a white bisbenzylamine compound S6.
[0071] (5) Synthesis of compound S7: Bis-benzylamine compound S6 (274 mg, 1.5 mmol) and N,N-diisopropylethylamine (DIEA, mL) were added to a 1 L two-necked round-bottom flask. 500 mL of anhydrous dichloromethane was added to the round-bottom flask, stirred to dissolve, and the air in the flask was replaced with argon to keep the entire system under argon protection. Pentafluorophenol ester S3 (1.0 g, 1.0 mmol) was dissolved in 50 mL of anhydrous dichloromethane solvent and slowly and uniformly injected into the round-bottom flask using a syringe pump. The entire injection process lasted for 30 hours. After the injection was completed, the reaction was allowed to continue for 24 hours. Most of the solvent was removed by rotary evaporation, 100 mL of dichloromethane was added to dissolve, and the mixture was washed with pure water and brine several times. The organic phase was collected and dried over anhydrous sodium sulfate. After filtration, the filtrate was subjected to rotary evaporation to remove most of the solvent to obtain a crude product. The crude product was purified by column chromatography (dichloromethane:methanol = 100:1) to obtain a white solid product S7.
[0072] 6) Synthesis of host 3: S7 (100 mg, 0.05 mmol) was added to a 50 mL three-necked round-bottom flask and dissolved in 50 mL of anhydrous dichloromethane. 5 mL of trifluoroacetic acid was slowly added dropwise to the round-bottom flask under an ice bath, and the mixture was allowed to warm to room temperature for 3 hours. After the reaction, the solvent was removed by rotary evaporation, and the solid was collected by filtration. The pH of ultrapure water was adjusted to 5-6 with dilute hydrochloric acid, and the resulting solid was washed and freeze-dried to obtain a dry solid (100 mg, 0.05 mmol). The resulting solid was dissolved in sodium hydroxide solution (100 mg, 0.05 mmol) and then dried in a freeze-dryer to obtain the tetralactam macrocyclic host 3.
[0073] Signal mechanism: Based on the indicator displacement effect (IDA), the binding ability of UA to water-soluble naphthyl tetralactam macrocyclic compounds (Ka =1.7×10 5 M -1 ) is significantly stronger than RF (K a =4.08×10 4 M -1 When UA is present, it competitively displaces RF from the complex, causing the charge transfer (CT) effect to disappear and the solution color to return from blue to pink (the absorption peak shifts from 600 nm to 571 nm). This signal change enables specific detection of UA through colorimetric changes.
[0074] Selective verification results such as Figure 12 As shown: In the presence of 10-fold concentration of interfering ions or other small molecules in sweat, the UA response signal deviation is <5%.
[0075] 4) Synthesis of the Glucose Sensor (Cavity Containing a Glucose Recognition Probe): Using chitosan as both a reducing agent and a stabilizer, silver nitrate was reduced to silver nanoparticles at 90°C. These silver nanoparticles were uniformly loaded into a chitosan matrix, resulting in a chitosan composite material loaded with silver nanoparticles (CS / Ag NCs).
[0076] Selective verification results such as Figure 12 As shown: In the presence of 10-fold concentrations of interfering ions or other small molecules in sweat, the glucose response signal deviation is <5%.
[0077] The sensing effects of calcium ion sensors, potassium ion sensors and uric acid sensors are as follows Figure 6 As shown, the original Br2-CNDI solution is colorless and has no effect on Ca 2+ No response. After grinding it with host 1 (azacrown ether), a covalent complex was formed to obtain a blue-purple material. 2+ When the concentration reaches saturation (15mM), the color gradually changes from purple to red. + After conjugation with gold nanoparticles (AuNPs), the hybrid system retained its original reddish-brown color in colloidal suspension, indicating that no significant plasmon coupling occurred in the unbound state. However, when host 2 was introduced into the AuNP system, K + The presence of induced a significant color shift from red to blue. This response is likely due to the selective binding of host 2 to K +ions, while also inducing partial aggregation of AuNPs, resulting in a plasmon resonance shift. Direct introduction of uric acid (UA) into a resorufin (RF) dye solution failed to induce a detectable color change, with the mixture retaining its initial pink color. To overcome this limitation, an indicator displacement assay (IDA) strategy was employed, utilizing a preassembled host-guest complex of host 3 (host3) and RF. This complex exhibits a stable blue color due to charge-transfer interactions within the host cavity. Upon addition of UA, competitive binding displaces RF from the macrocycle, restoring the pink color of the free dye.
