CN117214266A - Graphene-gold co-plating modified electrode, preparation method and application thereof, and enzyme sensor electrode - Google Patents
Graphene-gold co-plating modified electrode, preparation method and application thereof, and enzyme sensor electrode Download PDFInfo
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Landscapes
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention belongs to the technical field of biosensors, and particularly relates to a graphene-gold co-plating modified electrode, a preparation method and application thereof, and an enzyme sensor electrode. The graphene-gold co-plating modified electrode provided by the invention comprises a conductive substrate and a modification layer arranged on the surface of the conductive substrate; the modification layer is a mixture layer of graphene and gold simple substance; or the modification layer is a graphene layer and a gold simple substance layer which are stacked, and the graphene layer is in contact with the surface of the conductive substrate. The invention optimizes the biological molecule combination capacity of the electrode surface and the surface area of the catalytic reaction by the cooperation of the graphene and Jin Shanzhi, improves the density of the immobilized biological macromolecules of the electrode to the maximum extent, improves the detection limit, amplifies the signal response of the electrode, and ensures that the electrode reaction is more sensitive and accurate. The high-performance biosensor is suitable for the fields of medical care, environmental monitoring, food safety and the like.
Description
Technical Field
The invention belongs to the technical field of biosensors, and particularly relates to a graphene-gold co-plating modified electrode, a preparation method and application thereof, and an enzyme sensor electrode.
Background
The biosensor is used for detecting the concentration of biomolecules, and has the characteristics of high sensitivity, good reliability, rapid response and low cost. The biosensor is generally composed of a molecular recognition element that recognizes a biochemical reaction signal and a signal conversion element for converting the biochemical reaction signal into an electrical signal. The molecular recognition element in the biosensor is generally composed of an electrode and a material with electrocatalytic properties, the material with electrocatalytic properties is generally combined with the electrode through bonding or physical contact, the electrode is used for collecting current generated by biochemical reaction, and the material with electrocatalytic properties performs biochemical reaction with biomolecules to be detected for catalysis.
At present, the electrode material is generally nano metal, wherein gold has excellent conductivity and biocompatibility as a biosensor application material, but has low specific surface area, and the density of immobilized biomolecules on the electrode surface is limited, so that the sensitivity and detection limit of a biosensor are affected.
Disclosure of Invention
The invention aims to provide a graphene-gold co-plating modified electrode, a preparation method and application thereof, and an enzyme sensor electrode. The graphene-gold co-plating modified electrode provided by the invention has extremely high sensitivity and stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a graphene-gold co-plating modified electrode, which comprises a conductive substrate and a modification layer arranged on the surface of the conductive substrate; the modification layer is a mixture layer of graphene and gold simple substance; or the modification layer is a graphene layer and a gold simple substance layer which are stacked, and the graphene layer is in contact with the surface of the conductive substrate.
Preferably, when the modification layer is a mixture layer of graphene and gold simple substance, the mass ratio of the graphene to the gold simple substance in the modification layer is 1: (0.1-10);
when the modification layer is a graphene layer and a gold simple substance layer which are arranged in a laminated mode, the mass ratio of the graphene layer to the gold simple substance layer is 1: (0.1-10).
The invention provides a preparation method of a graphene-gold co-plating modified electrode, which is characterized in that when the modified layer is a mixture layer of graphene and gold simple substance, the preparation method comprises the following steps:
immersing a reference electrode, a counter electrode and a conductive substrate in a first electrolyte, wherein the first electrolyte is a mixed solution of graphene oxide, a gold-containing compound and water, and performing first electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode;
when the modification layer is a graphene layer and a gold simple substance layer which are stacked, the method comprises the following steps:
immersing a reference electrode, a counter electrode and a conductive substrate in a second electrolyte, wherein the second electrolyte is graphene oxide aqueous dispersion liquid, and performing second electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain a graphene modified electrode; and immersing a reference electrode, a counter electrode and a graphene modified electrode in a third electrolyte, wherein the third electrolyte is a gold-containing compound aqueous solution, and performing third electroplating on the surface of the graphene modified electrode by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode.
