CN109975382B - Tyrosinase biosensor with phosphorus-doped MXene modified electrode and preparation method and application thereof - Google Patents
Tyrosinase biosensor with phosphorus-doped MXene modified electrode and preparation method and application thereof Download PDFInfo
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Abstract
A tyrosinase biosensor with a phosphorus-doped MXene modified electrode and a preparation method and application thereof belong to the technical field of electrochemical biosensors. The invention includes a glassy carbon electrode; the glassy carbon electrode is a glassy carbon electrode with a surface modified tyrosinase/phosphorus doped MXene/chitosan. The preparation method comprises the following steps: preparing a tyrosinase/phosphorus-doped MXene/chitosan mixed solution, and dropwise adding the mixed solution onto the surface of a glassy carbon electrode to obtain the tyrosinase biosensor. It is applied to the detection of catechol, i.e. catechol. The biosensor preparation method provided by the invention has the characteristics of simplicity, low cost, high speed of manufacture, high enzyme activity, high detection precision and efficiency, low detection limit and the like, and can realize efficient detection of catechol.
Description
Technical Field
The invention relates to a tyrosinase biosensor with a phosphorus-doped MXene modified electrode, a preparation method and application thereof, in particular to a tyrosinase biosensor for trace detection of catechol, and belongs to the technical field of electrochemical biosensors.
Background
Catechol, a scientific name of catechol, widely exists in tea, fruits and vegetables, is one of important substrates for enzymatic browning reactions, and has a wide role in pharmaceutical and chemical production. In recent years, researchers have conducted extensive studies on the antioxidant, antiviral and anticancer effects of catechols such as protocatechuic acid and ellagic acid in tea leaves. At present, the determination of catechol mainly comprises gas chromatography, capillary electrophoresis, high performance liquid chromatography and the like. The method has high sensitivity and good stability, but the detection is time-consuming and labor-consuming, the equipment is expensive, the operation is complex, and the detection limit is still high. Therefore, the trace detection method of the catechol, which is simple and convenient to develop, high in sensitivity and low in detection limit, has important significance for researching the availability of the catechol in the living body.
Tyrosinase (or polyphenol oxidase) is a copper-containing metalloenzyme, widely present in animals, plants and microorganisms, and is a major catalyst for melanin formation. It has double-function catalysis, not only can catalyze hydroxylation reaction of monophenol or polyphenol substances without substituent groups at ortho positions, but also can catalyze dehydrogenation reaction of catechol. In the analytical field, tyrosinase is often used to prepare electrochemical biosensors for detecting a wide range of phenolic compounds based on its catalytic mechanism. Therefore, the tyrosinase biosensor has wide application prospect and commercial application potential in the aspects of environmental pollution detection, food component detection, medical care detection and the like. Although the current research work based on the tyrosinase electrochemical biosensor is few, the problems that the complex actual component detection cannot be processed, the detection performance is not high, the detection is not stable and the like still need to be solved.
The MXene material is a novel two-dimensional layered material and is prepared by etching a layered compound MAX material in a hydrofluoric acid solution. Wherein M is a transition metal element, A is a main group element III or IV, and X is a C or N element. MXene is named because it has a similar two-dimensional structure as graphene. MXene materials have high specific surface area, high conductivity and chemical stability, are reported to be used in the fields of biosensors, drug carriers and the like, are used for modifying biosensor electrodes, not only improve the electronic conductivity of enzyme and the detection limit and sensitivity of the enzyme, but also improve the stability of the enzyme, and have great application potential. It has been reported in the literature that MXene doped with a heteroatom (N, S, etc.) can further improve its conductivity and specific surface area.
Disclosure of Invention
The tyrosinase biosensor has the advantages of good selectivity, high catalytic activity, high reaction speed, wide linear range, low detection lower limit, good storage stability and the like, and can be used for trace analysis on catechol. The preparation method is simple, low in cost, capable of realizing on-line detection and suitable for food and biological monitoring.
According to the technical scheme, the tyrosinase biosensor based on the phosphorus-doped MXene modified electrode comprises a glassy carbon electrode, wherein the glassy carbon electrode is a glassy carbon electrode with the surface modified by tyrosinase/phosphorus-doped MXene/chitosan.
