CN110108775B - Electrochemical sensor for detecting chiral tyrosine molecules and preparation method thereof - Google Patents
Electrochemical sensor for detecting chiral tyrosine molecules and preparation method thereof Download PDFInfo
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Abstract
An electrochemical sensor for detecting chiral tyrosine molecules and a preparation method thereof. The sensor is a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor, wherein the sulfocyclodextrin-macroporous carbon hybrid is formed by embedding sulfocyclodextrin into pores of macroporous carbon by utilizing the physical adsorption effect of the macroporous carbon; the modified electrode is prepared by dripping cyclodextrin-macroporous carbon hybrid dispersion liquid on a glassy carbon electrode and drying. The electrochemical sensor provided by the invention fully utilizes the excellent conductivity of the macroporous carbon and the characteristic that cyclodextrin selectively identifies the chiral tyrosine molecules, so that the chiral detection of the chiral tyrosine molecules is realized, and the detection process is convenient, rapid, sensitive and accurate; the electrochemical sensor has the advantages of simple preparation process, easy implementation and low material cost, and has important application prospect in the field of chiral tyrosine molecule detection.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of supermolecular functional materials and electrochemical sensing, in particular to a preparation method of a cyclodextrin-macroporous carbon hybrid electrochemical sensor for chiral tyrosine molecule detection.
[ background of the invention ]
Amino acids are the most important chiral compounds in nature, and D-and L-amino acids often coexist in mammalian and human tissues and play important roles in protein synthesis and the nervous system. Among them, tyrosine (Tyr) is an important precursor of various biological signaling molecules, such as epinephrine, norepinephrine, and dopamine. As a chiral amino acid, the abnormality of the content of tyrosine molecules in human bodies can cause diseases such as diarrhea, depression, cardiovascular and cerebrovascular diseases and the like. Therefore, the establishment of a convenient, rapid, sensitive and accurate detection method for the chiral tyrosine molecules is of great significance. Electrochemical sensing analysis methods are receiving more and more attention due to the advantages of being fast, efficient, accurate, sensitive, simple in equipment, low in price and the like. In particular, the application of a novel functional material with excellent physicochemical properties to the construction of an electrochemical sensor to improve the detection performance of the sensor has attracted much research interest and attention from researchers. The macroporous carbon is a novel carbon material, has the advantages of excellent electronic conductivity, high specific surface area, adjustable physical and chemical properties, low price, easy obtainment and the like, and is widely used as an electrode material for preparing novel electrochemical sensing electrodes. However, the macroporous carbon electrochemical sensor has the problems of poor detection selectivity on a substrate and the like, so that the application of the sensor in the field of chiral amino acid sensing is limited. Cyclodextrins are macrocyclic compounds in which D-glucopyranose units are joined end to end by alpha-1, 4 glycosidic linkages to form a ring. Cyclodextrins, because of their specific structural features, are capable of selectively encapsulating small organic molecules (e.g., tyramine-based molecules) of matched structural size. In addition, the cyclodextrin has the characteristics of low price, safety, no toxicity, biocompatibility and the like, so that the cyclodextrin is widely applied to the construction of functional supramolecular materials. Therefore, the cyclodextrin/macroporous carbon hybrid electrode material can integrate respective advantages of macroporous carbon and cyclodextrin, so that selective bonding sites are added to the hybrid electrode material, and rapid and sensitive detection of the chiral tyrosine molecule is realized.
[ summary of the invention ]
The invention aims to provide an electrochemical sensor for detecting chiral tyrosine molecules, namely a sulfocyclodextrin-macroporous carbon hybrid and a preparation method thereof aiming at the technical analysis and combining the supramolecular selective bonding performance of cyclodextrin and the electrochemical performance of macroporous carbon, and the sulfocyclodextrin-macroporous carbon hybrid is applied to the construction of the electrochemical sensor so as to realize quick, sensitive and selective detection. Moreover, the preparation method is simple and is suitable for amplification synthesis and practical production application.
