CN111803087B - Organism nondestructive blood sugar detection device and preparation method thereof - Google Patents

Organism nondestructive blood sugar detection device and preparation method thereof Download PDF

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CN111803087B
CN111803087B CN202010534292.2A CN202010534292A CN111803087B CN 111803087 B CN111803087 B CN 111803087B CN 202010534292 A CN202010534292 A CN 202010534292A CN 111803087 B CN111803087 B CN 111803087B
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graphene
fiber fabric
composite fiber
carbon nanotube
counter electrode
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CN111803087A (en
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陈涛
姚瑶
吕甜
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Tongji University
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Tongji University
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/1486—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using enzyme electrodes, e.g. with immobilised oxidase
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/14532—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring glucose, e.g. by tissue impedance measurement
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/12—Manufacturing methods specially adapted for producing sensors for in-vivo measurements
    • A61B2562/125—Manufacturing methods specially adapted for producing sensors for in-vivo measurements characterised by the manufacture of electrodes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/16—Details of sensor housings or probes; Details of structural supports for sensors
    • A61B2562/164—Details of sensor housings or probes; Details of structural supports for sensors the sensor is mounted in or on a conformable substrate or carrier

Abstract

The invention relates to a nondestructive blood sugar detection device for organisms and a preparation method thereof, wherein the device comprises a working electrode and a counter electrode, the working electrode comprises a working electrode flexible substrate, a working electrode conductive substrate arranged on the working electrode flexible substrate and glucose oxidase loaded on the working electrode conductive substrate, and the counter electrode comprises a counter electrode flexible substrate, a counter electrode conductive substrate arranged on the counter electrode flexible substrate and a silver/silver chloride film plated on the counter electrode conductive substrate. The preparation method specifically comprises the following steps: the method comprises the steps of firstly obtaining graphene/carbon nanotube composite fiber fabrics, then taking two graphene/carbon nanotube composite fiber fabrics, respectively loading glucose oxidase to obtain a working electrode, plating a silver/silver chloride film to obtain a counter electrode, and finally placing the working electrode and the counter electrode side by side. Compared with the prior art, the invention establishes the relationship between the simulated interstitial fluid and the instant response current through a two-electrode system, can detect the blood sugar concentration change of organisms and has high sensitivity.

Description

Organism nondestructive blood sugar detection device and preparation method thereof
Technical Field
The invention belongs to the technical field of blood sugar detection, and particularly relates to a nondestructive blood sugar detection device for an organism and a preparation method thereof.
Background
According to relevant reports, the number of diabetic patients worldwide will reach 4 billion in 2030, which means that more and more people will be affected by the chronic disease, including its complications. For such patients, the current accurate blood glucose detection mode is mainly blood sampling detection through veins, but the mode can not continuously detect the change of blood glucose, but also seriously affects the life quality of patients and the compliance of long-term monitoring, so how to construct continuous, accurate and nondestructive blood glucose detection is a problem which is urgently needed to be solved at present.
To date, non-invasive blood glucose testing devices for humans have been reported to be based primarily on the detection of glucose concentrations in other bodily fluids of the human body, including tears, saliva, perspiration, and interstitial fluid. The method mainly comprises the steps of firstly extracting subcutaneous interstitial fluid to the surface of skin through pores by using a reverse iontophoresis method, then detecting the concentration of glucose in the extracted interstitial fluid, and finally achieving the purpose of human body nondestructive blood glucose detection.
Graphene materials are often used as conductive substrates of glucose sensors due to their excellent flexibility, conductivity and biocompatibility, however, complex modifications are usually required on the surfaces thereof to fix glucose oxidase on the electrode surfaces. In order to prevent the glucose oxidase from falling off, a perfluorosulfonic acid type polymer (Nafion) solution is usually coated, so that the conductivity of the electrode is reduced, and the sensitivity of the device is not ideal. Therefore, the development of a human body nondestructive blood sugar detection device with high accuracy, high sensitivity, simple structure and convenient operation has important significance.
Disclosure of Invention
The invention aims to provide a biological nondestructive blood sugar detection device and a preparation method thereof, which can directly establish the relationship between simulated interstitial fluid and instant response current through a two-electrode system, can detect the blood sugar concentration change of organisms and has high sensitivity.
The purpose of the invention is realized by the following technical scheme:
the utility model provides an organism nondestructive blood sugar detection device, detection device is including working electrode and the counter electrode that sets up side by side, working electrode includes the flexible basement of working electrode, locates the electrically conductive basement of working electrode on the flexible basement of working electrode and the glucose oxidase of load on the electrically conductive basement of working electrode, the counter electrode includes the flexible basement of counter electrode, locates the electrically conductive basement of counter electrode on the flexible basement of counter electrode and plates the silver/silver chloride membrane on the electrically conductive basement of counter electrode, forms two electrode systems. The graphene/carbon nanotube/silver chloride composite fiber fabric is formed by the working electrode conductive substrate and the glucose oxidase.
Preferably, the conductive substrate of the working electrode is made of graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber maintains a hollow structure, the thickness of the composite fiber fabric is 100-120 μm, preferably 120 μm, the number of graphene layers is 9-15, preferably 14, the thickness is 3-5 nm, preferably 5nm, and the thickness of the carbon nanotube is 10-30 μm, preferably 20 μm.
Preferably, the flexible substrate of the working electrode is made of polydimethylsiloxane, and the thickness of the flexible substrate of the working electrode is 0.8-1.5 mm, preferably 1.0 mm.
Preferably, the conductive substrate of the counter electrode is made of graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber maintains a hollow structure, the thickness of the composite fiber fabric is 100-120 μm, preferably 120 μm, the number of graphene layers is 9-15, preferably 14, the thickness is 3-5 nm, preferably 5nm, and the thickness of the carbon nanotube is 10-30 μm, preferably 20 μm.
Preferably, the counter electrode flexible substrate is made of polydimethylsiloxane, and the thickness of the counter electrode flexible substrate is 0.8-1.5 mm, preferably 1.0 mm. The polydimethylsiloxane flexible substrate is introduced into the organism nondestructive blood sugar detection device, so that the device has good flexibility, can be better attached to the skin of a human body without being damaged, and can be used for preparing a wearable human body nondestructive blood sugar detection device.
A preparation method of the organism nondestructive blood sugar detection device specifically comprises the following steps:
(a) sequentially growing a plurality of continuous graphene films, plating catalyst layers and buffer layers and growing oriented carbon nanotube arrays on the surface of the pretreated nickel fiber fabric, then etching to remove the nickel fiber fabric, the catalyst layers and the buffer layers, and cleaning and drying to obtain the graphene/carbon nanotube composite fiber fabric;
(b) directly transferring the graphene/carbon nanotube composite fiber fabric obtained in the step (a) to the surface of a flexible substrate of a working electrode, fixing the graphene/carbon nanotube composite fiber fabric by adopting silver colloid, loading glucose oxidase on the graphene/carbon nanotube composite fiber fabric, and drying to obtain the working electrode;
(c) directly transferring the graphene/carbon nanotube composite fiber fabric obtained in the step (a) to the surface of a flexible substrate of a counter electrode, fixing the graphene/carbon nanotube composite fiber fabric by using silver glue, and plating a silver/silver chloride film on the graphene/carbon nanotube composite fiber fabric by using an electrodeposition method twice to obtain the counter electrode;
(d) and (c) placing the working electrode obtained in the step (b) and the counter electrode obtained in the step (c) side by side to obtain the organism nondestructive blood sugar detection device.
Preferably, in the step (a), the nickel fiber fabric has a mesh number of 100 meshes, a diameter of 100 μm and an area of 0.75-1.5 cm2。
Preferably, in the step (a), the pretreatment process of the nickel fiber fabric is specifically as follows: ultrasonically cleaning in acetone for 5-10 min, washing with deionized water and ethanol for 3-5 times, and finally drying at 60-80 ℃ for 10-20 min.
Preferably, in the step (a), when a chemical vapor deposition method is adopted to grow the continuous multilayer graphene film, a mixed gas of argon and hydrogen is used as a carrier gas, methane is used as a carbon source, the reaction temperature is 950-1050 ℃, and the growth time is 2-15 min.