The invention also provides a preparation method of the tyrosinase biosensor based on the phosphorus-doped MXene modified electrode, which comprises the following steps of:
(1) preparing a tyrosinase solution: preparing a tyrosinase solution with the concentration of 1-10 mg/mL by using a phosphoric acid buffer solution with the concentration of 1-100 mmol/L, pH of 3.5-9.5;
(2) preparing a phosphorus-doped MXene solution: using water as a solvent, preparing an MXene solution with the concentration of 1-10 mg/mL, and performing ultrasonic treatment for more than 0.5 h;
(3) preparing a chitosan solution: preparing a chitosan solution with the concentration of 1-10 mg/mL by using water as a solvent, and performing ultrasonic treatment for more than 0.5 h;
(4) preparing a mixed solution of tyrosinase/phosphorus-doped MXene/chitosan: and (3) mixing the solutions prepared in the steps (1), (2) and (3) in a stirring or ultrasonic mode for more than 10min, wherein the concentration of tyrosinase, phosphorus-doped MXene and chitosan in the final mixed solution is 1-10 mg/mL, 0.1-10 mg/mL and 1-10 mg/mL.
(5) Preparing a glassy carbon electrode with surface modified tyrosinase/phosphorus doped MXene/chitosan: and (3) dripping 2-20 mu L of the tyrosinase/phosphorus doped MXene/chitosan mixed solution in the step (4) on the surface of the polished glassy carbon electrode, and drying with nitrogen to obtain the tyrosinase biosensor.
Further, in the step (2), the content of phosphorus element atoms in the phosphorus-doped MXene is 0.1% -10% of the total number of atoms.
Further, the phosphorus-doped MXene in the step (2) is prepared by the following steps: mixing MXene material with phosphorus-containing precursor, grinding, and placing in protective gas for heat treatment to obtain phosphorus-doped MXene material.
In the preparation method, the temperature of the heat treatment is preferably 300-1000 ℃ and the time is preferably 1-12 h.
In the preparation method, the grinding time is preferably 0.1-2 h.
In the above preparation method, the shielding gas comprises N2Or an inert gas, such as Ar; the flow rate of the protective gas is 20-200 mL/min.
In the above preparation method, preferably, the phosphorus-containing precursor includes one of triphenylphosphine, phosphoric acid, or a phosphate.
In the preparation method, the mass ratio of the MXene material to the phosphorus-containing precursor is preferably (0.02-1): 1; more preferably, the mass ratio of the MXene material to the precursor is (0.1-1): 1.
in the preparation method, the step of removing the residual phosphorus-containing precursor is preferably included after the phosphorus-doped MXene material is prepared. In particular to washing with deionized water or ethanol to remove the residual precursor.
In the above preparation method, preferably, the MXene material includes Ti3C2、Ti2C and Ti3One or a combination of more of CN. The MXene material is prepared from MAX phase materials through an etching reaction with HF solution, and has a graphene-like two-dimensional layered structure.
The invention also provides application of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode, and the tyrosinase biosensor is applied to detection of catechol, namely pyrocatechol;
the method comprises the following specific steps: the tyrosinase biosensor is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum electrode is used as a counter electrode, a three-electrode system is established, the three-electrode system is connected with an electrochemical workstation, the detection end of the working electrode is placed in a solution to be detected, the reduction current during electrochemical reaction in the solution to be detected is detected through the electrochemical workstation, and then phenol or catechol in the solution to be detected can be qualitatively or quantitatively determined according to a linear regression equation of the concentration of catechol and the change of the reduction current;
the linear regression equation of the change of the catechol concentration and the reduction current is as follows:
P=1.9743×10-7+ 0.4584C; wherein, P is the current change value in the detection of catechol and the unit is A; c is the concentration value of catechol in the solution to be detected, and the unit is mol/L; the linear detection range of the catechol is 1.0 multiplied by 10-7~3.6×10-5mol/L, the lower limit of detection is 5 nmol/L.
In the application, the electrolyte used when the three-electrode system detects the solution to be detected is preferably a phosphate buffer solution with the pH value of 4-9.
The invention has the beneficial effects that: the tyrosinase biosensor based on the phosphorus-doped MXene modified electrode is low in cost, simple to manufacture, good in stability and suitable for large-scale production. The phosphorus-doped MXene is used as a carrier of the tyrosinase, so that the conductivity can be improved, the electron transfer speed between the biosensor and a solution to be detected can be improved, the stable response current can be quickly obtained, the enzyme loading capacity is increased, the enzyme activity is maintained, the service life of the tyrosinase biosensor is longer, the tyrosinase activity is higher, the stability and the repeatability of the biosensor and the reliability of a sensor structure are greatly improved, and the detection level of the conventional biosensor is improved.
Drawings
Fig. 1 is a scanning electron micrograph of phosphorus-doped MXene in example 1.
FIG. 2 is a corresponding curve of current signals corresponding to the dropping of catechol with different solubility in the biosensor in example 2.