The technical scheme of the invention is as follows:
an electrochemical sensor for detecting chiral tyrosine molecules is a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor, and is constructed by taking a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode prepared by dripping cyclodextrin-macroporous carbon hybrid dispersion liquid on a glassy carbon electrode and drying as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a platinum wire electrode as a counter electrode and taking a phosphate buffer solution with the pH value of 7.0 and the concentration of 0.1mol/L as an electrolyte; the sulfocyclodextrin-macroporous carbon hybrid is prepared by simply and physically mixing sulfocyclodextrin and macroporous carbon, enabling the sulfocyclodextrin to enter a cavity of the macroporous carbon by utilizing the adsorption effect of the macroporous carbon, and combining the macroporous carbon cavity with sulfonated cyclodextrin by utilizing the non-covalent interaction.
The preparation method of the electrochemical sensor for detecting the chiral tyrosine molecules comprises the following steps:
step (1) Synthesis of macroporous carbon
Adopting a hard template method, taking silicon dioxide spheres as a template, taking cane sugar as a carbon source, and performing crosslinking carbonization synthesis, and further obtaining macroporous carbon which has a cavity diameter of 220-260nm and is regularly arranged after etching the silicon dioxide template by hydrofluoric acid; the method comprises the following specific steps:
1) preparing a silicon ball template, mixing and stirring absolute ethyl alcohol and 25% ammonia water for 10-20 minutes, adding tetraethoxysilane into the mixture, stirring the mixture at room temperature for 12-24 hours to obtain white emulsion, respectively centrifugally washing the white emulsion by using distilled water and the absolute ethyl alcohol for three times, and adjusting the pH value to be neutral. It was then dried in vacuo at 60 ℃ for 12 h. Then, the white powder is put into a tube furnace to be calcined for 5-12h at 500-600 ℃.
2) Dissolving sucrose in sulfuric acid (98%) solution to form sucrose solution, and mixing SiO2Adding the silicon ball template into the sucrose solution, and standing for 3-6h under the vacuum room temperature condition. Heating at 100 deg.C for 6-12h, and further heating at 160 deg.C for 3-6 h. And then the reaction system is put into a tubular furnace to be heated for 3 to 6 hours under the nitrogen environment at the temperature of 900 ℃, and carbonization is completed. Then the carbonized powder is treated by hydrofluoric acid to remove SiO2And finally, washing, centrifuging and drying the silicon ball template to obtain the macroporous carbon.
Step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
Mixing and dispersing the prepared macroporous carbon and the sulfocyclodextrin into water, and stirring for 1-4 hours at room temperature; after the reaction is finished, a water system microporous filter membrane with the diameter of 0.22 mu m is adopted for suction filtration, and the water system microporous filter membrane is washed by distilled water and then dried to obtain a target product, namely sulfocyclodextrin-macroporous carbon hybrid black powder (SCD-MPC);
step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
1) Polishing the glassy carbon electrode on chamois leather by polishing slurry according to the shape of 8 to a mirror surface, then sequentially carrying out ultrasonic cleaning in water and ultrasonic cleaning in an acetone aqueous solution, and naturally drying to obtain the glassy carbon electrode (GC) subjected to surface treatment;
2) adding the sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) powder obtained in the step (2) into a solution containing 0.5% of Nafion, and performing ultrasonic dispersion to obtain a dispersion liquid;
3) dripping the dispersion liquid obtained in the step (3) in the step 2) on the surface of the glassy carbon electrode after surface treatment, and drying in a vacuum drying oven at 40-50 ℃ to obtain a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode (SCD-MPC/GC);
4) and (3) putting the sulfoacid cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode prepared in the step (3) as a working electrode into a phosphoric acid buffer solution, taking an Ag/AgCl electrode as a reference electrode, taking a platinum wire electrode as a counter electrode, and performing cyclic voltammetry scanning to activate the prepared sulfoacid cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode to finally construct an electrochemical sensor for detecting chiral tyrosine molecules.
