CN114609205B - Preparation method of reference electrode for implanting electrochemical biosensor - Google Patents

Preparation method of reference electrode for implanting electrochemical biosensor Download PDF

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CN114609205B
CN114609205B CN202210262737.5A CN202210262737A CN114609205B CN 114609205 B CN114609205 B CN 114609205B CN 202210262737 A CN202210262737 A CN 202210262737A CN 114609205 B CN114609205 B CN 114609205B
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ferricyanide
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高志强
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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    • A61B5/1468—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 chemical or electrochemical methods, e.g. by polarographic means
    • A61B5/1473—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 chemical or electrochemical methods, e.g. by polarographic means invasive, e.g. introduced into the body by a catheter
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
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    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/265—Bioelectric electrodes therefor characterised by the electrode materials containing silver or silver chloride
    • A—HUMAN NECESSITIES
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    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/279—Bioelectric electrodes therefor specially adapted for particular uses
    • A61B5/28—Bioelectric electrodes therefor specially adapted for particular uses for electrocardiography [ECG]
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

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Abstract

The invention discloses a preparation method of a reference electrode for implanting an electrochemical biosensor, which comprises the following steps: a1 Electrolyzing the substrate electrode in a mixed solution of metal chloride and potassium chloride; a2 Transferring the electrolyte matrix electrode in the step A1) into a sodium acetate buffer solution containing potassium ferricyanide, and scanning from-0.8V to 0.5V at a speed of 2-20 mV/s; a3 Drying the scanned electrolyte matrix electrode; b1 Placing the prepared ferricyanide electrode precursor into a sodium chloride solution, and circularly scanning at a speed of 2-20 mV/s between 0-0.75V; b2 And (3) taking out the scanned ferricyanide electrode precursor, washing and drying. The invention uses ferricyanide as reference electrode material of the implanted electrochemical biosensor, and has extremely stable electrode potential.

