CN110806437A - Black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode and application thereof - Google Patents
Black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode and application thereof Download PDFInfo
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- CN110806437A CN110806437A CN201911121946.2A CN201911121946A CN110806437A CN 110806437 A CN110806437 A CN 110806437A CN 201911121946 A CN201911121946 A CN 201911121946A CN 110806437 A CN110806437 A CN 110806437A
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- black phosphorus
- cyclodextrin
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- 229910021397 glassy carbon Inorganic materials 0.000 title claims abstract description 56
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- 125000001493 tyrosinyl group Chemical class [H]OC1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 125000002849 D-tyrosine group Chemical group [H]N([H])[C@@]([H])(C(=O)[*])C([H])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
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- 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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- G—PHYSICS
- 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
- G01N27/416—Systems
- G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
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Abstract
The invention discloses a black phosphorus nanosheet/maltose group- β -cyclodextrin modified glassy carbon electrode and application thereof, and relates to the technical field of electrochemistry, wherein the electrode comprises a glassy carbon electrode and a black phosphorus nanosheet/maltose group- β -cyclodextrin composite coating coated on the glassy carbon electrode, and a black phosphorus nanosheet dispersion liquid and a maltose group- β -cyclodextrin solution are dropwise coated on the surface of the glassy carbon electrode, and the glassy carbon electrode is prepared after drying.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode and application thereof, and especially relates to application of the black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode in detection of an amino acid enantiomer.
Background
Chirality, which is a basic chemical property of the living world, affects life processes, and enantioselective recognition of chiral compounds is very important in the fields of biology, medical science, biotechnology, and the like. Almost all amino acids, except glycine, have chiral features. Amino acids are generally considered important enantiomeric compounds and can be used to evaluate important biomarkers for various metabolic diseases. Since the two chiral enantiomers of an amino acid have almost the same chemical and physical properties, it is difficult to distinguish the L/D type amino acid enantiomers, but the two chiral enantiomers of an amino acid have completely different biological activities, and it is important to distinguish the two enantiomers of an amino acid in medicinal chemistry, and biology for the purpose of screening, diagnosing, and treating metabolic diseases.
Single-layer Black Phosphorus (BP), also known as phospholenes, is a emerging feature in nanoscience and nanotechnology. BP is a novel two-dimensional nanomaterial consisting of a folded lattice configuration, and compared with other two-dimensional materials, BP has excellent biocompatibility, lower toxicity, unique semiconductor characteristics, low defect density, adjustable particle size, rapid hole migration, anisotropic conductivity and ultrahigh specific surface area. Therefore, BP has wide application prospect in the fields of energy storage, photoelectricity, catalysis and biomedicine.
β -Cyclodextrin (β -CD) is a cyclic oligosaccharide consisting of seven glucose units it is well known that β -CD has a frusto-conical amphiphilic structure containing a hydrophobic inner cavity (due to hydrocarbon chains) and a hydrophilic outer cavity (due to primary and secondary hydroxyl groups). The glucose units in CDs contain five chiral carbon atoms per unit, thus β -CD can provide a good chiral microenvironment for chiral identification of chiral enantiomers the macromolecular selectivity and enantioselectivity of β -CD paves the way for its widespread use in chiral separation, organocatalysis, electrochemical sensing and pharmaceuticals.derivatives exhibit better chiral recognition capabilities compared to β -CD because they can provide more active interaction sites for analytes.
The current research shows that the recognition capability of the modified electrode on the amino acid enantiomer can be effectively improved by applying the chiral carbon nanotube, the graphene oxide, the conductive polymer, the carbon quantum dots, the crown ether, the potato starch, the soluble starch, the human serum albumin and the chitosan to the modification of the surface of the glassy carbon electrode. In order to further improve the stability and the recognition capability of the electrode for detecting amino acid enantiomers, the continuous research on the modification of a glassy carbon electrode by a modified material is still urgent.