The volume usage ratio of the absolute ethyl alcohol, the ammonia water and the ethyl orthosilicate in the step (1) is as follows: 250mL, 25mL and 20 mL.
The mass volume usage ratio of the sucrose, the concentrated sulfuric acid (98%) and the distilled water in the step (1) is as follows: 2 g: 0.15 mL: 9.85 mL.
The mass dosage ratio of the macroporous carbon (MPC) and the Sulfocyclodextrin (SCD) in the step (2) is 6mg:1-5 mg.
And (3) the mass volume dosage ratio of the sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) to the 0.5% Nafion solution is 1.75-2.75mg:1 mL.
The dosage of the sulfocyclodextrin-macroporous carbon hybrid dispersion liquid dripped on the surface of the glassy carbon electrode in the step (3) is 4-6 mu L; the pH of the phosphoric acid buffer solution used for the activation electrode was 7.0.
The application of the electrochemical sensor for detecting the chiral tyrosine molecules is used for sensing and detecting the chiral tyrosine molecules, and the electrochemical sensing detection method comprises the following steps:
1.1, preparing a tyrosine sample comprising D-tyrosine and L-tyrosine into standard solutions with different concentrations by adopting a phosphate buffer solution, wherein the concentrations of the D-tyrosine and the L-tyrosine are respectively 0, 10.0, 20.0, 40.0, 60.0, 70.0, 80.0, 100.0, 110.0 and 120.0 mu mol/L; taking the prepared sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode as a working electrode, taking an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode, and placing the electrode in a prepared standard sample solution for differential pulse voltammetry scanning to obtain the peak current of a sample signal;
step 1.2, drawing a standard curve according to the concentration of the standard sample and the peak current of the detection signal;
and step 2, detecting the sample to be detected by adopting the method in the step 1.1 to obtain the peak current of the sample to be detected, and calculating the concentration content of the tyrosine compound molecules in the sample to be detected according to the standard curve drawn in the step 1.2.
The concentration range of the tyrosine sample standard solution is 0-120 mu mol/L of D-tyrosine and 0-120 mu mol/L of L-tyrosine, the pH value of the phosphoric acid buffer solution is 7.0, and the concentration of phosphate in the tyrosine sample standard solution is 0.1 mol/L; the differential pulse volt-ampere scanning parameters are pulse height of 50mV, pulse width of 100ms and scanning speed of 20 mV/s.
The invention has the advantages that: the cyclodextrin-macroporous carbon hybrid electrochemical sensor fully utilizes the excellent electronic conductivity of macroporous carbon and the supermolecule recognition characteristic of cyclodextrin to generate a sensitive electrochemical response signal for chiral tyrosine molecules, so that the electrochemical sensing detection of the chiral tyrosine molecules is realized, and the detection process is convenient, rapid, sensitive and accurate; the cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor has the advantages of simple preparation process, easy implementation and low material cost, and has important application prospect in the field of chiral tyrosine molecule sensitive detection.
[ description of the drawings ]
FIG. 1 is a schematic diagram of synthesis of a sulfocyclodextrin-macroporous carbon hybrid and preparation of a sensing electrode.
FIG. 2 is an infrared spectrum data of MPC, SCD and MPC-SCD.
FIG. 3 is thermogravimetric data of MPC, SCD and MPC-SCD.
FIG. 4 is a transmission electron microscope and scanning electron microscope image of MPC and MPC-SCD, where a is the MPC transmission electron microscope image, b is the MPC scanning electron microscope image, c is the energy spectrum area scan image under the MPC scanning electron microscope, d is the MPC-SCD transmission electron microscope image, e is the MPC-SCD scanning electron microscope image, and f is the energy spectrum area scan image under the MPC-SCD scanning electron microscope.