FIG. 3 is a graph of catechol concentration versus current signal calculated from the graph of FIG. 2 in example 2.
Detailed Description
Embodiment 1 tyrosinase biosensor with phosphorus-doped MXene modified electrode
The tyrosinase biosensor based on the phosphorus-doped MXene modified electrode comprises a glassy carbon electrode, wherein the glassy carbon electrode is a glassy carbon electrode with the surface modified with tyrosinase/phosphorus-doped MXene/chitosan. The preparation method comprises the following specific steps:
(1) preparing phosphorus-doped graphene: taking 1g of Ti3C2Grinding the material and 1g of triphenylphosphine in a mortar for 30min, then placing the ground material in a tube furnace, introducing Ar gas, controlling the flow rate to be 100mL/min, then heating to 800 ℃ for heat treatment for 2h, then cooling the tube furnace to room temperature, taking out a sample, washing the sample with deionized water for several times and drying to obtain phosphorus-doped Ti3C2A material. The phosphorus prepared in this example was doped with Ti3C2The material was characterized, as shown in the scanning electron micrograph of FIG. 1, the phosphorus-doped Ti prepared in this example3C2The material is of a layered structure, the atomic doping content of the phosphorus element is 1.32 percent, and the specific surface area is 49m2/g。
(2) Preparation of tyrosinase biosensor: preparing tyrosinase solution with concentration of 10mg/mL by using phosphoric acid buffer solution with concentration of 10mmol/L, pH of 6.0, and performing ultrasonic treatment for 10 min; preparing a water solution of phosphorus-doped MXene with the concentration of 10mg/mL, and carrying out ultrasonic treatment for 30 min; preparing a chitosan aqueous solution with the concentration of 1-10 mg/mL, and carrying out ultrasonic treatment for 30 min; mixing the three solutions to prepare a mixed solution with the tyrosinase concentration of 2.5mg/mL, the phosphorus-doped MXene concentration of 0.5mg/mL and the chitosan concentration of 1.5 mg/mL; and dripping 10 mu L of the mixed solution of the tyrosinase/phosphorus-doped MXene/chitosan on the surface of a glassy carbon electrode which is polished by aluminium oxide powder with the particle size of 1 mu m, 0.3 mu m and 0.05 mu m in sequence, drying for 4 hours by nitrogen to obtain the tyrosinase biosensor, and standing at the temperature of 4 ℃ for later use.
Example 2 application of tyrosinase biosensor with phosphorus-doped MXene modified electrode
The detection process is as follows: the tyrosinase biosensor based on the phosphorus-doped MXene modified electrode in the embodiment 1 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, a three-electrode system is established, and the three-electrode system is connected with an electrochemical workstation to detect the concentration of catechol in a solution to be detected.
The detection principle of the tyrosinase biosensor is as follows: the tyrosinase catalyzes and oxidizes the catechol into the catechol, the catechol obtains electrons on the electrode and is reduced into the catechol, and the concentration of the catechol in the liquid to be detected is quantitatively indicated by detecting the reduction current.
The main reaction formula of the detection process of the invention is as follows:
C6H6O2(catechol) + tyrosinase (oxidized form) → C6H4O2(o-phenylenediquinone) +2H++2e-→ C6H6O2(catechol) + tyrosinase (reduced form) + O2→ tyrosinase (oxidized form) + H2O
The catechol concentration was measured by chronoamperometry (i-t), and a Phosphate Buffer Solution (PBS) of 50mmol/L, pH =6.0 was added to the measuring cell, and a magnetic stirrer was placed therein to measure the current values of the substrates (catechol concentration) of different concentrations, as shown in fig. 2 and 3, respectively.
As can be seen from FIG. 3, the linear regression equation of the change of catechol concentration and reduction current is:
P=1.9743×10-7+0.4584C （1）；
in the formula (1), P is a current change value in the detection of catechol and is represented by A; c is the concentration value of catechol in the solution to be detected, and the unit is mol/L; the linear detection range of the catechol is 1.0 multiplied by 10-7 ~3.6×10-5mol/L, the lower limit of detection is 5 nmol/L.
