CN108469460B - Perspiration sensor and preparation method thereof - Google Patents

Perspiration sensor and preparation method thereof Download PDF

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CN108469460B
CN108469460B CN201810195194.3A CN201810195194A CN108469460B CN 108469460 B CN108469460 B CN 108469460B CN 201810195194 A CN201810195194 A CN 201810195194A CN 108469460 B CN108469460 B CN 108469460B
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electrode
pad
support plate
reference electrode
working electrode
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CN108469460A (en
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颜丹
李强华
董青龙
李冠华
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Shenzhen Refresh Biosensor Technology Co ltd
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Shenzhen Refresh Intelligent Electronic Co Ltd
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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
    • G01N27/02Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/128Microapparatus
    • 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
    • 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
    • A61B5/48Other medical applications
    • A61B5/4869Determining body composition
    • A61B5/4875Hydration status, fluid retention of the body
    • 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
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/04Arrangements of multiple sensors of the same type
    • A61B2562/043Arrangements of multiple sensors of the same type in a linear array

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  • Life Sciences & Earth Sciences (AREA)
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  • Measuring And Recording Apparatus For Diagnosis (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Abstract

The present invention provides a kind of perspiration sensors, including support plate, spring needle and electrode chip are provided on support plate, electrode chip is provided with working electrode and work pole external connection pad, working electrode is connect with work pole external connection pad by conducting wire, and work pole external connection pad is connect with the pad on support plate by lead key closing process, and electrode chip and spring needle are encapsulated on support plate by packaging plastic, the head of another pad of the bottom connection support plate of spring needle, working electrode and spring needle leaks out packaging plastic.Electrode chip is connect by lead key closing process with support plate, spring needle is arranged in support plate, the connection with reference electrode or other external circuits may be implemented by spring needle, working electrode and reference electrode face in this way, three-dimensional bioelectrochemical sensor is constituted, the micro constitutent in human sweat can be more accurately detected.

Description

Perspiration sensor and preparation method thereof
Technical field
The present invention relates to sensor technical fields, and in particular to a kind of perspiration sensor and preparation method thereof.
Background technique
Human sweat mainly by 98~99% water (pH value 4.2~7.5), sodium chloride (about 300mg/100mL), 1~ 2% other substances (including a small amount of urea, lactic acid, fatty acid, glucose etc.) composition.
When human body is when being moved, a large amount of sweat can be flowed out, when averagely containing Na in every liter of sweat+Less than 58.4mg, K+ Less than 10mg, Cl-When less than 45.4mg, human body will will appear a series of problems, so that human body is to view, the obvious mistake of auditory stimulation Quick, the regulating power of the antibody of body also decreases, it may appear that muscle cramp, dehydration, the even symptoms such as stupor, if it is possible to The content of the above-mentioned ion in these human sweats is detected in time, then people's early warning can be given in time, to avoid tragedy Occur, there are no the contents that related sensor and equipment can detect the micro constitutent in human sweat in time in the industry for current line.
Summary of the invention
The technical problem to be solved by the present invention is providing a kind of content that can detect the micro constitutent in human sweat Perspiration sensor.
A kind of perspiration sensor, including support plate are provided with spring needle and electrode chip on support plate, and electrode chip is provided with work Make electrode and work pole external connection pad, working electrode is connect with work pole external connection pad by conducting wire, work pole external connection weldering Disk is connect with the pad on support plate by lead key closing process, and electrode chip and spring needle are encapsulated on support plate by packaging plastic, The head of another pad of the bottom connection support plate of spring needle, working electrode and spring needle leaks out packaging plastic.
Preferably, further include reference electrode circuit board, reference electrode circuit board be provided with reference electrode, reference electrode external connection pad and First pore, reference electrode and reference electrode external connection pad are connected by conducting wire;
Reference electrode circuit board is set to the top of packaging plastic, and the head of spring needle resists reference electrode external connection pad;Reference electricity Pole is located at the top of working electrode, is sweat reaction compartment, sweat reaction compartment between reference electrode external connection pad and working electrode Another end face of reference electrode circuit board is connected to by the first pore.
Preferably, sweat reaction compartment is provided with gel.Gel, sweat can come in and (have water sorption), and it is past to stop enzyme Outflow.
Preferably, another end face of support plate is provided with the second water-absorbent material, the second water-absorbent material and gel and is inhaled by third The connection of water material.
Preferably, sweat reaction compartment is provided with gel;The side of sweat reaction compartment is provided with third water-absorbent material, the Three water-absorbent materials extend to the side of reference electrode circuit board.
Preferably, the first pore is located at the top of sweat reaction compartment;Or,
First pore is located at the side of sweat reaction compartment, and by sweat runner, (sweat runner is set to reference electrode electricity The bottom of road plate or the top of packaging plastic, sweat runner are capillary channel) it is connected to sweat reaction compartment, sweat runner and third Water-absorbent material is located at the not ipsilateral of sweat reaction compartment;Sweat flows to reaction electrode (work electricity by pore and sweat runner Pole), the side of reaction electrode has water-absorbent material (third water-absorbent material), and the sweat after reaction (measuring to sweat) is inhaled It walks.
