CN108426933B - Preparation method of electrochemical working electrode and detection method of blood sugar - Google Patents
Preparation method of electrochemical working electrode and detection method of blood sugar Download PDFInfo
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Abstract
The invention discloses a preparation method of an electrochemical working electrode, which comprises the following steps: cleaning ITO conductive glass, performing hydrophilic treatment, immersing the ITO conductive glass into a mixed solution of a metal salt solution and an alkali solution, taking out the ITO conductive glass, and drying the ITO conductive glass; soaking the ITO conductive glass dried in the step S1 in a mixed solution of a metal salt solution and an organic amine solution, and growing for 5-25h at 60-200 ℃, wherein a layer of semiconductor material is attached to the ITO conductive glass; and dropwise adding the conductive nano material on one surface of the ITO conductive glass on which the semiconductor nano material grows to obtain the electrochemical working electrode. The working electrode can amplify an electrochemical signal generated by lower-concentration blood sugar in the process of detecting the blood sugar, and has guiding significance for early diagnosis of diseases such as diabetes and the like in the fields of biomedicine and the like.
Description
Technical Field
The invention relates to the technical field of electrochemical detection of blood sugar, in particular to a preparation method of an electrochemical working electrode and a detection method of blood sugar.
Background
The inorganic nano material has great significance in human health and environment, has special physicochemical properties, has large specific surface area and high active sites, is more and more widely applied, and is widely applied to the fields of chemical industry, biology, medicine and the like. Hydrogen peroxide is an important molecule that underlies clinical, industrial and environmental fields. Many reports show the effect of the molecule in certain diseases, a blood glucose sensor can be manufactured by detecting the concentration of hydrogen peroxide generated when blood glucose is catalytically decomposed, the technology is applied to blood glucose detection, the normal value of blood glucose is known and real-time monitoring is carried out, initial judgment is carried out according to the comparison of the detected value and the normal value, the actual blood glucose level of an organism can be directly known, and the method has important significance for detecting potential risks of diabetes, diagnosing diabetes and treating effects of diabetes. With the development of detection technology, the blood glucose monitor with high sensitivity, high accuracy and simple operation has better prospect. There are various working electrodes used in electrochemical methods for measuring blood glucose, such as ITO/Ag working electrodes, but these methods have limitations in that a silver nanowire cannot be stably attached to an ITO glass plate, and the method is not suitable.
Disclosure of Invention
The present invention is directed to a method for preparing an electrochemical working electrode and a method for detecting blood glucose, which solves one or more of the above-mentioned problems of the prior art.
The invention provides a preparation method of an electrochemical working electrode, which comprises the following steps:
α 1, cleaning the ITO conductive glass, carrying out hydrophilic treatment, immersing the ITO conductive glass into a mixed solution of a metal salt solution and an alkali solution, taking out and drying;
α 3, dripping the conductive nano material on the surface of the ITO conductive glass on which the semiconductor nano material grows to obtain the electrochemical working electrode.
The ITO conductive glass is manufactured by plating a layer of Indium Tin Oxide (ITO) film on the basis of soda-lime-based or silicon-boron-based substrate glass by various methods such as sputtering, evaporation and the like.
The clear water treatment refers to that the ITO conductive glass is put into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, so that the surface of the ITO conductive glass has hydrophilic characteristics.
Wherein, the ITO conductive glass dried in the step S1 is immersed in the mixed solution of the metal salt solution and the organic amine solution, the growth temperature is preferably 80-150 ℃, and the growth time is preferably 10-15 h.
In some embodiments, the metal salt solution is Zn (NO)3)2、Zn(CH3COO)2、ZnCl2、ZnSO4、Cu(NO3)2、CuCl2、CuSO4At least one of (1).
In some embodiments, the alkaline solution is KOH, NaOH, Ba (OH)2、Ca(OH)2At least one of (1).
In some embodiments, the organic amine solution is at least one of hexamethylenetetramine, methylamine, ethylamine, isopropylamine, n-butylamine, phenethylamine, pyridine.
