CN114839241A - Detection substrate, detection method thereof and detection device - Google Patents

Detection substrate, detection method thereof and detection device Download PDF

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Publication number
CN114839241A
CN114839241A CN202210191325.7A CN202210191325A CN114839241A CN 114839241 A CN114839241 A CN 114839241A CN 202210191325 A CN202210191325 A CN 202210191325A CN 114839241 A CN114839241 A CN 114839241A
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China
Prior art keywords
detection
substrate
working electrode
micro flow
reference electrode
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Chinese (zh)
Inventor
梁魁
常天睿
常凌乾
李建
白一鸣
王杨
李虎
梁烁斌
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BOE Technology Group Co Ltd
Beihang University
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BOE Technology Group Co Ltd
Beihang University
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Priority to CN202210191325.7A priority Critical patent/CN114839241A/en
Publication of CN114839241A publication Critical patent/CN114839241A/en
Priority to PCT/CN2023/070531 priority patent/WO2023160267A1/en
Pending legal-status Critical Current

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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
    • G01N27/302Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/50273Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the means or forces applied to move the fluids
    • 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
    • G01N27/333Ion-selective electrodes or membranes
    • 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
    • G01N27/416Systems
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00Additional constructional details
    • B01L2300/08Geometry, shape and general structure
    • B01L2300/0861Configuration of multiple channels and/or chambers in a single devices
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01LCHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2400/00Moving or stopping fluids
    • B01L2400/04Moving fluids with specific forces or mechanical means
    • B01L2400/0403Moving fluids with specific forces or mechanical means specific forces
    • B01L2400/0415Moving fluids with specific forces or mechanical means specific forces electrical forces, e.g. electrokinetic

Abstract

The disclosure provides a detection substrate, a detection method and a detection device thereof. The detection substrate includes: a substrate base plate; the working electrode, the reference electrode and the micro-channel structure are arranged on one side of the substrate; the micro-channel structure comprises a liquid inlet, at least one detection chamber and a first micro-channel connected with the liquid inlet and the detection chamber, wherein the liquid inlet is used for receiving a substance to be detected, and the first micro-channel is used for conveying the substance to be detected to the detection chamber; the working electrode is used for generating a response potential relative to the reference electrode under the state of contacting with a substance to be detected so as to determine a target parameter of the substance to be detected according to the response potential.

Description

Detection substrate, detection method thereof and detection device
Technical Field
The present disclosure relates to the field of detection technologies, and in particular, to a detection substrate, a detection method thereof, and a detection apparatus thereof.
Background
Wearable healthy equipment can be in user's daily wearing and the in-process of using collection, the health status of monitoring user, has characteristics such as convenient to use, intelligent degree height. The development in the electronic medical appliance industry is particularly prominent in recent years.
Disclosure of Invention
The present disclosure provides a detection substrate, including:
a substrate base plate;
the working electrode, the reference electrode and the micro-channel structure are arranged on one side of the substrate; the micro-channel structure comprises a liquid inlet, at least one detection chamber and a first micro-channel connected with the liquid inlet and the detection chamber, wherein the liquid inlet is used for receiving a substance to be detected, and the first micro-channel is used for conveying the substance to be detected to the detection chamber;
wherein the working electrode and the reference electrode are arranged in the at least one detection chamber, at least one of the working electrode and the reference electrode is arranged in each detection chamber, and the working electrode is used for generating a response potential relative to the reference electrode under the state of contacting the substance to be detected so as to determine the target parameter of the substance to be detected according to the response potential.
In an alternative implementation, the first fluidic channel includes a bend that is S-shaped, serpentine, square wave shaped, zigzag shaped, or U-shaped.
In an optional implementation manner, the first micro flow channel further includes a linear portion, the linear portion is linear, and the linear portion is connected to one end of the bending portion, which is close to the liquid inlet and/or the detection chamber.
In an alternative implementation manner, the working electrode or the reference electrode is arranged in the detection chamber, and an orthographic projection of the detection chamber on the substrate covers an orthographic projection of the working electrode or the reference electrode on the substrate.
In an optional implementation manner, the micro flow channel structure includes a plurality of liquid inlets and a plurality of first micro flow channels, each of the detection chambers is correspondingly connected to at least one of the liquid inlets, and the detection chambers correspondingly connected to the liquid inlets are connected to the liquid inlets through the first micro flow channels.
In an optional implementation manner, the number of the detection chambers is plural, the micro flow channel structure further includes a plurality of second micro flow channels, the detection chambers are connected to the second micro flow channels in a one-to-one correspondence, and the second micro flow channels are intersected at an intersection position.
In an alternative implementation, the second microchannel is rectilinear in shape.
In an alternative implementation, the aspect ratio of the second fluidic channel is smaller than the aspect ratio of the first fluidic channel.
In an optional implementation manner, the micro flow channel structure further includes a liquid outlet, and a third micro flow channel connecting the detection chamber and the liquid outlet.
In an alternative implementation, the shape of the third microchannel includes an S-shape, a serpentine shape, a square wave shape, a zigzag shape, or a U-shape.
In an alternative implementation, the aspect ratio of the third microchannel is smaller than the aspect ratio of the first microchannel.
In an alternative implementation, the aspect ratio of the first microchannel is greater than or equal to 0.05 and less than or equal to 0.25.
In an alternative implementation, the depth of the first microchannel is greater than or equal to 20 μm and less than or equal to 40 μm.
In an optional implementation mode, the number of the detection chambers is multiple, and the detection chambers are communicated with each other;
a plurality of working electrodes are arranged on the substrate base plate, the working electrodes share one reference electrode, and different working electrodes are used for detecting different target parameters;
wherein each of the plurality of working electrodes and the reference electrode are located in a different one of the detection chambers.
In an alternative implementation, the distance between the working electrode and the reference electrode is greater than or equal to 2mm and less than or equal to 20 mm.
In an alternative implementation, the substance to be detected is sweat, and the target parameter includes at least one of: sodium ion concentration, potassium ion concentration, calcium ion concentration, chloride ion concentration, and pH.
In an alternative implementation, the working electrode and the reference electrode are located on one side surface of the substrate base plate;
the at least one detection chamber is positioned on the surface of one side, away from the substrate base plate, of the working electrode and the reference electrode, and the orthographic projection of the liquid inlet and the orthographic projection of the first micro-channel on the substrate base plate are not overlapped with the orthographic projection of the working electrode and the orthographic projection of the reference electrode on the substrate base plate.
The present disclosure provides a detection apparatus comprising any one of the detection substrates.
The present disclosure provides a detection method applied to any one of the detection substrates, the detection method including:
acquiring the response potential generated by the working electrode;
and determining a target parameter corresponding to the response potential according to a preset corresponding relation between the potential and the parameter.
The foregoing description is only an overview of the technical solutions of the present disclosure, and the embodiments of the present disclosure are described below in order to make the technical means of the present disclosure more clearly understood and to make the above and other objects, features, and advantages of the present disclosure more clearly understandable.