Disclosure of Invention
Aiming at the technical problems in the related art, the invention provides a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode and application thereof, and the glassy carbon electrode is modified by the black phosphorus nanosheet and the maltose- β -cyclodextrin, so that the electrochemical current response reproducibility of the modified electrode can be effectively improved, and the chiral recognition capability of the modified electrode on an amino acid enantiomer can be effectively improved.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
on one hand, the invention provides a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode, which comprises a glassy carbon electrode and a black phosphorus nanosheet/maltose- β -cyclodextrin composite coating coated on the glassy carbon electrode, and further the thickness of the coating of the black phosphorus nanosheet/maltose- β -cyclodextrin composite coating is 5-30 μm.
In one aspect, the invention provides a preparation method of the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode, which comprises the following steps:
1) dispersing black phosphorus powder in a solvent, and performing ultrasonic treatment and centrifugation to obtain a black phosphorus nanosheet dispersion liquid;
2) dissolving maltosyl- β -cyclodextrin in ultrapure water to obtain a maltosyl- β -cyclodextrin solution;
3) and (3) dripping the dispersion liquid obtained in the step 1) and the solution obtained in the step 2) on the surface of a glassy carbon electrode, and airing to obtain the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified electrode.
Further, the preparation process of the black phosphorus nanosheet is as follows:
A) dispersing black phosphorus powder in an N-methyl pyrrolidone solution, and carrying out ultrasonic treatment in an ice bath to obtain a brown dispersion liquid;
B) centrifuging the brown dispersion liquid, removing residual non-stripped black phosphorus particles, and collecting supernatant for later use;
C) and (3) centrifuging the supernatant before use, washing the supernatant for 2-3 times by using an ultrapure water solution to remove N-methylpyrrolidone, and preparing the ultrapure water into the black phosphorus nanosheet dispersion liquid.
Further, the preparation process of the black phosphorus nanosheet is as follows:
A) dispersing 2.0-5.0 mg of black phosphorus powder in 10-30 mL of N-methylpyrrolidone solution, and carrying out ultrasonic treatment in an ice bath for 6-11 h to obtain brown dispersion liquid;
B) centrifuging at 1000-2000 rpm for 2-5 min, removing residual non-stripped black phosphorus particles, collecting supernatant for later use, and storing in a refrigerator at-20 ℃;
C) before use, 1mL of supernatant is centrifuged at 10000-12000 rpm for 5-10 min, 5-20 mL of ultrapure water is used for washing for 2-3 times to remove N-methyl pyrrolidone, the black phosphorus nanosheet and the ultrapure water are prepared into a black phosphorus nanosheet dispersion liquid according to the volume ratio of 1:1, 1:2, 1:3, 1:4, 1:5 and the like, and the black phosphorus nanosheet is uniformly dispersed through ultrasonic treatment for 5-10 min. The thickness of the black phosphorus nanosheet is 2-100 nm (measured by AFM), and the transverse dimension is 10-50 μm.
Further, the preparation process of the maltosyl- β -cyclodextrin solution comprises the step of dissolving maltosyl- β -cyclodextrin in ultrapure water to obtain a solution with a concentration of 1-5 mg mL-1Preferably, the concentration of the maltosyl- β -cyclodextrin solution is 1mgmL-1、2mg mL-1、3mg mL-1、4mg mL-1、5mg mL-1。
Further, in the step 3), the sequence of dropping the dispersion liquid obtained in the step 1) and the solution obtained in the step 2) on the surface of the glassy carbon electrode is to drop the black phosphorus nanosheet dispersion liquid first and then drop the maltosyl- β -cyclodextrin solution, or to drop the maltosyl- β -cyclodextrin solution first and then drop the black phosphorus nanosheet dispersion liquid.
Further, in the step 3), the volume ratio of the dispersion obtained in the step 1) and the solution obtained in the step 2) (i.e., the black phosphorus nanosheet dispersion/maltosyl- β -cyclodextrin solution) is 4:8, 5:8, 6:8, 7:8, 8:8, 9:8, 10:8, 8:4, 8:5, 8:6, 8:7, 8:9, 8:10, and the like in μ L.