Preferably, the operating parameters of the first plating, the second plating and the third plating include: the potential is independently-0.5-1.5V, the scanning speed is independently 1-50 mV/s, and the scanning circle number is independently 5-50 circles.
Preferably, the mass content of graphene oxide in the graphene oxide aqueous dispersion is 0.1-10%.
Preferably, the mass content of the gold-containing compound in the gold-containing compound aqueous solution is 0.1-10%.
Preferably, the gold-containing compound is chloroauric acid and/or potassium gold cyanide.
The invention provides an application of the graphene-gold co-plating modified electrode in the preparation of a working electrode of a biosensor, wherein the graphene-gold co-plating modified electrode is prepared by the preparation method in the technical scheme.
The invention provides an enzyme sensor electrode, which comprises an electrode and biological enzyme loaded on the surface of the electrode; the electrode is the graphene-gold co-plating modified electrode according to the technical scheme or the graphene-gold co-plating modified electrode prepared by the preparation method according to the technical scheme.
Preferably, the biological enzymes include diaphorase and dehydrogenase.
The invention provides a graphene-gold co-plating modified electrode, which comprises a conductive substrate and a modification layer arranged on the surface of the conductive substrate; the modification layer is a mixture layer of graphene and gold simple substance; or the modification layer is a graphene layer and a gold simple substance layer which are stacked, and the graphene layer is in contact with the surface of the conductive substrate. According to the invention, graphene and Jin Shanzhi are compounded to serve as a modification layer of the electrode, a gold simple substance has good conductivity and stability, and meanwhile, good biocompatibility of the gold simple substance allows biomolecules (such as antibodies or enzymes) to be fixed on the gold surface so as to keep the functions of the biomolecules, thereby ensuring reliable and accurate biosensing of the electrode; the graphene is of a layered structure, has extremely high surface area, excellent electron mobility and excellent thermal conductivity, and improves the sensitivity and specificity of the electrode. According to the invention, through the cooperation of graphene and Jin Shanzhi, excellent biocompatibility of gold simple substance is combined with high surface area and conductivity of graphene, so that the biomolecule combination capacity of the electrode surface and the surface area of catalytic reaction are optimized, the density of electrode immobilized biomacromolecules is improved to the maximum extent, the detection limit is improved, the signal response of the electrode is amplified, and the reaction of the electrode is more sensitive and accurate. In conclusion, the graphene-gold co-plating modified electrode provided by the invention enhances signal response and detection capability through the modification layer; meanwhile, the consumption of gold is reduced, and the cost of the electrode is reduced. The electrode provided by the invention is suitable for high-performance biosensors in the fields of medical care, environmental monitoring, food safety and the like.
The invention provides a preparation method of the graphene-gold co-plating modified electrode. The graphene-gold co-plating modified electrode is obtained by electroplating on the surface of a conductive substrate by adopting a cyclic voltammetry. The preparation method is simple and feasible, and is suitable for industrial application.
Drawings
FIG. 1 is a scanning electron micrograph of a graphene-gold co-plated modified electrode prepared in example 1;
fig. 2 is a schematic diagram of the working principle of graphene-gold co-plating modification electricity provided by the invention;
FIG. 3 is a graph of the chronoamperometric response to pyruvic acid after enzyme loading of the graphene-gold co-plated modified electrode prepared in example 1;
FIG. 4 is a graph showing the chronoamperometric response to pyruvic acid after enzyme loading of the gold-plated sensor electrode prepared in comparative example 1;
FIG. 5 is a graph of the timed current response to pyruvic acid after enzyme loading of the graphene coated electrode prepared in comparative example 2;
FIG. 6 is a graph showing the chronoamperometric response to α -ketoglutarate after enzyme loading by the graphene-gold co-plated modified electrode prepared in example 1.