Drawings
In order to more clearly illustrate the embodiments of the present disclosure or technical solutions in related arts, the drawings used in the description of the embodiments or related arts will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present disclosure, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts. It should be noted that the sizes and shapes of the figures in the drawings are not to be considered true scale, but are merely intended to schematically illustrate the present invention. The same or similar reference numbers in the drawings identify the same or similar elements or elements having the same or similar functionality.
Fig. 1 schematically illustrates a schematic plan view of the working and reference electrodes provided by the present disclosure;
fig. 2 schematically illustrates a schematic plan structure of an inspection substrate provided by the present disclosure;
FIG. 3 is a partial block diagram schematically illustrating a micro flow channel structure at a first location;
FIG. 4 is a partial block diagram schematically illustrating a micro flow channel structure at a second position;
FIG. 5 is a partial block diagram schematically showing a micro flow channel structure at a third position;
FIG. 6 is a partial structural view schematically showing a micro flow channel structure at a fourth position;
fig. 7 schematically illustrates stability test results of a test substrate provided by the present disclosure;
fig. 8 schematically shows the results of the selective test of the detection substrate provided by the present disclosure.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure will be described clearly and completely with reference to the drawings in the embodiments of the present disclosure, and it is obvious that the described embodiments are some, but not all embodiments of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
In the drawings, the thickness of layers, films, panels, regions, etc. are exaggerated for clarity. Exemplary embodiments are described herein with reference to cross-sectional views that are schematic illustrations of idealized embodiments. As such, deviations from the shapes of the figures as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, regions illustrated or described as flat may typically have rough and/or nonlinear features. Further, the illustrated sharp corners may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
The present disclosure provides an inspection substrate, as shown in fig. 1 and 2, including: a substrate 11, a working electrode 12, a reference electrode 13 and a micro flow channel structure provided on one side of the substrate 11.
As shown in fig. 2, the micro flow channel structure includes a liquid inlet 21, at least one detection chamber 22, and a first micro flow channel 23 connecting the liquid inlet 21 and the detection chamber 22, wherein the liquid inlet 21 is used for receiving a substance to be detected, and the first micro flow channel 23 is used for delivering the substance to be detected to the detection chamber 22.
Wherein the working electrode 12 and the reference electrode 13 are arranged in at least one detection chamber 22, at least one of the working electrode 12 and the reference electrode 13 is arranged in each detection chamber 22, and the working electrode 12 is used for generating a response potential relative to the reference electrode 13 under the state of contacting with a substance to be detected so as to determine a target parameter of the substance to be detected according to the response potential.
The fact that at least one of the working electrode 12 and the reference electrode 13 is provided in each detection chamber 22 means that the working electrode 12 and the reference electrode 13 may be provided in each detection chamber 22 at the same time, or only one working electrode 12 or only one reference electrode 13 may be provided, which is not limited in the present disclosure.
For example, when the micro flow channel structure includes one detection chamber 22, the working electrode 12 and the reference electrode 13 may be provided in pairs in the one detection chamber 22.
For another example, when the micro flow channel structure includes a plurality of detection chambers 22, a pair of working electrode 12 and reference electrode 13 may be provided for each detection chamber 22; it is also possible to provide one working electrode 12 for each of a part of the detection chambers 22 and one reference electrode 13 for each of the other part of the detection chambers 22, as shown in fig. 2, the micro flow channel structure includes four detection chambers 22, wherein three detection chambers 22 are provided with one working electrode 12 and one reference electrode 13 is provided in each detection chamber 22; it is also possible to provide a pair of working electrode 12 and reference electrode 13 for each of a part of detection chambers 22, one working electrode 12 for each of another part of detection chambers 22, and one reference electrode 13 for each of the other part of detection chambers 22; and so on.
In the present disclosure, the working electrode 12 being disposed in the detection chamber 22 means that the working electrode 12 is disposed exposed inside the detection chamber 22. The reference electrode 13 is disposed in the detection chamber 22 means that the reference electrode 13 is disposed exposed inside the detection chamber 22.
In a specific implementation, the substance to be detected enters the first micro-channel 23 from the liquid inlet 21, and enters the detection chamber 22 through the first micro-channel 23. When the working electrode 12 in the detection process is in contact with the substance to be detected, the working electrode 12 can generate a response potential relative to the reference electrode 13, and the target parameter of the substance to be detected can be determined according to the response potential, so that the detection of the substance to be detected is realized.
According to the detection substrate provided by the disclosure, the working electrode 12 and the reference electrode 13 are arranged in the detection chamber 22 in the micro-channel structure, and the detection of the substance to be detected is completed in the detection chamber, so that the detection speed, sensitivity and accuracy can be improved as the detection chamber plays a role in enriching the substance to be detected. In addition, the micro flow channel structure has a small volume, so that the integration of the detection substrate can be improved, and the portability and the detection function of the detection device can be improved.
Alternatively, the substance to be detected may be a liquid such as sweat. The target parameter may include at least one of: sodium ion concentration, potassium ion concentration, calcium ion concentration, chloride ion concentration, pH value and other physiological parameters.
By adopting the detection substrate provided by the disclosure, the concentration of sodium ions, potassium ions, chloride ions, calcium ions and other target parameters in human sweat, such as the pH value of the human sweat and the like can be detected in a non-invasive manner.
Alternatively, if the working electrode 12 is provided in the detection chamber 22, the orthographic projection of the detection chamber 22 on the substrate 11 covers the orthographic projection of the working electrode 12 on the substrate 11. Thus, the working electrode 12 can be completely exposed in the detection chamber 22, so that the working electrode 12 in the detection chamber 22 can be contacted with the substance to be detected, and detection errors caused by the fact that the working electrode 12 is only partially contacted with the substance to be detected are avoided.
Referring to fig. 2, the orthographic projection of the detection chamber 22 on the substrate base plate 11 is a circle having a radius of 2.8 mm; the orthographic projection of the working electrode 12 on the substrate base plate 11 is a circle having a radius of 2.5 mm.
Alternatively, if the reference electrode 13 is provided in the detection chamber 22, the orthographic projection of the detection chamber 22 on the substrate 11 covers the orthographic projection of the reference electrode 13 on the substrate 11. Therefore, the reference electrode 13 can be completely exposed in the detection chamber 22, so that the reference electrode 13 in the detection chamber 22 can be contacted with the substance to be detected, and detection errors caused by the fact that the reference electrode 13 is only partially contacted with the substance to be detected are avoided.
Referring to fig. 2, the orthographic projection of the detection chamber 22 on the substrate base plate 11 is a circle having a radius of 2.8 mm; the orthographic projection of the reference electrode 13 on the substrate base plate 11 is a circle having a radius of 2.5 mm.
The substrate 11 may be a rigid substrate such as glass, or may be a flexible substrate such as polyimide, which is not limited in the present disclosure.
The thickness of the substrate base plate 11 may be in the order of micrometers, such as 10 μm, etc., and the present disclosure is not limited thereto.
When the substrate base plate 11 is a flexible substrate, it is helpful to realize a wearable noninvasive detection apparatus. When the detection substrate provided by the present disclosure is used in a wearable device, the flexible substrate 11 in a micron level can reduce irritation to the skin and protect the skin from being damaged.