Preferably, transcrystalline hole is provided at the working electrode of electrode chip, support plate is provided with the second pore, the first capillary Hole, sweat reaction compartment, transcrystalline hole and the second pore are sequentially communicated.
Preferably, working electrode is annular electrode, and above-mentioned transcrystalline hole is arranged in the middle part of working electrode.
Preferably, transcrystalline hole is located at the middle part of working electrode, and transcrystalline hole is conductive hole or insulated hole.
Preferably, transcrystalline hole is conductive hole, and the bottom side in transcrystalline hole is chip bonding pad, and chip bonding pad is annular pad, Transcrystalline hole is soldered to support plate pad by chip bonding pad, and support plate pad is annular pad, and support plate pad is located at the second pore Side.
The present invention also provides another perspiration sensors.
A kind of perspiration sensor, including support plate are provided with spring needle, electrode chip and signal processing chip on support plate, electricity Pole piece piece is provided with working electrode and work pole external connection pad, and working electrode and work pole external connection pad are connected by conducting wire It connects, work pole external connection pad is connect with signal processing chip by lead key closing process, and the pad on signal processing chip passes through Wire bonding is connected to support plate;
Electrode chip, spring needle and signal processing chip are encapsulated on support plate by packaging plastic, the bottom connection of spring needle The head of another pad of support plate, working electrode and spring needle leaks out packaging plastic.
Preferably, further include reference electrode circuit board, reference electrode circuit board be provided with reference electrode, reference electrode external connection pad and First pore, reference electrode and reference electrode external connection pad are connected by conducting wire;
Reference electrode circuit board is set to the top of packaging plastic, and the head of spring needle resists reference electrode external connection pad;Reference electricity Pole is located at the top of working electrode, is sweat reaction compartment, sweat reaction compartment between reference electrode external connection pad and working electrode Another end face of reference electrode circuit board is connected to by the first pore.
Preferably, sweat reaction compartment is provided with gel;Another end face of support plate is provided with the second water-absorbent material, and second inhales Water material is connected to gel by third water-absorbent material;Or,
Transcrystalline hole is provided at the working electrode of electrode chip, support plate is provided with the second pore, the first pore, sweat Reaction compartment, transcrystalline hole and the second pore are sequentially communicated;Transcrystalline hole is conductive hole, and the bottom side in transcrystalline hole is welded by chip Disk is soldered to support plate pad, and chip bonding pad is located at the side in transcrystalline hole, and support plate pad is located at the side of the second pore.
Transcrystalline hole, the English spelling of TSV are " Through Silicon Vias ", and the Chinese meaning is " logical across silicon wafer Road ".
The present invention also provides another perspiration sensors.
A kind of perspiration sensor, including support plate are provided with electrode chip on support plate, and electrode chip is provided with working electrode, Working electrode is annular electrode, and transcrystalline hole is provided in the middle part of working electrode;Transcrystalline hole is conductive hole, and the bottom in transcrystalline hole connects The bottom side of chip bonding pad, transcrystalline hole is soldered to support plate pad by chip bonding pad, and support plate pad is annular pad, support plate weldering The second pore is provided in the middle part of disk.
Spring needle is additionally provided on support plate;Electrode chip and spring needle are encapsulated on support plate by packaging plastic, spring needle Bottom connects another pad of support plate, the head leakage packaging plastic of working electrode and spring needle.
It preferably, further include reference electrode circuit board (capillary piece), reference electrode circuit board is provided with reference electrode, outside reference electrode Connection pad and the first pore, reference electrode are connected with reference electrode external connection pad by conducting wire;
Reference electrode circuit board is set to the top of packaging plastic, and the head of spring needle resists reference electrode external connection pad;Reference electricity Pole is located at the top of working electrode, is sweat reaction compartment, sweat reaction compartment between reference electrode external connection pad and working electrode Another end face of reference electrode circuit board is connected to by the first pore.
First pore, sweat reaction compartment, transcrystalline hole and the second pore are sequentially communicated.
In the present invention, the preparation method of working electrode includes:
A. one layer of chromium and one layer of gold are plated on resin film (being also possible to silicon based substrate, ceramic base material);
B. layer gold and layers of chrome are etched, production includes working electrode, pad and the circuit for connecting working electrode and pad;
C. a strata paraxylene is deposited;
D. the parylene layer on etched electrodes and pad exposes electrode and pad;Working electrode includes Na+Sensor Electrode, K+Sensor electrode and PVB electrode;PVB electrode is as Na+Sensor electrode, K+The reference electrode of sensor electrode, Na+Sensor electrode, K+Na is made on sensor electrode respectively+Ion selective membrane and K+ ion selective membrane, can visit in time Survey the Na in human sweat+、K+Content perspiration sensor, Na can be detected in time+、K+Content in human sweat, energy It is enough to give people's early warning in time, to avoid tragedy.