FIG. 5 is an electrochemical impedance spectrum of a bare electrode GC and MPC, SCD and MPC-SCD modified electrodes.
FIG. 6 is a cyclic voltammogram spectrum of a bare electrode GC and MPC, SCD and MPC-SCD modified electrodes.
FIG. 7 is a standard curve diagram for plotting D-tyrosine and L-tyrosine standard sample concentrations and detection signal peak current magnitudes of electrochemical sensors constructed by using a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode as a working electrode. Wherein, a is a differential pulse voltammogram of the electrochemical sensor in different concentrations of D-tyrosine, b is a standard curve chart of the D-tyrosine, c is a differential pulse voltammogram of the electrochemical sensor in different concentrations of L-tyrosine, and D is a standard curve chart of the L-tyrosine.
FIG. 8 is a standard curve diagram of the concentration of standard samples of D-tyrosine and L-tyrosine and the magnitude of peak current of detection signals of an electrochemical sensor constructed by using a macroporous carbon modified glassy carbon electrode as a working electrode. Wherein, a is a differential pulse voltammogram of the electrochemical sensor in different concentrations of D-tyrosine, b is a standard curve chart of the D-tyrosine, c is a differential pulse voltammogram of the electrochemical sensor in different concentrations of L-tyrosine, and D is a standard curve chart of the L-tyrosine.
[ detailed description ] embodiments
The present invention is further illustrated by the following examples.
Example 1:
firstly, the structure of an electrochemical sensor for detecting chiral tyrosine molecules,
the electrochemical sensor is formed by dripping and coating sulfocyclodextrin-macroporous carbon hybrid dispersion liquid on a glassy carbon electrode and drying the glassy carbon electrode to obtain a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode, taking the glassy carbon electrode as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a platinum wire electrode as a counter electrode and taking phosphoric acid buffer solution with the concentration of 0.1mol/L and the pH value of 7.0 as electrolyte; the sulfocyclodextrin-macroporous carbon hybrid is prepared by simply and physically mixing sulfocyclodextrin and macroporous carbon and enabling the cyclodextrin to enter a cavity of the macroporous carbon by utilizing the adsorption effect of the macroporous carbon.
Secondly, a preparation method of the electrochemical sensor for detecting the chiral tyrosine molecules comprises the following steps:
step (1) Synthesis of macroporous carbon
1) Preparing a silicon ball template, mixing 250mL of absolute ethyl alcohol and 25mL of 25% ammonia water, stirring for 20 minutes, adding 20mL of tetraethoxysilane, stirring for 12 hours at room temperature to obtain white emulsion, centrifuging and washing for three times by using distilled water and absolute ethyl alcohol respectively, and adjusting the pH value to be neutral. It was then dried in vacuo at 60 ℃ for 12 h. Subsequently, the white powder was calcined in a tube furnace at 550 ℃ for 5 hours.
2) 2.0g of sucrose and 0.15mL of 98% sulfuric acid were dissolved in 9.85mL of distilled water to prepare a sucrose solution (total volume: 10mL), and 2.0g of a silica sphere template was added to the sucrose solution and allowed to stand at room temperature under vacuum for 3 hours. It was then heated at 100 ℃ for 6h, followed by a further heating at 160 ℃ for 3 h. And then the reaction system is put into a tubular furnace to be heated for 3 hours at 900 ℃ in a nitrogen environment, and carbonization is completed. Then the carbonized powder is treated by hydrofluoric acid to remove SiO2Hard stencil, final washingWashing, centrifuging and drying to obtain the macroporous carbon.