[0078] Figure 7 These are scanning electron microscope images of the analyte before and after binding with body 1, body 2, and body 3. It can be seen that after the analyte binds to the macrocycle, it will enter the cavity of the macrocycle, and the distance between ions or small molecules will decrease, thereby achieving enrichment of the substance to be detected.
[0079] To elucidate the supramolecular recognition mechanism, density functional theory (DFT) calculations were systematically performed (e.g. Figure 8 The geometric configurations of the three host-guest systems were analyzed. The geometry optimization revealed different interaction modes: Ca 2+ Coordinated to the aza-crown ether oxygen atom (host 1) via ion-dipole interaction, K + Encapsulated within the 18-crown-6 cavity (body 2) (also ion-dipole interaction), uric acid (UA) is bound to the tetralactam macrocycle (body 3) via cooperative π-π stacking and hydrogen bonds (NH···O; CH···O).
[0080] 2. Based on the wearable multi-component sweat sensor patch obtained in step 1, a wearable multi-component sweat intelligent detection system is prepared, which specifically includes: A calibrated imaging system (ColorGrab) was used as the signal acquisition unit and Ca 2+ , K + The color spectrum of 6 concentration layers of UA and glucose was obtained, with 5 replicates per layer (n=30 initial dataset). The RGB channel intensities were normalized to percentage values (R%, G%, B%) to construct feature vectors, forming the basic dataset for machine learning (e.g. Figure 9 shown).
[0081] The data augmentation unit was used to generate data from the basic data set (n=30) through data variance, and the basic data set was amplified by 6 times (n=180) to form an augmented data set.
[0082] The machine learning analysis unit was trained using the augmented data set, and a 5-fold cross-validation was performed using the KNN algorithm (k=10, Euclidean distance) to obtain the optimized classification accuracy. The results are as follows: Figure 10As shown; it can be seen that Ca 2+ : 100% (0-10mM, 6 concentration gradients), K + : 97.2% (0-15mM), UA: 87.2% (0-250μM), Glu: 100% (0-250μM).
[0083] In summary, the present invention provides a wearable sensing multi-component sweat sensor patch, a preparation method thereof, and an intelligent detection system. The wearable sensing multi-component sweat sensor patch includes: an epidermal contact layer, which is used to contact the skin surface; a thermal stimulation layer, which is arranged on one side of the epidermal contact layer; a microfluidic channel, which is arranged on one side of the epidermal contact layer and is in the same layer as the thermal stimulation layer; a sensing layer, which is arranged at one end of the microfluidic channel; the sensing layer includes four independent chambers, and the four independent chambers are respectively loaded with different signal probes for color reaction with target substances in sweat; a breathable packaging layer, which is attached to the epidermal contact layer; the thermal stimulation layer, the microfluidic channel and the sensing layer are sandwiched between the epidermal contact layer and the breathable packaging layer. This invention uses capillary action to drive the directional transport of sweat and achieve simultaneous detection of four target compounds in sweat. The sensing layer uses different signal probes to selectively bind calcium ions, potassium ions, uric acid, and glucose. Nanoparticle aggregation or indicator displacement converts these molecular bindings into color signals. A thermal stimulation layer simultaneously optimizes sweat generation and collection, improving the sweat sensor patch's calibration and signal stability, making it suitable for real-time monitoring and exhibiting high sensitivity. Furthermore, the sweat sensor patch combines signal acquisition, data amplification, and machine learning to achieve highly selective, multi-index sweat analysis without electronic components. This sweat sensor patch is suitable for metabolic monitoring, sports medicine, and chronic disease management.
[0084] It should be understood that the application of the present invention is not limited to the above examples. For those skilled in the art, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.
Claims
1. A wearable multi-component sweat sensor patch, characterized in that: include: Epidermal contact layer, for contact with the skin surface; a thermal stimulation layer, disposed on one side of the epidermal contact layer; a microfluidic channel disposed on one side of the epidermal contact layer and in the same layer as the thermal stimulation layer; A sensing layer is provided at one end of the microfluidic channel; the sensing layer comprises four independent chambers, each of which is loaded with a different signal probe for performing a colorimetric reaction with a target in sweat; The breathable packaging layer is adhered to the epidermal contact layer; the thermal stimulation layer, the microfluidic channel and the sensing layer are sandwiched between the epidermal contact layer and the breathable packaging layer.
2. The wearable multi-component sweat sensor patch according to claim 1, characterized in that: The targets include calcium ions, potassium ions, uric acid, and glucose.