Preferably, Na+Sensor electrode, K+Sensor electrode is the working end of working electrode, and PVB electrode is reference electrode Working end.
Preferably, after step D further include:
E. silver layer is made on PVB electrode, the thickness of silver layer is less than the thickness of Parylene;
F. by Na+Ion selectivity coating solution is injected into Na+Sensor electrode;
G. by K+Ion selectivity coating solution is injected into K+Sensor electrode;
H. by PVB reference electrode solution coating to PVB electrode.
Preferably, by Na in step F+Ion selectivity coating solution are as follows:
By Na ionophore (0.5%~1.5%, w/w), Na-TFPB (0.3%~0.7%, w/w), PVC (25%~ 43%, w/w), DOS (60%~75%, w/w) mixes in proportion, then the 100mg mixture is dissolved in the four of (600~750) uL In hydrogen furans, Na is formed+Ion selectivity coating solution.
Preferably, by K in step G+Ion selectivity coating solution are as follows:
By valinomycins (1%~3%, w/w), NaTPB (0.3%~0.7%, w/w), PVC (30%~37%, w/w), DOS (55%~76%, w/w) is mixed in proportion, then the 100mg mixture is dissolved in the cyclohexanone of (300~400) uL, shape At K+Ion selectivity coating solution.
Preferably, by PVB reference electrode solution in step H are as follows:
79.1mg PVB and (40~60) mg NaCl are dissolved in 1ml methanol, then will (1~3) mg F127 with (0.1~ 0.3) mg multi-walled carbon nanotube is added in above-mentioned solution, finally prepares PVB reference electrode solution.
Preferably, step E further include: silver layer is made on Ag/AgCl electrode, the thickness of silver layer is less than Parylene Thickness;
Preferably, after step H further include:
I. FeCl3 solution is injected on Ag/AgCl electrode;
J. by Prussian blue media deposition in the layer gold of glucose sensor electrode, Prussian blue medium layer is obtained, Glucose oxidase/Chitosan/carbon nanotube mixed solution is coated in the Prussian blue medium layer obtained;
K. by Prussian blue media deposition in the layer gold of lactic acid sensor electrode, Prussian blue medium layer is obtained;It will gather Chitose/first requirement for solution deposition is dry on Prussian blue/Au layers of electrode;Then, it is coated lactate oxidase solution, is done It is dry;Finally, coating Chitosan/carbon nanotube mixed solution.
Preferably, by glucose oxidase in step J/Chitosan/carbon nanotube mixed solution are as follows:
J1. Chitosan is dissolved in 1%~3% acetic acid, using the magnetic agitation of 1h, formed 1% Chitosan it is molten Liquid;
J2. the Chitosan solution of formation and the single wall carbon of (1~3) 2mg/ml are received using the ultrasonic agitation of 30min or more Mitron is sufficiently mixed, and forms thick mixed solution;
J3. the thick mixed solution of formation is mixed with glucose oxidase solution, mixed volume ratio 2:1;
Wherein: glucose oxidase solution is that glucose oxidase is dissolved in PBS, (8~15) mg/ml, pH value 7.2.
It preferably, will be in step K: by Prussian blue media deposition in the layer gold of lactic acid sensor electrode are as follows:
Using cyclic voltammetry (from -0.5V~0.6V, opposite with Ag/AgCl reference electrode), Prussian blue medium is sunk Product carries out the electricity circulation in 10 periods in the layer gold of lactic acid sensor electrode, voltage changing rate 50mV/s, Prussian blue The allocation ratio of medium are as follows: 2.5mMol FeCl3:100mMol KCl:2.5mMol K3Fe(CN)6Solution: 100mMol HCl.
Preferably, layers of chrome with a thickness of 20~40nm, 30~100nm of thickness of layer gold, parylene layer with a thickness of 200~900nm, the diameter of electrode are 1~10mm, and the diameter of windowing is less than the diameter of electrode.
The beneficial effects of the present invention are: a kind of perspiration sensor, including support plate, spring needle and electrode cores are provided on support plate Piece, electrode chip are provided with working electrode and work pole external connection pad, and working electrode and work pole external connection pad pass through conductor wire Road connection, work pole external connection pad are connect with the pad on support plate by lead key closing process, and electrode chip and spring needle pass through Packaging plastic is encapsulated on support plate, another pad of the bottom connection support plate of spring needle, the head leakage of working electrode and spring needle Packaging plastic out.Electrode chip is connect by lead key closing process with support plate, and spring needle is arranged in support plate, may be implemented by spring needle With the connection of reference electrode or other external circuits, such working electrode and reference electrode face constitute three-dimensional bioelectrochemical Sensor is learned, the micro constitutent in human sweat can be more accurately detected.
Detailed description of the invention
Perspiration sensor of the invention is described further with reference to the accompanying drawing.