Detection shows that the infrared spectra of the prepared macroporous carbon (MPC) and sulfocyclodextrin macroporous carbon hybrid black powder (MPC-SCD) are characterized as follows: in FTIR, the MPC has no IR functionality and therefore no distinct characteristic peak in the IR range. SCD showed a typical characteristic absorption peak of 3422cm–1,νO-H；2926cm–1,
1162cm–1,νC-O-CAnd deltaO-H；1190cm–1，νas,S＝O；1410cm–1，νs,S＝O；620cm–1And 530cm–1，νS-O(ii) a The sulfocyclodextrin-macroporous carbon hybrid MPC-SCD shows most of characteristic peaks ascribed to the sulfocyclodextrin, and in addition, the sulfocyclodextrin is in 3422cm–1，1162cm–1And 1036cm–1The peak value of (A) is shifted to 3433cm–1，1217cm–1And 1155cm–1To (3).
FIG. 1 is a schematic diagram of synthesis of a sulfocyclodextrin-macroporous carbon hybrid and preparation of a sensing electrode. FIG. 2 is an infrared spectrum data of MPC, SCD and MPC-SCD.
Step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
Dispersing 6mg of the prepared macroporous carbon (MPC) powder and 1mg of Sulfocyclodextrin (SCD) into 2mL of water, and stirring at room temperature for 4 hours; after the reaction is finished, a water system microporous filter membrane with the diameter of 0.22 mu m is adopted for suction filtration, and a sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) is obtained after drying;
FIG. 3 is thermogravimetric spectrogram data of MPC, SCD and MPC-SCD, FIG. 4 is transmission electron microscope and scanning electron microscope images of MPC and MPC-SCD, in FIG. 4, a is MPC projection electron microscope image, b is MPC scanning electron microscope image, c is energy spectrum image under MPC scanning electron microscope, d is MPC-SCD transmission electron microscope image, e is MPC-SCD scanning electron microscope image, and f is energy spectrum image under MPC-SCD scanning electron microscope.
Step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
1) Firstly, polishing a glassy carbon electrode on a chamois leather by adopting 50nm polishing slurry according to a shape like a Chinese character '8' to a mirror surface, then sequentially carrying out ultrasonic cleaning in water and ultrasonic cleaning in an acetone aqueous solution, and naturally drying to obtain the glassy carbon electrode (GC) after surface treatment;
2) dispersing 2mg of sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) powder obtained in the step (2) into 1 mL0.5% Nafion solution, and carrying out ultrasonic treatment to obtain sulfocyclodextrin-macroporous carbon dispersion liquid;
3) dripping 5 mu L of the dispersion liquid on the surface of the glassy carbon electrode after surface treatment, and drying in a vacuum drying oven at 45 ℃ to obtain a sulfocyclodextrin-macroporous carbon modified glassy carbon electrode (SCD-MPC/GC);
4) and (2) putting the prepared sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode into 0.1mol/L phosphoric acid buffer solution with the pH value of 7.0, taking an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode, and performing cyclic voltammetry scanning to activate the prepared electrode to finally construct the electrochemical sensor for detecting chiral tyrosine molecules.
And (3) detection and display: the prepared sulfocyclodextrin-macroporous carbon hybrid modified electrode obviously enhances the electrochemical sensing sensitivity.
FIG. 5 is an electrochemical impedance spectrum of GC and MPC, SCD and MPC-SCD modified electrodes, and FIG. 6 is a cyclic voltammetry spectrum of GC and MPC, SCD and MPC-SCD modified electrodes.
Thirdly, the electrochemical sensor prepared by the invention is applied to the detection of chiral tyrosine molecules, and the specific sensing detection method comprises the following steps:
chiral tyrosine molecule samples are prepared into standard solutions with different concentrations by using 0.1mol/LpH7.0 phosphate buffer solution, wherein the tyrosine comprises D-tyrosine, L-tyrosine, and the concentrations of D-tyrosine are respectively 0, 10.0, 20.0, 40.0, 60.0, 70.0, 80.0, 100.0, 110.0 and 120.0 mu mol/L.