Detailed Description
The invention provides a graphene-gold co-plating modified electrode, which comprises a conductive substrate and a modification layer arranged on the surface of the conductive substrate; the modification layer is a mixture layer of graphene and gold simple substance; or the modification layer is a graphene layer and a gold simple substance layer which are stacked, and the graphene layer is in contact with the surface of the conductive substrate.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The graphene-gold co-plating modified electrode provided by the invention comprises a conductive substrate. In the present invention, the conductive substrate is preferably a screen-printed electrode. In the present invention, the material of the conductive substrate preferably includes, but is not limited to, titanium, nickel, zinc, steel, zinc, carbon, molybdenum, copper, gold, silver, platinum, palladium, indium tin oxide, fluorine-doped zinc oxide, antimony-doped tin oxide or aluminum-doped zinc oxide, and more preferably steel.
The graphene-gold co-plating modified electrode provided by the invention comprises a modified layer arranged on the surface of the conductive substrate.
In the invention, the modification layer is a mixture layer of graphene and gold simple substance. Or the modification layer is a graphene layer and a gold simple substance layer which are arranged in a stacked mode, and when the modification layer is a graphene layer and a gold simple substance layer which are arranged in a stacked mode, the graphene layer is in surface contact with the conductive substrate.
In the present invention, when the modification layer is a mixture layer of graphene and gold simple substance, the Jin Shanzhi is preferably gold nanoparticle. The particle size of the gold nanoparticles is preferably 100-200 nm. The Jin Shanzhi is supported on the surface of the graphene to form a mixture layer. The mass ratio of graphene to gold simple substance in the modification layer is preferably 1: (0.1 to 10), more preferably 1: (0.5 to 8), more preferably 1: (1-5).
In the present invention, when the modification layer is a graphene layer and a gold simple substance layer which are stacked, the Jin Shanzhi layer is preferably a gold nanoparticle layer. The mass ratio of the graphene layer to the gold simple substance layer is preferably 1: (0.1 to 10), more preferably 1: (0.5 to 8), more preferably 1: (1-5).
In the present invention, although the gold has excellent conductivity and biocompatibility, the lack of the advantage of large surface area of graphene limits the density of biomolecules that can be immobilized on the surface thereof, thereby affecting the sensitivity and detection limit of the biosensor. Furthermore, the relatively high gold costs may also pose an economic challenge to expanding the production of gold electrode biosensors. On the other hand, although graphene has a high surface area and electron mobility, graphene may suffer from aggregation due to strong interlayer van der waals force, thereby degrading the performance of the sensor. Furthermore, graphene alone tends to exhibit poor selectivity in sensing, as graphene tends to indiscriminately adsorb various types of molecules, which can lead to increased interference and false positive readings. Thus, while gold and graphene each have the advantage of being a biosensor electrode material, there are also significant limitations that, if used alone, may affect the performance of the biosensor.
The electrode is modified by the co-plating layer of the nano gold and the graphene, and the unique performance of the nano gold and the graphene which are mutually complemented is utilized, so that the overall performance of the biosensor electrode is improved. Gold has excellent electrochemical properties, including good conductivity and stability, and furthermore, gold's biocompatibility allows biomolecules (such as antibodies or enzymes) to maintain their function when immobilized on gold surfaces, thereby achieving accurate and precise biosensing. On the other hand, graphene consists of a single layer of carbon atoms arranged in a 2D honeycomb lattice, has extremely high surface area, excellent electron mobility and excellent thermal conductivity. These properties make it very suitable for increasing the sensitivity and specificity of the biosensor. When gold and graphene are coated together on an electrode, a synergistic effect is produced between them. In the invention, when the modification layer is a mixture layer of graphene and gold simple substance, gold nano particles can be uniformly dispersed on the graphene sheet, and abundant active sites are provided for biological molecule combination and catalytic reaction. In addition, the excellent biocompatibility of gold and the combination of the high surface area and conductivity of graphene greatly amplify the signal response, so that the reaction of the biosensor electrode is more sensitive and accurate. Therefore, gold and graphene are electroplated on the electrode surface of the biosensor, which is helpful for realizing a biosensor detection platform with high sensitivity, stability and reliability.