Fig. 1 is a kind of support plate of embodiment one of perspiration sensor of the present invention and the attachment structure schematic diagram of electrode chip.
Fig. 2 is a kind of structural schematic diagram of the embodiment one of perspiration sensor of the present invention.
Fig. 3 is the enlarged drawing at a kind of A of Fig. 2 of the embodiment one of perspiration sensor of the present invention.
Fig. 4 is the enlarged drawing at a kind of B of Fig. 2 of the embodiment one of perspiration sensor of the present invention.
Fig. 5 is a kind of structural schematic diagram of the embodiment two of perspiration sensor of the present invention.
Fig. 6 is a kind of structural schematic diagram of the embodiment three of perspiration sensor of the present invention.
Fig. 7 is a kind of structural schematic diagram of the example IV of perspiration sensor of the present invention.
Fig. 8 is a kind of structural schematic diagram of the embodiment five of perspiration sensor of the present invention.
In figure:
1- support plate;The second pore of 11-;2- spring needle;3- electrode chip;31- working electrode;32- work pole external connection weldering Disk;33- transcrystalline hole;4- packaging plastic;5- reference electrode circuit board;51- reference electrode;52- reference electrode external connection pad;First mao of 53- Pore;6- sweat reaction compartment;7- gel;The second water-absorbent material of 8-;01- third water-absorbent material;02- signal processing chip;03- Wire bonding conducting wire;04- bonded adhesives.
The explanation of term in the present invention:
1) sodium ion carrier X (SigmaAldrich company, the U.S. can provide), the preparation for Na+ optional membrane;
2) DOS sebacic acid dioctyl ester, the preparation for Na+ and K+ optional membrane;
3)Na-TFPB[C32H12BF24Na]sodium
Tetrakis [3,5-bis- (trifluoromethyl) phenyl] borate abbreviation Na-TFPB seeks its chemistry Formula, the preparation for Na+ optional membrane;
4) polyvinylchloride, the preparation for Na+ and K+ optional membrane;
5) tetrahydrofuran, the preparation for Na+ optional membrane;
6) valinomycins, the preparation for K+ optional membrane;
7) NaTPB sodium tetraphenylborate, the preparation for K+ optional membrane;
8) cyclohexanone, the preparation for K+ optional membrane;
9) PVB polyvinyl butyral (resin base BUTVARB-98), the preparation for PVB electrode;
10) NaCl and KCl solution, for PVB electrode, the preparation of Na+ and K+ optional membrane;
11) EDOT solution (3,4 ,-ethene dioxythiophene), the patented product of Bayer Bitterfeld GmbH is conducting polymer monomer, is Conducting matrix grain substrate, the preparation for Na+ and K+ sensor;
12) glucose oxidase, lactate oxidase are respectively used to the preparation of glucose, lactic acid sensor;
13) chitosan, the preparation for glucose, lactic acid sensor;
14) single-walled carbon nanotube, the preparation for glucose, lactic acid sensor;
15) multi-walled carbon nanotube, the preparation for PVB electrode;
16) FeCl3 solution, the preparation for Ag/AgCl reference electrode;
17) the 6 solution potassium ferricyanide of K3Fe (CN), the preparation for glucose, lactic acid sensor;
18) F127 block copolymer (PEO-PPO-PEO), the preparation for PVB electrode;(U.S. Sigma Aldrich is public Department can provide)
19) PET polyethylene terephthalate, the substrate for entire sensor module;
20) acetone, acetic acid, nitric acid, hydrochloric acid
21) PBS phosphate buffer is used for the preparation of glucose sensor;
22) Prussian blue (Prussian blue, 18 14H2O of chemical formula Fe7 (CN), or write into Fe4 [Fe (CN) 6] 3 NH2O, referred to as: PB.Chinese name: (OC-6-11)-Hexacyanoferrate (4-) iron (3+) (3:4) also known as Berlin blue, tribute indigo plant, barba hispanica, Milori blue, ferric ferrocyanide, Chinese blue, milori blue, Chinese blue.English name Prussian blue.It is a kind of ancient indigo plant Color dyestuff can be used to glazing and do oil painting dyestuff.) it is used for the preparation of glucose, lactic acid sensor;
23) NaPSS polyelectrolyte is used for the preparation of Ag/AgCl reference electrode;
24) Cr/Au/Ag, the circuit production for sensor;
25) Parylene, i.e. parylene, the circuit production for sensor.
Specific embodiment
With reference to the accompanying drawing 1~8 and pass through specific embodiment to further illustrate the technical scheme of the present invention.
The present invention provides a kind of perspiration sensors.