The material of the working electrode 12 may include, for example, a metal material such as gold, platinum, etc., which is not limited in this disclosure. The thickness of the working electrode 12 may be on the order of nanometers, such as 80 nm.
The material of the reference electrode 13 may include, for example, a metal material such as gold, platinum, etc., which is not limited in this disclosure. The reference electrode 13 is used to provide a reference potential that can be kept stable. The thickness of the reference electrode 13 may be in the order of nanometers, such as 80 nm.
When the detection substrate provided by the disclosure is used in a wearable device, the working electrode and the reference electrode 13 with nanometer-level thickness can reduce stimulation to the skin and protect the skin from being damaged.
The material of the micro flow channel structure may be an insulating material, such as polypropylene, photoresist, etc., which is not limited in this disclosure. In a specific implementation, the micro flow channel structure may be manufactured by any suitable process, such as an injection molding process, 3D printing, laser engraving, or photolithography, which is not limited in this disclosure.
In a specific implementation, the loading port 21 may be a groove with a cross section (i.e., a section parallel to the plane of the substrate base plate 11) in the shape of a circle, a triangle, a square, a rectangle, an ellipse, a parallelogram, a rhombus, a trapezoid, a pentagon, a hexagon, etc., which is not limited by the present disclosure.
The liquid inlet 21 shown in FIG. 2 has a circular groove structure. The input end of the first microchannel 23 may be located on the side wall of the circular recess.
The detection chamber 22 may be a protrusion having a cross section (i.e., a section parallel to the plane of the substrate base plate 11) in the shape of a circle, a triangle, a square, a rectangle, an oval, a parallelogram, a rhombus, a trapezoid, a pentagon, a hexagon, or the like, and the protrusion has a hollow structure. The detection chamber 22 shown in FIG. 2 is a circular convex structure. The output end of the first microchannel 23 may be located on the inner wall of the detection chamber 22.
Alternatively, the detection chamber 22 may have a cross-sectional dimension larger than that of the loading port 21. That is, the area of the detection chamber 22 projected forward on the substrate 11 is larger than the area of the inlet port 21 projected forward on the substrate 11.
Because the output that detects room 22 and first microchannel 23 is connected, inlet 21 is connected with the input of first microchannel 23, and the cross sectional dimension through setting up detection room 22 can be greater than the cross sectional dimension of inlet 21, can improve the transmission rate of liquid in first microchannel 23, ensures to detect the material and can be full of detection room 22 fast, improves detection speed.
In some examples, as shown in FIG. 2, the loading port 21 has a circular cross-sectional radius of 1.5mm and the detection chamber 22 has a circular cross-sectional radius of 2.8 mm.
In other examples, the liquid inlet 21 has a square cross-section with a side length of 4 mm; the detection chamber 22 has a rectangular cross-section with a length of 14.4mm and a width of 8.5 mm.
In specific implementations, the sizes of the cross sections (i.e., the sections parallel to the substrate base plate 11) of the loading port 21 and the detection chamber 22 can be set according to actual requirements, and the disclosure is not limited thereto.
Alternatively, the aspect ratio of the first micro flow channel 23 may be greater than or equal to 0.05, and less than or equal to 0.25. For example, the aspect ratio of the first microchannel 23 may be 0.1.
Optionally, the depth of the first microchannel 23 is greater than or equal to 20 μm and less than or equal to 40 μm.
In some examples, the first fluidic channel 23 is 25 μm deep. When the aspect ratio of the first micro flow channel 23 is 0.1, the width of the first micro flow channel 23 is 250 μm. When the aspect ratio of the first micro flow channel 23 is 0.05, the width of the first micro flow channel 23 is 500 μm. When the aspect ratio of the first microchannel 23 is 0.25, the width of the first microchannel 23 is 100 μm.
Note that the depth of the micro flow channel herein is a dimension of the micro flow channel in a direction perpendicular to the plane of the substrate base plate 11. The width of the micro flow channel is the dimension of the micro flow channel in the direction parallel to the plane of the substrate 11 and perpendicular to the liquid flow direction. The aspect ratio of the micro channel is the ratio of the depth to the width of the micro channel.
According to the pressure drop formula of the micro-channel:
Figure BDA0003524525510000081
and capillary pressure equation:
Figure BDA0003524525510000082
wherein Δ p is a pressure difference, L is a length of the micro flow channel, and w is a cross-sectional size of the micro flow channel. The cross section size of the micro-channel is reduced, and the pressure drop is increased; increasing the cross-sectional size of the microchannel increases the volume of the microchannel, which in turn leads to a prolonged filling time of the substance to be detected.
When the aspect ratio of the first microchannel 23 satisfies the above condition, both the pressure drop and the filling time can satisfy the requirements, so that the flowing uniformity and controllability of the substance to be detected in the first microchannel 23 are better. Tests have found that when the depth of the first micro flow channel 23 is 25 μm and the width is 250 μm, i.e. the aspect ratio of the first micro flow channel 23 can be 0.1, the flow uniformity and controllability of the substance to be detected in the first micro flow channel 23 are better.
Alternatively, the wall thickness of the first microchannel 23 may be 100 μm, which is not limited by the present disclosure.
Alternatively, as shown in fig. 3 and 4, the first micro flow channel 23 includes a curved portion 231, and the shape of the curved portion 231 is a curved shape such as an S-shape, a serpentine shape, a square wave shape, a zigzag shape, or a U-shape. In which fig. 3 shows a partial block diagram of the first microchannel 23 and the loading port 21 at the connection position (e.g., position a in fig. 2). Fig. 4 shows a partial configuration view of the first microchannel 23 and the detection chamber 22 at the connection position (e.g., position B in fig. 2).
Specifically, the longitudinal sectional shape of the first micro flow channel 23 may include a curved shape such as an S-shape, a serpentine shape, a square wave shape, a zigzag shape, or a U-shape. The longitudinal section of the first microchannel 23 is the section of the first microchannel 23 in the direction parallel to the plane of the substrate 11. As shown in fig. 2, the longitudinal sectional shape of the first microchannel 23 includes a serpentine shape.
The shape of the bending part 231 is a bending shape instead of a straight shape, so that the substance to be detected can directionally flow into the detection chamber 22 from the liquid inlet 21 through the first micro-channel 23, the substance to be detected is effectively prevented from flowing back in the first micro-channel 23, and the detection speed and stability can be improved.
Alternatively, as shown in fig. 3 and 4, the first microchannel 23 may further include a straight portion 232, and the shape of the straight portion 232 is a straight line.
Wherein, the straight line part 232 is connected to one end of the bending part 231 near the liquid inlet 21 and/or the detection chamber 22. Specifically, the straight portion 232 is connected to one end of the curved portion 231 near the liquid inlet 21 (as shown in fig. 3); or the straight line part 232 is connected with one end of the bending part 231 close to the detection chamber 22 (as shown in fig. 4); or the straight line part 232 is connected to both the end of the bending part 231 near the liquid inlet 21 and the end near the detection chamber 22 (as shown in fig. 3 and 4).
