CN111474222A - Renewable electrochemical sensor for simultaneously detecting epinephrine and uric acid and preparation method and application thereof - Google Patents
Renewable electrochemical sensor for simultaneously detecting epinephrine and uric acid and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a reproducible electrochemical sensor for simultaneously detecting epinephrine and uric acid, and belongs to the technical field of electrochemical analysis and detection. The application relates to a reproducible electrochemical sensor, which is a glassy carbon electrode coated with a porphyrin-based conjugated polymer P-TP-reduced graphene oxide rGO composite material on the surface and is marked as P-TP/rGO/GCE. In the sensor prepared by the invention, the P-TP/rGO/GCE modified electrode can effectively catalyze the electrooxidation of epinephrine and uric acid, and in addition, the sensor has the regeneration and self-cleaning effects of the electrochemical sensor through a simple electrochemical reduction process after detection. The reproducible electrochemical sensor has low cost, excellent reproducibility and stability, and practical application value in detecting biological micromolecules in human serum.
Description
Technical Field
The invention belongs to an electrochemical analysis and detection technology, and particularly relates to a renewable electrochemical sensor for simultaneously detecting epinephrine and uric acid and a preparation method thereof.
Background
Conjugated Organic Polymers (COPs) are a class of reticulated polymeric materials linked by strong covalent bonds. In recent years, materials of COPs have attracted attention because of their large specific surface area, excellent photoelectric properties, and catalytic ability. Porphyrin-based COPs, a special macrocyclic aromatic compound having a large conjugated pi-bond system, have been widely used as photocatalysts, electrocatalysts, oxidation catalysts, and the like. In the aspect of constructing an electrochemical sensor, porphyrin-based COPs show good conductivity by compounding with reduced graphene oxide, so that a P-TP/rGO material is modified on the surface of an electrode, the electro-catalytic response to a bioactive substance is realized, and a new application field is opened up for porphyrin-based conjugated organic polymer materials.
Epinephrine (AD) and Uric Acid (UA) play crucial roles in physiological systems, and they can coexist in serum and urine samples. Catecholamines are a substance of sympathetic and hormonal transmitters, present in most mammalian species. In addition to diagnostic screening for pheochromocytoma and neuroblastoma, catecholamine imbalance is associated with a range of neurological and autoimmune diseases. UA is the end product of purine metabolism in humans, and high levels thereof cause a variety of diseases such as hypertension, arthritis, leich-nihan syndrome, and the like. However, very low levels of UA are also associated with multiple sclerosis or oxidative stress. Therefore, monitoring AD and UA concentrations is of great importance in the clinical diagnosis of the associated diseases. At present, many methods are related to single-component determination of epinephrine or uric acid, such as spectrophotometry, flow injection, chemiluminescence, fluorescence, and electrochemical methods, but methods for simultaneous determination of two components are not many, and electrochemical methods have been paid general attention due to their advantages of high analysis speed, low cost, high sensitivity, and the like. However, in the case of the electrochemical method, chemical reactions occur on the surfaces of the electrode and the solution, and during the electrochemical reaction, due to the accumulation and deposition of analytes and products, the surface state of the electrochemical sensor is changed to passivate or deactivate the electrode, thereby affecting the sensitivity and selectivity of the electrode. Therefore, on the premise of not changing the surface and electrochemical performance of the electrochemical sensor, the simple electrochemical reduction method is adopted to remove the pollutants on the surface of the electrochemical sensor to achieve the regeneration and self-cleaning effects, and the method has important significance for the electrochemical analysis method.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a renewable electrochemical sensor which takes a porphyrin-based organic conjugated polymer-reduced graphene oxide composite material as a modifier and can simultaneously detect epinephrine and uric acid, and a preparation method and application thereof.
The technical scheme is as follows: the invention relates to a renewable electrochemical sensor for simultaneously detecting epinephrine and uric acid, which is P-TP/rGO/GCE and is formed by modifying a porphyrin-based conjugated polymer P-TP-reduced graphene oxide rGO composite material on the surface of a glassy carbon electrode GCE.
The preparation method of the renewable electrochemical sensor for simultaneously detecting epinephrine and uric acid comprises the following steps:
(1) preparation of P-TP/GO material: mixing porphyrin-based conjugated polymer P-TP and graphene oxide GO in DMF, and performing ultrasonic treatment to form a uniform dispersion; heating for reaction, centrifuging to remove supernatant, washing and drying to obtain P-TP/GO brown powder;
(2) dispersing and pretreating a P-TP/GO material: dissolving and dispersing P-TP/GO brown powder in absolute ethyl alcohol and a Nafion solvent to obtain a P-TP/GO dispersed suspension;
(3) preparation of P-TP/GO/GCE: grinding and polishing a glassy carbon electrode GCE, cleaning and drying, then dripping the dispersed suspension liquid of the P-TP/GO in the step (2) on the surface of the glassy carbon electrode GCE, and drying to obtain the P-TP/GO/GCE;
(4) and (4) carrying out electrochemical reduction on the P-TP/GO/GCE obtained in the step (3) to obtain the renewable electrochemical sensor P-TP/rGO/GCE.
