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CN108828043A - A kind of flexibility perspiration sensor and its preparation method and application - Google Patents

A kind of flexibility perspiration sensor and its preparation method and application Download PDF

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Publication number
CN108828043A
CN108828043A CN201810663005.0A CN201810663005A CN108828043A CN 108828043 A CN108828043 A CN 108828043A CN 201810663005 A CN201810663005 A CN 201810663005A CN 108828043 A CN108828043 A CN 108828043A
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electrode
chitosan
glucose
carbon nanotube
lusi
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张国军
李玉桃
丁帆
唐丽娜
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Hubei College of Chinese Medicine
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Hubei College of Chinese Medicine
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
    • 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
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    • 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
    • G01N27/308Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3271Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
    • G01N27/3272Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • 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

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Abstract

The present invention provides a kind of flexible perspiration sensors, including flexible substrates and the glucose working electrode for being set to the flexible substrates surface, lactic acid working electrode and reference electrode, the present invention aoxidizes the glucose (or lactic acid) in sweat using the glucose oxidase (or lactate oxidase) on electrode, generate hydrogen peroxide, reduction reaction can directly occur on the electrode for hydrogen peroxide, reduction current is detected by electrochemical workstation, the concentration of the glucose and lactic acid in sweat can be obtained further according to size of current and standard curve, the present invention accelerates the decomposition of hydrogen peroxide using Pu Lusi indigo plant layer, it is horizontal to improve response current.Sensor of the invention high sensitivity, reaches 10nM to the minimum detectability of glucose, reaches 1 μM to the minimum detectability of lactic acid.

Description

A kind of flexibility perspiration sensor and its preparation method and application
Technical field
The present invention relates to the technical field of sensor, in particular to a kind of flexible perspiration sensor and preparation method thereof and answer With.
Background technique
Flexible electronic technology is the new electronic technology by electronic device production on flexible substrates, because its is unique soft Property, ductility and efficiently, low cost the advantages that, the fields such as information, the energy, medical treatment, national defence have wide application prospect.
The rapid development of intellectual material and flexible electronic, be the environmental monitoring of people inside and outside and early warning, portable medical with And intelligently wearing application opens completely new road for human-computer interaction etc..Although the comparison of current wearable device research is burning hot, It is that its most of function still concentrates on exercise test, body-building auxiliary etc., the medical application value of most wearable devices is not Targets match needed for height and disease surveillance not on.
Rich in potentially large number of marker relevant to health and disease in human sweat, compared to more conventional blood and urine Liquid detection, sweat detection have the advantages such as non-intruding and real-time continuous monitoring, therefore the research of wearable flexible perspiration sensor One of emphasis as wearable healthy field of electronic device development.Compared to relatively at present acquisition human motion state (speed, away from From, cadence etc.) and sign physical data (heart rate, blood pressure, body temperature etc.) wearable health equipment, wearable sweat detection sets It is standby that there is the more direct and accurate meaning for determining human health status.It is reported that the gentle blood glucose level of sweat glucose water has connection System;Sweat lactic acid is one potential Sensitive mark of pressure local anemia, and skin temperature contains a series of diseases and skin The clinical information of damage, sweat samples can also realize the real-time tracking of non-intrusion type.Therefore flexible perspiration sensor is studied It is needed for the epoch.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of flexible perspiration sensors and its preparation method and application;This hair The flexible perspiration sensor of bright offer can realize the real-time tracking of sweat glucose and lactate level, and to sweat glucose and cream The detection limit of acid is low, and response sensitivity is high.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
A kind of flexibility perspiration sensor, it is electric including flexible substrates and the glucose work for being set to the flexible substrates surface Pole, lactic acid working electrode and reference electrode;
The glucose working electrode successively includes setting in first gold electrode of flexible substrates surface, is arranged described The mono- Pu Lusi indigo plant layer of first gold electrode surfaces and the chitosan-carbon nanometer that the mono- Pu Lusi indigo plant layer surface is set Pipe-glucose oxidase plural gel layer;
The lactic acid working electrode successively includes setting in second gold electrode of flexible substrates surface, and setting is described the The bis- Pu Lusi indigo plant layer of two gold electrode surfaces and the chitosan-carbon nanotube-that the bis- Pu Lusi indigo plant layer surface is set Lactate oxidase plural gel layer.
Preferably, the diameter of first gold electrode and the second gold electrode independently is 1~3mm;First gold electrode 40~60nm independently is with the thickness of the second gold electrode.