Embodiment one
A kind of perspiration sensor, including support plate 1 are provided with spring needle 2 and electrode chip 3 on support plate 1, and electrode chip 3 is set It is equipped with working electrode 31 and work pole external connection pad 32, working electrode 31 and work pole external connection pad 32 are connected by conducting wire It connects, by lead key closing process, (it is extremely outer that wire bonding conducting wire 03 connect work to work pole external connection pad 32 with the pad on support plate 1 Join the pad of pad 32 and support plate 1, the bottom of electrode chip 3 is adhered on support plate 1 by bonded adhesives 04) connection, electrode chip 3 It is encapsulated on support plate 1 with spring needle 2 by packaging plastic 4, another pad of the bottom connection support plate 1 of spring needle 2, working electrode 31 and spring needle 2 head leak out packaging plastic 4.
Further include reference electrode circuit board 5 (capillary piece) in the present embodiment, reference electrode circuit board 5 be provided with reference electrode 51, Reference electrode external connection pad 52 and the first pore 53, reference electrode 51 are connected with reference electrode external connection pad 52 by conducting wire;
Reference electrode circuit board 5 is set to the top of packaging plastic 4, and the head of spring needle 2 resists reference electrode external connection pad 52;Ginseng It is sweat reaction compartment 6 between reference electrode external connection pad 52 and working electrode 31 than the top that electrode 51 is located at working electrode 31, Sweat reaction compartment 6 is connected to another end face of reference electrode circuit board 5 by the first pore 53.
In the present embodiment, sweat reaction compartment 6 is provided with gel 7.
In the present embodiment, the side of sweat reaction compartment 6 is provided with third water-absorbent material 01, and third water-absorbent material 01 extends To the side of reference electrode circuit board 5.Alternatively, it is also possible to another end face of support plate 1 and is provided with the second water suction Material 8, the second water-absorbent material 8 are connected to gel 7 by third water-absorbent material 01.
In the present embodiment, the first pore 53 is located at the top of sweat reaction compartment 6;Or,
First pore 53 is located at the side of sweat reaction compartment 6, is connected to sweat reaction compartment 6 by sweat runner, Sweat runner is located at the not ipsilateral of sweat reaction compartment 6 with third water-absorbent material 01.
In the present invention, the preparation method of working electrode includes:
A. one layer of chromium and one layer of gold are plated on resin film;
B. layer gold and layers of chrome are etched, production includes the circuit of electrode, pad and connection electrode and pad;
C. a strata paraxylene is deposited;
D. the parylene layer on etched electrodes and pad exposes electrode and pad;Electrode includes Na+Sensor electricity Pole, K+Sensor electrode and PVB electrode;PVB electrode is as Na+Sensor electrode, K+The reference electrode of sensor electrode, in Na+ Sensor electrode, K+Na is made on sensor electrode respectively+Ion selective membrane and K+ ion selective membrane, can detect in time Na in human sweat+、K+Content perspiration sensor, Na can be detected in time+、K+Content in human sweat, can People's early warning is given in time, to avoid tragedy.
Preferably, Na+Sensor electrode, K+Sensor electrode is the working end of working electrode, and PVB electrode is reference electrode Working end.
Preferably, after step D further include:
E. silver layer is made on PVB electrode, the thickness of silver layer is less than the thickness of Parylene;
F. by Na+Ion selectivity coating solution is injected into Na+Sensor electrode;
G. by K+Ion selectivity coating solution is injected into K+Sensor electrode;
H. by PVB reference electrode solution coating to PVB electrode.
Preferably, by Na in step F+Ion selectivity coating solution are as follows:
By Na ionophore (0.5%~1.5%, w/w), Na-TFPB (0.3%~0.7%, w/w), PVC (25%~ 43%, w/w), DOS (60%~75%, w/w) mixes in proportion, then the 100mg mixture is dissolved in the four of (600~750) uL In hydrogen furans, Na is formed+Ion selectivity coating solution.
Preferably, by K in step G+Ion selectivity coating solution are as follows:
By valinomycins (1%~3%, w/w), NaTPB (0.3%~0.7%, w/w), PVC (30%~37%, w/w), DOS (55%~76%, w/w) is mixed in proportion, then the 100mg mixture is dissolved in the cyclohexanone of (300~400) uL, shape At K+Ion selectivity coating solution.
Preferably, by PVB reference electrode solution in step H are as follows:
79.1mg PVB and (40~60) mg NaCl are dissolved in 1ml methanol, then will (1~3) mg F127 with (0.1~ 0.3) mg multi-walled carbon nanotube is added in above-mentioned solution, finally prepares PVB reference electrode solution.
Preferably, step E further include: silver layer is made on Ag/AgCl electrode, the thickness of silver layer is less than Parylene Thickness;
Preferably, after step H further include:
I. FeCl3 solution is injected on Ag/AgCl electrode;
J. by Prussian blue media deposition in the layer gold of glucose sensor electrode, Prussian blue medium layer is obtained, Glucose oxidase/Chitosan/carbon nanotube mixed solution is coated in the Prussian blue medium layer obtained;
K. by Prussian blue media deposition in the layer gold of lactic acid sensor electrode, Prussian blue medium layer is obtained;It will gather Chitose/first requirement for solution deposition is dry on Prussian blue/Au layers of electrode;Then, it is coated lactate oxidase solution, is done It is dry;Finally, coating Chitosan/carbon nanotube mixed solution.