The invention provides a preparation method of a graphene-gold co-plating modified electrode, which is characterized in that when the modified layer is a mixture layer of graphene and gold simple substance, the preparation method comprises the following steps:
immersing a reference electrode, a counter electrode and a conductive substrate in a first electrolyte, wherein the first electrolyte is a mixed solution of graphene oxide, a gold-containing compound and water, and performing first electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode;
when the modification layer is a graphene layer and a gold simple substance layer which are stacked, the method comprises the following steps:
immersing a reference electrode, a counter electrode and a conductive substrate in a second electrolyte, wherein the second electrolyte is graphene oxide aqueous dispersion liquid, and performing second electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain a graphene modified electrode; and immersing a reference electrode, a counter electrode and a graphene modified electrode in a third electrolyte, wherein the third electrolyte is a gold-containing compound aqueous solution, and performing third electroplating on the surface of the graphene modified electrode by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode.
In the invention, when the modification layer is a mixture layer of graphene and gold simple substance, the preparation method of the graphene-gold co-plating modification electrode comprises the following steps: and immersing the reference electrode, the counter electrode and the conductive substrate in a first electrolyte, wherein the first electrolyte is a mixed solution of graphene oxide, a gold-containing compound and water, and performing first electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode. In the present invention, the reference electrode is preferably an Ag/AgCl electrode. The counter electrode is preferably a platinum wire. The conductive substrate serves as a working electrode. In the first electrolyte: the gold-containing compound is preferably chloroauric acid and/or potassium gold cyanide, more preferably chloroauric acid. In the first electrolyte: the mass ratio of graphene oxide to gold-containing compound is 1: (0.1 to 10), more preferably 1: (0.5 to 8), more preferably 1: (1-5). In the first electrolyte: the mass content of the graphene oxide is preferably 0.05 to 5%, more preferably 0.5 to 4%; the mass content of the gold-containing compound is preferably 0.05 to 5%, more preferably 0.5 to 4%. The preparation method of the first electrolyte preferably comprises the following steps: dispersing graphene oxide in water to obtain graphene oxide aqueous dispersion; dissolving a gold-containing compound in water to obtain a gold-containing compound aqueous solution; mixing the graphene oxide aqueous dispersion and the gold-containing compound aqueous solution. The mass content of graphene oxide in the graphene oxide aqueous dispersion is preferably 0.1 to 10%, more preferably 0.2 to 8%. The mass content of the gold-containing compound in the gold-containing compound aqueous solution is preferably 0.1 to 10%, more preferably 0.2 to 8%. The graphene oxide aqueous dispersion and the gold-containing compound aqueous solution are preferably mixed in equal volumes. In the present invention, the first plating is preferably performed using an electrochemical workstation, preferably a Cinnamomum electrochemical workstation, to which the present invention preferably connects the conductive substrate (working electrode). The operating parameters of the first plating preferably include: the potential is preferably-0.5 to 1.5V. The scanning speed is preferably 1 to 50mV/s, more preferably 10 to 40mV/s, still more preferably 20 to 30mV/s. The number of scanning turns is preferably 5 to 50 turns, more preferably 10 to 30 turns.
