CN113358729A - Packaging structure of fibrous wearable sweat sensor - Google Patents

Packaging structure of fibrous wearable sweat sensor Download PDF

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CN113358729A
CN113358729A CN202110702380.3A CN202110702380A CN113358729A CN 113358729 A CN113358729 A CN 113358729A CN 202110702380 A CN202110702380 A CN 202110702380A CN 113358729 A CN113358729 A CN 113358729A
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fiber
fibrous
layer
protein
electrode core
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CN113358729B (en
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罗梦颖
王栋
李沐芳
陆莹
蒋海青
赵青华
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Wuhan Textile University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00Measuring for diagnostic purposes; Identification of persons
    • A61B5/145Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/14507Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue specially adapted for measuring characteristics of body fluids other than blood
    • A61B5/14517Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue specially adapted for measuring characteristics of body fluids other than blood for sweat
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00Measuring for diagnostic purposes; Identification of persons
    • A61B5/145Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/1468Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means
    • A61B5/1477Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using chemical or electrochemical methods, e.g. by polarographic means non-invasive

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Abstract

The invention provides a packaging structure of a fibrous wearable sweat sensor. The structure comprises a fiber electrode core layer used for biosensing detection and a packaging layer coated on the surface of the fiber electrode core layer, wherein the packaging layer has hydrophilicity and permeability and is used for transmitting a substance to be detected to the fiber electrode core layer so as to realize biosensing detection. The fiber electrode core layer is preferably prepared by preparing a metal layer on the surface of a fiber substrate, then soaking the fiber substrate in protein phosphate buffer solution, reacting the metal layer on the surface of the fiber substrate under an acidic condition to obtain metal ions, and further reacting the metal ions with protein and phosphate to obtain the metal-protein-based fiber electrode core layer. The packaging structure who so obtains not only can protect electrode material, can also collect the sweat, provides stable detection environment for working electrode, and sensing efficiency and security homoenergetic obtain the guarantee, the preparation and the integration of the flexible wearable device of being convenient for.

Description

Packaging structure of fibrous wearable sweat sensor
Technical Field
The invention relates to the technical field of biosensing, in particular to a packaging structure of a fibrous wearable sweat sensor.
Background
Packaging is an indispensable processing technology in electronic devices, and aims to realize optimization of appearance and performance of products based on application environment requirements and use requirements of the products. At present, flexible wearable electronic equipment is concerned by researchers and broad masses at home and abroad due to the characteristics of portability, sensitivity, flexibility, continuous work and the like. However, research is mainly focused on realizing and optimizing the detection capability of the device, and the packaging research of the device is still less.
Patent CN211560068U discloses a novel fiber electrode, an electrode buckle packaging mechanism and a body parameter measurement garment, the fiber electrode is packaged by a magnetic electrode buckle, but the method cannot ensure the flexibility of the fiber electrode.
Patent CN112164828A discloses a fibrous flexible aluminum ion battery and a preparation method thereof, wherein graphene fibers, aluminum wires and glass fibers are respectively used as a positive electrode, a negative electrode and a diaphragm, and are packaged by a polypropylene heat-shrinkable tube to obtain the fibrous flexible aluminum ion battery. The method can ensure the flexibility of the fibrous battery, but is not suitable for a fibrous wearable sweat sensor and cannot collect and transmit sweat.
In view of the above, there is a need to design an improved package structure of a fiber-shaped wearable sweat sensor to solve the above problems.
Disclosure of Invention
In order to overcome the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide a packaging structure for a fibrous wearable sweat sensor. This structure not only can protect electrode material, can also collect the sweat, provides stable detection environment for working electrode, the preparation and the integration of the flexible wearable device of being convenient for.
In order to achieve the purpose, the invention provides a packaging structure of a fibrous wearable sweat sensor, which comprises a fiber electrode core layer for biosensing detection and a packaging layer coated on the surface of the fiber electrode core layer, wherein the packaging layer has hydrophilicity and permeability and is used for transmitting a substance to be detected to the fiber electrode core layer so as to achieve biosensing detection.
As a further development of the invention, the encapsulation layer comprises an outer coating fiber.
As a further improvement of the invention, the wrapping fiber is spirally wound on the surface of the fiber electrode core layer.
As a further improvement of the invention, the packaging layer comprises a plurality of wrapping fibers, and the wrapping fibers are wrapped on the surface of the fiber electrode core layer in parallel.