Further, in the step 3), the drying is performed by one or more of air, an infrared lamp and nitrogen flow.
Further, the drying time in the step 3) is 2-60 min. The drying time is 2, 5, 10, 30, 60min and the like.
On the other hand, the invention provides a method for detecting an amino acid enantiomer, which is used for detecting the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode or the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode prepared by the method in an electrolyte solution.
Further, the amino acids are tyrosine, tryptophan, histidine, phenylalanine, and the like.
Further, the electrolyte solution is one or more of inorganic salt and inorganic acid buffer solution.
Compared with the existing glassy carbon electrode, the electrode prepared by the method is based on the synergistic effect between the black phosphorus nanosheet and the maltosyl- β -cyclodextrin, has high selectivity, has good water solubility, can efficiently capture target molecules and efficiently detect by utilizing the multi-active site and cavity structure of the maltosyl- β -cyclodextrin, improves the enrichment degree of an object to be detected around the electrode by utilizing the large surface area, good adsorption catalysis performance and high electron mobility of the black phosphorus nanosheet, accelerates the electron transfer efficiency between the electrode and electrolyte, and can obtain stable current response, accelerate the reaction efficiency, improve the molecular recognition capability and have good biocompatibility when the prepared glassy carbon electrode is used for electrochemically detecting the L/D type enantiomer of the amino acid.
The black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode is obtained by dispersing and attaching the black scale nanosheets to the surface of the glassy carbon electrode by utilizing the original performance of maltosyl- β -cyclodextrin, so that the specific surface area of the electrode is increased, the enrichment of an object to be detected on the surface of the electrode is enhanced, and the cavity structure and the molecular recognition capability of the maltosyl- β -cyclodextrin are also reserved, thereby ensuring good conductive capability and the characteristics of recognized molecules.
The invention has the beneficial effects that the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode utilizes the catalytic activity of the black phosphorus nanosheet and the multi-active site contained in the maltosyl- β -cyclodextrin to realize the identification of the amino acid enantiomer, particularly effectively identify the L/D enantiomer for tyrosine, tryptophan, histidine, phenylalanine and the like, the material can be coated on the surface of the glassy carbon electrode to form a film, and the black phosphorus nanosheet/maltosyl- β -cyclodextrin material adopted has the advantages of good biocompatibility, no toxicity, environmental protection, good stability and the like and is expected to become an electrode modified material widely applied when the prepared glassy carbon electrode electrochemically detects the amino acid L/D enantiomer based on the synergistic effect between the black phosphorus nanosheet/maltosyl- β -cyclodextrin material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a black phosphorus nanosheet modified glassy carbon electrode (G2- β -CD/BP NSs/GCE, FIG. 1A) and a black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode (G2- β -CD/BP NSs/GCE, FIG. 1B);
FIG. 2 is a comparison graph of square wave voltammetry curves for detecting tyrosine enantiomers by various electrodes, wherein a bare electrode (bareGCE, FIG. 2A), a black phosphorus nanosheet modified electrode (BP NSs/GCE, FIG. 2B) and a maltosyl- β -cyclodextrin modified glassy carbon electrode (G2- β -CD/GCE, FIG. 2C), a black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode (G2- β -CD/BP NSs/GCE, FIG. 2D) are shown, a is L-Tyr, B is D-Tyr, and the difference of identification capacities can be seen from the current separation condition of the two curves of a and B;
FIG. 3 is a square wave voltammogram of a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode for detecting tyrosine enantiomers (L-Tyr (a) and D-Tyr (b)) at different concentrations;
FIG. 4 is a linear graph of a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode for detecting tyrosine enantiomers at different concentrations;
FIG. 5(A) is a graph comparing the recognition efficiency of a black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode (G2- β -CD/BP NSs/GCE) for detecting tyrosine enantiomer (Tyr), tryptophan enantiomer (Trp), histidine enantiomer (His) and phenylalanine (Phe), and (B) a chemical structural diagram of Tyr, Trp, His and Phe.