Description

Preparation method of reference electrode for implanting electrochemical biosensor
Technical Field
The invention relates to a preparation method of a reference electrode for implanting an electrochemical biosensor.
Background
As one of the core components of an electrochemical biosensor, the performance of the reference electrode directly affects the stability, sensitivity and lifetime of the biosensor.
The reference electrodes of existing implantable electrochemical biosensors are all silver/silver chloride electrodes, particularly, the reference electrodes used in implantable continuous glucose monitoring systems, such as Guardian, dexcom G6 of Dekang, and FreeStyle Libre 2 of Atlantic diabetes care.
Silver/silver chloride electrodes have been widely used in various medical devices, such as electrodes for electrocardiographs, where the skin of the human body is very effective in preventing silver ions from entering the body, and where the short contact of the silver/silver chloride electrode with the skin does not adversely affect. However, when used as a reference electrode for an implantable continuous glucose monitoring system, the protective effect of the skin is no longer present, and under such circumstances, silver ions can enter the body directly by prolonged direct contact with human tissue (typically 7-14 days). To minimize or eliminate the risk of silver ions entering the body, all implantable electrochemical biosensors are coated with a semi-permeable/biocompatible membrane to block the direct contact of the silver/silver chloride electrode with human tissue while minimizing the exudation of silver ions.
For the potential toxicity of silver/silver chloride electrodes, particularly silver ions, there is a need to develop a reference electrode that is low or non-toxic and that can be used in implantable electrochemical biosensors.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a preparation method of a reference electrode for an implanted electrochemical biosensor, and a cobalt iron cyanide electrode prepared by the method has excellent electrochemical performance and can be used as the reference electrode of the implanted electrochemical biosensor.
In order to achieve the above purpose, the present invention provides the following technical solutions: a method of preparing a reference electrode for implantation into an electrochemical biosensor, comprising the steps of:
a) Preparation of ferricyanide electrode:
a1 Electrolyzing the matrix electrode in a mixed solution of metal chloride and potassium chloride to obtain an electrolytic matrix electrode; wherein the concentration of the metal chloride is 0.1-2 mmol/L, the concentration of the potassium chloride is 0.01-0.2 mol/L, and the electrolysis voltage is-0.9 to-1.5V;
a2 Transferring the electrolyte matrix electrode in the step A1) into a sodium acetate buffer solution containing potassium ferricyanide, and scanning from-0.8V to 0.5V at a scanning speed of 2-20 mV/s; wherein the concentration of the potassium ferricyanide is 0.5-10 mmol/L;
a3 Drying the scanned electrolyte matrix electrode in the step A2), thereby obtaining a ferricyanide electrode precursor;
b) Curing of ferricyanide electrode:
b1 Placing the prepared ferricyanide electrode precursor into a sodium chloride solution, and circularly scanning at a speed of 2-20 mV/s between 0-0.75V;
b2 And B), taking out the scanned ferricyanide electrode precursor in the step B1), washing and drying to obtain the ferricyanide electrode.
Preferably, the substrate electrode includes a glassy carbon electrode, a printed carbon electrode, a metal electrode, or a printed metal electrode.
Preferably, the metal chloride salt includes cobalt chloride, copper chloride, zinc chloride, iron chloride, chromium chloride, titanium chloride, manganese chloride, nickel chloride, aluminum chloride, silver chloride, tin chloride, or indium chloride.
Preferably, in the step A1), the concentration of the metal chloride is 0.5-1.2 mmol/L, and the concentration of the potassium chloride is 0.05-0.12 mol/L.
Preferably, in the step A1), the electrolysis voltage is-1.0 to-1.2V.
Preferably, in the step A2), the concentration of the potassium ferricyanide is 1 to 5mmol/L.
Preferably, in step A2), the scanning speed is 5 to 15mV/s.
Preferably, in the step B1), the concentration of the sodium chloride is 0.05 to 0.5mol/L.
Preferably, in step B1), the scanning speed is 5 to 15mV/s.
Preferably, the drying environment of the step A3) and the drying environment of the step B2) are the same, the temperature is 22-30 ℃, the relative humidity is 45-90%, and the drying time is 30-120 min.
In summary, the invention has the following beneficial effects:
1. the ferricyanide is used as a reference electrode material of the implantable electrochemical biosensor, and has extremely stable electrode potential;
2. ferricyanide in the invention only releases or absorbs alkali metal ions in the oxidation-reduction reaction process, and has no toxic or side effect on human bodies.
Drawings
FIG. 1 is a cyclic voltammogram of a cobalt ferricyanide electrode in 1.0mol/L sodium chloride solution, potential scan rate: 1. 100mV/s,2, 50mV/s,3, 20mV/s,4, 5mV/s;
FIG. 2 is a graph of the redox potential versus sodium ion concentration for a cobalt iron cyanide electrode at 25 ℃;
FIG. 3 is a graph showing the stability of the potential of cobalt ferricyanide electrodes in PBS buffer;
fig. 4 shows the results of an implantation experiment with a cobalt ferricyanide reference electrode and a dynamic glucometer with a silver/silver chloride reference electrode.
Detailed Description
In order to find a reference electrode material that can replace silver/silver chloride while maintaining a silver/silver chloride electrode as one of the most prominent features of the reference electrode-the high stability of the electrode potential. We find that Prussian blue substances (ferricyanide) are particularly suitable as reference electrode materials for implantable electrochemical biosensors. Apart from having an extremely stable electrode potential, it does not release silver ions during the redox reaction, unlike silver/silver chloride electrodes, ferricyanide (for example cobalt ferricyanide) only releases or absorbs alkali metal ions during its redox reaction (M + ) Typically sodium or potassium ions, the reaction equation is as follows:
based on the above, the invention designs a preparation method of a reference electrode for implanting an electrochemical biosensor, which comprises the following steps:
a) Preparation of ferricyanide electrode:
a1 Electrolyzing the substrate electrode in a mixed solution of metal chloride and potassium chloride for 10-60 s to obtain an electrolytic substrate electrode; wherein the concentration of the metal chloride is 0.1-2 mmol/L, the concentration of the potassium chloride is 0.01-0.2 mol/L, and the electrolysis voltage is-0.9 to-1.5V; the matrix electrode comprises a glassy carbon electrode, a printed carbon electrode, a metal electrode or a printed metal electrode;