Thus, by arranging the straight line part 232 (as shown in fig. 3) at one end of the bending part 231 close to the liquid inlet 21, that is, the interface between the first micro-channel 23 and the liquid inlet 21 is not a gentle curve but a straight line, so that the flowing speed of the liquid from the liquid inlet 21 to the first micro-channel 23 can be increased, and the substance to be detected can be ensured to be filled in the detection chamber 22 quickly. By providing a straight portion 232 (as shown in fig. 4) at one end of the curved portion 231 close to the detection chamber 22, that is, the interface between the first microchannel 23 and the detection chamber 22 is not a gentle curve, but a straight line, the flow rate of the liquid from the first microchannel 23 to the detection chamber 22 can be increased, and it is ensured that the detection chamber 22 can be filled with the substance to be detected quickly.
In an alternative implementation manner, as shown in fig. 2, the micro flow channel structure may include a plurality of liquid inlets 21 and a plurality of first micro flow channels 23, each detection chamber 22 may be correspondingly connected to at least one liquid inlet 21, and the correspondingly connected detection chambers 22 are connected to the liquid inlets 21 through the first micro flow channels 23.
By arranging the liquid inlets 21, the time for filling the detection chamber 22 with the substance to be detected can be shortened, and the detection speed is further improved.
When the number of detection chambers 22 is one, the plurality of liquid inlets 21 may be connected to the same detection chamber 22 through the first micro flow channel 23. The liquid inlets 21 are connected with the first micro-channels 23 in a one-to-one correspondence.
When the number of the detection chambers 22 is plural, each of the plural detection chambers 22 may be connected to at least one of the liquid inlets 21. The liquid inlet 21 and the first micro flow channel 23 may be connected in a one-to-one correspondence.
As shown in fig. 2, the number of the liquid inlets 21 is eight, the number of the detection chambers 22 is four, each detection chamber 22 is correspondingly connected with two liquid inlets 21, and each liquid inlet 21 is connected to the corresponding detection chamber 22 through a first micro-channel 23. It was found that, in the micro flow channel structure shown in FIG. 2, the substance to be detected can fill each detection chamber 22 within 15 minutes.
When the number of the detection chambers 22 is plural, as shown in fig. 2, the micro flow channel structure may further include a plurality of second micro flow channels 24, the detection chambers 22 are connected to the second micro flow channels 24 in a one-to-one correspondence, and the plurality of second micro flow channels 24 are intersected at an intersection position.
As shown in fig. 2, the second microchannel 24 of each detection chamber 22 may be disposed on the side of the detection chamber 22 near the center of the microchannel structure.
As shown in fig. 2, the micro flow channel structure includes two pairs of oppositely disposed detection chambers 22, each pair of oppositely disposed detection chambers 22 corresponds to a central connecting line, and the intersection of the two central connecting lines is the intersection of the second micro flow channels 24.
Through set up second microchannel 24 on each detection room 22, and a plurality of second microchannels 24 intersect at cross position department, can communicate a plurality of detection rooms 22 like this, make and wait to detect the material and mix in second microchannel 24, improve the uniformity that waits to detect the material in the detection of different detection rooms, improve the uniformity of testing result.
Alternatively, the second microchannel 24 may be linear in shape, as shown in fig. 2.
Specifically, the second microchannel 24 has a linear longitudinal sectional shape. The longitudinal section of the second microchannel 24 is the section of the second microchannel 24 in the direction parallel to the plane of the substrate 11.
Referring to fig. 5, a partial block diagram of the detection chamber 22 and the second microchannel 24 at the connection position (e.g., position C in fig. 2) is shown.
The shape through setting up the second microchannel is the straight line form, can improve the flow efficiency of waiting to detect the material between a plurality of detection rooms for the material that waits to detect in a plurality of detection rooms can the intensive mixing, further improves the uniformity of different detection room testing results.
Alternatively, the cross-sectional area of the second fluidic channel 24 may be greater than the cross-sectional area of the first fluidic channel 23. Wherein, the cross section of the second micro flow channel 24 is the cross section of the second micro flow channel 24 in the direction perpendicular to the liquid flow direction, and the cross section of the first micro flow channel 23 is the cross section of the first micro flow channel 23 in the direction perpendicular to the liquid flow direction.
The cross sectional area of the second micro-channel 24 is larger than that of the first micro-channel 23, so that the flow speed of the substance to be detected in the second micro-channel 24 can be increased, the substance to be detected is ensured to be fully mixed in the second micro-channel 24, and the consistency of the substance to be detected in different detection chambers 22 is improved. In addition, because the cross-sectional area of the first micro-channel 23 is smaller, the siphon effect is more obvious, the directional transmission of the substance to be detected from the liquid inlet 21 to the detection chamber 22 is ensured, and the liquid backflow is further prevented.
Wherein the aspect ratio of the second microchannel 24 can be smaller than the aspect ratio of the first microchannel 23. Therefore, the sample introduction speed and the internal flow speed of the substance to be detected can be balanced, the substance to be detected is fully mixed in the second micro-channel 24, and the consistency of detection results of different detection chambers is ensured.
The depth of the second microchannel 24 may be equal to the depth of the first microchannel 23.
When the aspect ratio of the first micro-channel 23 is 0.1, the aspect ratio of the second micro-channel 24 may be 0.025.
When the first fluidic channel 23 and the second fluidic channel 24 are both 25 μm deep, the second fluidic channel 24 has a width of 1000 μm (corresponding to an aspect ratio of 0.025), or 1500 μm (corresponding to an aspect ratio of 1/60), and so on.
In an alternative implementation, the microchannel structure further includes a liquid outlet 25, and a third microchannel 26 connecting the detection chamber 22 and the liquid outlet 25.
Through setting up liquid outlet 25 and third microchannel 26, help the waste liquid discharge that finishes of detecting, prevent that the inside emergence of microchannel structure from blockking up. Through continuously discharging waste liquid and further introducing a new substance to be detected, a detection result with high real-time performance can be obtained.
When the liquid inlet 21 is disposed toward a first direction (e.g., a direction perpendicular to the paper surface in fig. 2), the liquid outlet 25 may be disposed toward a second direction (e.g., a direction perpendicular to the first direction) which is upward in the paper surface in fig. 2. This prevents the discharged waste liquid from entering the inlet again.
The shape of the liquid outlet 25 may be rectangular, circular, etc., and the present disclosure is not limited thereto. The size of the liquid outlet 25 may be, for example, 2mm, which is not limited by the present disclosure.
In particular implementations, the microchannel structure may include a liquid outlet 25; a plurality of exit ports 25 may also be included, for example, one exit port 25 is connected to each of the plurality of detection chambers 22.
As shown in fig. 2, the microchannel structure only sets up a liquid outlet 25, this liquid outlet 25 connects a detection room 22, through second microchannel 24 intercommunication between a plurality of detection rooms 22, the waste liquid in a plurality of detection rooms 22 is discharged through a liquid outlet 25, can ensure like this to detect the material and fully mix in inside, further improve the uniformity that detects the material in the different detection rooms 22, improve the uniformity of testing result, avoid owing to detect the test error that the material leads to in the inflow speed nonconformity of each inlet 21.