In the figure CTyrTyrosine concentration; potential of potential; current.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1
Mixing 2.0mg of black phosphorus powder and 10mL of N-methylpyrrolidone, carrying out ultrasonic treatment in an ice bath for 6h to obtain brown dispersion liquid, then centrifuging at 1000rpm for 5min to remove residual non-stripped black phosphorus particles, collecting supernatant liquid for later use, wherein the supernatant liquid is the dispersion liquid of the black phosphorus nanosheet dispersed in the N-methylpyrrolidone, and storing in a refrigerator at-20 ℃. Before use, 1mL of supernatant is centrifuged at 10000rpm for 5min, and 5mL of ultrapure water is used for washing for 2 times to remove N-methylpyrrolidone, so as to obtain brown dispersion liquid of the black phosphorus nanosheet.
10mg of maltosyl- β -cyclodextrin was prepared into 2mg mL of ultrapure water-1And standing by.
Respectively transferring 6 mu L and 8 mu L of black phosphorus nanosheet dispersion liquid and maltosyl- β -cyclodextrin solution, dripping and coating on the surface of a glassy carbon electrode in a layered manner, and airing in the air for 60min to obtain the black phosphorus nanosheet.
Example 2
Mixing 4.0mg of black phosphorus powder and 20mL of N-methylpyrrolidone, carrying out ultrasonic treatment in an ice bath for 8 hours to obtain brown dispersion liquid, then centrifuging at 2000rpm for 5 minutes to remove residual non-stripped black phosphorus particles, collecting supernatant liquid for later use, wherein the supernatant liquid is the dispersion liquid of the black phosphorus nanosheet dispersed in the N-methylpyrrolidone, and storing in a refrigerator at-20 ℃. Before use, 1mL of supernatant was centrifuged at 12000rpm for 10min, and washed with 10mL of ultrapure water for 3 times to remove N-methylpyrrolidone, thereby obtaining a brown dispersion of black phosphorus nanosheets.
20mg of maltosyl- β -cyclodextrin was prepared into 5mg mL of ultrapure water-1And standing by.
Respectively transferring 8 mu L and 10 mu L of black phosphorus nanosheet dispersion liquid and maltosyl- β -cyclodextrin solution, dropwise coating the mixture on the surface of a glassy carbon electrode in a layered manner, and airing the mixture for 10min in an infrared lamp to obtain the black phosphorus nanosheet.
Example 3
Mixing 5.0mg of black phosphorus powder and 30mL of N-methylpyrrolidone, carrying out ultrasonic treatment in an ice bath for 11h to obtain brown dispersion liquid, then centrifuging at 2000rpm for 5min to remove residual non-stripped black phosphorus particles, collecting supernatant liquid for later use, wherein the supernatant liquid is the dispersion liquid of the black phosphorus nanosheet dispersed in the N-methylpyrrolidone, and storing in a refrigerator at-20 ℃. Before use, 1mL of supernatant is centrifuged at 10000rpm for 5min, and 10mL of ultrapure water is used for washing for 2 times to remove N-methylpyrrolidone, so as to obtain brown dispersion liquid of the black phosphorus nanosheet.
5mg of maltosyl- β -cyclodextrin was prepared in 1mg mL of ultrapure water-1And standing by.
Respectively transferring 8 mu L and 8 mu L of the black phosphorus nanosheet dispersion solution and the maltosyl- β -cyclodextrin solution, dropwise coating the mixture on the surface of a glassy carbon electrode in a layered manner, and airing the mixture for 5min in an infrared lamp to obtain the black phosphorus nanosheet.