Preferably, when the continuous multilayer graphene film is grown by adopting a chemical vapor deposition method, the volume ratio of argon, hydrogen and methane is 20 (2-8) to (2-5), and preferably 20:4: 3.
Preferably, in the step (a), the catalyst layer and the buffer layer are plated by evaporation at a pressure of (8-30) × 10-4Pa, preferably 8X 10-4Pa, the speed of evaporating the catalyst layer is 0.3-0.7 nm/s, preferably 0.5nm/s, and the speed of evaporating the buffer layer is 2-3 nm/s, preferably 2.5 nm/s.
Preferably, in the step (a), the composition of the catalyst layer is Fe, and the composition of the buffer layer is Al2O3。
Preferably, in the step (a), the thickness ratio of the catalyst layer to the buffer layer is (0.05-0.15): 1, preferably 0.1: 1.
Preferably, in the step (a), when the oriented carbon nanotube array is grown by a chemical vapor deposition method, a mixed gas of argon and hydrogen is used as a carrier gas, ethylene is used as a carbon source, a reaction temperature is 740 to 760 ℃, and a growth time is 2 to 10 min.
Preferably, when the oriented carbon nanotube array is grown by using a chemical vapor deposition method, the volume ratio of argon, hydrogen and ethylene is 40 (4-12) to (1-3), and preferably 40:8: 2.
The chemical vapor deposition method is a common method for growing graphene or carbon nanotubes, and the graphene or carbon nanotubes grown by the method have fewer impurities and structural defects, so the graphene or carbon nanotubes have good conductivity and biocompatibility and can be used as electrode materials of biosensors.
Preferably, in the step (a), a mixed solution of ferric chloride and nitric acid (deionized water is used as a solvent) is used as an etching solution to etch the nickel fiber fabric, the catalyst layer and the buffer layer for 1-3 hours, preferably 2 hours.
Preferably, in the step (a), the molar concentration ratio of the ferric chloride to the nitric acid is (1-3): 3, and preferably 1: 3.
Preferably, in the step (a), the drying temperature is 70-85 ℃, and the drying time is 30-60 min.
Preferably, in the step (b), glucose oxidase is loaded by using a dropping method and a phosphate buffer solution of glucose oxidase, and the dropping volume of the phosphate buffer solution of glucose oxidase is 50-100 [ mu ] L/(0.1-0.2 cm)2Graphene/carbon nanoRice-tube composite fiber fabric), preferably 100. mu.L/0.15 cm2Graphene/carbon nanotube composite fiber fabric.
Preferably, in the step (b), the mass concentration of the glucose oxidase in the phosphate buffer solution of the glucose oxidase is 40-60 mg mL-1。
Preferably, in step (b), the drying is carried out at normal temperature and low pressure, the low pressure being-50 to-70 kPa. The low pressure drying avoids the activity reduction of the glucose oxidase.
Preferably, in step (b), the working electrode flexible substrate is prepared by the following steps: uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of (5-10) to 1, preferably 10:1, and heating and curing at 70-80 ℃ for 40-60 min to obtain the composite material. The polydimethylsiloxane and the curing agent are both purchased from Dow Corning company and used in combination, and the type of the curing agent is 184.
Preferably, in the step (c), the counter electrode flexible substrate is prepared by the following steps: uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of (5-10) to 1, preferably 10:1, and heating and curing at 70-80 ℃ for 40-60 min to obtain the composite material. The polydimethylsiloxane and the curing agent are both purchased from Dow Corning company and used in combination, and the type of the curing agent is 184.
Preferably, in the step (c), the process of plating the silver/silver chloride film is specifically as follows: firstly, taking a silver electrode as an anode, taking a graphene/carbon nanotube composite fiber fabric as a cathode, taking a mixed solution of potassium nitrate and silver nitrate (a solvent is deionized water) as an electrolyte, plating a silver film on the graphene/carbon nanotube composite fiber fabric, then taking the silver-plated graphene/carbon nanotube composite fiber fabric as a working electrode, taking a platinum wire as a counter electrode, taking a saturated calomel electrode as a reference electrode, and taking a mixed solution of potassium chloride and hydrochloric acid (a solvent is deionized water) as an electrolyte, and chlorinating the silver film to obtain the graphene/carbon nanotube/silver chloride composite fiber fabric. Preferably, in the mixed solution of potassium nitrate and silver nitrate, the molar concentration ratio of potassium nitrate to silver nitrate is (500-1500): 3-7, and preferably the molar concentration ratio of potassium nitrate to silver nitrate is 200: 1. More preferably, the molar concentration of potassium nitrate is 0.5 to 1.5mol L-1The molar concentration of silver nitrate is 3-7 mmol L-1。
Preferably, the molar concentration ratio of the potassium chloride to the hydrochloric acid in the mixed solution of the potassium chloride and the hydrochloric acid is (50-150): (5-15), and preferably the molar concentration ratio of the potassium chloride to the hydrochloric acid is 10: 1. More preferably, the molar concentration of the potassium chloride is 0.05-0.15 mol L-1The molar concentration of the hydrochloric acid is 5-15 mmol L-1。
The method comprises the following steps of growing a graphene/carbon nanotube composite fiber fabric on a nickel fiber fabric by a secondary chemical vapor deposition method, etching the nickel fiber fabric, a catalyst layer and a buffer layer, transferring the graphene/carbon nanotube composite fiber fabric to a flexible substrate, loading glucose oxidase on the surface of the graphene/carbon nanotube composite fiber fabric by a dripping coating method and a normal-temperature low-pressure drying method, constructing a working electrode of a biological body-nondestructive blood glucose detection device, plating a silver/silver chloride film on the graphene/carbon nanotube composite fiber fabric to obtain a counter electrode, forming a two-electrode system, and calculating the responsiveness of the device to a glucose solution by the following formula when the two-electrode system is used for measuring the glucose concentration: s (. mu.A mM)-1cm-2)＝ΔI(μA)/[Δc(mM)×A(cm2)]Wherein, S is sensitivity, Delta I is response current variation, Delta c is glucose concentration variation, and A is electrode area. Likewise, the invention can calculate the lowest detection limit of the device by the following formula: l isoD3.3 σ/S, wherein LoDAt the lowest detection limit, S is the slope of the linear relationship between the on-demand response current and the glucose concentration, and σ is the standard deviation of the data sets.
According to the invention, the glucose oxidase is loaded on the surface of the graphene/carbon nanotube composite fiber fabric in a normal-temperature low-pressure drying mode, and under a low-pressure environment, the carbon nanotubes can enter a protein shell of the glucose oxidase to serve as a redox medium between the glucose oxidase and an electrode to transmit electrons, so that the glucose oxidase and the electrode have good charge transmission, and the device has high sensitivity (12.39 muA muM)-1cm-2) Moreover, glucoseThe oxidase is not easy to fall off, the problem that the glucose oxidase is difficult to directly transmit electrons to the surface of the electrode is solved, the loading process of the glucose oxidase is simplified, and other substances are not required to be coated to protect the glucose oxidase, so that the conductivity of the electrode cannot be reduced, and in addition, the carbon nano tube directly grows on the surface of the graphene to accelerate the transmission of charges, so that the device has good sensitivity. Therefore, the two-electrode system organism nondestructive testing blood sugar detection device provided by the invention has good stability, and the response current is still 80.8% of the initial response current after continuous testing for 15 days. Meanwhile, the two-electrode system organism nondestructive blood sugar detection device provided by the invention has good flexibility, the detection result is hardly influenced under different bending angles (0-90 degrees), 99.43% of response current retention rate can be kept, 90.94% of response current retention rate is still obtained after continuous bending for 50 times at 60 degrees, and good bending stability is obtained, because the graphene/carbon nanotube composite fiber fabric and the polydimethylsiloxane substrate have good flexibility, so that the device has excellent flexibility stability.