Taking the prepared sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode as a working electrode, taking an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode, and placing the electrode in the prepared standard sample solution for differential pulse voltammetry scanning, wherein the parameters are pulse height of 50mV, pulse width of 100ms and sweep rate of 20mV/s, so as to obtain the peak current of a sample signal;
drawing a standard curve according to the concentration of the standard sample and the peak current of the detection signal, as shown in FIG. 7;
the detection sensitivity of the electrochemical sensor constructed by using the sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode as the working electrode to the substrate sample is 27.56 muA/mM of D-tyrosine and 21.37 muA/mM of L-tyrosine respectively, as shown in FIG. 7. The detection sensitivity of the electrochemical sensor constructed by using the macroporous carbon modified glassy carbon electrode as a working electrode to a substrate sample is 11.05 muA/mM of D-tyrosine and 9.6 muA/mM of L-tyrosine respectively, as shown in figure 8. By comparison, the electrochemical sensor provided by the embodiment has higher sensitivity and better chiral recognition capability.
Example 2:
firstly, the specific structure of the electrochemical sensor for detecting tyramine chiral molecules is the same as that of the embodiment 1.
Secondly, a preparation method of the electrochemical sensor for detecting the chiral tyrosine molecules comprises the following steps:
step (1) Synthesis of macroporous carbon
The synthesis of macroporous carbon was performed by the hard template method, which was the same as in example 1.
Step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
The amount of Sulfocyclodextrin (SCD) was changed to 2mg, as in example 1;
step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
The amount of sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) powder was changed to 2.5mg, as in example 1.
And (3) detection and display: the prepared sulfocyclodextrin-macroporous carbon hybrid modified electrode obviously enhances the electrochemical sensing sensitivity.
And thirdly, the application of the electrochemical sensor prepared by the invention in detecting chiral tyrosine molecules, and the specific sensing detection method is the same as that in the embodiment 1.
The detection sensitivity of the electrochemical sensor provided by the embodiment to the substrate sample is 34.83 mu A/mM of D-tyrosine and 29.94 mu A/mM of L-tyrosine respectively.
Example 3:
firstly, the specific structure of the electrochemical sensor for detecting tyramine chiral molecules is the same as that of the embodiment 1.
Secondly, a preparation method of the electrochemical sensor for detecting the chiral tyrosine molecules comprises the following steps:
step (1) Synthesis of macroporous carbon
The synthesis of macroporous carbon was performed by the hard template method, which was the same as in example 1.
Step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
The dosage of Sulfocyclodextrin (SCD) is changed to 3mg, the reaction time is changed to 3h, and the rest is the same as the example 1;
step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
The specific procedure was the same as in example 1.
And (3) detection and display: the prepared sulfocyclodextrin-macroporous carbon hybrid modified electrode obviously enhances the electrochemical sensing sensitivity.
And thirdly, the application of the electrochemical sensor prepared by the invention in detecting chiral tyrosine molecules, and the specific sensing detection method is the same as that in the embodiment 1.
The detection sensitivity of the electrochemical sensor provided by the embodiment to the substrate sample is respectively 38.71 muA/mM of D-tyrosine and 34.72 muA/mM of L-tyrosine.
Example 4:
firstly, the specific structure of the electrochemical sensor for detecting tyramine chiral molecules is the same as that of the embodiment 1.
Secondly, a preparation method of the electrochemical sensor for detecting the chiral tyrosine molecules comprises the following steps:
step (1) Synthesis of macroporous carbon
The synthesis of macroporous carbon was performed by the hard template method, which was the same as in example 1.
Step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
The dosage of Sulfocyclodextrin (SCD) is changed to 4mg, the reaction time is changed to 2h, and the rest is the same as the example 1;
step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
The amount of sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) powder was changed to 2.75mg, as in example 1.
And (3) detection and display: the prepared sulfocyclodextrin-macroporous carbon hybrid modified electrode obviously enhances the electrochemical sensing sensitivity.