In the invention, when the modification layer is a graphene layer and a gold simple substance layer which are stacked, the preparation method of the graphene-gold co-plating modification electrode comprises the following steps: immersing a reference electrode, a counter electrode and a conductive substrate in a second electrolyte, wherein the second electrolyte is graphene oxide aqueous dispersion liquid, and performing second electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain a graphene modified electrode; and immersing a reference electrode, a counter electrode and a graphene modified electrode in a third electrolyte, wherein the third electrolyte is a gold-containing compound aqueous solution, and performing third electroplating on the surface of the graphene modified electrode by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode. The reference electrode, the counter electrode and the conductive substrate are immersed in a second electrolyte, wherein the second electrolyte is graphene oxide aqueous dispersion liquid, and a cyclic voltammetry is adopted to carry out second electroplating on the surface of the conductive substrate, so that the graphene modified electrode is obtained. In the present invention, the reference electrode used for the second plating is preferably an Ag/AgCl electrode. The counter electrode is preferably a platinum wire. The conductive substrate serves as a working electrode. The mass content of graphene oxide in the graphene oxide aqueous dispersion is 0.1-10%, more preferably 0.2-8%. The second electroplating is preferably carried out using an electrochemical workstation, preferably a Chen Hua electrochemical workstation, to which the present invention preferably connects the conductive substrate (working electrode). The operating parameters of the second plating preferably include: the potential is preferably-0.5 to 1.5V. The scanning speed is preferably 1 to 50mV/s, more preferably 10 to 40mV/s, still more preferably 20 to 30mV/s. The number of scanning turns is preferably 5 to 50 turns, more preferably 10 to 30 turns. After the graphene modified electrode is obtained, the reference electrode, the counter electrode and the graphene modified electrode are immersed in a third electrolyte, wherein the third electrolyte is a gold-containing compound aqueous solution, and a cyclic voltammetry is adopted to carry out third electroplating on the surface of the graphene modified electrode, so that the graphene-gold co-plating modified electrode is obtained. In the present invention, the reference electrode used for the third plating is preferably an Ag/AgCl electrode. The counter electrode is preferably a platinum wire. The graphene modified electrode is used as a working electrode. The mass content of the gold-containing compound in the gold-containing compound aqueous solution is 0.1-10%, more preferably 0.2-8%. The gold-containing compound is preferably chloroauric acid and/or potassium gold cyanide, more preferably chloroauric acid. The third electroplating is preferably performed using an electrochemical workstation, preferably a Chen Hua electrochemical workstation, to which the graphene-modified electrode (working electrode) is preferably connected. The operating parameters of the third plating preferably include: the potential is preferably-0.5 to 1.5V. The scanning speed is preferably 1 to 50mV/s, more preferably 10 to 40mV/s, still more preferably 20 to 30mV/s. The number of scanning turns is preferably 5 to 50 turns, more preferably 10 to 30 turns.
The invention provides an application of the graphene-gold co-plating modified electrode in the preparation of a working electrode of a biosensor, wherein the graphene-gold co-plating modified electrode is prepared by the preparation method in the technical scheme.
The graphene-gold co-plating modified electrode surface is preferably used as the working electrode of the biosensor after biomacromolecules are fixed on the surface. The biological macromolecules preferably include proteins and/or DNA.
The biosensor is preferably used for detecting pyruvic acid, phenylpyruvic acid, glucose, uric acid, urea, ascorbic acid, lactic acid, glutamic acid, cholesterol, antibodies, enzymes or nucleic acids.
The invention provides an enzyme sensor electrode, which comprises an electrode and biological enzyme loaded on the surface of the electrode; the electrode is the graphene-gold co-plating modified electrode according to the technical scheme or the graphene-gold co-plating modified electrode prepared by the preparation method according to the technical scheme.
In the present invention, the biological enzymes preferably include Diaphorase (Diaphorase) and dehydrogenase. The diaphorase is preferably NADP + Type (2). The dehydrogenase preferably comprises an alanine dehydrogenase or a glutamate dehydrogenase. The volume ratio of the diaphorase to the dehydrogenase is preferably 0.25: (0.3-0.39).
The invention provides a preparation method of the enzyme sensor electrode, which comprises the following steps:
dissolving biological enzyme in a buffer solution to obtain a biological enzyme solution;
and coating the biological enzyme solution on the surface of the electrode, and curing to obtain the enzyme sensor electrode.
The invention dissolves the biological enzyme in the buffer solution to obtain the biological enzyme solution. In the present invention, the buffer solution is preferably a TAPS buffer. The volume ratio of the biological enzyme to the buffer solution is preferably (0.55-0.64): (1.04-1.1).