In some embodiments, the concentration of the metal salt solution is 0.01M to 0.1M, the concentration of the alkali solution is 0.01M to 0.05M, the concentration of the organic amine solution is 0.01M to 0.1M, the volume ratio of the metal salt solution to the alkali solution is 1:2 to 2:1, the volume ratio of the metal salt solution to the organic amine solution is 1:2 to 2:1, and the dropwise addition amount of the conductive nanomaterial is 1 μ L to 10 μ L. Wherein the dropping amount of the conductive nanomaterial is preferably 1 to 5 μ L.
In some embodiments, the conductive nanomaterial is a silver nanowire having a diameter of 20-200nm and a length of 10-30 μm. Wherein, the diameter of the conductive nano material is preferably 20-30nm, and the length is preferably 20-30 μm.
In some embodiments, a method of preparing a conductive nanomaterial includes the steps of:
β 1, adding the glycol solution into a glass container, heating to 160-170 ℃, and mixing the glycol solution of the copper salt and AgNO3In the presence of a glycol solutionPouring into a glass container, wherein the concentration of the glycol solution of copper salt is 0.001-0.01M, AgNO3The concentration of the ethylene glycol solution is 0.1-1M, the ethylene glycol solution of copper salt and AgNO3The volume ratio of the ethylene glycol solution is 1:1-1:10, and then the ethylene glycol solution of polyvinylpyrrolidone is dripped at a constant speed;
In some embodiments, the copper salt solution is Cu (NO)3)2、CuSO4、CuCl2、CuI2、CuBr2At least one of (1).
In some embodiments, the molecular weight of the polyvinylpyrrolidone is in the range of 10000-1300000, the concentration of the ethylene glycol solution of the polyvinylpyrrolidone is in the range of 0.1-1M (based on the monomer of the polyvinylpyrrolidone), and the dropping speed of the polyvinylpyrrolidone solution is in the range of 40 mL/min-60 mL/min.
Wherein the molecular weight range of the polyvinylpyrrolidone is preferably 40000-55000. The dropping speed range of the dropping polyvinylpyrrolidone solution is preferably 48mL/min to 58 mL/min.
A method for detecting blood sugar comprises the following steps: the electrode manufactured by the preparation method of the electrochemical working electrode is used as a working electrode, and cyclic voltammetry detection is carried out on the concentration of hydrogen peroxide generated by blood glucose decomposition through an electrochemical workstation.
Has the advantages that: the semiconductor nano material synthesized by the preparation method of the electrochemical working electrode provided by the embodiment of the invention is uniform in distribution and size, has a larger specific surface area and has good biocompatibility. The diameter of the synthesized conductive material nano silver wire is 20-30nm, the length is 70-80 mu m, the conductive material nano silver wire is in a long and thin shape, so that the conductive material nano silver wire has more active sites and is a biological friendly material, the conductive material nano silver wire and the semiconductor nano silver wire can be well combined, and the semiconductor nano material can stably contain and fix the nano silver wire and has better electrochemical response signals on hydrogen peroxide generated by blood sugar decomposition.
According to the method for detecting the blood sugar, provided by the embodiment of the invention, the conductive glass ITO with the semiconductor material is utilized, the nano silver wire is dripped on the surface of the conductive glass ITO to be used as a working electrode of a three-electrode system, and the electrochemical detection method is carried out on the concentration of hydrogen peroxide generated by the decomposition of the blood sugar, so that the semiconductor material and the nano silver wire achieve a synergistic effect, the lower concentration of the hydrogen peroxide can be detected, the detection of the blood sugar in the biological material is more convenient, and the method can be used as a good blood sugar enzyme-free sensor.
Drawings
FIG. 1 is a schematic structural view of an electrochemical working electrode of example 1;
FIG. 2 is an SEM photograph of ZnO nanorods of the semiconductor material of example 1;
FIG. 3 is an enlarged view of a portion of FIG. 2;
fig. 4 is an SEM image of the conductive nanomaterial silver nanowire of example 1;
FIG. 5 is an enlarged view of a portion of FIG. 4;
FIG. 6 is a cyclic voltammogram in the electrochemical testing of experiments 1-4
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are only for illustrating the performance of the present invention more clearly and are not limited to the following examples.