Preferably, chitosan in the chitosan-carbon nanotube-glucose oxidase plural gel layer, carbon nanotube and The mass ratio of glucose oxidase is (5~50):(1~2):(5~10).
Preferably, chitosan, carbon nanotube and cream in the chitosan-carbon nanotube-lactate oxidase plural gel layer The mass ratio of acid oxidase is (5~50):(1~2):(20~40).
Preferably, the reference electrode is Ag/AgCl reference electrode;The diameter of the reference electrode is 0.5~2mm, thick Degree is 40~60nm.
The present invention provides the preparation methods of flexibility perspiration sensor described in above scheme, include the following steps:
The first gold electrode, the second gold electrode and reference electrode are prepared on flexible substrates surface;
Mono- Pu Lusi indigo plant is deposited in the first gold electrode and the second gold electrode surfaces using electrochemical cyclic voltammetry respectively Layer and bis- Pu Lusi indigo plant layer;
It is done after mono- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-glucose oxidase mixed gel solution It is dry, form glucose working electrode;
It is dry after bis- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-lactate oxidase mixed gel solution, Lactic acid working electrode is formed, flexible perspiration sensor is obtained.
Preferably, the deposition voltage of the electrochemical cyclic voltammetry stands alone as -0.5~0.5V, and scanning circle number stands alone as 1 ~10 circles.
Preferably, in the chitosan-carbon nanotube-glucose oxidase mixed gel solution chitosan mass concentration It is 0.5%~5%, the concentration of carbon nanotube is 1.0~2.0mg/L, and the concentration of glucose oxidase is 5.0~10.0mg/L; Chitosan-carbon nanotube-glucose oxidase mixed gel the solution mono- Pu Lusi indigo plant layer surface drop coating amount be 5~ 30μL/mm2
Preferably, the mass concentration of chitosan is in the chitosan-carbon nanotube-lactate oxidase mixed gel solution 0.5%~5%, the concentration of carbon nanotube is 1.0~2.0mg/L, and the concentration of lactate oxidase is 20~40mg/L;The shell is poly- Sugar-carbon nanotube-lactate oxidase mixed gel solution is 5~30 μ L/mm in the drop coating amount of bis- Pu Lusi indigo plant layer surface2
The present invention provides the soft of the preparation of preparation method described in flexibility perspiration sensor described in above scheme or above scheme Property perspiration sensor sweat detection in application.
The present invention provides a kind of flexible perspiration sensors, including flexible substrates and are set to the flexible substrates surface Glucose working electrode, lactic acid working electrode and reference electrode;Flexible perspiration sensor of the invention includes glucose work electricity Pole and lactic acid working electrode are, it can be achieved that real-time tracking to glucose in sweat and lactate level;Glucose work of the invention Electrode includes the first gold electrode, and the mono- Pu Lusi indigo plant layer of the first gold electrode surfaces is arranged in and is arranged in mono- Pu Lusi indigo plant layer The chitosan-carbon nanotube on surface-glucose oxidase plural gel layer;Lactic acid working electrode successively includes the second gold electrode, The bis- Pu Lusi indigo plant layer of second gold electrode surfaces is set and the chitosan-carbon nanometer of bis- Pu Lusi indigo plant layer surface is set Pipe-lactate oxidase plural gel layer.The present invention is using the glucose oxidase (or lactate oxidase) on electrode in sweat Glucose (or lactic acid) aoxidized, generate hydrogen peroxide, reduction reaction can directly occur on the electrode for hydrogen peroxide, generate Reduction current can be detected by external detection device, the grape in sweat can be obtained further according to size of current and standard curve The concentration of sugar and lactic acid.In the present invention, Pu Lusi indigo plant layer can accelerate the decomposition of hydrogen peroxide, and it is horizontal to improve response current;This Invention embeds enzyme using chitosan, keeps the activity of enzyme, accelerates electron transmission using carbon nanotube, improves the spirit of electrode Sensitivity.Embodiment the result shows that, examined using glucose and lactic acid of the perspiration sensor provided by the invention to various concentration When survey, with the raising of glucose and lactic acid concn, detects reduction peak and constantly reduce, illustrate that sensor rings glucose and lactic acid Should be good, sensor of the invention reaches 10nM to the minimum detectability of glucose, reaches 1 μM to the minimum detection limit of lactic acid; And in the detection process minimal amount of glucose or lactic acid are added into human sweat after, sensor can be responded immediately, Illustrate that transducer sensitivity provided by the invention is very high.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flexible perspiration sensor of the invention;
In Fig. 1:1- glucose working electrode, 2- lactic acid working electrode, 3- reference electrode, 4- conducting wire, 5- external wire, 6- Flexible substrates;
Fig. 2 is the circulation that flexible perspiration sensor detects different glucose solution in the embodiment of the present invention 4 Voltammogram;
Fig. 3 is the standard working curve of concentration of glucose and current value in the embodiment of the present invention 4;
Fig. 4 is that the circulation that flexible perspiration sensor detects various concentration lactic acid solution in the embodiment of the present invention 4 lies prostrate Antu;
Fig. 5 is the standard working curve of lactic acid concn and current value in the embodiment of the present invention 4;
Fig. 6 is the real-time work that flexible perspiration sensor detects glucose in human sweat in the embodiment of the present invention 4 Make curve;
Fig. 7 is the real-time working that flexible perspiration sensor detects lactic acid in human sweat in the embodiment of the present invention 4 Curve.