In the step (1), the preparation of the porphyrin-based conjugated polymer P-TP comprises the following steps:
1) preparation of TP: dissolving 4-alkynylbenzaldehyde in a mixture of nitrobenzene and propionic acid, heating to 120 ℃, and adding fresh pyrrole; after stirring at 120 ℃ for 2h, cooling to room temperature, standing overnight, then filtering the mixture to give dark brown crystals, washing with methanol until the filtrate is colourless, and recrystallising (CH)2Cl2/CH3OH) purifying the crystals to obtain purple solid TP;
2) preparation of P-TP: TP and CuCl were dissolved in TMEDA and 1% pyridine/dichloromethane; stirring the mixed solution for 36h at 30 ℃ in an air atmosphere, cooling to room temperature, filtering and washing precipitates with water, chloroform, methanol and acetone to remove unreacted monomers and catalysts, and performing Soxhlet extraction for 48h with water, methanol and tetrahydrofuran to further purify the target polymer; the target product is dried for 24h at 100 ℃ to obtain the P-TP.
Further, the molar ratio of 4-alkynylbenzaldehyde to pyrrole in the step 1) is 1:1, and the molar ratio of TP to CuCl in the step 2) is 1: 4.
In the step (1), the preparation of the P-TP/GO material is specifically that porphyrin-based conjugated polymer P-TP and graphene oxide GO are mixed in 10m L DMF, ultrasonic treatment is carried out for 5min to form a uniform dispersion, then the solution is heated to 30 ℃, after reaction for 12h, the obtained mixture is centrifuged at 10000 rpm, supernatant is removed, then the mixture is washed with anhydrous acetone and ethanol for three times respectively, and finally, after drying at 40 ℃ overnight, brown powder of the P-TP/GO is obtained.
Further, in the step (1), the mass ratio of the P-TP to the GO is 5-10:1, wherein the optimal ratio is 8: 1.
In the step (2), the concentration of the P-TP/GO dispersion suspension is 0.5-2mg/m L. in the step (2), the Nafion solvent can fix the electrode material, so that the electrode material is not easy to fall off.
In the step (3), the grinding, polishing, cleaning and drying of the glassy carbon electrode GCE refers to: the glassy carbon electrode GCE with the diameter of 2mm is respectively polished by alumina slurry with the diameter of 0.3mm and alumina slurry with the diameter of 0.05mm to a mirror surface, and then is respectively ultrasonically cleaned for 5min by ethanol/distilled water and distilled water with the volume ratio of 1: 1.
In the step (3), a microinjector is used for dropwise coating the P-TP/GO dispersed suspension liquid on the surface of the glassy carbon electrode, and then the glassy carbon electrode is dried for 5-10 minutes under argon flow.
Furthermore, in the step (3), the diameter of the glassy carbon electrode GCE is 2mm, and the amount of the suspension dripped on the surface of the glassy carbon electrode is 5-10 mu L.
In the step (4), the electrochemical reduction is performed at a potential of-1.0-0.2V and a scanning rate of 30-80mVs by using cyclic voltammetry-1And circularly scanning for 20-40 circles in 0.1-0.5M PBS solution. .
Preferably, in the step (4), the electrochemical reduction is performed at a potential of-1.0 to 0.2V and a scanning rate of 50mVs by cyclic voltammetry-1And the solution is cyclically scanned for 20 circles in 0.2M PBS.
The electrochemical sensor is applied to simultaneous detection of epinephrine and uric acid.