Example 1:
preparing a conductive nano material:
50mL of ethylene glycol solution is weighed and added into a three-necked flask, heated for 1.2h at 165 ℃, and 1.4mg of CuCl is weighed2，1.2740g AgNO3Dissolved in 2.6mL and 15mL of ethylene glycol solution respectively, wherein the CuCl is2In a concentration of 0.004M, AgNO3In a concentration of 0.05M, 3.7296g of polyvinylpyrrolidone having a molecular weight of 29000 are weighed out and dissolved in 48mL of ethylene glycol, wherein the concentration of the ethylene glycol solution of polyvinylpyrrolidone is 0.7M (based on polyvinylpyrrolidone monomer), and 2.6mL of CuCl is added2Solution and 15mL of AgNO3Pouring the solution into a three-necked bottle, finally dropwise adding 48mL of polyvinylpyrrolidone solution into the reaction solution at a dropping speed of 48mL/h, stopping heating after the titration is finished, and cooling to room temperatureAnd (3) precipitating by using acetone, cleaning by using the acetone, centrifuging, and finally dispersing the product in ethanol. The resulting product silver nanowires were visible by Scanning Electron Microscopy (SEM) in fig. 4 and 5.
21.95mg of Zn (CH) are weighed out3COO)2·2H2O, 16.83mg KOH, dissolved in 10mL deionized water, respectively, wherein Zn (CH)3COO)2·2H2O concentration of 0.01M and KOH concentration of 0.03M, 35.05mg of hexamethylenetetramine and 74.37mg of Zn (NO)3)2·6H2O, dissolved in 5mL of deionized water respectively, wherein the concentration of the hexamethylenetetramine is 0.05M, and Zn (NO) is added3)2·6H2The O concentration was 0.05M.
Soaking ITO conductive glass in 5mL of Zn (CH)3COO)2·2H2And O, slowly dripping 5mL of KOH solution while performing ultrasonic treatment, performing ultrasonic treatment for 15min after dripping, placing the obtained product in a 65-DEG C oven for 15min, taking out the ITO conductive glass, placing the obtained product in a 50-DEG C oven for 5min, taking out the ITO conductive glass, and repeating the steps. After one repetition, 5mL of Zn (NO) was added3)2·6H2And uniformly mixing the O solution and 5mL of hexamethylenetetramine solution, pouring the mixture into a reaction kettle, immersing the ITO conductive glass into the solution, enabling the side with the ITO conductive glass to incline downwards, and placing the reaction kettle in a 120 ℃ oven for reaction for 20 hours. And after 20h, taking out the ITO conductive glass, rinsing the ITO conductive glass with deionized water, and then placing the ITO conductive glass in a 65 ℃ drying oven for 2h to dry. The obtained product ZnO nano-rod can be seen by Scanning Electron Microscope (SEM) in figures 2 and 3.
And dripping 10 mu L of nano silver wires on the ITO conductive glass on which the ZnO nanorods grow, drying the ITO conductive glass by a blower, and preparing the working electrode ITO/ZnO/Ag, wherein the working electrode comprises ITO conductive glass 1, a semiconductor material layer 2 formed by the ZnO nanorods and a conductive material layer formed by the nano silver wires, as shown in figure 1.
Example 2:
preparing a conductive nano material:
50mL of ethylene glycol solution is weighed and added into a three-necked bottle, the bottle is heated for 1.2h at 165 ℃, and 0.672mg of CuCl is weighed2，0.085g AgNO3Respectively dissolved in 5mL and 5mL of ethylene glycolIn alcoholic solution, wherein CuCl2In a concentration of 0.001M, AgNO30.1M, then 0.444g polyvinylpyrrolidone with molecular weight of 10000 is weighed and dissolved in 40mL of glycol, wherein the concentration of the glycol solution of the polyvinylpyrrolidone is 0.1M (calculated by polyvinylpyrrolidone monomer), and 5mL of CuCl is added2Solution and 5mL of AgNO3Pouring the solution into a three-necked bottle, finally dropwise adding 40mL of polyvinylpyrrolidone solution into the reaction solution at a dropping speed of 40mL/h, stopping heating after titration, cooling to room temperature, using acetone for sedimentation, then using acetone for cleaning, centrifuging, and finally dispersing the product into ethanol to obtain the product silver nanowire.