Specific embodiment
The present invention provides a kind of flexible perspiration sensors, including flexible substrates and are set to the flexible substrates surface Glucose working electrode, lactic acid working electrode and reference electrode;
The glucose working electrode successively includes setting in first gold electrode of flexible substrates surface, is arranged described The mono- Pu Lusi indigo plant layer of first gold electrode surfaces and the chitosan-carbon nanometer that the mono- Pu Lusi indigo plant layer surface is set Pipe-glucose oxidase plural gel layer;
The lactic acid working electrode successively includes setting in second gold electrode of flexible substrates surface, and setting is described the The bis- Pu Lusi indigo plant layer of two gold electrode surfaces and the chitosan-carbon nanotube-that the bis- Pu Lusi indigo plant layer surface is set Lactate oxidase plural gel layer.
Flexibility perspiration sensor provided by the invention includes flexible substrates.In the present invention, the flexible substrates are preferably Polyetherimide (PEI) substrate, polyethylene terephthalate (PET) substrate, polyimides (PI) substrate or poly dimethyl Siloxanes (PDMS) substrate;The present invention does not have special restriction to the size of the substrate, is adjusted according to sensor size ?.
Flexibility perspiration sensor provided by the invention includes the glucose working electrode that the flexible substrates surface is arranged in. In the present invention, the glucose working electrode successively includes the first gold electrode that flexible substrates surface is arranged in, and setting is the The mono- Pu Lusi indigo plant layer of one gold electrode surfaces and chitosan-carbon nanotube-grape that mono- Pu Lusi indigo plant layer surface is set Carbohydrate oxidase plural gel layer.In the present invention, first gold electrode is preferably disc-shaped electrode, first gold electrode Diameter is preferably 1~3mm, more preferably 1.5~2.5mm, most preferably 2mm;The thickness of first gold electrode is preferably 40 ~60nm, more preferably 45~55nm, most preferably 50nm.
In the present invention, the Pu Lusi indigo plant layer can accelerate hydrogen peroxide (in enzyme electrode transforming glucose and lactic acid Between product) decomposition, so that the response current for improving sensor is horizontal.In a specific embodiment of the present invention, preferably according to heavy The product time controls the thickness of Pu Lusi indigo plant layer.
In the present invention, chitosan, carbon nanometer in the chitosan-carbon nanotube-glucose oxidase plural gel layer The mass ratio of pipe and glucose oxidase is preferably (5~50):(1~2):(5~10), more preferably (10~20):1.5:(6 ~8);In the present invention, the chitosan can embed enzyme, keep the activity of enzyme, and carbon nanotube can accelerate enzyme and turn The electron transmission of change process improves the sensitivity of electrode;The present invention does not have particular/special requirement to the carbon nanotube, uses this field Carbon nanotube known to technical staff.
Flexibility perspiration sensor provided by the invention includes the lactic acid working electrode that the substrate surface is arranged in.In this hair In bright, the lactic acid working electrode successively includes the second gold electrode that the flexible substrates surface is arranged in, and is arranged in the second gold medal The bis- Pu Lusi indigo plant layer of electrode surface and chitosan-carbon nanotube-lactic acid oxidation that bis- Pu Lusi indigo plant layer surface is set Enzyme plural gel layer;The diameter and thickness of second gold electrode is preferably identical with the diameter and thickness of the first gold electrode, herein It repeats no more;The bis- Pu Lusi indigo plant layer is preferably identical with mono- Pu Lusi indigo plant layer, and details are not described herein.
In the present invention, chitosan, carbon nanotube in the chitosan-carbon nanotube-lactate oxidase plural gel layer Mass ratio with lactate oxidase is preferably (5~50):(1~2):(20~40), more preferably (10~20):1.5:30.