Preferably, by glucose oxidase in step J/Chitosan/carbon nanotube mixed solution are as follows:
J1. Chitosan is dissolved in 1%~3% acetic acid, using the magnetic agitation of 1h, formed 1% Chitosan it is molten Liquid;
J2. the Chitosan solution of formation and the single wall carbon of (1~3) 2mg/ml are received using the ultrasonic agitation of 30min or more Mitron is sufficiently mixed, and forms thick mixed solution;
J3. the thick mixed solution of formation is mixed with glucose oxidase solution, mixed volume ratio 2:1;
Wherein: glucose oxidase solution is that glucose oxidase is dissolved in PBS, (8~15) mg/ml, pH value 7.2.
It preferably, will be in step K: by Prussian blue media deposition in the layer gold of lactic acid sensor electrode are as follows:
Using cyclic voltammetry (from -0.5V~0.6V, opposite with Ag/AgCl reference electrode), Prussian blue medium is sunk Product carries out the electricity circulation in 10 periods in the layer gold of lactic acid sensor electrode, voltage changing rate 50mV/s, Prussian blue The allocation ratio of medium are as follows: 2.5mMol FeCl3:100mMol KCl:2.5mMol K3Fe(CN)6Solution: 100mMol HCl.
Preferably, layers of chrome with a thickness of 20~40nm, 30~100nm of thickness of layer gold, parylene layer with a thickness of 200~900nm, the diameter of electrode are 1~10mm, and the diameter of windowing is less than the diameter of electrode.
Embodiment two
A kind of perspiration sensor, including support plate 1 are provided with spring needle 2 and electrode chip 3 on support plate 1, and electrode chip 3 is set It is equipped with working electrode 31 and work pole external connection pad 32, working electrode 31 and work pole external connection pad 32 are connected by conducting wire It connects, by lead key closing process, (it is extremely outer that wire bonding conducting wire 03 connect work to work pole external connection pad 32 with the pad on support plate 1 Join the pad of pad 32 and support plate 1, the bottom of electrode chip 3 is adhered on support plate 1 by bonded adhesives 04) connection, electrode chip 3 It is encapsulated on support plate 1 with spring needle 2 by packaging plastic 4, another pad of the bottom connection support plate 1 of spring needle 2, working electrode 31 and spring needle 2 head leak out packaging plastic 4.
Further include reference electrode circuit board 5 (capillary piece) in the present embodiment, reference electrode circuit board 5 be provided with reference electrode 51, Reference electrode external connection pad 52 and the first pore 53, reference electrode 51 are connected with reference electrode external connection pad 52 by conducting wire;
Reference electrode circuit board 5 is set to the top of packaging plastic 4, and the head of spring needle 2 resists reference electrode external connection pad 52;Ginseng It is sweat reaction compartment 6 between reference electrode external connection pad 52 and working electrode 31 than the top that electrode 51 is located at working electrode 31, Sweat reaction compartment 6 is connected to another end face of reference electrode circuit board 5 by the first pore 53.
In the present embodiment, transcrystalline hole 33 is provided at the working electrode 31 of electrode chip 3, support plate 1 is provided with the second capillary Hole 11, the first pore 53, sweat reaction compartment 6, transcrystalline hole 33 and the second pore 11 are sequentially communicated.
In the present embodiment, working electrode 31 is annular electrode, and above-mentioned transcrystalline hole 33 is arranged in the middle part of working electrode 31.
In the present embodiment, transcrystalline hole 33 is conductive hole, and the bottom side in transcrystalline hole 33 is chip bonding pad, and chip bonding pad is ring Shape pad, transcrystalline hole 33 are soldered to support plate pad by chip bonding pad, and support plate pad is annular pad, and support plate pad is located at second The side of pore 11.
In the present embodiment, transcrystalline hole 33 is located at the middle part of working electrode 31, and transcrystalline hole 33 is insulated hole.
Alternative solution as one preferred, transcrystalline hole 33 are conductive hole, and the bottom side in transcrystalline hole 33 is welded by chip Disk is soldered to support plate pad, and chip bonding pad is located at the side in transcrystalline hole 33, and support plate pad is located at the side of the second pore 11;This Sample can save the technique of wire bonding.
Embodiment three
A kind of perspiration sensor, including support plate 1 are provided with spring needle 2, electrode chip 3 and signal processing chip on support plate 1 02, electrode chip 3 is provided with working electrode 31 and work pole external connection pad 32, and working electrode 31 and work pole external connection pad 32 are logical Conducting wire connection is crossed, work pole external connection pad 32 is connect with signal processing chip 02 by lead key closing process, signal processing Pad on chip 02 is connected to support plate 1 by wire bonding;
Electrode chip 3, spring needle 2 and signal processing chip 02 are encapsulated on support plate 1 by packaging plastic 4, the bottom of spring needle 2 Portion connects another pad of support plate 1, the head leakage packaging plastic 4 of working electrode 31 and spring needle 2.