The invention combines the reverse iontophoresis method, can be used for measuring the blood sample detection of organisms including pigskin, nude mouse and human body, and particularly extracts the subcutaneous interstitial fluid of the human body to the skin surface, the glucose oxidase on the working electrode and the glucose in the glucose generate enzymatic reaction, the purpose of nondestructively detecting the blood sugar of the human body is realized by testing the electron transfer amount in the reaction process, the linear relation between the response current and the glucose concentration is established by in vitro experiments, and the device is attached to the skin surfaces of the nude mouse and volunteers for detection, and the experimental result shows that the two-electrode system organism nondestructive blood sugar detection device can realize accurate and nondestructive human blood sugar detection.
Compared with the prior art, the beneficial effects and originality of the invention are mainly embodied in the following aspects:
(1) the two-electrode system organism nondestructive blood sugar detection device designed by the invention greatly simplifies the structure of the device (the existing device structure is mostly a three-electrode system); and the relation between the simulated interstitial fluid and the instant response current is directly established through in vitro experiments, so that the result calculation process is simplified, and the blood sugar level can be quickly obtained. The invention realizes accurate and nondestructive human blood sugar detection and has great practical application value.
(2) According to the invention, the graphene/carbon nanotube composite fiber fabric is used as the conductive substrate of the organism nondestructive blood glucose detection device, and the carbon nanotube can be used as an oxidation-reduction medium between glucose oxidase and an electrode while the rapid electron transmission rate is achieved, so that the complex operation of glucose oxidase fixation is simplified, and the use of substances with poor conductivity to protect the glucose oxidase is avoided, so that the device has high sensitivity.
Drawings
Fig. 1a and 1b are scanning electron microscope photographs of graphene/carbon nanotube composite fiber fabrics at different magnifications;
FIG. 2 is a Raman spectrum of the graphene/carbon nanotube composite fiber fabric;
FIG. 3 is an infrared spectrum of a graphene/carbon nanotube composite fiber fabric, glucose oxidase, and a graphene/carbon nanotube/glucose oxidase composite fiber fabric;
fig. 4 is a scanning electron microscope photograph of the graphene/carbon nanotube/silver chloride composite fiber fabric;
FIG. 5a is a graph of the instantaneous current response of a two-electrode system biological non-destructive glucose testing device to different glucose concentrations;
FIG. 5b is a graph showing the relationship between the instantaneous current and the glucose concentration of the two-electrode system biological nondestructive blood glucose test device responding to different glucose concentrations;
FIG. 6 shows a two-electrode system for a 5mmol L non-destructive blood glucose test device for fifteen consecutive days-1The instant response current change curve of the glucose solution;
FIG. 7a shows a two-electrode system for nondestructive blood glucose test of a living body with 5mmol L-1The instant response current change curve of the glucose solution;
FIG. 7b is the result of the stability test of the two-electrode system organism nondestructive blood glucose test device after being continuously bent 50 times at a bending angle of 60 °;
FIG. 8 is a linear relationship between the response current and the glucose concentration in the simulated interstitial fluid, which is established in the in vitro experiment of the two-electrode system organism nondestructive blood glucose detection device;
FIG. 9a is a graph showing the response current with time after injecting a 10 wt% glucose solution into nude mice;
FIG. 9b is a graph comparing the change of blood glucose level with time after injecting a 10 wt% glucose solution into nude mice measured by a commercial blood glucose meter and by a bio-based non-destructive blood glucose test device;
FIG. 10a is a graph of response current versus time for a two-electrode system biological non-destructive blood glucose monitor device monitoring blood glucose levels in a volunteer for eight consecutive hours;
FIG. 10b is a graph of blood glucose concentration over time for a volunteer monitored for eight consecutive hours by a two-electrode system biological non-destructive blood glucose test device;
FIG. 11 is a schematic view showing the structure of a device for non-destructive examination of blood glucose in living body.
In the figure: 1-a working electrode; 101-graphene/carbon nanotube/glucose oxidase composite fiber fabric; 102-a working electrode flexible substrate; 2-a counter electrode; 201-graphene/carbon nanotube/silver chloride composite fiber fabric; 202-counter electrode flexible substrate.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
As shown in fig. 11, a nondestructive blood glucose detection device for living body, the detection device includes a working electrode 1 and a counter electrode 2 arranged side by side, the working electrode 1 includes a working electrode flexible substrate 102, a working electrode conductive substrate arranged on the working electrode flexible substrate 102, and glucose oxidase loaded on the working electrode conductive substrate, the working electrode conductive substrate and the glucose oxidase form a graphene/carbon nanotube/glucose oxidase composite fiber fabric 101, the counter electrode 2 includes a counter electrode flexible substrate 202, a counter electrode conductive substrate arranged on the counter electrode flexible substrate 202, and a silver/silver chloride film plated on the counter electrode conductive substrate, the counter electrode conductive substrate and the silver/silver chloride film form a graphene/carbon nanotube/silver chloride composite fiber fabric 201, the material of the working electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber fabric keeps a hollow structure, the thickness of the composite fiber fabric is 120 micrometers, the number of layers of graphene is 14, the thickness of the graphene is 5nm, the thickness of the carbon nanotube is 20 micrometers, the material of the working electrode flexible substrate 102 is polydimethylsiloxane, the thickness of the working electrode flexible substrate is 1.0mm, the material of the counter electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber fabric keeps a hollow structure, the thickness of the composite fiber fabric is 120 micrometers, the number of layers of graphene is 14, the thickness of the graphene is 5nm, the thickness of the carbon nanotube is 20 micrometers, the material of the counter electrode flexible substrate 202 is polydimethylsiloxane, and the thickness of the counter electrode flexible substrate is 1.0 mm.
The detection device is prepared by the following steps:
(1) the area is 0.75cm2Ultrasonically cleaning a nickel fiber fabric with the mesh number of 100 and the diameter of 100 mu m for 5min by using acetone, alternately cleaning the nickel fiber fabric for 3 times by using deionized water and ethanol, drying the nickel fiber fabric (the drying temperature is 80 ℃ and the drying time is 10min), then placing the nickel fiber fabric in a tubular furnace, and growing a continuous multilayer graphene film on the surface of the nickel fiber fabric by using a chemical vapor deposition method, wherein argon (400sccm) and hydrogen (80sccm) are used as carrier gases, methane (60sccm) is used as a carbon source, and the tubular furnace is used for 25 ℃ for min-1Heating to 1000 ℃ at the heating rate, and growing for 10min to obtain the nickel/graphene composite fiber fabric.
(2) Coating the surface of the nickel/graphene composite fiber fabric on the surface of the nickel/graphene composite fiber fabric by an electron beam evaporation coating system (purchased from Shenyang scientific instruments Co., Ltd., model number ZDF-5227, the same below)-4Evaporating 1nm Fe and 10nm Al sequentially at the speed of 0.5nm/s and 2.5nm/s under Pa2O3Respectively as a catalyst layer and a buffer layer for growing the carbon nano tube.
(3) Will be plated with a catalyst layer and a bufferPlacing the layered nickel/graphene composite fiber fabric in a tubular furnace, growing an oriented carbon nanotube array by a secondary chemical vapor deposition method, taking argon (200sccm) and hydrogen (40sccm) as carrier gases, taking ethylene (10sccm) as a carbon source, and using the tubular furnace at 25 ℃ for min-1Heating to 750 ℃ at the heating rate, and growing for 5min to obtain the nickel/graphene/carbon nanotube composite fiber fabric.
(4) Putting the nickel/graphene/carbon nanotube composite fiber fabric into ferric chloride (1mol L)-1) And nitric acid (3mol L)-1) Soaking the mixed solution (solvent is deionized water, the same is used below) for 2 hours until the nickel fiber fabric, the catalyst layer and the buffer layer are completely etched, cleaning with deionized water, and drying (drying temperature is 80 ℃ and drying time is 40min) to obtain the graphene/carbon nanotube composite fiber fabric.
(5) Mixing polydimethylsiloxane and curing agent (available from Dow Corning Corp., model 184, the same below) at a mass ratio of 10:1, heating and curing at 70 deg.C for 40min to obtain flexible substrate of working electrode, and taking out the flexible substrate with area of 0.15cm2The graphene/carbon nano tube composite fiber fabric is used as a working electrode conductive substrate and placed on the surface of a polydimethylsiloxane working electrode flexible substrate, silver colloid is used for fixing one end of the graphene/carbon nano tube composite fiber fabric, and 100 mu L of 60mg mL is dropwise added on the graphene/carbon nano tube composite fiber fabric-1And drying the phosphate buffer solution of glucose oxidase for 2 hours at normal temperature and low pressure (the pressure is-50 kPa) to obtain the graphene/carbon nano tube/glucose oxidase composite fiber fabric which is used as a working electrode of a biological nondestructive blood glucose detection device.