a2 Transferring the electrolyte matrix electrode in the step A1) into a sodium acetate buffer solution containing potassium ferricyanide, and scanning from-0.8V to 0.5V at a scanning speed of 2-20 mV/s; wherein the concentration of potassium ferricyanide is 0.5-10 mmol/L, the concentration of sodium acetate is 0.02-0.5 mol/L, and the pH is 4-5.5;
a3 Drying the scanned electrolyte matrix electrode in the step A2), thereby obtaining a ferricyanide electrode precursor; wherein the drying temperature is 22-30 ℃, the relative humidity is 45-90%, and the drying time is 30-120 min;
b) Curing of ferricyanide electrode:
b1 Placing the prepared ferricyanide electrode precursor into a sodium chloride solution, and circularly scanning for 20-60 min at a speed of 2-20 mV/s between 0-0.75V; wherein the concentration of sodium chloride is 0.01-1 mol/L;
b2 Taking out the scanned ferricyanide electrode precursor in the step B1), washing and drying to obtain a ferricyanide electrode; wherein the drying temperature is 22-30 ℃, the relative humidity is 45-90%, and the drying time is 30-120 min.
In the above technical solution, the metal chloride salt includes cobalt chloride, copper chloride, zinc chloride, ferric chloride, chromium chloride, titanium chloride, manganese chloride, nickel chloride, aluminum chloride, silver chloride, tin chloride or indium chloride.
In a preferred embodiment, in step A1), the concentration of the metal chloride is 0.5 to 1.2mmol/L and the concentration of the potassium chloride is 0.05 to 0.12mol/L; the electrolysis time is 20-40 s, and the electrolysis voltage is-1.0 to-1.2V.
In a preferred embodiment, in the step A2), the concentration of potassium ferricyanide is 1-5 mmol/L and the concentration of sodium acetate is 0.1-0.2 mol/L; the scanning speed is 5-15 mV/s.
In a preferred embodiment, in step B1), the concentration of sodium chloride is 0.05 to 0.5mol/L; the scanning speed is 5-15 mV/s.
Specific examples:
example S1:
(1) Preparation of cobalt ferricyanide electrode: electrolyzing the glassy carbon electrode in cobalt chloride with the concentration of 1mmol/L and potassium chloride with the concentration of 0.1mol/L for 30s, wherein the electrolysis voltage is-1.2V, so as to obtain an electrolysis matrix electrode; washing the electrolytic substrate electrode with water and transferring it into 0.1mol/L sodium acetate buffer solution containing potassium ferricyanide with a concentration of 5mmol/L potassium ferricyanide and a pH of 4.5, then slowly scanning from-0.8V to 0.5V at a speed of 10 mV/s; if a thicker cobalt ferricyanide electrode needs to be prepared, repeating the operation for 2-8 times; drying the scanned electrolyte matrix electrode in a strictly controlled environment, wherein the drying temperature is 25 ℃, the relative humidity is 65%, and the drying time is 60min;
(2) Curing of cobalt ferricyanide electrode: putting the prepared cobalt ferricyanide electrode precursor into 0.1mmol/L sodium chloride solution, and circularly scanning for 30min at a speed of 10mV/s between 0 and 0.75V; then, taking out the scanned cobalt iron cyanide electrode precursor, washing with water, and drying in a strictly controlled environment to obtain a cobalt iron cyanide electrode; wherein the drying temperature is 25deg.C, the relative humidity is 65%, and the drying time is 60min.
Examples S2 to S5 and comparative example S6:
the process parameters were the same as S1 except that the metal chloride salt and its concentration were adjusted as shown in table 1 below:
as shown in FIG. 1, the cobalt iron cyanide electrode exhibits excellent redox properties in 1.0mol/L sodium chloride solution, its cyclic voltammogram shows typical surface electrochemical characteristics, and has all the characteristics of highly reversible redox species, which allows it to be used as a reference electrode.
Further, it was found that the oxidation-reduction potential (electrode potential) of cobalt ferricyanide is determined by the concentration (activity) of sodium ions as shown in fig. 2; between 0.001 and 1mol/L, the electrode potential of cobalt ferricyanide and the concentration of sodium ions show the following typical Nernst relationship, as shown in equation 1:
at low electrolyte concentration, at room temperature of 25 ℃, equation 1 can be reduced to equation 2:
this is in combination with experimental results E=0.3885+0.0059log [ Na ] of the electrode potential and sodium ion concentration of cobalt iron cyanide electrode at 25 ℃ + ]And consistent.
The electrode potential of both the implanted silver/silver chloride reference electrode and the implanted cobalt ferricyanide is determined by the concentration of an ion in the body fluid (e.g., interstitial fluid or blood). The electrode potential of the silver/silver chloride reference electrode is determined by chloride ions, while the electrode potential of cobalt ferricyanide is determined by sodium ions. The concentrations of chloride and sodium ions in blood and interstitial fluid remain substantially unchanged, so that both provide a relatively stable reference potential when used as reference electrodes for implantable electrochemical biosensors.
As an implantable reference electrode, it is most important that it is capable of having stable reference potential properties during testing. For this, we tested the stability of the electrode potential of cobalt ferricyanide in PBS buffer solution. As shown in fig. 3, the maximum fluctuation of the electrode potential of cobalt ferricyanide was only 1.3% in the continuous test for up to 30 days, and the requirement as a reference electrode of the implantable electrochemical biosensor was fully satisfied.
On this basis, we applied the glucose biosensor with cobalt ferricyanide reference electrode and the glucose biosensor with silver/silver chloride reference electrode to a dynamic glucometer (the manufacture of the glucose biosensor refers to chinese patent CN113325058A, which was implanted in the same receptor, and in the continuous 20-day test, the results of glucose monitoring by these two glucose biosensors are highly consistent, as shown in fig. 4.
In summary, cobalt ferricyanide electrodes have excellent electrochemical properties and can be used as reference electrodes for implantable electrochemical biosensors. For example, when used as a reference electrode for a dynamic glucose meter, the results remain highly consistent compared to a dynamic glucose meter with a silver/silver chloride electrode as the reference electrode.
The scanning referred to in this application is potential scanning.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above examples, and all technical solutions belonging to the concept of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.