It further include reference electrode circuit board 5 in the present embodiment, reference electrode circuit board 5 is provided with reference electrode 51, outside reference electrode Connection pad 52 and the first pore 53, reference electrode 51 are connected with reference electrode external connection pad 52 by conducting wire.
In the present embodiment, sweat reaction compartment 6 is provided with gel 7;Another end face of support plate 1 is provided with the second water-absorbent material 8, the second water-absorbent material 8 is connected to gel 7 by third water-absorbent material 01.
Example IV
A kind of perspiration sensor, including support plate 1 are provided with spring needle 2, electrode chip 3 and signal processing chip on support plate 1 02, electrode chip 3 is provided with working electrode 31 and work pole external connection pad 32, and working electrode 31 and work pole external connection pad 32 are logical Conducting wire connection is crossed, work pole external connection pad 32 is connect with signal processing chip 02 by lead key closing process, signal processing Pad on chip 02 is connected to support plate 1 by wire bonding;
Electrode chip 3, spring needle 2 and signal processing chip 02 are encapsulated on support plate 1 by packaging plastic 4, the bottom of spring needle 2 Portion connects another pad of support plate 1, the head leakage packaging plastic 4 of working electrode 31 and spring needle 2.
It further include reference electrode circuit board 5 in the present embodiment, reference electrode circuit board 5 is provided with reference electrode 51, outside reference electrode Connection pad 52 and the first pore 53, reference electrode 51 are connected with reference electrode external connection pad 52 by conducting wire.
It is provided with transcrystalline hole 33 at the working electrode 31 of electrode chip 3, support plate 1 is provided with the second pore 11, and first mao Pore 53, sweat reaction compartment 6, transcrystalline hole 33 and the second pore 11 are sequentially communicated;Transcrystalline hole 33 is conductive hole, transcrystalline hole 33 Bottom side support plate pad is soldered to by chip bonding pad, chip bonding pad is located at the side in transcrystalline hole 33, and support plate pad is located at The side of second pore 11.
Embodiment five
A kind of perspiration sensor, including support plate 1, electrode chip 3 is provided on support plate 1, and electrode chip 3 is provided with work electricity Pole 31, working electrode 31 are annular electrode, and the middle part of working electrode 31 is provided with transcrystalline hole 33;Transcrystalline hole 33 is conductive hole, is worn The bottom of geode 33 connects chip bonding pad, and the bottom side in transcrystalline hole 33 is soldered to support plate pad, support plate weldering by chip bonding pad Disk is annular pad, and the second pore 11 is provided in the middle part of support plate pad.
Spring needle 2 is additionally provided on support plate 1;Electrode chip 3 and spring needle 2 are encapsulated on support plate 1 by packaging plastic 4, bullet The head of another pad of the bottom connection support plate 1 of spring needle 2, working electrode 31 and spring needle 2 leaks out packaging plastic 4.
Further include reference electrode circuit board 5 (capillary piece) in the present embodiment, reference electrode circuit board 5 be provided with reference electrode 51, Reference electrode external connection pad 52 and the first pore 53, reference electrode 51 are connected with reference electrode external connection pad 52 by conducting wire;
Reference electrode circuit board 5 is set to the top of packaging plastic 4, and the head of spring needle 2 resists reference electrode external connection pad 52;Ginseng It is sweat reaction compartment 6 between reference electrode external connection pad 52 and working electrode 31 than the top that electrode 51 is located at working electrode 31, Sweat reaction compartment 6 is connected to another end face of reference electrode circuit board 5 by the first pore 53.
First pore 53, sweat reaction compartment 6, transcrystalline hole 33 and the second pore 11 are sequentially communicated.
Of the invention is not limited to the above embodiment, and the technical solution of above-mentioned each embodiment of the invention can be handed over each other Fork combination form new technical solution, in addition it is all using equivalent replacement formed technical solution, all fall within the present invention claims guarantor It protects in range.

Claims (7)

1. a kind of perspiration sensor, including support plate (1), which is characterized in that be provided with spring needle (2) and electricity on the support plate (1) Pole piece piece (3), the electrode chip (3) are provided with working electrode (31) and work pole external connection pad (32), the working electrode (31) it is connect with the work pole external connection pad (32) by conducting wire, the work pole external connection pad (32) and the support plate (1) pad on is connected by lead key closing process, and the electrode chip (3) and spring needle (2) are encapsulated in by packaging plastic (4) On the support plate (1), the bottom of the spring needle (2) connects another pad of the support plate (1), the working electrode (31) The packaging plastic (4) is leaked out with the head of spring needle (2);It further include reference electrode circuit board (5), the reference electrode circuit board (5) It is provided with reference electrode (51), reference electrode external connection pad (52) and the first pore (53), the reference electrode (51) and reference Pole external connection pad (52) is connected by conducting wire;
The reference electrode circuit board (5) is set to the top of the packaging plastic (4), and the head of the spring needle (2) resists described Reference electrode external connection pad (52);The reference electrode (51) is located at the top of the working electrode (31), the reference electrode external connection It is sweat reaction compartment (6) that the sweat reaction compartment (6) passes through described the between pad (52) and the working electrode (31) One pore (53) is connected to another end face of the reference electrode circuit board (5);
The working electrode (31) is annular electrode, is provided with transcrystalline hole (33), the load in the middle part of the working electrode (31) Plate (1) is provided with the second pore (11), first pore (53), sweat reaction compartment (6), transcrystalline hole (33) and second Pore (11) is sequentially communicated.