As a further improvement of the invention, the packaging layer comprises a plurality of wrapping fibers, and the wrapping fibers are wrapped on the surface of the fiber electrode core layer in a criss-cross structure.
As a further improvement of the invention, the wrapping fiber is one or more of cotton thread, hemp, wool, silk, terylene, nylon, acrylic fiber and spandex.
As a further improvement of the invention, the surface of the fiber electrode core layer is fixed with a biological sensitive active substance.
As a further improvement of the present invention, the fiber electrode core layer is prepared by the following method:
s1, preparing a metal layer on the surface of a fiber base material;
s2, preparing a protein phosphate buffer solution with the pH value less than or equal to 7;
s3, soaking the fiber base material processed in the step S1 in the protein phosphate buffer solution in the step S2 for reaction for a preset time, reacting the metal layer on the surface of the fiber base material under an acidic condition to obtain metal ions, and further reacting the metal ions with protein and phosphate to obtain the metal-protein based fiber electrode core layer.
As a further improvement of the invention, in step S1, the metal layer is one or more of simple substances or compounds of copper, zinc, calcium, aluminum, magnesium, iron, nickel and cobalt; the fiber substrate is a conductive fiber substrate.
In a further improvement of the present invention, in step S2, the pH of the protein phosphate buffer is 4.5 to 7; the protein comprises but is not limited to one or more of bovine serum albumin, horseradish peroxidase, laccase, glucose oxidase and amylase; the phosphate salt includes hydrogen phosphate and/or dihydrogen phosphate.
The invention has the beneficial effects that:
1. the invention provides a packaging structure of a fibrous wearable sweat sensor, which comprises a fiber electrode core layer for biosensing detection and a packaging layer coated on the surface of the fiber electrode core layer. So set up, not only can protect electrode material, can also collect the sweat, for working electrode provides stable detection ring border, sensing efficiency and security homoenergetic obtain the guarantee, and have higher flexibility, can directly contact with the human body, the preparation and the integration of the wearable device of the flexibility of being convenient for.
2. The packaging structure of the fibrous wearable sweat sensor provided by the invention can be used for preparing the folded yarn with different spatial arrangement structures by regulating and controlling the process parameters of the external fiber such as twist, twist direction, weaving structure and the like. The sweat shows different wetting and permeation rates on the double-twisted folded yarn with different structures, and simultaneously shows different electrochemical sensing performances, and by establishing the relation between the sweat diffusion and the sensor performance, the deep research on the recognition of the electronic generation signal output of the sweat diffusion marker can be realized, so that the practical application of the fibrous wearable electrochemical biosensor is promoted.
3. According to the packaging structure of the fibrous wearable sweat sensor, the fiber electrode core layer is preferably prepared by preparing a metal layer on the surface of a fiber substrate, then soaking the metal layer in a protein phosphate buffer solution, reacting the metal layer on the surface of the fiber substrate under an acidic condition to obtain metal ions, and further reacting the metal ions with protein and phosphate to obtain the metal-protein-based fiber electrode core layer. The invention utilizes acidolysis and chelation of the metal layer to fix protein, thereby forming a large amount of protein-inorganic composite multidimensional structures with controllable structures, having higher activity and high stability, and the residual metal layer can also improve the conductivity of the substrate, thereby improving the electrochemical sensing performance of the working electrode.
Drawings
In fig. 1, a, b, and c are schematic views of three packaging structures provided by the present invention, respectively.
Fig. 2 a, b and c are schematic cross-sectional views of three package structures in fig. 1.
FIG. 3 is an electron microscope image of carbon fibers with a horseradish peroxidase-inorganic composite three-dimensional structure grown on the surface prepared in example 2.
FIG. 4 is an electron microscope image of the stainless steel conductive fiber with the surface-grown horseradish peroxidase-inorganic composite three-dimensional structure prepared in example 3.
In the figure, 1-fiber electrode core layer; 2-packaging layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme of the present invention are shown in the specific embodiments, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The packaging structure of the fibrous wearable sweat sensor provided by the invention comprises a fiber electrode core layer 1 for biological sensing detection and a packaging layer 2 coated on the surface of the fiber electrode core layer 1, wherein the packaging layer has hydrophilicity and permeability and is used for transmitting a substance to be detected to the fiber electrode core layer 1 so as to realize biological sensing detection. So set up, not only can protect electrode material, can also collect the sweat, provide stable measuring environment for working electrode. The fiber electrode containing the packaging structure has high flexibility, is light and convenient, can be directly contacted with a human body, and has great potential in the field of wearable electrochemical sensors.