(6) Uniformly mixing polydimethylsiloxane and a curing agent according to a mass ratio of 10:1, heating and curing at 70 ℃ for 40min to obtain a counter electrode flexible substrate, and taking the counter electrode flexible substrate with an area of 0.15cm2The graphene/carbon nano tube composite fiber fabric is used as a counter electrode conductive substrate and placed on the surface of a polydimethylsiloxane counter electrode flexible substrate, silver glue is used for fixing one end of the graphene/carbon nano tube composite fiber fabric, a silver/silver chloride film is deposited on the surface of the graphene/carbon nano tube composite fiber fabric through a two-step electrodeposition method, and firstly, 1mol L of silver/silver chloride film is deposited on the surface of the graphene/carbon nano tube composite fiber fabric-1Potassium nitrate and5mmol L-1in the silver nitrate mixed electrolyte (the solvent is deionized water, the same below), a silver electrode is taken as an anode, a graphene/carbon nano tube composite fiber fabric is taken as a cathode, a silver film is deposited on the surface of the cathode, and then 0.1mol L of silver film is used-1And 10mmol L of potassium chloride-1The mixed solution of hydrochloric acid (solvent is deionized water, the same applies below) is used as electrolyte, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a silver film on the graphene/carbon nanotube composite fiber fabric is chlorinated, a silver/silver chloride film is formed on the surface of the graphene/carbon nanotube composite fiber fabric, and the graphene/carbon nanotube/silver chloride composite fiber fabric is obtained and is used as a counter electrode of a biological nondestructive blood sugar detection device.
(7) And (4) placing the electrodes obtained in the step (5) and the step (6) side by side to obtain the two-electrode system organism nondestructive blood sugar detection device.
In this embodiment, a graphene/carbon nanotube composite fiber fabric is grown on a nickel fiber fabric by a secondary chemical vapor deposition method, as can be seen from fig. 1a and 1b, after the secondary chemical vapor deposition method is performed, a carbon nanotube array is successfully grown on the surface of graphene, after the nickel fiber fabric serving as a substrate, and a residual catalyst and a buffer layer are etched, the carbon nanotubes shrink, and a wrinkled graphene film (fig. 1a) can be clearly seen at the bottom of the growth of the carbon nanotubes in the figure, as can be seen from a scanning electron microscope photograph shown in fig. 1b, the height of the finally obtained aligned carbon nanotubes grown on the graphene film is about 20 μm. FIG. 2 is a Raman spectrum of graphene/carbon nanotube composite fiber fabric, and D and G peaks appear at 1340cm-1And 1580cm-1Here, the intensity ratio of the two peaks indicates that the obtained graphene/carbon nanotube composite fiber fabric has less structural defects, and therefore, the material has excellent conductivity (76.13 + -1.68 omega cm)-2) Can be used as a conductive substrate of a biological sensing device.
FIG. 3 is an infrared spectrum diagram showing that glucose oxidase is successfully immobilized on the surface of graphene/carbon nanotube composite fiber fabric by drying at normal temperature and low pressure, wherein 1544cm appears in the diagram-1And 1650cm-1Two characteristic peaks at (a) respectively correspond to N-H covalent bond vibration of two amino groups of glucose oxidase and are 1100cm-1The characteristic peak appeared here indicates the tensile vibration of the C-O bond in the glucose oxidase structure.
Fig. 4 is a scanning electron microscope photograph of the graphene/carbon nanotube/silver chloride composite fiber fabric, and it can be seen that the silver/silver chloride film is uniformly covered on the surface of the graphene/carbon nanotube composite fiber fabric, which proves that the graphene/carbon nanotube/silver chloride composite fiber fabric successfully obtained in this embodiment can be used as a counter electrode of a two-electrode system organism nondestructive blood glucose detection device.
Key technical indicators of the sensing device mainly include sensitivity and minimum detection limit. The two-electrode system organism nondestructive blood sugar detection device shows good responsiveness to glucose, as shown in the instant current curve of fig. 5a, the response current gradually decreases with the increase of the glucose concentration, the instant current response curve shows a regular step-like curve, and the responsiveness of the device to the glucose solution can be calculated through the relationship between the instant response current and the glucose concentration of fig. 5b and the following formula, wherein the sensitivity of the device is 12.39 muA muM-1cm-2。
S(μA mM-1cm-2)＝ΔI(μA)/[Δc(mM)×A(cm2)]
Wherein S is sensitivity, Delta I is response current variation, Delta c is glucose concentration variation, and A is electrode area. Specifically, in this example, the values of Δ I and Δ c can be obtained from FIG. 5b, where A is 0.15cm2。
Similarly, the invention calculates the lowest detection limit of the device to be 0.37 μmol L by the following formula-1。
LoD＝3.3σ/S
Wherein L isoDAt the lowest detection limit, S is the slope of the linear relationship between the on-demand response current and glucose concentration (i.e., device sensitivity), and σ is the standard deviation of the data sets. In particular, in this embodiment, the values of S and σ can be obtained from FIG. 5b, which are12.39μA μM-1cm-2And 1.389. mu.A. mu.M-1cm-2。
FIG. 6 shows the stability test of the two-electrode system organism nondestructive blood sugar detection device at 5mmol L-1The glucose solution of the same device is tested for 15 days continuously, the change of the response current is observed, and compared with the test result of the first day, the response current after 15 days can still be kept at 80.8 percent which is higher than the value reported in the prior literature. The reason why the response current gradually decreases with the lapse of time is mainly two reasons, one is that the activity of the glucose oxidase itself decreases with the lapse of time, and the other is that the glucose oxidase slightly falls off during the daily test washing, which is also the reason for the decrease of the response current.
Fig. 7a and 7b show that the flexibility of the two-electrode system organism nondestructive blood glucose detection device is improved, the whole device has good flexibility due to the graphene/carbon nanotube composite fiber fabric and the polydimethylsiloxane flexible substrate, the device is bent at 0-90 degrees, and the performance of the device is not obviously affected, as shown in fig. 7a, after the same device is bent at 0 degree, 30 degrees, 60 degrees and 90 degrees, the device is bent at 5mmol L-1The on-demand response current in the glucose solution did not change significantly. After the device was continuously bent 50 times at 60 °, the instantaneous response current of the device remained at the initial 90.94%, as shown in fig. 7b, demonstrating good flexibility of the device.
For the purpose of non-destructive testing of blood sugar in human body, the present embodiment utilizes reverse iontophoresis to extract the interstitial fluid of subcutaneous tissue of human body to the surface of skin, so as to achieve the purpose of non-destructive testing of blood sugar in human body by testing the concentration of glucose in the interstitial fluid of human body. In this embodiment, an in vitro experiment is performed through a Franz diffusion cell and pigskin, a graphene/carbon nanotube/silver chloride composite fiber fabric is used as a working electrode, a graphene/carbon nanotube/glucose oxidase composite fiber fabric is used as a counter electrode, simulated interstitial fluid in the diffusion cell below the pigskin is extracted from the surface of the pigskin through a reverse iontophoresis method, then the graphene/carbon nanotube/glucose oxidase composite fiber fabric is used as the working electrode, and the graphene/carbon nanotube/glucose oxidase composite fiber fabric is used as the working electrodeThe nanotube/silver chloride composite fiber fabric is used as a counter electrode to detect the glucose concentration in the simulated interstitial fluid extracted to the surface of the pig skin, so that the relationship between the instant response current and the glucose concentration in the simulated interstitial fluid extracted from the subcutaneous tissue is established, as shown in fig. 8, the instant response current and the glucose concentration have a good linear relationship and conform to a functional relationship (R is 14.786x + 135.51) of y20.9894) where x represents the glucose concentration in the simulated interstitial fluid in mmol L-1And y represents the current density measured by a two-electrode system biological nondestructive blood glucose monitoring device, and the unit is mu A cm-2。
On the basis, in the embodiment, a 10 wt% glucose solution is injected into a healthy nude mouse, the two-electrode system organism nondestructive blood glucose detection device is attached to the abdomen of the nude mouse, interstitial fluid of the two-electrode system organism nondestructive blood glucose detection device is extracted by a reverse iontophoresis method, the response current of the two-electrode system organism nondestructive blood glucose detection device to the glucose in the interstitial fluid is detected, and the blood glucose of the nude mouse can be calculated through a linear relation shown in fig. 8. As shown in fig. 9a, after the glucose solution is injected, the response current detected by the organism nondestructive blood glucose detection device for detecting the blood glucose level of the nude mouse is obviously increased, the blood glucose level of the nude mouse calculated by the result is also sharply increased, the normal level is recovered after 2-3 h, the trend of the blood glucose change of the nude mouse detected by the commercial blood glucose meter is consistent, and the error is small (fig. 9b), which proves that in the process, the two-electrode system organism nondestructive blood glucose detection device always keeps sensitive and accurate monitoring on the blood glucose change of the nude mouse.