And thirdly, the application of the electrochemical sensor prepared by the invention in detecting chiral tyrosine molecules, and the specific sensing detection method is the same as that in the embodiment 1.
The detection sensitivity of the electrochemical sensor provided by the embodiment to the substrate sample is 33.68 muA/mM of D-tyrosine and 27.85 muA/mM of L-tyrosine respectively.
Example 5:
firstly, the specific structure of the electrochemical sensor for detecting tyramine chiral molecules is the same as that of the embodiment 1.
Secondly, a preparation method of the electrochemical sensor for detecting the chiral tyrosine molecules comprises the following steps:
step (1) Synthesis of macroporous carbon
The synthesis of macroporous carbon was performed by the hard template method, which was the same as in example 1.
Step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
The dosage of Sulfocyclodextrin (SCD) is changed to 5mg, the reaction time is changed to 1h, and the rest is the same as the example 1;
step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
The specific procedure was the same as in example 1.
And (3) detection and display: the prepared sulfocyclodextrin-macroporous carbon hybrid modified electrode obviously enhances the electrochemical sensing sensitivity.
And thirdly, the application of the electrochemical sensor prepared by the invention in detecting chiral tyrosine molecules, and the specific sensing detection method is the same as that in the embodiment 1.
The detection sensitivity of the electrochemical sensor provided by the embodiment to the substrate sample is 24.84 muA/mM of D-tyrosine and 22.34 muA/mM of L-tyrosine respectively.
Claims (9)
1. An electrochemical sensor for detecting a chiral tyrosine molecule, comprising: the electrochemical sensor is constructed by using a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode prepared by dripping and coating sulfocyclodextrin-macroporous carbon hybrid dispersion liquid on the glassy carbon electrode and then drying the glassy carbon electrode as a working electrode, using an Ag/AgCl electrode as a reference electrode, using a platinum wire electrode as a counter electrode and using a phosphoric acid buffer solution with the pH value of 7.0 and the concentration of 0.1mol/L as an electrolyte; the sulfocyclodextrin-macroporous carbon hybrid is prepared by physically mixing sulfocyclodextrin and macroporous carbon, allowing the sulfocyclodextrin to enter a cavity of the macroporous carbon under the adsorption action of the macroporous carbon, and combining the macroporous carbon cavity with sulfonated cyclodextrin under the non-covalent interaction.
2. The method of claim 1 for preparing an electrochemical sensor for detecting chiral tyrosine molecules, comprising the steps of:
step (1) Synthesis of macroporous carbon
Synthesizing macroporous carbon by adopting a hard template method, hydrolyzing ethyl orthosilicate by using a mixed solvent of absolute ethyl alcohol and 25% ammonia water to obtain silicon dioxide spheres as a template, and performing crosslinking carbonization synthesis by using cane sugar as a carbon source, so as to obtain the regularly arranged macroporous carbon with the cavity diameter of 220-260nm after etching the silicon dioxide template by using hydrofluoric acid;
step (2) Synthesis of sulfocyclodextrin-macroporous carbon hybrid
Dispersing the prepared macroporous carbon (MPC) and the sulfocyclodextrin into water, and stirring for 1-4h at room temperature; after the reaction is finished, a water system microporous filter membrane with the diameter of 0.22 mu m is adopted for suction filtration, and the mixture is washed by distilled water and then dried to obtain sulfocyclodextrin-macroporous carbon hybrid black powder (SCD-MPC);
step (3) preparation of sulfonic cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode electrochemical sensor
1) Polishing the glassy carbon electrode on the chamois leather by adopting polishing slurry to a mirror surface, then sequentially carrying out ultrasonic cleaning in water and ultrasonic cleaning in an acetone aqueous solution, and naturally drying to obtain a glassy carbon electrode (GC) with a treated surface;
2) dispersing the sulfocyclodextrin-macroporous carbon hybrid (SCD-MPC) powder obtained in the step (2) into a solution containing 0.5% of Nafion, and carrying out ultrasonic treatment to obtain sulfocyclodextrin-macroporous carbon hybrid dispersion liquid;
3) dripping the dispersion liquid obtained in the step (3) in the step 2) on the surface of the glassy carbon electrode after surface treatment, and drying in a vacuum drying oven at 40-50 ℃ to obtain a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode (SCD-MPC/GC);
4) and (3) putting the sulfoacid cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode prepared in the step (3) as a working electrode into a phosphoric acid buffer solution, taking an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode, and performing cyclic voltammetry scanning to activate the prepared sulfoacid cyclodextrin-macroporous carbon hybrid modified glassy carbon electrode to finally construct an electrochemical sensor for detecting chiral tyrosine molecules.