Flexibility perspiration sensor provided by the invention includes the reference electrode that the substrate surface is arranged in.In the present invention In, the reference electrode is preferably Ag/AgCl reference electrode;The reference electrode is preferably disc-shaped electrode, the reference electricity The diameter of pole is preferably 0.5~2mm, more preferably 1~1.5mm;The thickness of the reference electrode is preferably 40~60nm, more excellent It is selected as 50nm.
In the present invention, the glucose working electrode, lactic acid working electrode and reference electrode are preferably provided at flexible base The same surface at bottom, the present invention do not have the specific location of the glucose working electrode, lactic acid working electrode and reference electrode Particular/special requirement is configured according to position known to art technology.In a specific embodiment of the present invention, the reference electricity It is highly preferred to be arranged in glucose working electrode and lactic acid working electrode middle position, as shown in Figure 1.
The present invention using electrode surface glucose oxidase (or lactate oxidase) in sweat glucose (or cream Acid) it is aoxidized, hydrogen peroxide is generated, reduction reaction can directly occur on the electrode for hydrogen peroxide, by reduction reaction electricity The concentration of glucose in sweat (or lactic acid) can be obtained in the detection of stream.
The present invention provides the preparation methods of flexibility perspiration sensor described in above scheme, include the following steps:
The first gold electrode, the second gold electrode and reference electrode are prepared on flexible substrates surface;
Mono- Pu Lusi indigo plant is deposited in the first gold electrode and the second gold electrode surfaces using electrochemical cyclic voltammetry respectively Layer and bis- Pu Lusi indigo plant layer;
It is done after mono- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-glucose oxidase mixed gel solution It is dry, form glucose working electrode;
It is dry after bis- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-lactate oxidase mixed gel solution, Lactic acid working electrode is formed, flexible perspiration sensor is obtained.
The present invention prepares the first gold electrode, the second gold electrode and reference electrode on flexible substrates surface.The present invention is to first The preparation method of gold electrode, the second gold electrode and reference electrode does not have particular/special requirement, uses system well known to those skilled in the art Preparation Method.In a specific embodiment of the present invention, the preparation method of first gold electrode and the second gold electrode is preferably wrapped It includes:Gold electrode is patterned in flexible substrates using photoetching, ion beam evaporation methods and lift-off technology, then using photoetching and Oxygen plasma etch technology exposes electrode activity face;The present invention to the photoetching, ion beam evaporation, lift-off technology and The concrete operation method of oxygen plasma etch technology does not have particular/special requirement, uses method well known to those skilled in the art, energy Access the present invention claims the first gold electrode and the second gold electrode.
In a specific embodiment of the present invention, the preparation method of the reference electrode preferably includes following steps:
Silver electrode is prepared on flexible substrates surface;
Chlorination is carried out in silver electrode surface using dry cell method, obtains Ag/AgCl reference electrode.
In the present invention, described that the first gold medal electricity is prepared in the method and above scheme of flexible substrates surface preparation silver electrode Pole is consistent with the method for the second gold electrode, and details are not described herein.
The present invention does not have particular/special requirement to the dry cell method, uses dry cell method well known to those skilled in the art, energy It is enough to obtain one layer of silver chlorate in silver electrode surface.In a specific embodiment of the present invention, it is preferable to use a section 1.5V's is dry Battery, platinum electrode connect dry battery cathode, and silver electrode connects dry cell anode, silver electrode is immersed in saturated potassium chloride solution It is electroplated, when the complete blackening of silver electrode surface obtains Ag/AgCl reference electrode of the invention.
After obtaining the first gold electrode and the second gold electrode, the present invention using electrochemical cyclic voltammetry in the first gold electrode and Second gold electrode surfaces deposit mono- Pu Lusi indigo plant layer and bis- Pu Lusi indigo plant layer respectively.In the present invention, the electrochemistry is followed The deposition voltage of ring voltammetry is independently preferably -0.5~0.5V, more preferably -0.3~0.3V, and scanning circle number is independently excellent It is selected as 1~10 circle, more preferably 3~8 circles, most preferably 5 circles;In the present invention, the deposition is preferably with deposition liquid FeCl3, KCl and K3Fe(CN)6Mixed solution;FeCl in the deposition liquid3Concentration be preferably 2.5mM, the concentration of KCl is excellent It is selected as 100mM, K3Fe(CN)6Concentration be preferably 2.5mM;In the present invention, the scanning circle number of the electrochemical cyclic voltammetry More, the Pu Lusi indigo plant layer of gold electrode surfaces deposition is thicker, within the scope of the invention by the control of scanning circle number, it is ensured that general This blue layer of Shandong has higher catalytic efficiency to hydrogen peroxide.