The packaging layer 2 comprises outer-coated fibers, and is coated on the surface of the fiber electrode core layer 1 through twisting or weaving processes.
Referring to fig. 1 and 2, the sheath fiber is spirally wound around the surface of the fiber electrode core layer 1.
Or, the packaging layer 2 includes a plurality of external fibers, and the plurality of external fibers are coated on the surface of the fiber electrode core layer 1 in parallel.
Or, the packaging layer 2 includes a plurality of external fibers, and the plurality of external fibers are wrapped on the surface of the fiber electrode core layer 1 in a criss-cross structure.
The outer wrapping fiber is one or more of cotton thread, hemp, wool, silk, terylene, nylon, acrylic fiber and spandex.
The surface chemical modification technology or the plasma technology is utilized to prepare the wrapping fibers with different hydrophilicity and hydrophobicity, and the plied yarns with different spatial arrangement structures are prepared by regulating and controlling the process parameters such as twist, twist direction, weaving structure and the like. The sweat shows different wetting and permeation rates on the double-twisted folded yarn with different structures, and simultaneously shows different electrochemical sensing performances, and the deep research on the recognition of the electronic generation signal output of the sweat diffusion marker is realized by establishing the relation between the sweat diffusion and the sensor performances, so that the practical application of the fibrous wearable electrochemical biosensor is promoted.
The surface of the fiber electrode core layer 1 is fixed with a biological sensitive active substance, and the fiber electrode core layer has the function of detecting a certain component and content in biological fluid.
The fiber electrode core layer 1 is prepared by the following method:
s1, preparing a metal layer on the surface of a fiber base material;
s2, preparing a protein phosphate buffer solution with the pH value less than or equal to 7;
s3, soaking the fiber base material processed in the step S1 in the protein phosphate buffer solution described in the step S2 for reaction for a preset time, reacting the metal layer on the surface of the fiber base material under an acidic condition to obtain metal ions, and further reacting the metal ions with protein and phosphate to obtain the metal-protein-based fiber electrode core layer 1.
In step S1, the metal layer is one or more of copper, zinc, calcium, aluminum, magnesium, iron, nickel, cobalt, and their compounds, preferably a metal. The metal layer slowly releases metal ions under an acidic condition, and the metal ions are chelated with protein and phosphate to obtain the metal-protein chelate with the multidimensional structure. When the metal simple substance is a metal simple substance, the metal simple substance in the metal layer is oxidized into a metal oxide, and slowly reacts under an acidic condition to generate metal ions; meanwhile, metal ions are chelated with protein and phosphate to obtain a metal-protein chelate with a multidimensional structure, and the metal-protein chelate grows on the surface of the base material; the final remaining metal layer can also provide electrical conductivity to the working electrode. Therefore, the working electrode prepared by the invention has good conductivity and biosensing performance.
The fiber substrate is preferably a conductive fiber substrate, such as carbon fiber, metal organic composite fiber, or the like. The diameter of the conductive fiber can extend from nanometer to micron, and the conductive yarn with larger diameter range can be obtained by twisting the fiber and the like. The prepared fiber-based working electrode with the surface provided with the metal-protein chelate with the multidimensional structure can be used in the field of wearable electrochemical sensing, and has good sensing property and flexibility. The conductive base material is selected to further enhance the conductivity of the working electrode prepared by the method, and the method can be better applied to the fields of electrochemical sensing, enzyme fuel cells, electrocatalysis and the like.
In step S2, the pH value of the protein phosphate buffer solution is 4.5-7. Certain acidity provides conditions for metal ions released from the metal layer, but too strong acidity may affect the activity of the protein.
The protein comprises but is not limited to one or more of bovine serum albumin, horseradish peroxidase, laccase, glucose oxidase and amylase; the phosphate comprises hydrogen phosphate and/or dihydrogen phosphate,for example NaH2PO4、Na2HPO4、KH2PO4、K2HPO4And the like. The concentration of phosphate radical ions is 0.001 mM-2M, the reaction temperature is 5-40 ℃, and the reaction time is 2-72 h.