Alternatively, the shape of the third microchannel 26 may include a curved shape such as an S-shape, a serpentine shape, a square wave shape, a zigzag shape, or a U-shape.
Specifically, the longitudinal cross-sectional shape of the third micro flow channel 26 may include a curved shape such as an S-shape, a serpentine shape, a square waveform shape, a zigzag shape, or a U-shape. The longitudinal section of the third microchannel 26 is the section of the third microchannel 26 in the direction parallel to the plane of the substrate 11.
As shown in fig. 2, the third microchannel 26 has a serpentine longitudinal cross-sectional shape. Referring to fig. 6, a partial structure of the third microchannel 26 at the connection position (e.g., position D in fig. 2) with the detection chamber 22 is shown.
By setting the third micro flow channel 26 to be a curved shape rather than a straight shape, the substance to be detected can be directionally flowed from the detection chamber 22 to the liquid outlet 25 through the third micro flow channel 26, thereby effectively preventing the substance to be detected from flowing back in the third micro flow channel 26, ensuring timely and effective discharge of waste liquid, avoiding interference of the backflow of the waste liquid on the substance to be detected in the detection chamber, and further improving the detection stability and accuracy.
Alternatively, the cross-sectional area of the third fluidic channel 26 may be larger than the cross-sectional area of the first fluidic channel 23. Wherein the cross section of the third microchannel 26 is the cross section of the third microchannel 26 in the direction perpendicular to the liquid flow, and the cross section of the first microchannel 23 is the cross section of the first microchannel 23 in the direction perpendicular to the liquid flow.
By setting the cross-sectional area of the third microchannel 26 to be larger than the cross-sectional area of the first microchannel 23, the flow speed of the waste liquid in the third microchannel 26 can be increased, and the waste liquid can be discharged in time. In addition, because the cross-sectional area of the first micro-channel 23 is smaller, the siphon effect is more obvious, the directional transmission of the substance to be detected from the liquid inlet 21 to the detection chamber 22 is ensured, and the liquid backflow is further prevented.
Wherein the aspect ratio of the third microchannel 26 may be smaller than the aspect ratio of the first microchannel 23. Like this, can make the sampling velocity and the outflow speed of waiting to detect the material comparatively balanced, ensure on the one hand to detect the material and can accomplish in detection room 22 and detect, on the other hand ensures that the waste liquid that finishes detecting can in time discharge.
The depth of the third microchannel 26 may be equal to the depth of the first microchannel 23.
When the aspect ratio of the first microchannel 23 is 0.1, the aspect ratio of the third microchannel 26 may be 1/24.
When the depth of the first micro flow channel 23 and the third micro flow channel 26 is 25 μm, the width of the third micro flow channel 26 is 600 μm (corresponding to an aspect ratio of 1/24), in which case the waste liquid for which the detection is completed can be discharged within 5 minutes.
When the depth of the first fluidic channel 23 and the third fluidic channel 26 is 25 μm, the width of the third fluidic channel 26 can also be 200 (corresponding to an aspect ratio of 0.125), in which case the aspect ratio of the first fluidic channel 23 can be greater than 0.125.
Alternatively, the wall thickness of the third fluidic channel 26 may be 150 μm, which is not limited by this disclosure.
Alternatively, the cross-sectional shapes (i.e., the cross-sections perpendicular to the liquid flow direction) of the first micro flow channel 23, the second micro flow channel 24, and the third micro flow channel 26 may be circular, elliptical, square, rectangular, pentagonal, hexagonal, etc., which is not limited by the present disclosure.
In a specific implementation, the working electrode 12 and the reference electrode 13 may be located on an inner surface of the detection chamber 22 on a side close to the substrate 11, an inner surface of the detection chamber 22 on a side away from the substrate 11, an inner sidewall surface of the detection chamber 22, and the like, which is not limited in this disclosure.
In the disclosed example, the working electrode 12 and the reference electrode 13 are both located on the inner surface of the detection chamber 22 on the side close to the substrate base plate 11. Specifically, the working electrode 12 and the reference electrode 13 are located on one side surface of the substrate base plate 11, and the at least one detection cell 22 is located on one side surface of the working electrode 12 and the reference electrode 13 facing away from the substrate base plate 11.
The orthographic projection of the liquid inlet 21 on the substrate base plate 11 is not overlapped with the orthographic projection of the working electrode 12 and the reference electrode 13 on the substrate base plate 11. The orthographic projection of the first microchannel 23 on the substrate 11 does not overlap with the orthographic projections of the working electrode 12 and the reference electrode 13 on the substrate 11.
That is, neither the working electrode 12 nor the reference electrode 13 is exposed in the liquid inlet 21 and the first microchannel 23, so that it is ensured that the substances to be detected contacting the working electrode 12 and the reference electrode 13 are mixed liquids, and the consistency of the substances to be detected in the detection chambers 22 is ensured.
In an alternative implementation, the number of the detection chambers 22 is plural, and the plural detection chambers 22 are communicated with each other. For example, the plurality of detection chambers 22 may communicate with each other through the second microchannel 24.
In this implementation, a plurality of working electrodes 12 may be disposed on the substrate 11, the plurality of working electrodes 12 may share one reference electrode 13, and different working electrodes 12 are used for detecting different target parameters. Each of the plurality of working electrodes 12 and reference electrodes 13 may be located in a different detection chamber 22.
As shown in fig. 1, one reference electrode 13 and three working electrodes 12 are disposed on the substrate 11, and the three working electrodes 12 are disposed on the left side, the upper side and the right side of the reference electrode 13, respectively, which is not limited in the present disclosure. The three working electrodes 12 may be used to detect the sodium ion concentration, the potassium ion concentration, and the PH of the substance to be detected, respectively, for example, and the disclosure is not limited thereto.
As shown in fig. 2, four detection chambers 22 are provided in the micro flow channel structure, and one reference electrode 13 and each of the three working electrodes 12 are respectively located in different detection chambers 22, that is, one working electrode 12 is provided for each of the three detection chambers 22, and one common reference electrode 13 is provided in one detection chamber 22.
By providing a plurality of working electrodes 12 sharing one reference electrode 13, the contact area between the working electrodes 12 and the substance to be detected in each detection chamber 22 can be increased, and the detection sensitivity can be improved. In addition, since the response potentials generated by the working electrodes 12 are all relative to the potential of the same reference electrode 13, the consistency of the detection results of the detection chambers 22 can be improved.
The inventors found that when the distance between the working electrode 12 and the reference electrode 13 is too small, the signal-to-noise ratio of the detection result is low; when the distance between the working electrode 12 and the reference electrode 13 is too large, the intensity of the detection signal is too weak.
In order to balance the intensity of the detection signal and the signal-to-noise ratio, optionally, the distance between the working electrode 12 and the reference electrode 13 is greater than or equal to 2mm, and less than or equal to 20 mm.
Alternatively, when a plurality of working electrodes 12 are provided on the substrate base plate 11, the distances between the respective working electrodes 12 and the reference electrode 13 may be equal.
As shown in fig. 1, the orthographic projection shapes of the working electrode 12 and the reference electrode 13 on the substrate 11 are circular, and the radii are both 2.5 mm. The center-to-center distance between each working electrode 12 and the reference electrode 13 was 12 mm.