The present invention is molten in mono- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-glucose oxidase mixed gel It is dry after liquid, form glucose working electrode.In the present invention, the chitosan-carbon nanotube-glucose oxidase mixing is solidifying The mass concentration of chitosan is preferably 0.5%~5% in sol solution, and more preferably 1%~4%, the concentration of carbon nanotube is preferred For 1.0~2.0mg/L, more preferably 1.5mg/L, the concentration of glucose oxidase is preferably 5.0~10.0mg/L, more preferably 6~8mg/L;The solvent of the mixed gel solution is water.In the present invention, the chitosan can embed enzyme, lead to Crossing gel embedding can be fixed on the electrode by enzyme;The carbon nanotube can accelerate the transmitting of electronics during enzymatic reaction, Improve the sensitivity of sensor.
In the present invention, the chitosan-carbon nanotube-glucose oxidase mixed gel solution preparation method is preferred For:The chitosan of acetate dissolution and carbon nanotube aqueous dispersions will be used to mix, and obtain mixed liquor, then by glucose oxidase solution It instills in mixed liquor, obtains chitosan-carbon nanotube-glucose oxidase mixed gel solution.The present invention uses acetic acid by shell Glycan dissolution, the concentration and dosage of Dichlorodiphenyl Acetate of the present invention do not have particular/special requirement, can be completely dissolved chitosan;The present invention There is no particular/special requirement to the preparation method of carbon nanotube aqueous dispersions, using method well known to those skilled in the art, can obtain To evenly dispersed carbon nanotube aqueous dispersions;Glucose oxidase is configured to solution and instilled in mixed liquor by the present invention, It can guarantee that glucose oxidase is evenly distributed in mixed gel solution.
In the present invention, the chitosan-carbon nanotube-glucose oxidase mixed gel solution is blue in mono- Pu Lusi The drop coating amount of layer surface is preferably 5~30 μ L/mm2, more preferably 20 μ L/mm2
After the completion of drop coating, drop coating is had chitosan-carbon nanotube-glucose oxidase mixed gel solution by the present invention One gold electrode is dried;The present invention preferably carries out standing and drying at room temperature;The present invention is to the dry time without spy It is different to require, the moisture in gel solution can be evaporated complete.In drying process, the moisture in mixed gel solution is waved Hair, chitosan form gel dry glue, so that enzyme and carbon nanotube be made preferably to be fixed on electrode surface, and are able to maintain the work of enzyme Property.
The present invention is in bis- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-lactate oxidase mixed gel solution After dry, formed lactic acid working electrode, obtain flexible perspiration sensor.In the present invention, the chitosan-carbon nanotube-cream The mass concentration of chitosan is preferably 0.5%~5% in acid oxidase mixed gel solution, and more preferably 1%~4%, carbon is received The concentration of mitron is preferably 1.0~2.0mg/L, more preferably 1.5mg/L, and the concentration of lactate oxidase is preferably 20~40mg/ L, more preferably 25~35mg/L.The solvent of the mixed gel solution is water.
In the present invention, the chitosan-carbon nanotube-lactate oxidase mixed gel solution preparation method and above-mentioned Chitosan-carbon nanotube-chitosan oxidizing ferment mixed gel solution preparation method is consistent in scheme, and details are not described herein.
In the present invention, the chitosan-carbon nanotube-lactate oxidase mixed gel solution is in bis- Pu Lusi indigo plant layer The drop coating and drying process on surface preferably with chitosan-carbon nanotube in above scheme-chitosan oxidizing ferment mixed gel solution Identical with drying process in the drop coating of mono- Pu Lusi indigo plant layer surface, details are not described herein.
The present invention provides the soft of the preparation of preparation method described in flexibility perspiration sensor described in above scheme or above scheme Property perspiration sensor sweat detection in application.It is enterprising that perspiration sensor provided by the invention can be directly attached to human skin Row test, is tested after also collecting sweat.
Flexible perspiration sensor of the invention in application process, by glucose working electrode, lactic acid working electrode and Reference electrode is connected by conducting wire with external detection device, as shown in Figure 1;The present invention is not special to the external detection device It is required that using external detection device well known to those skilled in the art and, it is specific such as picoammeter or electrochemical workstation. In the detection process, perspiration sensor contacts (or dripping the sweat being collected into working sensor electrode surface), root with sweat The concentration of the glucose and lactic acid in sweat is obtained according to the current value that external detection device detects.