The device is used for detecting the blood sugar of a human body, and specifically comprises the following steps: the two electrodes forming the device are downwards attached to the wrist part of a human body, the two electrodes of the device are in direct contact with the skin of the human body, the electrodes are connected with an electrochemical workstation through copper wires, and the blood glucose change condition of a volunteer in one day is monitored.
The experimental results prove that the two-electrode system organism nondestructive blood sugar detection device designed and prepared by the invention successfully realizes accurate and nondestructive detection on the blood sugar of a human body, and has great advantages.
Example 2
As shown in fig. 11, a nondestructive blood glucose detection device for living body, the detection device includes a working electrode 1 and a counter electrode 2 arranged side by side, the working electrode 1 includes a working electrode flexible substrate 102, a working electrode conductive substrate arranged on the working electrode flexible substrate 102, and glucose oxidase loaded on the working electrode conductive substrate, the working electrode conductive substrate and the glucose oxidase form a graphene/carbon nanotube/glucose oxidase composite fiber fabric 101, the counter electrode 2 includes a counter electrode flexible substrate 202, a counter electrode conductive substrate arranged on the counter electrode flexible substrate 202, and a silver/silver chloride film plated on the counter electrode conductive substrate, the counter electrode conductive substrate and the silver/silver chloride film form a graphene/carbon nanotube/silver chloride composite fiber fabric 201, the material of the working electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 117 micrometers, the number of graphene layers is 12, the thickness of the graphene/carbon nanotube composite fiber fabric is 4nm, the thickness of the carbon nanotube composite fiber is 16 micrometers, the working electrode flexible substrate 102 is made of polydimethylsiloxane and is 0.8mm, the counter electrode conductive substrate is made of graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 117 micrometers, the number of graphene layers is 12, the thickness of the composite fiber fabric is 4nm, the thickness of the carbon nanotube is 16 micrometers, the counter electrode flexible substrate 202 is made of polydimethylsiloxane and is 0.8 mm.
The detection device is prepared by the following steps:
(1) the area is 1.5cm2The nickel fiber fabric with 100 meshes and 100 mu m diameter is ultrasonically cleaned for 10min by acetone and then is usedAlternately cleaning with deionized water and ethanol for 3 times and drying (drying temperature is 70 ℃ and drying time is 15min), then placing the nickel fiber fabric in a tubular furnace, growing a continuous multilayer graphene film on the surface of the nickel fiber fabric by a chemical vapor deposition method, taking argon (400sccm) and hydrogen (60sccm) as carrier gases, taking methane (60sccm) as a carbon source, and using the tubular furnace at 25 ℃ for min-1Heating to 1050 ℃ at the heating rate, growing for 15min, closing methane and hydrogen after the growth is finished, cooling to room temperature, and taking out a sample to obtain the nickel/graphene composite fiber fabric.
(2) By an electron beam evaporation coating system, the surface of the nickel/graphene composite fiber fabric is 1 multiplied by 10-3Evaporating 1nm Fe and 10nm Al sequentially at the speed of 0.4nm/s and 2nm/s under Pa2O3Respectively as a catalyst layer and a buffer layer for growing the carbon nano tube.
(3) Putting the nickel/graphene composite fiber fabric plated with the catalyst layer and the buffer layer into a tubular furnace, growing an oriented carbon nanotube array by a secondary chemical vapor deposition method, taking argon (200sccm) and hydrogen (25sccm) as carrier gases, ethylene (5sccm) as a carbon source, and using the tubular furnace at 25 ℃ for min-1Heating to 740 ℃ at the heating rate, wherein the growth time is 5min, closing the ethylene and the hydrogen after the growth is finished, cooling to room temperature, and taking out the sample to obtain the nickel/graphene/carbon nano tube composite fiber fabric.
(4) Putting the nickel/graphene/carbon nano tube composite fiber fabric into ferric chloride (2mol L)-1) And nitric acid (3mol L)-1) Soaking the mixed solution for 2 hours until the nickel fiber fabric, the catalyst layer and the buffer layer are completely etched, washing with deionized water and drying (the drying temperature is 85 ℃ and the drying time is 30min) to obtain the graphene/carbon nanotube composite fiber fabric.
(5) Uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of 8:1, heating and curing at 80 ℃ for 40min to obtain a flexible working electrode substrate, and taking the flexible working electrode substrate with the area of 0.12cm2The graphene/carbon nano tube composite fiber fabric is used as a conductive substrate of a working electrode and transferred to the surface of a flexible substrate of a polydimethylsiloxane working electrode, and the graphene/carbon nano tube composite fabric is fixed by silver colloidOne end of the fiber fabric is dripped with 50 mu L of 60mg mL on the graphene/carbon nanotube composite fiber fabric-1And drying the glucose oxidase solution for 1.5h at normal temperature and low pressure (the pressure is-60 kPa) to obtain the graphene/carbon nano tube/glucose oxidase composite fiber fabric which is used as a working electrode of a biological nondestructive blood glucose detection device.
(6) Uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of 8:1, heating and curing at 80 ℃ for 40min to obtain a counter electrode flexible substrate, and taking the counter electrode flexible substrate with the area of 0.12cm2The graphene/carbon nano tube composite fiber fabric is used as a counter electrode conductive substrate and transferred to the surface of a polydimethylsiloxane counter electrode flexible substrate, a silver/silver chloride film is deposited on the surface of the graphene/carbon nano tube composite fiber fabric through a two-step electrodeposition method, and 0.8mol L of silver/silver chloride film is firstly deposited-1Potassium nitrate and 6mmol L-1In the silver nitrate mixed electrolyte, a silver electrode is taken as an anode, graphene/carbon nano tube composite fiber fabric is taken as a cathode, a layer of silver film is deposited on the surface of the cathode, and 0.12mol L of silver film is added-1And 12mmol L of potassium chloride-1The mixed solution of hydrochloric acid is used as electrolyte, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a silver film on the graphene/carbon nano tube composite fiber fabric is chlorinated, a silver/silver chloride film is formed on the surface of the graphene/carbon nano tube composite fiber fabric, and the graphene/carbon nano tube/silver chloride composite fiber fabric is obtained and used as a counter electrode of a biological body nondestructive blood sugar detection device.
(7) And (4) placing the electrodes obtained in the step (5) and the step (6) side by side to obtain the two-electrode system organism nondestructive blood sugar detection device. The two-electrode system organism nondestructive blood sugar detection device can realize accurate and nondestructive detection of the blood sugar of the organism.