In some examples, the orthographic shape of the working electrode 12 and the reference electrode 13 on the substrate base plate 11 may also be a rectangle, the length of the rectangle being 6mm and the width being 3 mm.
In a specific implementation, the shape, size and spacing of the working electrode 12 and the reference electrode 13 can be adjusted according to actual requirements, which is not limited by the present disclosure.
The inventor conducts a repeatability test on the response potential measured by the detection substrate shown in fig. 2, and the result of the test shown in fig. 7 shows that the test error of the response potential is within 10%, which indicates that the test stability of the detection substrate is high.
Since different working electrodes 12 can be used to detect different target parameters of the substance to be detected. Specifically, the plurality of working electrodes 12 may include a working electrode for detecting a sodium ion concentration (hereinafter, referred to as a sodium ion working electrode), a working electrode for detecting a potassium ion concentration (hereinafter, referred to as a potassium ion working electrode), a working electrode for detecting a calcium ion concentration (hereinafter, referred to as a calcium ion working electrode), a working electrode for detecting a chloride ion concentration (hereinafter, referred to as a chloride ion working electrode), and a working electrode for detecting a pH value (hereinafter, referred to as a pH value working electrode).
Each working electrode 12 may be coated with an ion selective solution corresponding to a target parameter. In addition, a Nafion film can be coated on the surface of one side of the working electrode 12, which is far away from the substrate 11, and the film has selective permeability, so that the utilization rate of the electrode can be improved, the effect of protecting the electrode is achieved, the reliability of the electrode is improved, and the accuracy and the sensitivity of detection are improved.
The surface of one side of the reference electrode 13, which is far away from the substrate base plate 11, can be provided with an Ag/AgCl film made of a main material such as gold, and the surface of one side of the Ag/AgCl film, which is far away from the substrate base plate 11, can be provided with a reference film, so that the reference film can effectively reduce the drift generated in the measurement, and the detection accuracy and sensitivity can be ensured. In addition, a Nafion film can be coated on the surface of one side of the reference film, which is far away from the substrate base plate 11, and the film has selective permeability, so that the utilization rate of the electrode can be improved, the function of protecting the electrode is achieved, the reliability of the electrode is improved, and the accuracy and the sensitivity of detection are improved.
The following describes the detection principles of the above-mentioned working electrodes 12.
The principle of sodium ion concentration detection: a sodium ion selective carrier X is fixed to the working electrode 12 and generates a response potential by recognizing sodium ions in the substance to be detected. The response potential is proportional to the logarithm of the sodium ion concentration.
The detection principle of potassium ion concentration is as follows: the working electrode 12 is fixed with a potassium ion selective carrier valinomycin which generates a response potential by identifying potassium ions in the substance to be detected. The response potential is proportional to the logarithm of the potassium ion concentration.
Calcium ion concentration detection principle: a calcium ion selective carrier ETH129 is fixed to the working electrode 12 and generates a response potential by recognizing calcium ions in the substance to be detected. The response potential is proportional to the logarithm of the calcium ion concentration.
The detection principle of the chloride ion concentration is as follows: the working electrode 12 is fixed with Ag/AgCl ink, and when the working electrode 12 is immersed in a solution containing chloride ions, a corresponding response potential is generated, and the response potential is in direct proportion to the logarithm of the concentration of the chloride ions.
pH value detection principle: polyaniline (PANI) is modified on the working electrode 12, and when the working electrode 12 is immersed in a solution, PANI contacts with hydrogen ions in the solution to generate a corresponding response potential. The response potential is proportional to the pH.
The following describes the preparation of several working electrodes 12 and reference electrodes 13.
First, a bare electrode is prepared on the substrate base plate 11.
The preparation process of the bare electrode comprises the following steps:
s501, ultrasonically cleaning a flexible Polyimide film (Polyimide, PI) namely a substrate base plate by respectively adopting acetone, ethanol and ultrapure water for 115 minutes, and drying by using nitrogen after cleaning;
s502, spin-coating AZ1500 photoresist with the thickness of 2-3 mu m on the PI film;
s503, placing the membrane coated with the photoresist in a hot plate at 95 ℃ for baking for 1 minute;
s504, placing the membrane in a photoetching machine, and exposing for 10 seconds under ultraviolet light;
s505, immersing the exposed membrane into a developing solution for developing for 60 seconds, and drying;
s506, placing the membrane in a magnetron sputtering instrument, and sequentially sputtering 30nmCr and 50 nmAu;
and S507, immersing the sputtered sample into a stripping solution for 30 minutes, and stripping redundant metal to form a bare electrode.
The bare electrode is then modified on the side of the bare electrode facing away from the substrate base plate 11.
The modification process of the sodium ion working electrode and the reference electrode 13 comprises the following steps:
s701, preparing an ion selective solution. Mixing a sodium ion carrier X, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (Na-TFPB), polyvinyl chloride (PVC) and bis (2-ethoxyethyl) sebacate (DOS) according to the weight ratio of 1:0.5:33: 65.5. 100mg of the above mixture was dissolved in 660. mu.l of Tetrahydrofuran (THF). The solution is cooled at 4 ℃ for standby;
and S702, preparing a reference membrane solution. Reference electrode 13 membrane mixture was prepared by dissolving 79.1mg of polyvinyl butyral (PVB) and 50mg of sodium chloride (NaCl) in 1ml of Methanol (methane), 2mg of polyether F127 and 0.2mg of multi-walled carbon nanotubes (Multiwall carbon nanotubes) were added to the reference membrane mixture solution. Storing the solution for later use;
and S703, preprocessing the bare electrode of the working electrode. Depositing a solution containing 0.01M3, 4-Ethylenedioxythiophene (EDOT) and 0.1M sodium polystyrene sulfonate (NaPSS) onto the bare electrode of the working electrode by constant current electrochemical polymerization of an external Ag/AgCl electrode;
s704, dripping 20 mul of sodium ion selective membrane mixture onto the bare electrode which is subjected to the step 703 to prepare a sodium ion working electrode; dripping 20 mul of reference solution onto the bare electrode coated with Ag/AgCl to prepare a reference electrode 13;
s705, 20 μ l of Nafion solution is dripped on the sodium ion working electrode and the reference electrode 13 prepared in the step S704 to form a gel layer.