When carrying out the quantitative determination of glucose and lactic acid using flexible perspiration sensor provided by the invention, preferably match respectively The standard solution containing glucose and lactic acid is made, the standard for measuring current value and concentration of glucose and current value and lactic acid concn is bent Line determines the concentration of glucose or lactic acid in sweat to be measured according to standard curve and test gained current value.
Flexible perspiration sensor provided by the invention and its preparation method and application is carried out below with reference to embodiment detailed Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) the first gold electrode and the second gold electrode are prepared:PEI substrate uses acetone, isopropanol and oxygen plasma respectively first Body is cleaned, and then using one layer 30nmCr/50nmAu layers on photoresist and electron beam evaporation technique photoetching, then uses acetone Cr layers of solution washes away, the Parylene insulating layer of redeposited upper one layer of 500nm thickness finally exposes golden electricity with oxygen plasma Pole.
(2) one layer of Pu Lusi is deposited in the first gold electrode and the second gold electrode surfaces using electrochemical cyclic voltammetry respectively Indigo plant, deposition voltage:- 0.5~0.5V, sweep speed:20mV/s, scanning circle number:1 circulation;Deposition liquid is FeCl3, KCl and K3Fe(CN)6Mixed solution, wherein FeCl3Concentration be 2.5mM, the concentration of KCl is 100mM, K3Fe(CN)6Concentration be 2.5mM;
(3) 20 microlitres of Tu are dripped on Pu Lusi indigo plant layer with micropipette rifle contain chitosan (0.5wt%), carbon nanotube The mixed gel solution of (1.0mg/mL) and glucose oxidase (5.0mg/mL) form glucose finally by being dried overnight Working electrode.
(4) 20 microlitres of Tu are dripped on the Pu Lusi indigo plant layer of another gold electrode with micropipette rifle contain chitosan (0.5%%), carbon nanotube 1.0mg/mL) and lactate oxidase (20mg/mL) mixed gel solution, finally by dried Night forms lactic acid working electrode.
(5) silver electrode is prepared on flexible substrates surface according to the method for step (1), takes the dry cell of 1.5V, platinum electrode connects It connects in dry battery cathode, silver electrode connects dry cell anode, and silver electrode is immersed in saturation KCl solution and carries out chlorination, works as silver Prove that plating is completed when the complete blackening of electrode surface, reference electrode Ag/AgCl is successfully prepared.
Embodiment 2
(1) the first gold electrode and the second gold electrode are prepared:PEI substrate uses acetone, isopropanol and oxygen plasma respectively first Body is cleaned, and then using one layer 30nmCr/50nmAu layers on photoresist and electron beam evaporation technique photoetching, then uses acetone Cr layers of solution washes away, the Parylene insulating layer of redeposited upper one layer of 500nm thickness finally exposes golden electricity with oxygen plasma Pole.
(2) one layer of Pu Lusi is deposited in the first gold electrode and the second gold electrode surfaces using electrochemical cyclic voltammetry respectively Indigo plant, deposition voltage:- 0.4~0.4V, sweep speed:20mV/s, scanning circle number:3 circulations, deposition liquid are FeCl3, KCl and K3Fe(CN)6Mixed solution, wherein FeCl3Concentration be 2.5mM, the concentration of KCl is 100mM, K3Fe(CN)6Concentration be 2.5mM;
(3) 20 microlitres of Tu are dripped on Pu Lusi indigo plant layer with micropipette rifle contain chitosan (5wt%), carbon nanotube The mixed gel solution of (2.0mg/mL) and glucose oxidase (10.0mg/mL) form glucose finally by being dried overnight Working electrode.
(4) with micropipette rifle drip on the Pu Lusi indigo plant layer of another gold electrode 20 microlitres of Tu contain chitosan (5%), Carbon nanotube 2.0mg/mL) and the mixed gel solution of lactate oxidase (40mg/mL) form cream finally by being dried overnight Sour working electrode.
(5) silver electrode is prepared on flexible substrates surface according to the method for step (1), takes the dry cell of 1.5V, platinum electrode connects It connects in dry battery cathode, silver electrode connects dry cell anode, and silver electrode is immersed in saturation KCl solution and carries out chlorination, works as silver Prove that plating is completed when the complete blackening of electrode surface, reference electrode Ag/AgCl is successfully prepared.