Example 3
As shown in fig. 11, a nondestructive blood glucose detection device for living body, the detection device includes a working electrode 1 and a counter electrode 2 arranged side by side, the working electrode 1 includes a working electrode flexible substrate 102, a working electrode conductive substrate arranged on the working electrode flexible substrate 102, and glucose oxidase loaded on the working electrode conductive substrate, the working electrode conductive substrate and the glucose oxidase form a graphene/carbon nanotube/glucose oxidase composite fiber fabric 101, the counter electrode 2 includes a counter electrode flexible substrate 202, a counter electrode conductive substrate arranged on the counter electrode flexible substrate 202, and a silver/silver chloride film plated on the counter electrode conductive substrate, the counter electrode conductive substrate and the silver/silver chloride film form a graphene/carbon nanotube/silver chloride composite fiber fabric 201, the material of the working electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 110 micrometers, the number of layers of graphene is 10, the thickness of the graphene is 3.5nm, the thickness of the carbon nanotube is 13 micrometers, the material of the working electrode flexible substrate 102 is polydimethylsiloxane, the thickness of the working electrode flexible substrate is 1.5mm, the material of the counter electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 110 micrometers, the number of layers of graphene is 10, the thickness of the graphene is 3.5nm, the thickness of the carbon nanotube is 13 micrometers, the material of the counter electrode flexible substrate 202 is polydimethylsiloxane, and the thickness of the counter electrode flexible substrate is 1.5 mm.
The detection device is prepared by the following steps:
(1) the area is 1.0cm2Ultrasonically cleaning a nickel fiber fabric with the mesh number of 100 and the diameter of 100 mu m for 5min by using acetone, alternately cleaning the nickel fiber fabric for 5 times by using deionized water and ethanol, drying the nickel fiber fabric (the drying temperature is 60 ℃ and the drying time is 20min), then placing the nickel fiber fabric in a tubular furnace, growing a continuous multilayer graphene film on the surface of the nickel fiber fabric by using a chemical vapor deposition method, taking argon (400sccm) and hydrogen (80sccm) as carrier gases, taking methane (50sccm) as a carbon source, and taking the tubular furnace for 25 ℃ for min-1Heating to 1000 ℃ at the heating rate, wherein the growth time is 10min, closing methane and hydrogen after the growth is finished, cooling to room temperature, and taking out a sample to obtain the nickel/graphene composite fiber fabric.
(2) By an electron beam evaporation coating system, the surface of the nickel/graphene composite fiber fabric is 9 multiplied by 10-4Evaporating 0.8nm Fe and 10nm Al at the speed of 0.3nm/s and 2.8nm/s under Pa in sequence2O3Respectively as growth carbon nanotubesCatalyst and buffer layers of nanotubes.
(3) Putting the nickel/graphene composite fiber fabric plated with the catalyst and the buffer layer into a tubular furnace, growing an oriented carbon nanotube array by a secondary chemical vapor deposition method, taking argon (200sccm) and hydrogen (45sccm) as carrier gases, taking ethylene (6sccm) as a carbon source, and using the tubular furnace at 25 ℃ for min-1Heating to 760 ℃ at the heating rate, wherein the growth time is 5min, closing ethylene and hydrogen after the growth is finished, cooling to room temperature, and taking out a sample to obtain the nickel/graphene/carbon nano tube composite fiber fabric.
(4) Putting the nickel/graphene/carbon nano tube composite fiber fabric into ferric chloride (3mol L)-1) And nitric acid (3mol L)-1) Soaking the mixed solution for 2 hours until the nickel fiber fabric, the catalyst layer and the buffer layer are completely etched, washing with deionized water and drying (the drying temperature is 70 ℃ and the drying time is 60min) to obtain the graphene/carbon nanotube composite fiber fabric.
(5) Uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of 8:1, heating and curing at 80 ℃ for 60min to obtain a flexible working electrode substrate, and taking the flexible working electrode substrate with the area of 0.17cm2The graphene/carbon nanotube composite fiber fabric is used as a working electrode conductive substrate and transferred to the surface of a polydimethylsiloxane working electrode flexible substrate, one end of the graphene/carbon nanotube composite fiber fabric is fixed by silver glue, and 100 mu L of 40mg mL of solution is dripped on the graphene/carbon nanotube composite fiber fabric-1And drying the glucose oxidase solution for 2.5 hours at normal temperature and low pressure (the pressure is-55 kPa) to obtain the graphene/carbon nano tube/glucose oxidase composite fiber fabric which is used as a working electrode of a biological nondestructive blood glucose detection device.
(6) Uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of 8:1, heating and curing at 80 ℃ for 60min to obtain a counter electrode flexible substrate, and taking the counter electrode flexible substrate with the area of 0.17cm2The graphene/carbon nano tube composite fiber fabric is used as a counter electrode conductive substrate and transferred to the surface of a polydimethylsiloxane counter electrode flexible substrate, one end of the graphene/carbon nano tube composite fiber fabric is fixed by silver glue, and the graphene/carbon nano tube composite fiber is subjected to two-step electrodepositionDepositing silver/silver chloride film on the surface of the fabric, firstly, 1.2mol L-1Potassium nitrate and 4mmol L-1In the silver nitrate mixed electrolyte, a silver electrode is taken as an anode, graphene/carbon nano tube composite fiber fabric is taken as a cathode, a layer of silver film is deposited on the surface of the cathode, and 0.1mol L of silver film is added-1And 12mmol L of potassium chloride-1The mixed solution of hydrochloric acid is used as electrolyte, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a silver film on the graphene/carbon nano tube composite fiber fabric is chlorinated, a silver/silver chloride film is formed on the surface of the graphene/carbon nano tube composite fiber fabric, and the graphene/carbon nano tube/silver chloride composite fiber fabric is obtained and is used as the counter electrode of a biological body nondestructive blood sugar detection device.
(7) And (4) placing the electrodes obtained in the step (5) and the step (6) side by side to obtain the two-electrode system organism nondestructive blood sugar detection device. The two-electrode system organism nondestructive blood sugar detection device can realize accurate and nondestructive detection of the blood sugar of the organism.
Example 4
As shown in fig. 11, a nondestructive blood glucose detection device for living body, the detection device includes a working electrode 1 and a counter electrode 2 arranged side by side, the working electrode 1 includes a working electrode flexible substrate 102, a working electrode conductive substrate arranged on the working electrode flexible substrate 102, and glucose oxidase loaded on the working electrode conductive substrate, the working electrode conductive substrate and the glucose oxidase form a graphene/carbon nanotube/glucose oxidase composite fiber fabric 101, the counter electrode 2 includes a counter electrode flexible substrate 202, a counter electrode conductive substrate arranged on the counter electrode flexible substrate 202, and a silver/silver chloride film plated on the counter electrode conductive substrate, the counter electrode conductive substrate and the silver/silver chloride film form a graphene/carbon nanotube/silver chloride composite fiber fabric 201, the material of the working electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 118 μm, the number of graphene layers is 15, the thickness of the graphene layer is 5nm, the thickness of the carbon nanotube is 17 μm, the working electrode flexible substrate 102 is made of polydimethylsiloxane and is 0.8mm, the counter electrode conductive substrate is made of graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 118 μm, the number of graphene layers is 15, the thickness of the graphene layer is 5nm, the thickness of the carbon nanotube is 17 μm, the counter electrode flexible substrate 202 is made of polydimethylsiloxane and is 0.8 mm.
The detection device is prepared by the following steps:
(1) the area is 1.2cm2Ultrasonically cleaning a nickel fiber fabric with the mesh number of 100 and the diameter of 100 mu m for 5min by using acetone, alternately cleaning the nickel fiber fabric for 5 times by using deionized water and ethanol, drying the nickel fiber fabric (the drying temperature is 70 ℃ and the drying time is 15min), then placing the nickel fiber fabric in a tubular furnace, growing a continuous multilayer graphene film on the surface of the nickel fiber fabric by using a chemical vapor deposition method, taking argon (400sccm) and hydrogen (40sccm) as carrier gases, taking methane (40sccm) as a carbon source, and taking the tubular furnace for 25 ℃ for min-1Heating to 950 ℃ at the heating rate, growing for 2min, closing methane and hydrogen after the growth is finished, cooling to room temperature, and taking out a sample to obtain the nickel/graphene composite fiber fabric.
(2) By an electron beam evaporation coating system, the surface of the nickel/graphene composite fiber fabric is 1.2 multiplied by 10-3Evaporating 1nm Fe and 15nm Al sequentially at the speed of 0.6nm/s and 2.3nm/s under Pa2O3Respectively as catalyst and buffer layer for growing carbon nanotube.