The modification process of the potassium ion working electrode and the reference electrode 13 comprises the following steps:
s801, preparing an ion selective solution. Sodium-potassium carrier valinomycin, sodium tetraphenylborate (NaTPB), polyvinyl chloride (PVC) and bis (2-ethoxyethyl) sebacate (DOS) are mixed according to the weight ratio of 2:0.5:33: 64.5. 100mg of the above mixture was dissolved in 350. mu.l of cyclohexanone. The solution is stored at 4 ℃ for standby;
and S802, preparing a reference membrane solution. Reference electrode 13 membrane mixture was prepared by dissolving 79.1mg of polyvinyl butyral (PVB) and 50mg of sodium chloride (NaCl) in 1ml of Methanol (methane), 2mg of polyether F127 and 0.2mg of multi-walled carbon nanotubes (Multiwall carbon nanotubes) were added to the reference membrane mixture solution. Storing the solution for later use;
and S803, preprocessing the bare electrode of the working electrode. Depositing a solution containing 0.01M3, 4-Ethylenedioxythiophene (EDOT) and 0.1M sodium polystyrene sulfonate (NaPSS) onto the bare electrode of the working electrode by constant current electrochemical polymerization of an external Ag/AgCl electrode;
s804, dripping and casting 20 mu l of potassium ion selective membrane mixture on the bare electrode which is finished in the step 803 to prepare a potassium ion working electrode; dripping 20 mul of reference solution onto the bare electrode coated with Ag/AgCl to prepare a reference electrode 13;
s805, 20ul of Nafion solution is dripped on the potassium ion working electrode and the reference electrode 13 prepared in the step S804, and a gel layer is formed.
The modification process of the calcium ion working electrode and the reference electrode 13 comprises the following steps:
and S901, preparing an ion selective solution. Mixing a calcium ion carrier ETH129, sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate (Na-TFPB), polyvinyl chloride (PVC) and bis (2-ethoxyethyl) sebacate (DOS) according to the weight ratio of 1:0.5:33: 65.5. 100mg of the above mixture was dissolved in 660. mu.l of Tetrahydrofuran (THF). The solution is cooled at 4 ℃ for standby;
and S902, preparing a reference membrane solution. Reference electrode 13 membrane mixture was prepared by dissolving 79.1mg of polyvinyl butyral (PVB) and 50mg of sodium chloride (NaCl) in 1ml of Methanol (methane), 2mg of polyether F127 and 0.2mg of multi-walled carbon nanotubes (Multiwall carbon nanotubes) were added to the reference membrane mixture solution. Storing the solution for later use;
and S903, preprocessing the bare electrode of the working electrode. Depositing a solution containing 0.01M3, 4-Ethylenedioxythiophene (EDOT) and 0.1M sodium polystyrene sulfonate (NaPSS) onto the bare electrode of the working electrode by constant current electrochemical polymerization of an external Ag/AgCl electrode;
s904, dripping 20 mul of calcium ion selective membrane mixture onto the bare electrode which is finished in the step 903 to prepare a calcium ion working electrode, and dripping 20 mul of reference solution onto the bare electrode coated with Ag/AgCl to prepare a reference electrode 13;
s905, 20ul of Nafion solution is dripped on the calcium ion working electrode and the reference electrode 13 prepared in the step S904, and a gel layer is formed.
The modification process of the chloride ion working electrode and the reference electrode 13 comprises the following steps:
s1001 and preparation of a reference membrane solution. And (4) preparing a reference membrane solution. Reference electrode 13 membrane mix was prepared by dissolving 79.1mg of polyvinyl butyral (PVB) and 50mg of sodium chloride (NaCl) in 1ml of Methanol (Methanol). Storing the solution for later use;
and S1002, preprocessing the bare electrode of the working electrode. Depositing a solution containing 0.01M3, 4-Ethylenedioxythiophene (EDOT) and 0.1M sodium polystyrene sulfonate (NaPSS) onto the bare electrode of the working electrode by constant current electrochemical polymerization of an external Ag/AgCl electrode;
s1003, coating Ag/AgCl printing ink on the bare electrode which is subjected to the step 1002 to prepare a chloride ion working electrode; dripping 20 mul of reference solution onto the bare electrode coated with Ag/AgCl to prepare a reference electrode 13;
the modification process of the pH value working electrode and the reference electrode 13 comprises the following steps:
s1101, Polymerizing Aniline (PANI) in 0.1M aniline and 1M HCl solution;
s1102, immersing bare electrodes of the working electrode and the reference electrode in tetrachloroauric acid to deposit for 30S to modify the surfaces of the electrodes;
s1103, performing PANI deposition for 25 cycles from-0.2 to 1V at 200mV/S by using cyclic voltammetry to obtain a pH working electrode;
s1104, 20ul of Nafion solution is dripped onto the pH value working electrode and the reference electrode to form a gel layer.
The proportion of the sensitive membrane solution can enable the detection effect to reach the best.
Wherein, the concentration range of sodium ion detection is 10-160mM, and the sensitivity is 101 mV/decade; the concentration range of potassium ion detection is 1-20mM, and the sensitivity is 81 mV/decade; the concentration range of calcium ion detection is 0.1-20mM, and the sensitivity is 30 mV/decade; the concentration range of the chloride ion detection is 10-120mM, and the sensitivity is 30 mV/decade; the pH value detection range is 3-8mM, and the sensitivity is 50 mV/decade.
The use of the Nafion membrane ensures that sweat can be detected in a long time, and the reduction of detection sensitivity caused by the dissolution consumption of the sensitive membrane material under long-time detection is effectively avoided.
After the preparation of each of the working electrode 12 and the reference electrode 13 is completed, a micro flow channel structure may be prepared on the side of the working electrode 12 facing away from the substrate base plate 11. The method specifically comprises the following steps:
s601, spin-coating SU8-2025 photoresist of 100um on a working electrode;
s602, photoetching the micro-channel pattern by adopting a common photoetching process;
and S603, after the photoetching is finished, washing the redundant part by using a degumming solution to obtain the micro-channel structure.
In one example, a detection substrate may be placed on the forearm of a subject to generate sweat (a substance to be detected) by exercise. The sweat to be detected flows to the detection chamber 22 through the liquid inlet 21, the liquid to be detected is detected in the detection chamber 22, and the detected waste liquid flows out from the liquid outlet.
The inventors also tested the selectivity of each working electrode. The detection substrate was immersed in 100ml of the solution, and standard solutions of sodium, potassium, and calcium ions were added to the solution, respectively. The detection substrate is provided with a sodium ion working electrode, a potassium ion working electrode and a calcium ion working electrode. As shown in fig. 8, the three working electrodes have high selectivity for specific ions, which means that the working electrodes are not interfered by other substances when detecting corresponding ions.
In the disclosure, the sensitive membrane of the ion selective carrier is spin-coated on the working electrode, so that high-sensitivity and high-accuracy detection can be realized only by trace sweat; by arranging a plurality of working electrodes, the detection of multi-target parameters can be realized, and the concentration of one or more ions in the substance to be detected can be detected simultaneously; by spin-coating a mixed reference solution of PVB, multi-walled carbon nanotubes and sodium chloride on the reference electrode, signal drift in the detection process can be reduced, and the detection accuracy is improved.
It should be noted that the cross-sectional dimension herein refers to the largest dimension of the cross-section, for example, when the cross-section is a circle, the cross-sectional dimension is the diameter of the circle; when the cross section is a regular polygon, the size of the cross section is the diameter of a circumscribed circle of the regular polygon. In addition, the distance between the working electrode and the reference electrode refers to the minimum distance between the working electrode and the reference electrode.
The present disclosure provides a detection apparatus comprising any one of the detection substrates.
As can be appreciated by those skilled in the art, the inspection apparatus has the advantages of the inspection substrate described above.