Embodiment 3
(1) the first gold electrode and the second gold electrode are prepared:PEI substrate uses acetone, isopropanol and oxygen plasma respectively first Body is cleaned, and then using one layer 30nmCr/50nmAu layers on photoresist and electron beam evaporation technique photoetching, then uses acetone Cr layers of solution washes away, the Parylene insulating layer of redeposited upper one layer of 500nm thickness finally exposes golden electricity with oxygen plasma Pole.
(2) one layer of Pu Lusi is deposited in the first gold electrode and the second gold electrode surfaces using electrochemical cyclic voltammetry respectively Indigo plant, deposition voltage:- 0.3~0.3V, sweep speed:20mV/s, scanning circle number:5 circulations, deposition liquid are FeCl3, KCl and K3Fe(CN)6Mixed solution, wherein FeCl3Concentration be 2.5mM, the concentration of KCl is 100mM, K3Fe(CN)6Concentration be 2.5mM;
(3) 20 microlitres of Tu are dripped on Pu Lusi indigo plant layer with micropipette rifle contain chitosan (3wt%), carbon nanotube The mixed gel solution of (1.5mg/mL) and glucose oxidase (8.0mg/mL) form glucose finally by being dried overnight Working electrode.
(4) 20 microlitres of Tu are dripped on the Pu Lusi indigo plant layer of another gold electrode with micropipette rifle contain chitosan (2.5%), carbon nanotube 1.5mg/mL) and lactate oxidase (30mg/mL) mixed gel solution, finally by dried Night forms lactic acid working electrode.
(5) silver electrode is prepared on flexible substrates surface according to the method for step (1), takes the dry cell of 1.5V, platinum electrode connects It connects in dry battery cathode, silver electrode connects dry cell anode, and silver electrode is immersed in saturation KCl solution and carries out chlorination, works as silver Prove that plating is completed when the complete blackening of electrode surface, reference electrode Ag/AgCl is successfully prepared.
Embodiment 4
The flexible perspiration sensor that embodiment 1 obtains is characterized:
(1) glucose solution of various concentration is detected using cyclic voltammetry:Flexible sweat prepared by embodiment 1 Liquid sensor is connect by conducting wire with electrochemical workstation, and flexible perspiration sensor is immersed in the glucose solution of various concentration In tested;The glucose solution of certain concentration is added in PBS solution, obtaining concentration is respectively 10nM, 100nM, 1 μ M, 10 μM, 100 μM of glucose solution detect the PBS solution without glucose, as blank control;Test voltage For -0.9~0.8V.
Gained testing result is as shown in Figure 2 to 3, and wherein Fig. 2 is the cyclic voltammogram of different glucose solution, figure 3 be the standard working curve figure of concentration of glucose and current value.According to fig. 2 as can be seen that the raising with concentration of glucose is examined The reduction peak measured is constantly reducing, and illustrates that the sensor is good to the response of glucose;According to Fig. 3 as can be seen that glucose When concentration is greater than 10nM, current value and concentration of glucose are in good linear relationship, the R of fitting a straight line2Value is 0.994, this hair Bright sensor is limited to 10nM to the lowest detection of glucose.
(2) lactic acid solution of various concentration is detected using cyclic voltammetry:Detection method is consistent in (1), will Glucose in solution replaces with lactic acid, and obtaining concentration is respectively 10nM, 100nM, 1 μM, 10 μM, 100 μM of lactic acid solution.
Gained testing result is as shown in Fig. 4~Fig. 5, and wherein Fig. 4 is the cyclic voltammogram of various concentration lactic acid solution, Fig. 5 For the standard working curve figure of lactic acid concn and current value;According to Fig. 4 as can be seen that detecting with the raising of lactic acid concn Reduction peak is constantly reducing, and illustrates that the sensor is good to the response of lactic acid;According to Fig. 5 as can be seen that lactic acid concn is greater than 1 μM When, current value and lactic acid concn are in good linear relationship, the R of fitting a straight line2Value is 0.97, and sensor of the invention is to lactic acid Lowest detection be limited to 1 μM.
(3) to the real-time measurement of human sweat's glucose and lactic acid:200 microlitres of human sweats are collected, is dripped and is being implemented Real-time measurement is carried out on flexible sensor prepared by example 1, is then added into human sweat's sample and adds 20 microlitres of 1mM's respectively Glucose and lactic acid solution, the response condition of detection sensor;
For acquired results as shown in Fig. 6~Fig. 7, Fig. 6 is that flexible perspiration sensor detects glucose in human sweat Real-time working curve, Fig. 7 is the real-time working curve that flexible perspiration sensor detects lactic acid in human sweat.According to Fig. 6~Fig. 7 can be seen that flexible perspiration sensor provided by the invention and can carry out in real time to human sweat's glucose and lactic acid It detects, when glucose and lactic acid concn change in sweat, sensor can respond immediately, show the change of electric current Change, illustrates that sensor of the invention has very high sensitivity.