3. The method for preparing the electrochemical sensor for detecting the chiral tyrosine molecule according to claim 2, wherein the electrochemical sensor comprises: the volume usage ratio of the absolute ethyl alcohol, the ammonia water and the ethyl orthosilicate in the step (1) is as follows: 250mL, 25mL and 20 mL;
the mass dosage ratio of the macroporous carbon (MPC) and the Sulfocyclodextrin (SCD) in the step (2) is 6mg:1-5 mg.
4. The method for preparing the electrochemical sensor for detecting the chiral tyrosine molecule according to claim 2, wherein the electrochemical sensor comprises: the dosage ratio of the sulfocyclodextrin-macroporous carbon hybrid (MPC-SCD) to the 0.5% Nafion in the step (3) is 1.75-2.75mg:1 mL.
5. The method for preparing the electrochemical sensor for detecting the chiral tyrosine molecule according to claim 2, wherein the electrochemical sensor comprises: the dosage of the sulfocyclodextrin-macroporous carbon hybrid dispersion liquid dripped on the surface of the glassy carbon electrode in the step (3) is 4-6 mu L; the pH of the phosphoric acid buffer solution used for the activation electrode was 7.0.
6. The use of the electrochemical sensor for detecting chiral tyrosine molecules of claim 1, which is used for detecting chiral tyrosine molecules, wherein the electrochemical sensing detection method comprises the following steps:
step 1, drawing a standard curve of the concentration of a tyrosine sample and the detection peak current
Step 1.1, dissolving a tyrosine sample by using a phosphoric acid buffer solution to prepare standard solutions with different concentrations; the electrochemical sensor for detecting the chiral tyrosine molecules is prepared according to the method of claim 2, namely a sulfocyclodextrin-macroporous carbon hybrid modified glassy carbon electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and the glassy carbon electrode is placed in a prepared standard sample solution to carry out differential pulse voltammetry scanning to obtain the peak current of a sample signal;
step 1.2, drawing a standard curve according to the concentration of the standard sample and the peak current of the detection signal;
and step 2, detecting the sample to be detected by adopting the method in the step 1.1 to obtain the peak current of the sample to be detected, and calculating the concentration content of the tyrosine compound molecules in the sample to be detected through the standard curve drawn in the step 1.2.
7. The use of an electrochemical sensor according to claim 6, wherein the tyrosine sample comprises D-tyrosine and L-tyrosine; the concentration range of the standard solution of the tyrosine sample is 0-120 mu mol/L of D-tyrosine and 0-120 mu mol/L of L-tyrosine.
8. The use of the electrochemical sensor for detecting chiral tyrosine molecules as claimed in claim 6, wherein: the pH of the phosphate buffer solution in the step 1 is 7.0, and the concentration of phosphate in the tyrosine sample standard solution is 0.1 mol/L.
9. The use of the electrochemical sensor for detecting chiral tyrosine molecules as claimed in claim 6, wherein: in the step 1, the differential pulse voltammetry scanning parameters are that the pulse height is 50mV, the pulse width is 100ms, and the scanning speed is 20 mV/s.
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