Example 4
Mixing 5.0mg of black phosphorus powder and 20mL of N-methylpyrrolidone, carrying out ultrasonic treatment in an ice bath for 9h to obtain brown dispersion liquid, then centrifuging at 2000rpm for 5min to remove residual non-stripped black phosphorus particles, collecting supernatant liquid for later use, wherein the supernatant liquid is the dispersion liquid of the black phosphorus nanosheet dispersed in the N-methylpyrrolidone, and storing in a refrigerator at-20 ℃. Before use, 1mL of supernatant was centrifuged at 12000rpm for 5min, and washed with 10mL of ultrapure water for 2 times to remove N-methylpyrrolidone, to obtain a brown dispersion of black phosphorus nanosheets.
15mg of maltosyl- β -cyclodextrin was prepared into 3mg mL of ultrapure water-1And standing by.
Respectively transferring and taking 7 mu L and 10 mu L of black phosphorus nanosheet dispersion liquid and maltosyl- β -cyclodextrin solution, dripping and coating the solution on the surface of a glassy carbon electrode in a layered manner, and airing the glassy carbon electrode for 2min in nitrogen flow to obtain the black phosphorus nanosheet.
Example 5 detection
Using the glassy carbon electrode prepared in example 1 as a working electrode, a platinum wire as a counter electrode, and Ag/AgCl as a reference electrode, amino acid enantiomers (tyrosine, tryptophan, histidine, and phenylalanine were selected for detection, respectively) were detected in a phosphate buffer solution (0.1M, pH 7.0). The scanning electron microscope image and the detection result of the modified glassy carbon electrode are as follows:
the morphology of black phosphorus nanosheets (BP NSs) and black phosphorus nanosheets/maltosyl- β -cyclodextrin (G2- β -CD/BP NSs) films on glassy carbon electrodes was studied using a field emission scanning electron microscope (FE-SEM). As can be seen from FIG. 1A, the BP NSs films exhibit a non-uniform and discontinuous lamellar structure, and FIG. 1B shows that G2- β -CD crosslinks with the BP NSs, promoting effective immobilization of the BP NSs and enabling a synergistic effect to be generated between G2- β -CD and the BP NSs.
Analysis of the tyrosine (Tyr) enantiomer Using Square Wave Voltammetry (SWV) it can be observed from FIG. 2A that the SWV peak potentials and peak current responses of the L-Tyr and D-Tyr enantiomers at the bare electrode (bare GCE) almost overlap, indicating that bare GCE has no ability to chirally recognize the Tyr enantiomer due to the absence of a chiral microenvironment, G2- β -CD/GCE (Peak Current response ratio I of L-Tyr to D-Tyr)L/ID1.15; peak potential difference Δ Ep ═ ED-EL12mV, FIG. 2C) with BP NSs/GCE (I)L/ID＝1.10，ΔEp＝ED-EL8mV, fig. 2B), due to the hydrophobic cavity of G2- β -CD and the chiral hydroxyl (-OH) group that can selectively interact with Tyr enantiomer it is clear from fig. 2D that the chiral recognition efficiency of Tyr enantiomer (I) is seenL/ID＝1.51，ΔEp＝ED-EL20mV) reached a maximum at G2- β -CD/BP NSs/GCE, mainly due to the chiral cavity structure of G2- β -CD and the excellent conductivity of the-OH group, BP NSs, and the synergy between G2- β -CD and BPNSs, such that the prepared G2- β -CD/BP NSs/GCE shows higher chiral selectivity for Tyr.
As can be seen from FIGS. 3 and 4, the tyrosine (Tyr) enantiomer concentration and the peak current value show good linear relationship in the concentration range of 0.01-1mM, and L-Tyr and D-Tyr on the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified electrode (G2- β -CD/BP NSs/GCE) respectively have good determination coefficients (R is 2- β -CD/BP NSs/GCE)2 L-Tyr0.99147 and R2 D-Trp＝0.99583)。
As can be seen from FIG. 5, the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified electrode (G2- β -CD/BP NSs/GCE) has a weak recognition effect on tryptophan, histidine and phenylalanine enantiomers due to host-guest size matching principles and different aromatic groups, G2- β -CD/BP NSs/GCE shows good stereospecificity for the four amino acid enantiomers (including Tyr, Trp, His and Phe). A single aromatic ring of Tyr and Phe readily penetrates into the cavity of G2- β -CD, while G2- β -CD/BP NSs/GCE has a higher recognition efficiency for Tyr than Phe, which may be due to the Phe not containing a phenolic hydroxyl group.