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-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. A preparation method of a tyrosinase biosensor with a phosphorus-doped MXene modified electrode is characterized by comprising the following steps:
the tyrosinase biosensor with the phosphorus-doped MXene modified electrode specifically comprises a glassy carbon electrode with a surface modified with tyrosinase/phosphorus-doped MXene/chitosan;
the preparation process of the phosphorus-doped MXene comprises the following steps: mixing MXene material and phosphorus-containing precursor according to the mass ratio of 0.1-1: 1, mixing; grinding, and performing heat treatment in protective gas to obtain a phosphorus-doped MXene material; the content of phosphorus element atoms in the phosphorus-doped MXene is 0.1% -10% of the total atomic number;
the phosphorus-containing precursor is specifically one of triphenylphosphine, phosphoric acid or phosphate;
the MXene material comprises Ti3C2、Ti2C and Ti3CN or a combination of more of CN;
the method comprises the following specific steps:
(1) preparing a tyrosinase solution: preparing a tyrosinase solution with the concentration of 1-10 mg/mL by using a phosphoric acid buffer solution with the concentration of 1-100 mmol/L, pH of 3.5-9.5;
(2) preparing a phosphorus-doped MXene solution: using water as a solvent, preparing an MXene solution with the concentration of 1-10 mg/mL, and carrying out ultrasonic treatment on the MXene solution for more than 0.5 h;
(3) preparing a chitosan solution: preparing a chitosan solution with the concentration of 1-10 mg/mL by using water as a solvent, and carrying out ultrasonic treatment on the chitosan solution for more than 0.5 h;
(4) preparing a mixed solution of tyrosinase/phosphorus-doped MXene/chitosan: mixing the solutions prepared in the step (1), the step (2) and the step (3) in a stirring or ultrasonic mode, wherein the mixing time is more than 10min, the concentration of tyrosinase in the final mixed solution is 1-10 mg/mL, the concentration of phosphorus-doped MXene is 0.1-10 mg/mL, and the concentration of chitosan is 1-10 mg/mL;
(5) preparing a glassy carbon electrode with surface modified tyrosinase/phosphorus doped MXene/chitosan: and (3) dripping 2-20 mu L of the tyrosinase/phosphorus doped MXene/chitosan mixed solution obtained in the step (4) on the surface of the polished glassy carbon electrode, and drying with nitrogen to obtain the tyrosinase biosensor.
2. The preparation method of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode according to claim 1, wherein the phosphorus-doped MXene is prepared by the following steps: mixing MXene material and phosphorus-containing precursor according to the mass ratio of 0.02-1: 1, fully mixing, then grinding for 0.1-2 h, and carrying out heat treatment in an inert gas protector at 300-1000 ℃ for 1-12 h, wherein the flow rate of protective gas is 20-200 mL/min, thus obtaining the phosphorus-doped MXene material.
3. The preparation method of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode according to claim 2, wherein the preparation method comprises the following steps: the preparation of the phosphorus-doped MXene further comprises the step of removing the residual phosphorus-containing precursor; in particular to washing with deionized water or ethanol to remove the residual precursor.
4. The preparation method of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode according to claim 3, wherein the preparation method comprises the following steps: the MXene material is prepared from MAX phase materials through an etching reaction with HF solution, and has a graphene-like two-dimensional layered structure.
5. The tyrosinase biosensor with the phosphorus-doped MXene modified electrode prepared by the method of any one of claims 1-4.
6. The application of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode prepared by the method of claim 1 is characterized in that: applying it to the detection of catechol, i.e. catechol; the method comprises the following specific steps: the method comprises the steps of establishing a three-electrode system by taking the tyrosinase biosensor as a working electrode, taking Ag/AgCl as a reference electrode and a platinum electrode as a counter electrode, connecting the three-electrode system with an electrochemical workstation, placing the detection end of the working electrode in a solution to be detected, detecting the reduction current in the solution to be detected during electrochemical reaction through the electrochemical workstation, and then qualitatively or quantitatively determining catechol in the solution to be detected according to a linear regression equation of the concentration of catechol and the change of the reduction current.
7. The application of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode according to claim 6, wherein the linear regression equation of the catechol concentration and the reduction current change is as follows: p =1.9743 × 10-7+ 0.4584C; wherein, P is the current change value in the detection of catechol and the unit is A; c is the concentration value of catechol in the solution to be detected, and the unit is mol/L;
the linear detection range of the catechol is 1.0 multiplied by 10-7~3.6×10-5mol/L, the lower limit of detection is 5 nmol/L.
8. The application of the tyrosinase biosensor with the phosphorus-doped MXene modified electrode according to claim 6, is characterized in that: the electrolyte used when the three-electrode system detects the solution to be detected is specifically phosphate buffer solution with the pH value of 4-9.
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| CN114838851B (en) * | 2021-01-30 | 2024-04-02 | 苏州北科纳米科技有限公司 | Preparation method of MXene flexible micro-force sensor |
| CN113484385A (en) * | 2021-03-11 | 2021-10-08 | 桂林理工大学 | Biosensor for immobilizing cholesterol oxidase based on MXene material and detection method thereof |
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