In particular implementations, the detection devices provided by the present disclosure may include one or more detection substrates. When the inspection apparatus includes a plurality of inspection substrates, the substrate may be shared by the plurality of inspection substrates. The response potential produced by the working electrode is relative to the potential of a reference electrode on the same detection substrate as the working electrode.
In some examples, the detection device may be a wearable device, such as a bracelet, a hair band, or the like. In other examples, the detection device may also be a portable detection device or the like.
The present disclosure provides a detection method applied to any one of the detection substrates. The detection method comprises the following steps:
step S01: acquiring the response potential generated by the working electrode.
Step S02: and determining a target parameter corresponding to the response potential according to a preset corresponding relation between the potential and the parameter.
In a specific implementation, the corresponding relation between the potential and the parameter can be obtained by testing the response potential of the ionic standard solution with different concentrations. Wherein, the parameter is the known concentration of the ion standard solution, and the potential is the response potential measured when the ion standard solution is used as the solution to be detected.
It should be noted that the detection method may further include more steps, which may be determined according to actual needs, and the disclosure is not limited thereto. For detailed description and technical effects of the detection method, reference may be made to the above description of the detection substrate and the detection apparatus, which are not repeated herein.
The embodiments in the present specification are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
Finally, it should also be noted that, unless otherwise defined, the terms "first," "second," and the like, as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. Also, 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. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect.
The above detailed description is made on the detection substrate, the detection method and the detection device provided by the present disclosure, and specific examples are applied herein to explain the principle and the implementation of the present disclosure, and the description of the above embodiments is only used to help understand the method and the core idea of the present disclosure; meanwhile, for a person skilled in the art, based on the idea of the present disclosure, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present disclosure should not be construed as a limitation to the present disclosure.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This disclosure is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
It will be understood that the present disclosure is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the present disclosure is limited only by the appended claims.
Reference herein to "one embodiment," "an embodiment," or "one or more embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present disclosure. Moreover, it is noted that instances of the word "in one embodiment" are not necessarily all referring to the same embodiment.
In the description provided herein, numerous specific details are set forth. However, it is understood that embodiments of the disclosure may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
In the claims, any reference signs placed between parentheses shall not be construed as limiting the claim. The word "comprising" does not exclude the presence of elements or steps not listed in a claim. The word "a" or "an" preceding an element does not exclude the presence of a plurality of such elements. The disclosure may be implemented by means of hardware comprising several distinct elements, and by means of a suitably programmed computer. In the unit claims enumerating several means, several of these means may be embodied by one and the same item of hardware. The usage of the words first, second and third, etcetera do not indicate any ordering. These words may be interpreted as names.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solutions of the present disclosure, not to limit them; although the present disclosure has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present disclosure.

Claims (19)

1. An inspection substrate comprising:
a substrate base plate;
the working electrode, the reference electrode and the micro-channel structure are arranged on one side of the substrate; the micro-channel structure comprises a liquid inlet, at least one detection chamber and a first micro-channel connected with the liquid inlet and the detection chamber, wherein the liquid inlet is used for receiving a substance to be detected, and the first micro-channel is used for conveying the substance to be detected to the detection chamber;
wherein the working electrode and the reference electrode are arranged in the at least one detection chamber, at least one of the working electrode and the reference electrode is arranged in each detection chamber, and the working electrode is used for generating a response potential relative to the reference electrode under the state of contacting the substance to be detected so as to determine the target parameter of the substance to be detected according to the response potential.
2. The detection substrate according to claim 1, wherein the first micro flow channel comprises a curved portion having a shape of S, serpentine, square wave, zigzag, or U.
3. The detection substrate according to claim 2, wherein the first micro flow channel further comprises a linear portion having a linear shape, and the linear portion is connected to an end of the curved portion near the liquid inlet and/or the detection chamber.
4. The detection substrate of claim 1, wherein the working electrode or the reference electrode is disposed within the detection chamber, and an orthographic projection of the detection chamber on the substrate covers an orthographic projection of the working electrode or the reference electrode on the substrate.
5. The detection substrate according to claim 1, wherein the micro flow channel structure comprises a plurality of the liquid inlets and a plurality of the first micro flow channels, each of the detection chambers is correspondingly connected to at least one of the liquid inlets, and the correspondingly connected detection chambers are connected to the liquid inlets through the first micro flow channels.
6. The detection substrate according to claim 5, wherein the number of the detection chambers is plural, the micro flow channel structure further comprises a plurality of second micro flow channels, the detection chambers are connected to the second micro flow channels in a one-to-one correspondence, and the plurality of second micro flow channels meet at a crossing position.
7. The detection substrate according to claim 6, wherein the second micro flow channel has a linear shape.
8. The detection substrate of claim 6, wherein an aspect ratio of the second microchannel is smaller than an aspect ratio of the first microchannel.
9. The detection substrate according to claim 1, wherein the micro flow channel structure further comprises a liquid outlet, and a third micro flow channel connecting the detection chamber and the liquid outlet.
10. The detection substrate according to claim 9, wherein the third micro flow channel has a shape including an S-shape, a serpentine shape, a square waveform shape, a zigzag shape, or a U-shape.
11. The detection substrate of claim 9, wherein an aspect ratio of the third microchannel is smaller than an aspect ratio of the first microchannel.
12. The detection substrate according to any one of claims 1 to 11, wherein an aspect ratio of the first micro flow channel is greater than or equal to 0.05 and less than or equal to 0.25.
13. The detection substrate according to claim 12, wherein the depth of the first micro flow channel is 20 μm or more and 40 μm or less.
14. The detection substrate according to any one of claims 1 to 11, wherein the number of the detection chambers is plural, and the plural detection chambers are communicated with each other;
a plurality of working electrodes are arranged on the substrate base plate, the working electrodes share one reference electrode, and different working electrodes are used for detecting different target parameters;
wherein each of the plurality of working electrodes and the reference electrode are located in a different one of the detection chambers.
15. The detection substrate according to any one of claims 1 to 11, wherein the distance between the working electrode and the reference electrode is greater than or equal to 2mm and less than or equal to 20 mm.
16. The detection substrate according to any one of claims 1 to 11, wherein the substance to be detected is sweat, and the target parameter comprises at least one of: sodium ion concentration, potassium ion concentration, calcium ion concentration, chloride ion concentration, and pH.
17. The detection substrate according to any one of claims 1 to 11, wherein the working electrode and the reference electrode are located on one side surface of the substrate;
the at least one detection chamber is positioned on the surface of one side, away from the substrate base plate, of the working electrode and the reference electrode, and the orthographic projection of the liquid inlet and the orthographic projection of the first micro-channel on the substrate base plate are not overlapped with the orthographic projection of the working electrode and the orthographic projection of the reference electrode on the substrate base plate.
18. An assay device comprising an assay substrate according to any one of claims 1 to 17.
19. An inspection method applied to the inspection substrate according to any one of claims 1 to 17, the inspection method comprising:
acquiring the response potential generated by the working electrode;
and determining a target parameter corresponding to the response potential according to a preset corresponding relation between the potential and the parameter.
CN202210191325.7A 2022-02-28 2022-02-28 Detection substrate, detection method thereof and detection device Pending CN114839241A (en)

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