After the biological enzyme solution is obtained, the biological enzyme solution is coated on the surface of the electrode, and the enzyme sensor electrode is obtained after solidification. The invention has no special requirements for the specific implementation of the coating. The curing temperature is preferably room temperature and the curing time is preferably 30min.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Dispersing graphene oxide in water to obtain 1mL of 1wt% (w/v) graphene oxide dispersion liquid, and dissolving chloroauric acid in water to obtain 1mL of 1wt% (w/v) chloroauric acid aqueous solution;
1mL of a 1wt% (w/v) graphene oxide dispersion liquid is uniformly mixed with 1mL of a 1wt% (w/v) chloroauric acid aqueous solution, and the obtained mixed slurry is used as an electrolyte;
the screen printing electrode is used as a working electrode and is connected to a Chen Hua electrochemical workstation, 0.3mL of electrolyte is taken, and the reference electrode, the counter electrode and the working electrode are immersed in the electrolyte. And (3) setting the potential range to be-0.5-1.5V by using a cyclic voltammetry, scanning at a scanning speed of 20mV/s for 10 circles, and electroplating a modification layer consisting of graphene and gold nanoparticles on the surface of the working electrode to obtain the graphene-gold co-plating modification electrode.
FIG. 1 is a scanning electron micrograph of a graphene-gold co-plated modified electrode prepared in example 1; as can be seen from fig. 1: a uniform co-plating modification layer is formed on the surface of the working electrode.
Comparative example 1
Dissolving chloroauric acid in water to obtain 1mL of 1wt% (w/v) chloroauric acid aqueous solution;
the screen printing electrode is used as a working electrode and connected to a Chen Hua electrochemical workstation, 0.3mL of 1wt% (w/v) chloroauric acid aqueous solution is used as electrolyte, and the reference electrode, the counter electrode and the working electrode are immersed in the electrolyte. And (3) setting the potential range to be-0.5-1.5V by using a cyclic voltammetry, scanning at a scanning speed of 20mV/s for 10 circles, and electroplating a modification layer consisting of gold nanoparticles on the surface of the working electrode to obtain the gold plating electrode.
Comparative example 2
Dispersing graphene oxide in water to obtain 1mL of 1wt% (w/v) graphene oxide dispersion liquid;
the screen printing electrode is used as a working electrode and is connected to a Chen Hua electrochemical workstation, 0.3mL of 1wt% (w/v) graphene oxide dispersion liquid is used as electrolyte, and the reference electrode, the counter electrode and the working electrode are immersed in the electrolyte. And (3) setting the potential range to be-0.5-1.5V by using a cyclic voltammetry, scanning at a scanning speed of 20mV/s for 10 circles, and electroplating a modification layer consisting of graphene on the surface of the working electrode to obtain the graphene coating electrode.
Example 2
Yellow-transfer enzyme (NADP) + Type) 0.25 mu L, alanine dehydrogenase 0.39 mu L, and dissolved in 1.04 mu LTAPS buffer solution, uniformly mixed and uniformly coated on the surface of the graphene-gold co-plating modified electrode prepared in example 1, and then the mixture is placed at room temperature for fixing for 25min, thus obtaining the enzyme modified co-plating modified electrode.
Comparative example 4
Yellow-transfer enzyme (NADP) + Type) 0.25. Mu.L, alanine dehydrogenase 0.39. Mu.L, dissolved in 1.04. Mu.L of LTAPS buffer solution, uniformly mixed and uniformly coated on the surface of the gold-plated electrode prepared in comparative example 1, and then fixed at room temperature for 25min to obtain the enzyme-modified gold-plated electrode.
Comparative example 5
Yellow-transfer enzyme (NADP) + Type) 0.25 mu L, alanine dehydrogenase 0.39 mu L, and dissolved in 1.04 mu LTAPS buffer solution, uniformly mixed and uniformly coated on the surface of the graphene coated electrode prepared in comparative example 2, and then the graphene coated electrode is fixed at room temperature for 25min to obtain the enzyme modified graphene coated electrode.
Test example 1
The enzyme-loaded electrodes prepared in example 2, comparative example 4 and comparative example 5 were used as working electrodes and connected to an IVIUM workstation, 30mM KCl solution was used as electrolyte, and the reference electrode, counter electrode and working electrode were immersed in 300. Mu.L containing 1mM NH 4 Cl and 20. Mu.M NADP + And (3) in the electrolyte.