After the surface of the fiber electrode core layer prepared by the method is coated with the coated fiber, the metal-protein chelate structure on the surface of the fiber electrode core layer can be well protected, and the fiber electrode core layer is prevented from being exposed outside and damaged due to friction or the influence of the external environment.
Example 1
The utility model provides a packaging structure of wearable sweat sensor of fibrous, uses the carbon fiber of surface mounting glucose oxidase as the electrode sandwich layer, is the heliciform with cotton yarn and twines on the electrode, and the distance between two adjacent helices is 10 mu m for glucose detects in the sweat, detects the lower limit and is 50 nmol/L.
Example 2
Compared with embodiment 1, the packaging structure of the fibrous wearable sweat sensor is characterized in that carbon fibers with lactase fixed on the surfaces are used as an electrode core layer, a plurality of cotton yarns are parallelly coated on the electrode, the distance between every two adjacent cotton yarns is 6 microns and is used for detecting lactic acid in sweat, and the lower detection limit is 500 nmol/L.
Example 3
The utility model provides a packaging structure of fibrous wearable sweat sensor, embodiment 1 compares, the difference lies in, with a plurality of cotton yarn criss-cross cladding on the electrode, the distance between two horizontal adjacent cotton yarn is 6 mu m, and the distance between two vertical adjacent cotton yarn is 4 mu m for glucose detects in the sweat, detects the lower limit for 50nmol/L sensing detection.
Example 4
A fibrous wearable sweat sensor packaging structure, compared to example 1, except that the electrode core layer is prepared by the following steps:
s1, metallization of surface of conductive material
And (3) cleaning the carbon fibers to remove stains on the surface. Then, coarsening, sensitizing and activating treatment are carried out in sequence.
The cleaning method comprises the following steps: and putting the carbon fiber into an ethanol solution, and ultrasonically cleaning for 1-2 min.
Coarsening: soaking the cleaned carbon fiber in 5M NaOH solution for coarsening, wherein the reaction temperature is as follows: 30 ℃, reaction time: taking out for 30min, cleaning, and drying;
sensitization: 40ml/L HCl is taken as a solvent to prepare 10g/L SnCl2·2H2And (3) O sensitizing solution, namely immersing the coarsened carbon fiber in the sensitizing solution, wherein the reaction temperature is as follows: 30 ℃, reaction time: and (3) 30 min.
And (3) activation: 20ml/L HCl is used as a solvent to prepare 0.5g/L PdCl2And (3) an activating solution, wherein the sensitized carbon fiber is immersed in the activating solution, and the reaction temperature is as follows: 30 ℃, reaction time: and (3) 30 min.
And (3) soaking the activated carbon fiber in plating solution to prepare the carbon fiber with the copper metal layer on the surface. The plating solution comprises 14g/L of copper sulfate, 46g/L of potassium citrate and 4.2g/L of Na2CO3、9g/L NaOH、0.5g/L NiSO4And 51ml/L formaldehyde. Reaction temperature: 30 ℃, reaction time: and (3) 30 min.
S2. preparation of protein buffer solution
0.5g/L horseradish peroxidase solution (pH about 6) was prepared, containing 8.0g/L NaCl, 0.2g/L KCl, 1.44g/L Na2HPO40.24g/L KH2PO4The solution was mixed.
S3, growth of metal-enzyme multidimensional structure on surface of metallized electrode
And (3) soaking the carbon fiber with the copper metal layer on the surface in the horseradish peroxidase solution, reacting for 24 hours at room temperature, taking out, cleaning and drying to obtain the metal-enzyme-based working electrode with the three-dimensional structure. The prepared working electrode has high catalytic activity and can be repeatedly used.
Referring to fig. 3, it can be seen that a large amount of flower-like structure material consisting of copper ions-horseradish peroxidase-phosphate grows uniformly on the surface of the carbon fiber. The metal-enzyme multi-dimensional structure working electrode with high conductivity is obtained by synchronously carrying out acidolysis and chelation reaction on the metal layer. After being packaged, the packaging material can be used for preparing a flexible sweat sensing detection device and has the advantages of high sensing detection sensitivity, efficiency and safety.
Example 5
A packaging structure for a fibrous wearable sweat sensor, which differs from that of example 7 in that the carbon fiber in step S1 is replaced with a stainless steel metal fiber. The rest is substantially the same as that of example 7, and will not be described again.