(3) Putting the nickel/graphene composite fiber fabric plated with the catalyst and the buffer layer into a tubular furnace, growing an oriented carbon nanotube array by a secondary chemical vapor deposition method, taking argon (200sccm) and hydrogen (20sccm) as carrier gases, taking ethylene (6sccm) as a carbon source, and using the tubular furnace at 25 ℃ for min-1Heating to 755 ℃ at the heating rate, wherein the growth time is 2min, closing the ethylene and the hydrogen after the growth is finished, cooling to room temperature, and taking out the sample to obtain the nickel/graphene/carbon nano tube composite fiber fabric.
(4) Putting the nickel/graphene/carbon nano tube composite fiber fabric into ferric chloride (2mol L)-1) And nitric acid (3mol L)-1) Soaking the mixture in the mixed solution for 1 hour until the nickel is platedAnd completely etching the fiber fabric, the catalyst layer and the buffer layer, washing with deionized water and drying (the drying temperature is 85 ℃ and the drying time is 30min) to obtain the graphene/carbon nanotube composite fiber fabric.
(5) Uniformly mixing polydimethylsiloxane and a curing agent according to a mass ratio of 9:1, heating and curing at 70 ℃ for 60min to obtain a flexible working electrode substrate, and taking the flexible working electrode substrate with an area of 0.2cm2The graphene/carbon nanotube composite fiber fabric is taken as a conductive substrate of a working electrode and transferred to the surface of a flexible substrate of a polydimethylsiloxane working electrode, one end of the graphene/carbon nanotube composite fiber fabric is fixed by silver glue, and 100 mu L of 40mg mL of 100 mu L of the graphene/carbon nanotube composite fiber fabric is dripped on the graphene/carbon nanotube composite fiber fabric-1And drying the glucose oxidase solution for 1h at normal temperature and low pressure (the pressure is-70 kPa) to obtain the graphene/carbon nano tube/glucose oxidase composite fiber fabric which is used as a working electrode of a biological nondestructive blood glucose detection device.
(6) Uniformly mixing polydimethylsiloxane and a curing agent according to a mass ratio of 9:1, heating and curing at 70 ℃ for 60min to obtain a counter electrode flexible substrate, and taking the counter electrode flexible substrate with an area of 0.2cm2The graphene/carbon nano tube composite fiber fabric is used as a counter electrode conductive substrate and transferred to the surface of a polydimethylsiloxane counter electrode flexible substrate, one end of the graphene/carbon nano tube composite fiber fabric is fixed by silver glue, a silver/silver chloride film is deposited on the surface of the graphene/carbon nano tube composite fiber fabric through a two-step electrodeposition method, and 0.5mol L of silver/silver chloride film is firstly deposited-1Potassium nitrate and 3mmol L of-1In the silver nitrate mixed electrolyte, a silver electrode is taken as an anode, graphene/carbon nano tube composite fiber fabric is taken as a cathode, a layer of silver film is deposited on the surface of the cathode, and 0.05mol L of silver film is added-1And 5mmol L of potassium chloride-1The mixed solution of hydrochloric acid is used as electrolyte, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a silver film on the graphene/carbon nano tube composite fiber fabric is chlorinated, a silver/silver chloride film is formed on the surface of the graphene/carbon nano tube composite fiber fabric, and the graphene/carbon nano tube/silver chloride composite fiber fabric is obtained and is used as the counter electrode of a biological body nondestructive blood sugar detection device.
(7) And (4) placing the electrodes obtained in the step (5) and the step (6) side by side to obtain the two-electrode system organism nondestructive blood sugar detection device. The two-electrode system organism nondestructive blood sugar detection device can realize accurate and nondestructive detection of the blood sugar of the organism.
Example 5
As shown in fig. 11, a nondestructive blood glucose detection device for living body, the detection device includes a working electrode 1 and a counter electrode 2 arranged side by side, the working electrode 1 includes a working electrode flexible substrate 102, a working electrode conductive substrate arranged on the working electrode flexible substrate 102, and glucose oxidase loaded on the working electrode conductive substrate, the working electrode conductive substrate and the glucose oxidase form a graphene/carbon nanotube/glucose oxidase composite fiber fabric 101, the counter electrode 2 includes a counter electrode flexible substrate 202, a counter electrode conductive substrate arranged on the counter electrode flexible substrate 202, and a silver/silver chloride film plated on the counter electrode conductive substrate, the counter electrode conductive substrate and the silver/silver chloride film form a graphene/carbon nanotube/silver chloride composite fiber fabric 201, the material of the working electrode conductive substrate is graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 105 micrometers, the number of graphene layers is 9, the thickness of the graphene layer is 3nm, the thickness of the carbon nanotube layer is 10 micrometers, the working electrode flexible substrate 102 is made of polydimethylsiloxane and is 1.2mm, the counter electrode conductive substrate is made of graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure, the thickness of the composite fiber fabric is 105 micrometers, the number of graphene layers is 9, the thickness of the composite fiber fabric is 3nm, the thickness of the carbon nanotube layer is 10 micrometers, the counter electrode flexible substrate 202 is made of polydimethylsiloxane and is 1.2 mm.
The detection device is prepared by the following steps:
(1) the area is 0.9cm2Ultrasonic cleaning nickel fiber fabric with 100 mesh and diameter of 100 μm with acetone for 5min, alternately cleaning with deionized water and ethanol for 5 times, drying at 75 deg.C for 10min, and placing the nickel fiber fabric in a tubeIn the formula furnace, a continuous multilayer graphene film is grown on the surface of the nickel fiber fabric by a chemical vapor deposition method, argon (400sccm) and hydrogen (160sccm) are used as carrier gases, methane (100sccm) is used as a carbon source, and the temperature of the tubular furnace is 25 ℃ for min-1Heating to 970 ℃ at the heating rate, wherein the growth time is 10min, closing methane and hydrogen after the growth is finished, cooling to room temperature, and taking out a sample to obtain the nickel/graphene composite fiber fabric.
(2) By an electron beam evaporation coating system, the surface of the nickel/graphene composite fiber fabric is coated at 2.5 multiplied by 10-3Evaporating 1nm Fe and 8nm Al sequentially at the speed of 0.6nm/s and 3nm/s under Pa2O3Respectively as catalyst and buffer layer for growing carbon nanotube.
(3) Putting the nickel/graphene composite fiber fabric plated with the catalyst and the buffer layer into a tubular furnace, growing an oriented carbon nanotube array by a secondary chemical vapor deposition method, taking argon (200sccm) and hydrogen (60sccm) as carrier gases, taking ethylene (15sccm) as a carbon source, and using the tubular furnace at 25 ℃ for min-1Heating to 743 ℃, growing for 10min, closing ethylene and hydrogen after the growth is finished, cooling to room temperature, and taking out a sample to obtain the nickel/graphene/carbon nanotube composite fiber fabric.
(4) Putting the nickel/graphene/carbon nano tube composite fiber fabric into ferric chloride (3mol L)-1) And nitric acid (3mol L)-1) Soaking the mixed solution for 3 hours until the nickel fiber fabric, the catalyst layer and the buffer layer are completely etched, washing with deionized water and drying (the drying temperature is 75 ℃ and the drying time is 50min) to obtain the graphene/carbon nanotube composite fiber fabric.
(5) Uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of 5:1, heating and curing at 80 ℃ for 60min to obtain a flexible substrate of the working electrode, and arranging the flexible substrate with the area of 0.17cm2The graphene/carbon nanotube composite fiber fabric is taken as a conductive substrate of a working electrode and transferred to the surface of a flexible substrate of a polydimethylsiloxane working electrode, one end of the graphene/carbon nanotube composite fiber fabric is fixed by silver glue, and 100 mu L of 40mg mL of 100 mu L of the graphene/carbon nanotube composite fiber fabric is dripped on the graphene/carbon nanotube composite fiber fabric-1Glucose oxidase solutionAnd drying at normal temperature and low pressure (the pressure is-65 kPa) for 2h to obtain the graphene/carbon nanotube/glucose oxidase composite fiber fabric which is used as a working electrode of a biological nondestructive blood glucose detection device.