3. The wearable multi-component sweat sensor patch according to claim 1, characterized in that: The signal probes include a calcium ion recognition probe, a potassium ion recognition probe, a uric acid recognition probe, and a glucose recognition probe; the calcium ion recognition probe is a naphthalene diimide modified with an azacrown ether; the potassium ion recognition probe is a gold nanoparticle modified with 4'-aminodibenzo-18-crown-6; the uric acid recognition probe is a complex of a water-soluble naphthyl tetralactam macrocyclic compound and a phenolic dye resorufin; and the glucose recognition probe is a chitosan composite material loaded with silver nanoparticles.
4. The wearable multi-component sweat sensor patch according to claim 1, characterized in that: The material of the skin contact layer and the breathable packaging layer is selected from one of polyethylene terephthalate, thermoplastic polyurethane, and polydimethylsiloxane; the skin contact layer and the breathable packaging layer are provided with through holes with a pore size of 1.0mm-1.4mm.
5. The wearable multi-component sweat sensor patch according to claim 1, characterized in that: The thermal stimulation layer includes a first arc-shaped thermal stimulation chamber and a second arc-shaped thermal stimulation chamber that are symmetrically arranged; the microfluidic channel and the sensing layer are located between the first arc-shaped thermal stimulation chamber and the second arc-shaped thermal stimulation chamber.
6. The wearable multi-component sweat sensor patch according to claim 1, characterized in that: The cross-section of the microfluidic channel in the thickness direction of the wearable sensing multi-component sweat sensor patch is trapezoidal.
7. A method for preparing the wearable multi-component sweat sensor patch according to any one of claims 1 to 6, characterized in that: Including steps: performing plasma treatment on the epidermal contact film to obtain an epidermal contact layer; injecting a thermal stimulation material into the mold on one side of the epidermis contact layer to obtain a thermal stimulation layer; forming a tree-like fractal channel network on the epidermal contact layer by using a printing and demoulding process to obtain a microfluidic channel; In situ synthesizing a signal probe at one end of the microfluidic channel to form a sensing layer with four independent chambers; The thermal stimulation layer, the microfluidic channel and the sensing layer are covered with a breathable packaging film, and laminated with the epidermal contact layer to prepare a wearable sensing multi-component sweat sensing patch.
8. The method for preparing the wearable multi-component sweat sensor patch according to claim 7, characterized in that: The signal probes include calcium ion recognition probes, potassium ion recognition probes, uric acid recognition probes, and glucose recognition probes; The preparation steps of the calcium ion recognition probe include: mixing and grinding dibromo-substituted naphthalene diimide and azacrown ether under the catalysis of anhydrous potassium carbonate and copper sulfate, and heating the mixture in the absence of solvent to obtain the calcium ion recognition probe; The preparation steps of the potassium ion recognition probe include: preparing gold nanoparticles by using a sodium citrate reduction method, and then modifying the gold nanoparticles by using 4'-aminodibenzo-18-crown-6 to obtain the potassium ion recognition probe.
9. The method for preparing the wearable multi-component sweat sensor patch according to claim 8, characterized in that: The uric acid recognition probe is a complex of a water-soluble naphthyl tetralactam macrocyclic compound and a phenolazine dye resorufin; and the preparation method of the complex of a water-soluble naphthyl tetralactam macrocyclic compound and a phenolazine dye resorufin comprises the following steps: 2,6-dihydroxynaphthalene and trimesic acid were mixed, and the intermediate was constructed through ethyl bromide substitution, paraformaldehyde bridging and amination reaction; The intermediate is used to achieve a ring-closing reaction between a diester and a diamine in dichloromethane by a pseudo-high dilution method to form a rigid skeleton with 2,6-diethoxynaphthalene as a hydrophobic side wall and four lactam bonds as polar sites; The rigid skeleton is hydrolyzed with trifluoroacetic acid to form an ester group and alkalized to introduce a sodium carboxylate hydrophilic group to obtain a water-soluble naphthyl tetralactam macrocyclic compound; The water-soluble naphthyl tetralactam macrocyclic compound and the phenolazine dye resorufin are subjected to an indicator displacement reaction to obtain a complex.
10. A wearable multi-component sweat intelligent detection system, characterized in that: include: The wearable multi-component sweat sensor patch according to any one of claims 1 to 6; a signal acquisition unit, configured to acquire a color spectrum of the sensing layer on the wearable multi-component sweat sensor patch to form a basic data set; a data amplification unit, configured to amplify the basic data set to form an amplified data set; The machine learning analysis unit is used to perform training using the amplified data set and output a sweat detection result based on the color spectrum collected by the signal collection unit.
Citation Information
Patent Citations
Wearable sweat detection device
CN118830835A
Wearable aptamer electrochemical sensor as well as preparation method and application thereof
CN120009365A
Wearable sweat sensor
WO2021107871A1