43.9mg of Zn (CH) are weighed out3COO)2·2H2O, 5.611mg KOH, dissolved in 10mL deionized water, respectively, wherein Zn (CH)3COO)2·2H2O concentration of 0.02M and KOH concentration of 0.01M, 14.02mg of hexamethylenetetramine and 29.76mg of Zn (NO)3)2·6H2O, dissolved in 10mL of deionized water respectively, wherein the concentration of the hexamethylenetetramine is 0.01M, and Zn (NO) is added3)2·6H2The concentration of O was 0.01M.
Soaking ITO conductive glass in 5mL of Zn (CH)3COO)2·2H2And O, slowly dripping 10mL of KOH solution while performing ultrasonic treatment, performing ultrasonic treatment for 15min after dripping, placing the obtained product in a 65-DEG C oven for 15min, taking out the ITO conductive glass, placing the obtained product in a 50-DEG C oven for 5min, taking out the ITO conductive glass, and repeating the steps. After one repetition, 5mL of Zn (NO) was added3)2·6H2And uniformly mixing the O solution and 10mL of hexamethylenetetramine solution, pouring the mixture into a reaction kettle, immersing the ITO conductive glass into the solution, enabling the side with the ITO conductive glass to incline downwards, and placing the reaction kettle in a 120 ℃ oven for reaction for 20 hours. And after 20h, taking out the ITO conductive glass, rinsing the ITO conductive glass with deionized water, and then placing the ITO conductive glass in a 65 ℃ drying oven for 2h for drying to obtain the product ZnO nanorod.
And dripping 1 mu L of nano silver wire on the ITO conductive glass on which the ZnO nano rods grow, and drying by using a blower to obtain the working electrode ITO/ZnO/Ag.
Example 3:
preparing a conductive nano material:
50mL of ethylene glycol solution was weighed into a three-necked flask, heated at 170 ℃ for 4 hours, and 1.34mg of CuCl was weighed2，1.7g AgNO3Dissolved in 1mL and 10mL of ethylene glycol solution respectively, wherein the CuCl is2In a concentration of 0.01M, AgNO3Is 1M, then 6.66g of polyvinylpyrrolidone with molecular weight of 1300000 are weighed out and dissolved in 60mL of ethylene glycol, wherein the concentration of the ethylene glycol solution of polyvinylpyrrolidone is 1M (calculated by polyvinylpyrrolidone monomer), and 1mL of CuCl is added2Solution and 10mL of AgNO3Pouring the solution into a three-necked bottle, finally dropwise adding 60mL of polyvinylpyrrolidone solution into the reaction solution at a dropping speed of 60mL/h, stopping heating after titration, cooling to room temperature, using acetone for sedimentation, then using acetone for cleaning, centrifuging, and finally dispersing the product into ethanol to obtain the product silver nanowire.
Weighing 219.5mg Zn (CH)3COO)2·2H2O, 28.06mg KOH, dissolved in 10mL deionized water, respectively, wherein Zn (CH)3COO)2·2H2O concentration was 0.1M and KOH concentration was 0.05M, and 140.18mg of hexamethylenetetramine and 297.5mg of Zn (NO) were weighed3)2·6H2O, dissolved in 10mL of deionized water respectively, wherein the concentration of the hexamethylenetetramine is 0.1M, and Zn (NO) is added3)2·6H2The concentration of O was 0.1M.
Soaking ITO conductive glass in 10mL of Zn (CH)3COO)2·2H2And O, slowly dripping 5mL of KOH solution while performing ultrasonic treatment, performing ultrasonic treatment for 15min after dripping, placing the obtained product in a 65-DEG C oven for 15min, taking out the ITO conductive glass, placing the obtained product in a 50-DEG C oven for 5min, taking out the ITO conductive glass, and repeating the steps. After one repetition, 10mL of Zn (NO) was added3)2·6H2And uniformly mixing the O solution and 5mL of hexamethylenetetramine solution, pouring the mixture into a reaction kettle, immersing the ITO conductive glass into the solution, enabling the side with the ITO conductive glass to incline downwards, and placing the reaction kettle in a 120 ℃ oven for reaction for 20 hours. Taking out the ITO conductive glass after 20h, rinsing the ITO conductive glass with deionized water, and placing the ITO conductive glass in a 65 ℃ drying oven for 2h for dryingThus obtaining the product ZnO nano-rod.