The response of the electrode prepared in example 2, comparative example 4 and comparative example 5 after enzyme loading to pyruvic acid was measured by a chronoamperometry (CA method). And when CA is measured, setting voltage to-0.70V, scanning a CA diagram for 15000s, adding pyruvic acid solution into the electrolyte after current is stable, enabling the concentration of pyruvic acid solution in the mixed electrolyte to be 1mM, and storing data after current is stable.
FIG. 3 is a graph of the chronoamperometric response to pyruvic acid after enzyme loading of the graphene-gold co-plated modified electrode prepared in example 1; as shown in FIG. 3, at 6800s, a significant current response of about-740 nA was observed after the introduction of the pyruvic acid solution. After subtracting the background current (quantified as-650 nA), an absolute current response of 90nA was obtained. This response current exhibited significant stability during the subsequent 3 hour test. This stability is indicative of the consistency and reliability of the electrochemical detection over an extended period of time, which is critical in practical applications. The results of fig. 3 demonstrate that the nanoscale gold and graphene co-plated modified electrode prepared in example 1 exhibits a sensitive and durable response to pyruvic acid, indicating the potential selectivity and efficiency of the electrode prepared in example 1 in pyruvic acid detection. The current response in fig. 3 demonstrates the sensitivity and time stability of the nanogold and graphene co-plating modified electrode prepared in example 1.
FIG. 4 is a graph showing the chronoamperometric response to pyruvic acid after enzyme loading of the gold-plated sensor electrode prepared in comparative example 1. As can be seen from fig. 4: at 6800s, no reduction current was present after introducing a 1mM pyruvic acid solution, indicating that the enzyme was not immobilized on the working electrode prepared in comparative example 1, and thus no change in the pyruvic acid concentration in the solution could be sensed. As can be seen from FIG. 4, the gold-plated electrode alone is insensitive to detection of pyruvic acid.
FIG. 5 is a graph of the timed current response to pyruvic acid after enzyme loading of the graphene coated electrode prepared in comparative example 2. As can be seen from FIG. 5, after addition of pyruvic acid to the solution (at 500 s), a reduction current of about 1000nA was observed, indicating that a change in the pyruvic acid concentration was sensitively detected after the electrode prepared in comparative example 2 was loaded with the enzyme; however, the reduction current generated after enzyme loading of the electrode prepared in comparative example 2 gradually decreases within 300s and then tends to be balanced, which shows that the enzyme sensor electrode with the graphene coating only can sensitively detect the change of the pyruvic acid concentration, but has poor stability and can only realize detection in a short time.
Example 3
Yellow-transfer enzyme (NADP) + Type) 0.25 mu L, glutamate dehydrogenase 0.3 mu L, and dissolving in 1.1 mu LTAPS buffer solution, uniformly mixing, uniformly coating on the surface of the graphene-gold co-plating modified electrode prepared in the example 1, and standing at room temperature for 25min to obtain the enzyme modified co-plating modified electrode.
Test example 2
The enzyme-modified electrode prepared in example 3 was used as a working electrode and connected to an IVIUM workstation, a 30mM KCl solution was used as an electrolyte, and a reference electrode, a counter electrode and a working electrode were immersed in 300. Mu.L containing 1mM NH 4 Cl and 20. Mu.M NADP + And (3) in the electrolyte.
The response of the electrode prepared in example 3 to α -ketoglutaric acid was measured by chronoamperometry (CA method). And when CA is measured, setting voltage to-0.75V, scanning a CA diagram for 15000s, adding alpha-ketoglutaric acid solution into the electrolyte after current is stable, enabling the concentration of the alpha-ketoglutaric acid solution in the mixed electrolyte to be 1mM, and storing data after the current is stable.
FIG. 6 is a graph showing the chronoamperometric response to α -ketoglutarate after enzyme loading by the graphene-gold co-plated modified electrode prepared in example 1. As shown in FIG. 6, at 700s, a significant current response of about-600. Mu.A was observed after the introduction of the alpha-ketoglutarate solution. After subtracting the background current (quantified as-110 μA), an absolute current response of 490 μA was obtained. The nano gold and graphene prepared in the embodiment 1 have sensitive response to alpha-ketoglutarate after enzyme loading by the co-plating modified electrode, and the detection signal intensity is about 5 times of that of pyruvic acid.