Referring to fig. 4, it can be seen that another shape of the metallo-enzyme multi-dimensional structure material grows on the surface of the stainless steel metal fiber. Therefore, the structure of the metal-enzyme chelate can be regulated by regulating the kind of the substrate.
Examples 6 to 11
A packaging structure of a fibrous wearable sweat sensor, which is different from embodiment 7 in that a cotton fiber is used as a base material, the types and thicknesses of metal layers are shown in table 2, and the rest are substantially the same as embodiment 7, and are not repeated herein.
Table 2 preparation conditions and conductivity test results of examples 7 to 14
Figure BDA0003127083510000081
As can be seen from table 2, when the substrate is a non-conductive substrate, a metal-protein based working electrode having a certain conductivity can also be obtained. The thicker the metal plating layer, the lower the resistance and the better the conductivity, indicating that the remaining metal layer can impart conductivity to the electrode.
In summary, the package structure of the fibrous wearable sweat sensor provided by the invention includes a fiber electrode core layer for biosensing detection and a package layer coated on the surface of the fiber electrode core layer. So set up, not only can protect electrode material, can also collect the sweat, for working electrode provides stable detection ring border, sensing efficiency and security homoenergetic obtain the guarantee, and have higher flexibility, can directly contact with the human body, the preparation and the integration of the wearable device of the flexibility of being convenient for. The fiber electrode core layer preferably utilizes acidolysis and chelation of the metal layer to fix protein, so that a large number of protein-inorganic composite multidimensional structures with controllable structures are formed, the fiber electrode core layer has higher activity and high stability, and the residual metal layer can also improve the conductivity of the base material, thereby improving the electrochemical sensing performance of the working electrode.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.

Claims (10)

1. The utility model provides a fibrous wearable sweat sensor's packaging structure, its characterized in that, including the fibre electrode sandwich layer that is used for biosensing to detect with the cladding the encapsulation layer on fibre electrode sandwich layer surface, the encapsulation layer has hydrophilicity and permeability for will wait to detect the material transmit to fibre electrode sandwich layer realizes the biosensing and detects.
2. The encapsulation structure of the fibrous wearable sweat sensor of claim 1 wherein the encapsulation layer comprises outer-coated fibers.
3. The encapsulation structure of the fibrous wearable sweat sensor of claim 2 wherein the outer wrapping fiber is helically wound around the surface of the fiber electrode core.
4. The encapsulated structure of a fibrous wearable sweat sensor of claim 2 wherein said encapsulation layer comprises a number of overclad fibers wrapped parallel to the surface of said fiber electrode core layer.
5. The encapsulated structure of a fibrous wearable sweat sensor of claim 2 wherein said encapsulated layer comprises a plurality of overwrap fibers coated on the surface of said fiber electrode core in a criss-cross configuration.
6. The encapsulation structure of the fibrous wearable sweat sensor of claim 2, wherein the outer wrapping fiber is one or more of cotton, hemp, wool, silk, polyester, nylon, acrylic, spandex.
7. The encapsulation structure of a fibrous wearable sweat sensor of claim 1 where a biologically sensitive active substance is immobilized on the surface of the fibrous electrode core.
8. The encapsulation structure of the fibrous wearable sweat sensor of any of claims 1 to 7, wherein the fibrous electrode core layer is prepared by:
s1, preparing a metal layer on the surface of a fiber base material;
s2, preparing a protein phosphate buffer solution with the pH value less than or equal to 7;
s3, soaking the fiber base material processed in the step S1 in the protein phosphate buffer solution described in the step S2 for reaction for a preset time, reacting the metal layer on the surface of the fiber base material under an acidic condition to obtain metal ions, and further reacting the metal ions with protein and phosphate to obtain the metal-protein-based fiber electrode core layer.
9. The encapsulation structure of the fibrous wearable sweat sensor of claim 8, wherein in step S1, the metal layer is one or more of the elements or compounds of copper, zinc, calcium, aluminum, magnesium, iron, nickel, cobalt; the fiber substrate is a conductive fiber substrate.
10. The encapsulation structure of a fibrous wearable sweat sensor of claim 8, wherein in step S2, the pH of the protein phosphate buffer is 4.5-7; the protein comprises but is not limited to one or more of bovine serum albumin, horseradish peroxidase, laccase, glucose oxidase and amylase; the phosphate salt includes hydrogen phosphate and/or dihydrogen phosphate.
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