Claims (9)

1. A method of preparing a reference electrode for implantation into an electrochemical biosensor, comprising the steps of:
a) Preparation of ferricyanide electrode:
a1 Electrolyzing the matrix electrode in a mixed solution of metal chloride and potassium chloride to obtain an electrolytic matrix electrode; wherein the concentration of the metal chloride is 0.1-2 mmol/L, the concentration of the potassium chloride is 0.01-0.2 mol/L, and the electrolysis voltage is-0.9 to-1.5V;
a2 Transferring the electrolyte matrix electrode in the step A1) into a sodium acetate buffer solution containing potassium ferricyanide, and scanning from-0.8V to 0.5V at a scanning speed of 2-20 mV/s; wherein the concentration of the potassium ferricyanide is 0.5-10 mmol/L;
a3 Drying the scanned electrolyte matrix electrode in the step A2), thereby obtaining a ferricyanide electrode precursor;
b) Curing of ferricyanide electrode:
b1 Placing the prepared ferricyanide electrode precursor into a sodium chloride solution, and circularly scanning at a speed of 2-20 mV/s between 0-0.75V;
b2 Taking out the scanned ferricyanide electrode precursor in the step B1), washing and drying to obtain a ferricyanide electrode;
the drying environment of the step A3) and the drying environment of the step B2) are the same, the temperature is 22-30 ℃, the relative humidity is 45-90%, and the drying time is 30-120 min.
2. The method of preparing a reference electrode for implantation of an electrochemical biosensor according to claim 1, wherein the substrate electrode comprises a glassy carbon electrode, a printed carbon electrode, a metal electrode, or a printed metal electrode.
3. The method of preparing a reference electrode for implantation of an electrochemical biosensor according to claim 2, wherein the metal chloride salt comprises cobalt chloride, copper chloride, zinc chloride, ferric chloride, chromium chloride, titanium chloride, manganese chloride, nickel chloride, aluminum chloride, silver chloride, tin chloride, or indium chloride.
4. The method for preparing a reference electrode for implanting an electrochemical biosensor according to claim 1, wherein in the step A1), the concentration of the metal chloride salt is 0.5 to 1.2mmol/L and the concentration of the potassium chloride is 0.05 to 0.12mol/L.
5. The method for preparing a reference electrode for implanting an electrochemical biosensor according to claim 4, wherein in the step A1), the electrolysis voltage is-1.0 to-1.2V.
6. The method for preparing a reference electrode for implanting an electrochemical biosensor according to claim 1, wherein in the step A2), the concentration of potassium ferricyanide is 1 to 5mmol/L.
7. The method for preparing a reference electrode for implanting an electrochemical biosensor according to claim 6, wherein in the step A2), the scanning speed is 5 to 15mv/s.
8. The method for preparing a reference electrode for implanting an electrochemical biosensor according to claim 1, wherein in the step B1), the concentration of sodium chloride is 0.05 to 0.5mol/L.
9. The method for preparing a reference electrode for implanting an electrochemical biosensor according to claim 8, wherein in the step B1), the scanning speed is 5 to 15mv/s.
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