And (3) dropwise adding 5 mu L of nano silver wire on the ITO conductive glass on which the ZnO nano rods grow, and drying by using a blower to obtain the working electrode ITO/ZnO/Ag.
The method for simulating blood sugar detection comprises the following steps:
opening an electrochemical workstation switch, opening operation software, pouring 20ML phosphate buffer solution as electrolyte, dropwise adding a proper amount of hydrogen peroxide solution, and respectively inserting a working electrode and a reference electrode: silver/silver chloride electrode, counter electrode: and (3) a platinum sheet electrode, namely connecting the alligator clip with each electrode, selecting a test mode to be cyclic voltammetry, setting various parameters, and starting the test by clicking.
Preparation of 0.02M phosphate buffer:
first, 0.2M, 100mL Na was prepared2HPO4Solution and NaH2PO4Solution: 7.1628g of Na were weighed2HPO4·12H2O, 3.1202g of NaH2PO4·2H2O, respectively adding 100mL of deionized water, and respectively measuring 62mL of Na in the solution2HPO4Solution and 38mL of NaH2PO4Pouring the solution into a beaker, mixing uniformly, weighing 10mL of the mixed solution, adding water to dilute the mixed solution to 100mL, weighing 0.7455g of KCl, and dissolving the solution in 100mL of the mixed solution to prepare 0.02M phosphate buffer solution containing chloride ions.
Preparation of 55mM hydrogen peroxide solution:
measuring 1.42mL of 30% hydrogen peroxide solution, diluting to 25mL, and diluting 1mL of the solution to 10 mL.
Experiment 1: bare ITO electrode assay phosphate buffer containing 0.1mM hydrogen peroxide:
taking bare ITO without ZnO nanorods as a working electrode, measuring 36.4 mu L of 55mM hydrogen peroxide solution, putting the solution into 20mL of phosphate buffer solution, wherein the voltage range is-0.8V-0V, taking an Ag/AgCl electrode as a reference electrode, and taking a platinum sheet electrode as a counter electrode to perform cyclic voltammetry. The test results obtained are seen by the cyclic voltammogram of fig. 6.
Experiment 2: ITO/ZnO/Ag electrode assay phosphate buffer containing 1mM hydrogen peroxide:
dripping 10 mu L of nano silver wire on the ITO with the ZnO nano rod, blowing the nano silver wire by a blower for drying, taking the nano silver wire as a working electrode, measuring 364 mu L of 55mM hydrogen peroxide solution, putting the hydrogen peroxide solution into 20mL of phosphoric acid buffer solution, wherein the voltage range is-0.8V-0V, taking an Ag/AgCl electrode as a reference electrode, and taking a platinum sheet electrode as a counter electrode for carrying out cyclic voltammetry. The test results obtained are seen by the cyclic voltammogram of fig. 6.
Experiment 3: ITO/ZnO/Ag electrode assay phosphate buffer containing 0.5mM hydrogen peroxide:
dripping 10 mu L of nano silver wire on the ITO with the ZnO nano rod, blowing the nano silver wire by a blower for drying, taking the nano silver wire as a working electrode, measuring 182 mu L of 55mM hydrogen peroxide solution, putting the hydrogen peroxide solution into 20mL of phosphoric acid buffer solution, wherein the voltage range is-0.8V-0V, taking an Ag/AgCl electrode as a reference electrode, and taking a platinum sheet electrode as a counter electrode for carrying out cyclic voltammetry test. The test results obtained are seen by the cyclic voltammogram of fig. 6.
Experiment 4: ITO/ZnO/Ag electrode assay phosphate buffer containing 0.1mM hydrogen peroxide:
dripping 10 mu L of nano silver wire on the ITO with the ZnO nano rod, blowing the nano silver wire by a blower for drying, taking the nano silver wire as a working electrode, measuring 36.4 mu L of 55mM hydrogen peroxide solution, putting the hydrogen peroxide solution into 20mL of phosphoric acid buffer solution, wherein the voltage range is-0.8V-0V, taking an Ag/AgCl electrode as a reference electrode, and taking a platinum sheet electrode as a counter electrode for carrying out cyclic voltammetry test. The test results obtained are seen by the cyclic voltammogram of fig. 6.