The results of the above examples and comparative examples show that the nano-gold and graphene co-plating modified biosensor electrode provided by the invention has high sensitivity and stability, wherein the stability comes from the fact that the gold nanoparticle comparative example 2 proves that the reduction current of the electrode with only graphene plating but no gold plating quickly tends to be balanced, and the instability is shown; the sensitivity comes from graphene, and comparative example 1 demonstrates that no pyruvic acid is detected by an electrode with only a gold coating and no graphene coating. The electrode with the nano gold and graphene co-plating layer provided by the invention is sensitive and stable, and can effectively detect pyruvic acid and alpha-ketoglutaric acid.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. The graphene-gold co-plating modified electrode is characterized by comprising a conductive substrate and a modification layer arranged on the surface of the conductive substrate;
the modification layer is a mixture layer of graphene and gold simple substance;
or the modification layer is a graphene layer and a gold simple substance layer which are stacked, and the graphene layer is in contact with the surface of the conductive substrate.
2. The graphene-gold co-plating modified electrode according to claim 1, wherein when the modified layer is a mixture layer of graphene and gold simple substance, the mass ratio of graphene to gold simple substance in the modified layer is 1: (0.1-10);
when the modification layer is a graphene layer and a gold simple substance layer which are arranged in a laminated mode, the mass ratio of the graphene layer to the gold simple substance layer is 1: (0.1-10).
3. The method for preparing the graphene-gold co-plating modified electrode according to claim 1 or 2, wherein when the modified layer is a mixture layer of graphene and gold simple substance, the method comprises the following steps:
immersing a reference electrode, a counter electrode and a conductive substrate in a first electrolyte, wherein the first electrolyte is a mixed solution of graphene oxide, a gold-containing compound and water, and performing first electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode;
when the modification layer is a graphene layer and a gold simple substance layer which are stacked, the method comprises the following steps:
immersing a reference electrode, a counter electrode and a conductive substrate in a second electrolyte, wherein the second electrolyte is graphene oxide aqueous dispersion liquid, and performing second electroplating on the surface of the conductive substrate by adopting a cyclic voltammetry to obtain a graphene modified electrode; and immersing a reference electrode, a counter electrode and a graphene modified electrode in a third electrolyte, wherein the third electrolyte is a gold-containing compound aqueous solution, and performing third electroplating on the surface of the graphene modified electrode by adopting a cyclic voltammetry to obtain the graphene-gold co-plating modified electrode.
4. The method of claim 3, wherein the operating parameters of the first, second and third electroplating comprise: the potential range is independently-0.5-1.5V, the scanning speed is independently 1-50 mV/s, and the scanning circle number is independently 5-50.
5. The method according to claim 3 or 4, wherein the mass content of graphene oxide in the graphene oxide aqueous dispersion is 0.1 to 10%.
6. The method according to claim 3 or 4, wherein the mass content of the gold-containing compound in the gold-containing compound aqueous solution is 0.1 to 10%.
7. The method according to claim 3 or 4, wherein the gold-containing compound is chloroauric acid and/or potassium gold cyanide.
8. The graphene-gold co-plating modified electrode of claim 1 or 2 or the graphene-gold co-plating modified electrode prepared by the preparation method of any one of claims 3 to 7, and application thereof in preparing a working electrode of a biosensor.
9. An enzyme sensor electrode, characterized by comprising an electrode and a biological enzyme supported on the surface of the electrode; the electrode is a graphene-gold co-plating modified electrode according to claim 1 or 2 or a graphene-gold co-plating modified electrode prepared by the preparation method according to any one of claims 3 to 7.
10. The enzyme sensor electrode according to claim 9, wherein the biological enzyme comprises a diaphorase and a dehydrogenase.
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| CN1463362A (en) * | 2001-06-14 | 2003-12-24 | 松下电器产业株式会社 | Biosensor |
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