(6) Uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of 5:1, heating and curing at 80 ℃ for 60min to obtain a flexible substrate of the counter electrode, and arranging the flexible substrate with the area of 0.17cm2The graphene/carbon nanotube composite fiber fabric is used as a counter electrode conductive substrate and transferred to the surface of a polydimethylsiloxane counter electrode flexible substrate, one end of the graphene/carbon nanotube composite fiber fabric is fixed by silver glue, a silver/silver chloride film is deposited on the surface of the graphene/carbon nanotube composite fiber fabric by a two-step electrodeposition method, and 1.5mol L of silver/silver chloride film is firstly deposited-1Potassium nitrate and 7mmol L-1In the silver nitrate mixed electrolyte, a silver electrode is taken as an anode, graphene/carbon nano tube composite fiber fabric is taken as a cathode, a layer of silver film is deposited on the surface of the cathode, and 0.15mol L of silver film is added-1And 15mmol L of potassium chloride-1The mixed solution of hydrochloric acid is used as electrolyte, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a silver film on the graphene/carbon nano tube composite fiber fabric is chlorinated, a silver/silver chloride film is formed on the surface of the graphene/carbon nano tube composite fiber fabric, and the graphene/carbon nano tube/silver chloride composite fiber fabric is obtained and is used as the counter electrode of a biological body nondestructive blood sugar detection device.
(7) And (4) placing the electrodes obtained in the step (5) and the step (6) side by side to obtain the two-electrode system organism nondestructive blood sugar detection device. The two-electrode system organism nondestructive blood sugar detection device can realize accurate and nondestructive detection of the blood sugar of the organism.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A nondestructive blood sugar detection device of an organism is characterized by comprising a working electrode and a counter electrode which are arranged side by side, wherein the working electrode comprises a working electrode flexible substrate, a working electrode conductive substrate arranged on the working electrode flexible substrate and glucose oxidase loaded on the working electrode conductive substrate, the counter electrode comprises a counter electrode flexible substrate, a counter electrode conductive substrate arranged on the counter electrode flexible substrate and a silver/silver chloride film plated on the counter electrode conductive substrate,
the conductive substrate of the working electrode is made of graphene/carbon nanotube composite fiber fabric, the graphene/carbon nanotube composite fiber keeps a hollow structure,
the material of the counter electrode conductive substrate is graphene/carbon nano tube composite fiber fabric, the graphene/carbon nano tube composite fiber keeps a hollow structure,
the graphene/carbon nanotube composite fiber fabric is obtained by growing through a secondary chemical vapor deposition method.
2. The device for the non-invasive measurement of blood glucose in a living being according to claim 1, wherein the flexible substrate of the working electrode is polydimethylsiloxane.
3. The device for the non-invasive measurement of blood glucose in a living body according to claim 1, wherein the flexible substrate of the counter electrode is polydimethylsiloxane.
4. A method for manufacturing the device for the non-destructive testing of blood glucose in living organisms according to any of claims 1 to 3, wherein the method for manufacturing comprises the following steps:
(a) sequentially growing a plurality of continuous graphene films, plating a catalyst layer and a buffer layer and growing an oriented carbon nanotube array on the surface of the pretreated nickel fiber fabric, then etching to remove the nickel fiber fabric, the catalyst layer and the buffer layer, and then cleaning and drying to obtain the graphene/carbon nanotube composite fiber fabric;
(b) taking the graphene/carbon nanotube composite fiber fabric obtained in the step (a), transferring the graphene/carbon nanotube composite fiber fabric to the surface of a flexible substrate of a working electrode, loading glucose oxidase on the graphene/carbon nanotube composite fiber fabric, and drying to obtain the working electrode;
(c) taking the graphene/carbon nano tube composite fiber fabric obtained in the step (a), transferring the graphene/carbon nano tube composite fiber fabric to the surface of a flexible substrate of a counter electrode, and plating a silver/silver chloride film on the graphene/carbon nano tube composite fiber fabric to obtain the counter electrode;
(d) and (c) placing the working electrode obtained in the step (b) and the counter electrode obtained in the step (c) side by side to obtain the organism nondestructive blood sugar detection device.
5. The method for preparing a device for the non-destructive examination of blood glucose in living organisms according to claim 4, wherein the pretreatment process of the nickel fiber fabric in the step (a) is specifically as follows: ultrasonically cleaning in acetone for 5-10 min, washing with deionized water and ethanol for 3-5 times, and finally drying at 60-80 ℃ for 10-20 min.
6. The method for preparing the device for nondestructive testing of blood sugar in an organism according to claim 4, wherein in the step (a), when a continuous multilayer graphene film is grown, a mixed gas of argon and hydrogen is used as a carrier gas, methane is used as a carbon source, the reaction temperature is 950-1050 ℃, the growth time is 2-15 min, and the volume ratio of argon, hydrogen and methane is 20 (2-8) to (2-5);
in the step (a), the pressure of plating is (8-30) x 10 when plating the catalyst layer and the buffer layer-4Pa, the plating speed of the catalyst layer is 0.3-0.7 nm/s, and the plating speed of the buffer layer is 2-3 nm/s;
in the step (a), the component of the catalyst layer is Fe, and the component of the buffer layer is Al2O3The thickness ratio of the catalyst layer to the buffer layer is (0.05-0.15): 1;
in the step (a), when the oriented carbon nanotube array grows, mixed gas of argon and hydrogen is used as carrier gas, ethylene is used as a carbon source, the reaction temperature is 740-760 ℃, the growth time is 2-10 min, and the volume ratio of argon, hydrogen and ethylene is 40 (4-12) to (1-3);
in the step (a), the drying temperature is 70-85 ℃, and the drying time is 30-60 min.
7. The method for preparing a device for the nondestructive testing of blood sugar in an organism according to claim 4, characterized in that in step (a), a mixed solution of ferric chloride and nitric acid is used as an etching solution to etch the nickel fiber fabric, the catalyst layer and the buffer layer for 1-3 h, and the molar concentration ratio of ferric chloride to nitric acid is (1-3): 3.
8. The method for preparing a device for the nondestructive testing of blood sugar in an organism according to claim 4, characterized in that in step (b), glucose oxidase is loaded by phosphate buffer solution of glucose oxidase, and the dropping volume of the phosphate buffer solution of glucose oxidase is 50-100 μ L/(0.1-0.2 cm)2Graphene/carbon nanotube composite fiber fabric), wherein the mass concentration of the glucose oxidase in phosphate buffer solution of the glucose oxidase is 40-60 mg mL-1；
In the step (b), drying is carried out at normal temperature and low pressure, wherein the low pressure is-50 to-70 kPa;
in the step (b), the preparation process of the flexible substrate of the working electrode comprises the following steps: uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of (5-10) to 1, and heating and curing at 70-80 ℃ for 40-60 min to obtain the composite material.
9. The method for preparing a device for the non-destructive examination of blood glucose in living organisms according to claim 4, wherein in the step (c), the counter electrode flexible substrate is prepared by: uniformly mixing polydimethylsiloxane and a curing agent according to the mass ratio of (5-10) to 1, and heating and curing at 70-80 ℃ for 40-60 min to obtain the composite material.
10. The method for preparing a device for the non-invasive measurement of blood glucose in a living body according to claim 4, wherein the step (c) of plating the silver/silver chloride film comprises the following steps: firstly, taking a silver electrode as an anode, taking a graphene/carbon nanotube composite fiber fabric as a cathode, taking a mixed solution of potassium nitrate and silver nitrate as an electrolyte, plating a silver film on the graphene/carbon nanotube composite fiber fabric, then taking the silver-plated graphene/carbon nanotube composite fiber fabric as a working electrode, taking a platinum wire as a counter electrode, taking a saturated calomel electrode as a reference electrode, and taking a mixed solution of potassium chloride and hydrochloric acid as an electrolyte, and chlorinating the silver film to obtain the graphene/carbon nanotube/silver chloride composite fiber fabric;
in the mixed solution of the potassium nitrate and the silver nitrate, the molar concentration ratio of the potassium nitrate to the silver nitrate is (500-1500) to (3-7);
in the mixed solution of the potassium chloride and the hydrochloric acid, the molar concentration ratio of the potassium chloride to the hydrochloric acid is (50-150) to (5-15).
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