It is tested according to the flexible perspiration sensor that the method in (1), (2), (3) prepares embodiment 2~3, gained Test result is similar with the above results.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of flexibility perspiration sensor, electric including flexible substrates and the glucose work for being set to the flexible substrates surface Pole, lactic acid working electrode and reference electrode;
The glucose working electrode successively includes setting in first gold electrode of flexible substrates surface, is arranged described first The mono- Pu Lusi indigo plant layer of gold electrode surfaces and chitosan-carbon nanotube-Portugal that the mono- Pu Lusi indigo plant layer surface is set Grape carbohydrate oxidase plural gel layer;
The lactic acid working electrode successively includes setting in second gold electrode of flexible substrates surface, is arranged in second gold medal The bis- Pu Lusi indigo plant layer of electrode surface and chitosan-carbon nanotube-lactic acid that the bis- Pu Lusi indigo plant layer surface is set Oxidizing ferment plural gel layer.
2. flexibility perspiration sensor according to claim 1, which is characterized in that first gold electrode and the second gold electrode Diameter independently be 1~3mm;The thickness of first gold electrode and the second gold electrode independently is 40~60nm.
3. flexibility perspiration sensor according to claim 1, which is characterized in that the chitosan-carbon nanotube-glucose The mass ratio of chitosan, carbon nanotube and glucose oxidase is (5~50) in oxidizing ferment plural gel layer:(1~2):(5~ 10)。
4. flexibility perspiration sensor according to claim 1, which is characterized in that the chitosan-carbon nanotube-lactic acid oxygen The mass ratio for changing chitosan, carbon nanotube and lactate oxidase in enzyme plural gel layer is (5~50):(1~2):(20~40).
5. flexibility perspiration sensor according to claim 1, which is characterized in that the reference electrode is Ag/AgCl reference Electrode;The diameter of the reference electrode is 0.5~2mm, with a thickness of 40~60nm.
6. the preparation method of flexibility perspiration sensor, includes the following steps described in Claims 1 to 5 any one:
The first gold electrode, the second gold electrode and reference electrode are prepared on flexible substrates surface;
Using electrochemical cyclic voltammetry the first gold electrode and the second gold electrode surfaces deposit respectively mono- Pu Lusi indigo plant layer and Bis- Pu Lusi indigo plant layer;
It is dry after mono- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-glucose oxidase mixed gel solution, shape At glucose working electrode;
It is dry after bis- Pu Lusi indigo plant layer surface drop coating chitosan-carbon nanotube-lactate oxidase mixed gel solution, it is formed Lactic acid working electrode obtains flexible perspiration sensor.
7. preparation method according to claim 6, which is characterized in that the deposition voltage of the electrochemical cyclic voltammetry is only It stands as -0.5~0.5V, scanning circle number stands alone as 1~10 circle.
8. preparation method according to claim 6, which is characterized in that the chitosan-carbon nanotube-glucose oxidase The mass concentration of chitosan is 0.5%~5% in mixed gel solution, and the concentration of carbon nanotube is 1.0~2.0mg/L, grape The concentration of carbohydrate oxidase is 5.0~10.0mg/L;The chitosan-carbon nanotube-glucose oxidase mixed gel solution exists The drop coating amount of mono- Pu Lusi indigo plant layer surface is 5~30 μ L/mm2
9. preparation method according to claim 6, which is characterized in that the chitosan-carbon nanotube-lactate oxidase is mixed The mass concentration for closing chitosan in gel solution is 0.5%~5%, and the concentration of carbon nanotube is 1.0~2.0mg/L, lactic acid oxygen The concentration for changing enzyme is 20~40mg/L;The chitosan-carbon nanotube-lactate oxidase mixed gel solution is in bis- Pu Lusi The drop coating amount of blue layer surface is 5~30 μ L/mm2
10. preparation side described in flexibility perspiration sensor or claim 6~9 any one described in Claims 1 to 5 any one Application of the flexible perspiration sensor of method preparation in sweat detection.
CN201810663005.0A 2018-06-25 2018-06-25 A kind of flexibility perspiration sensor and its preparation method and application Pending CN108828043A (en)

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Application publication date: 20181116