The method for detecting the amino acid enantiomer by using the black phosphorus nanosheet/maltose- β -cyclodextrin modified electrode prepared by the invention is convenient, efficient, time-saving and low in cost, and can be used for simply, conveniently, rapidly, qualitatively and quantitatively analyzing the amino acid enantiomer.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode is characterized by comprising a glassy carbon electrode and a black phosphorus nanosheet/maltose- β -cyclodextrin composite coating coated on the glassy carbon electrode.
2. The preparation method of the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode according to claim 1, comprising the steps of:
1) dispersing black phosphorus powder in a solvent, and performing ultrasonic treatment and centrifugation to obtain a black phosphorus nanosheet dispersion liquid;
2) dissolving maltosyl- β -cyclodextrin in ultrapure water to obtain a maltosyl- β -cyclodextrin solution;
3) and (3) dripping the dispersion liquid obtained in the step 1) and the solution obtained in the step 2) on the surface of a glassy carbon electrode, and airing to obtain the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified electrode.
3. The method for preparing the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode according to claim 2, wherein the preparation process of the black phosphorus nanosheet is as follows:
A) dispersing black phosphorus powder in an N-methyl pyrrolidone solution, and carrying out ultrasonic treatment in an ice bath to obtain a brown dispersion liquid;
B) centrifuging the brown dispersion liquid, removing residual non-stripped black phosphorus particles, and collecting supernatant for later use;
C) and (3) centrifuging the supernatant before use, washing the supernatant for 2-3 times by using an ultrapure water solution to remove N-methylpyrrolidone, and preparing the ultrapure water into the black phosphorus nanosheet dispersion liquid.
4. The method for preparing the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode according to claim 2, wherein the maltosyl- β -cyclodextrin solution is prepared by dissolving maltosyl- β -cyclodextrin in ultrapure water to obtain a concentration of 1-5 mg mL-1The maltosyl- β -cyclodextrin solution.
5. The method for preparing a black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode according to claim 2, wherein in the step 3), the sequence of dropping the dispersion liquid obtained in the step 1) and the solution obtained in the step 2) on the surface of the glassy carbon electrode is that the black phosphorus nanosheet dispersion liquid is firstly dropped and then the maltosyl- β -cyclodextrin solution is dropped, or the maltosyl- β -cyclodextrin solution is firstly dropped and then the black phosphorus nanosheet dispersion liquid is dropped.
6. The method for preparing the black phosphorus nanosheet/maltosyl- β -cyclodextrin modified glassy carbon electrode according to claim 2, wherein in the step 3), the dispersion obtained in the step 1) and the solution obtained in the step 2) are applied in a volume-to-use ratio of 4:8, 5:8, 6:8, 7:8, 8:8, 9:8, 10:8, 8:4, 8:5, 8:6, 8:7, 8:9 or 8: 10.
7. The preparation method of the black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode according to claim 2, wherein in the step 3), air drying is performed in one or more modes of air, an infrared lamp and nitrogen flow, and the air drying time in the step 3) is 2-60 min.
8. A method for detecting amino acid enantiomers, which is characterized in that a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode of claim 1 or a black phosphorus nanosheet/maltose- β -cyclodextrin modified glassy carbon electrode prepared by the method of any one of claims 2 to 7 is used for detection in an electrolyte solution.
9. The method of claim 8, wherein the amino acid is tyrosine, tryptophan, histidine, or phenylalanine.
10. The method according to claim 8, wherein the electrolyte solution is one or more of an inorganic salt and an inorganic acid buffer solution.
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