As can be seen from fig. 6, bare ITO as the working electrode had no reduction peak on the cyclic voltammogram, indicating that bare ITO did not respond to hydrogen peroxide; after hydrogen peroxide is added, the ITO/ZnO/Ag electrode is used as a working electrode, a reduction peak appears on a cyclic voltammogram, and the reduction peak becomes more and more obvious along with the increase of the concentration of the hydrogen peroxide, which shows that the ITO/ZnO/Ag electrode is used as the working electrode and has high sensitivity to the hydrogen peroxide, and is suitable for monitoring the hydrogen peroxide component in blood sugar.
The ZnO nanorods in the embodiment provided by the invention are uniformly distributed, uniform in size and large in specific surface area, provide more transmission channels for the silver nanowires on a nanoscale, improve the electron transmission rate, can well accommodate and fix the silver nanowires, provide larger specific surface area for the silver nanowires, and enhance the test stability of the silver nanowires. The used conductive material nano silver wire is in a slender line shape and has more active sites, so that the zinc oxide nano rod and the nano silver wire can be combined advantageously, and an electrochemical signal generated by blood sugar with lower concentration can be amplified in the detection process, so that the conductive material nano silver wire has guiding significance for early diagnosis of diseases such as diabetes and the like in the fields of biomedicine and the like.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these should also be construed as being within the scope of the present invention.
Claims (6)
1. A method of making an electrochemical working electrode, comprising the steps of:
α 1, cleaning the ITO conductive glass, performing hydrophilic treatment, and soaking the ITO conductive glass in 0.01M Zn (CH)3COO)2Dripping 0.03M KOH solution into the solution at the same time, taking out and drying;
α 2, the ITO conductive glass baked in step α 1 is dipped in 0.05M Zn (NO)3)2Growing the film for 20 hours at 120 ℃ in a mixed solution of the solution and 0.05M hexamethylenetetramine solution, and attaching a layer of ZnO nano-rods on the ITO conductive glass;
α 3, dripping the nano silver wires dispersed in the ethanol on one surface of the ITO conductive glass on which the ZnO nano rods grow, and air-drying to obtain the electrochemical working electrode;
the preparation method of the nano silver wire dispersed in the ethanol comprises the following steps:
β 1, adding the glycol solution into a glass container, heating to 160-170 ℃, and mixing the glycol solution of the copper salt and AgNO3The glycol solution of copper salt is poured into a glass container, wherein the concentration of the glycol solution of copper salt is 0.001-0.01M, AgNO3The concentration of the ethylene glycol solution is 0.1-1M, the ethylene glycol solution of copper salt and AgNO3B ofThe volume ratio of the glycol solution is 1:1-1:10, and then the glycol solution of polyvinylpyrrolidone is dripped at a constant speed;
β 2, stopping heating after finishing the dropwise addition, cooling to room temperature, using acetone to settle the solution and washing for a plurality of times, centrifuging and precipitating, and then dispersing in ethanol to obtain the nano silver wire dispersed in the ethanol.
2. The method of claim 1, wherein the Zn (CH) is selected from the group consisting of3COO)2The volume ratio of the solution to the KOH solution is 1: 2-2: 1, and the Zn (NO) is3)2The volume ratio of the solution to the hexamethylenetetramine solution is 1: 2-2: 1, and the dripping amount of the nano silver wires dispersed in the ethanol is 1-10 mu L.
3. The method of claim 1, wherein the nanosilver wire dispersed in ethanol has a diameter of 20 to 200nm and a length of 10 to 30 μm.
4. The method of claim 1, wherein the copper salt solution is Cu (NO)3)2、CuSO4、CuCl2、CuI2、CuBr2At least one of (1).
5. The method for preparing an electrochemical working electrode according to claim 1, wherein the molecular weight of the polyvinylpyrrolidone is 10000-1300000, the concentration of the ethylene glycol solution of the polyvinylpyrrolidone is 0.1-1M, and the dropping speed of the dropwise addition of the polyvinylpyrrolidone solution is 40-60 mL/min.
6. A method for detecting blood sugar is characterized by comprising the following steps: the electrode prepared by the method for preparing the electrochemical working electrode according to any one of claims 1 to 5 is used as a working electrode, and cyclic voltammetry detection is carried out on the concentration of hydrogen peroxide generated by the decomposition of blood glucose through an electrochemical workstation.
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