2. perspiration sensor as described in claim 1, which is characterized in that the sweat reaction compartment (6) is provided with gel (7);
The side of the sweat reaction compartment (6) is provided with third water-absorbent material (01), and the third water-absorbent material (01) extends To the side of the reference electrode circuit board (5).
3. perspiration sensor as claimed in claim 2, which is characterized in that first pore (53) is located at sweat reaction The top in space (6);Or,
First pore (53) is located at the side of the sweat reaction compartment (6), is connected to the sweat by sweat runner Liquid reaction compartment (6), sweat runner are capillary channel, and the sweat runner and the third water-absorbent material (01) are located at the sweat Liquid reaction compartment (6) it is not ipsilateral.
4. perspiration sensor as claimed in claim 3, which is characterized in that the transcrystalline hole (33) is conductive hole, the transcrystalline hole (33) bottom side is chip bonding pad, and the chip bonding pad is annular pad, and the transcrystalline hole (33) is welded by chip bonding pad It is connected to support plate pad, the support plate pad is annular pad, and the support plate pad is located at the side of second pore (11).
5. a kind of perspiration sensor, including support plate (1), which is characterized in that be provided with spring needle (2), electrode on the support plate (1) Chip (3) and signal processing chip (02), the electrode chip (3) are provided with working electrode (31) and work pole external connection pad (32), the working electrode (31) is connect with the work pole external connection pad (32) by conducting wire, work pole external connection Pad (32) is connect with the signal processing chip (02) by lead key closing process, the weldering on the signal processing chip (02) Disk is connected to the support plate (1) by wire bonding;The electrode chip (3), spring needle (2) and signal processing chip (02) are logical It crosses packaging plastic (4) to be encapsulated on the support plate (1), the bottom of the spring needle (2) connects another weldering of the support plate (1) The head of disk, the working electrode (31) and spring needle (2) leaks out the packaging plastic (4);
It further include reference electrode circuit board (5), the reference electrode circuit board (5) is provided with reference electrode (51), reference electrode external connection weldering Disk (52) and the first pore (53), the reference electrode (51) are connected with reference electrode external connection pad (52) by conducting wire;
The reference electrode circuit board (5) is set to the top of the packaging plastic (4), and the head of the spring needle (2) resists described Reference electrode external connection pad (52);The reference electrode (51) is located at the top of the working electrode (31), the reference electrode external connection It is sweat reaction compartment (6) that the sweat reaction compartment (6) passes through described the between pad (52) and the working electrode (31) One pore (53) is connected to another end face of the reference electrode circuit board (5);
The working electrode (31) is annular electrode, is provided with transcrystalline hole (33), the load in the middle part of the working electrode (31) Plate (1) is provided with the second pore (11), first pore (53), sweat reaction compartment (6), transcrystalline hole (33) and second Pore (11) is sequentially communicated.
6. a kind of perspiration sensor, including support plate (1), which is characterized in that be provided with electrode chip (3), institute on the support plate (1) It states electrode chip (3) to be provided with working electrode (31), the working electrode (31) is annular electrode, the working electrode (31) Middle part is provided with transcrystalline hole (33);The transcrystalline hole (33) is conductive hole, and the bottom side of the transcrystalline hole (33) passes through chip For pad solder to support plate pad, the support plate pad is annular pad, is provided with the second pore in the middle part of the support plate pad (11);
Spring needle (2) are additionally provided on the support plate (1);The electrode chip (3) and spring needle (2) are sealed by packaging plastic (4) On the support plate (1), the bottom of the spring needle (2) connects another pad of the support plate (1), the working electrode (31) and the head of spring needle (2) leaks out the packaging plastic (4).
7. the preparation method of perspiration sensor as described in any one of claims 1 to 6, which is characterized in that the system of working electrode Preparation Method includes:
A. one layer of chromium and one layer of gold are plated on matrix;
B. layer gold and layers of chrome are etched, production includes working electrode, pad and the circuit for connecting working electrode and pad;
C. a strata paraxylene is deposited;
D. the parylene layer on etched electrodes and pad exposes working electrode and pad;Working electrode includes Na+Sensor Electrode, K+Sensor electrode and PVB electrode;PVB electrode is as Na+Sensor electrode, K+The reference electrode of sensor electrode.
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