Specifically, the application comprises the following steps: the electrochemical sensor P-TP/rGO/GCE is used as a working electrode, the working electrode, a counter electrode and a reference electrode are placed in a PBS (phosphate buffer solution) with the pH value of 7.40.2M, the scanning potential is set to be-0.2-0.6V, and the differential pulse condition is as follows: the amplitude is 0.05V, the pulse period is 0.5s, the pulse width is 0.05s, differential pulse voltammetry curves of adrenaline and uric acid with different concentrations on a P-TP/rGO/GCE electrode are recorded, a linear relation graph of the concentrations of the adrenaline and the uric acid and the current is obtained, different human serum samples are respectively added into a measuring medium, the differential pulse voltammetry curves of the P-TP/rGO/GCE electrodes with the different human serum samples are collected, the detection concentration of the sensor is obtained, and the detection concentration is calculated by a standard adding recovery method.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) compared with the traditional method, the invention has the advantages of simple preparation and simple operation: the porphyrin-based conjugated polymer (P-TP) -reduced graphene oxide (rGO) compound is used as an electrode material, and a uniform film is formed on the surface of the electrode by a simple drop coating and natural air drying method, so that the preparation process is simple and convenient, and the operation is easy;
(2) good selectivity and high sensitivity: the simultaneous determination of epinephrine and uric acid can be realized, and the linear range is as follows: 0.05-100 mu M, the detection limit is as low as 3.01nM, which is of great significance for monitoring human health;
(3) good reproducibility and strong practicability: the method is characterized in that the adrenalin and the uric acid with the same concentration are measured by using 6 parallel sensors, the Relative Standard Deviation (RSD) is less than 5%, and the sensors are applied to the measurement of a plurality of serum samples, and through a standard addition experiment, the standard addition recovery rate is between 94.6% and 109.2%, which shows that the sensors have good accuracy and strong practicability in the measurement of actual samples;
(4) has better regeneration and self-cleaning effects: the regenerated electrode has obviously prolonged service life, can be repeatedly used for detecting the object to be detected, and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the preparation process of a P-TP/GO composite;
FIG. 2 is a scanning electron micrograph of a P-TP/GO composite;
FIG. 3 is a differential pulse voltammogram of epinephrine and uric acid on bare electrode and regenerable electrochemical sensor (P-TP/rGO/GCE);
FIG. 4a is a differential pulse voltammogram of different concentrations of epinephrine and uric acid on the electrochemical sensor; FIG. 4b is a graph of the concentration of epinephrine and uric acid versus current;
FIG. 5 is a differential pulse voltammetry curve of epinephrine and uric acid before and after regeneration on the surface of a P-TP/rGO/GCE electrode (curve a is P-TP/GO/GCE, curve b is P-TP/rGO/GCE, curve c is P-TP/rGO/GCE after 200 cycles of testing, and curve d is P-TP/rGO/GCE after regeneration and self-cleaning);
FIG. 6 is a differential pulse voltammetry curve of a serum sample detected by the sensor (a. serum, b. serum +2 μ M AD +2 μ M UA, c. serum +5 μ M AD +5 μ M UA, d. serum +10 μ M AD +10 μ M UA);
FIG. 7 shows the repeatability (A, B) and reproducibility (C, D) results for the electrochemical sensor P-TP/rGO/GCE.
Detailed Description
The present invention will be further described with reference to the following examples.
Material source:
graphene oxide dispersions, Nafion, epinephrine (AD), Uric Acid (UA), 4-alkynylbenzaldehyde, and pyrrole are all available from alatin chemicals limited (shanghai, china), Dimethylformamide (DMF), N, N, N ', N' -Tetramethylethylenediamine (TMEDA), cuprous chloride (CuCl), dichloromethane (CH2Cl2), methanol, and ethanol are available from Spectrochem pvt.co., <tttransfer = "L" &ttt/t >ttd.
Example 1
A reproducible electrochemical sensor P-TP/rGO/GCE for simultaneously detecting epinephrine and uric acid is a glassy carbon electrode coated with a porphyrin-based conjugated polymer (P-TP) -reduced graphene oxide (rGO) composite material on the surface. The preparation process is shown in figure 1, and the specific preparation method comprises the following steps:
(1) preparation of TP 4-alkynylbenzaldehyde (0.3g, 2.3mmol) was dissolved in a mixture of nitrobenzene (4.6m L) and propionic acid (8.6m L), heated to 120 ℃ and fresh pyrrole (0.18m L, 2.6mmol) was added, stirred at 120 ℃ for 2h, cooled to room temperature, left to stand overnight, and the mixture was filtered to give dark brown crystals, washed with methanol until the filtrate was colorless and recrystallized (CH)2Cl2/CH3OH) to yield a purple solid (95mg, 30% yield).
(2) Preparation of P-TP (92mg, 0.13mmol) and CuCl (64mg, 0.53mmol) were dissolved in TMEDA (1.55m L) and 1% pyridine/dichloromethane (190m L.) the mixture was stirred at 30 ℃ for 36h under an air atmosphere, after cooling to room temperature, the precipitate was filtered and washed with water, chloroform, methanol and acetone to remove unreacted monomers and catalyst, and finally Soxhlet extraction was performed with water, methanol and tetrahydrofuran for 48h to purify the target polymer, which was dried at 100 ℃ for 24h to obtain P-TP.
(3) P-TP/GO is prepared by mixing P-TP (10mg) and GO (2mg) in 10m L DMF, carrying out ultrasonic treatment for 5min to form a uniform dispersion, heating the solution to 30 ℃, reacting for 12h, centrifuging the obtained mixture at 10000 rpm, removing supernatant, washing with anhydrous acetone and ethanol for three times respectively, finally drying at 40 ℃ overnight to obtain brown powder of P-TP/GO (5:1), and preparing the P-TP/GO composite material with the P-TP and GO ratio of 8:1 to 10:1 by using the same method.
A scanning electron microscope image of the prepared P-TP/GO composite material is shown in fig. 2, and according to the image, the P-TP is in a lamellar structure and is uniformly distributed on the surface of graphite oxide.
(4) Dispersing and pretreating a P-TP/GO electrode material: weighing the P-TP/GO solid powder prepared in the step (3), adding 95% absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain a P-TP/GO dispersion liquid.
(5) The pretreatment method of the glassy carbon electrode comprises the following steps: GCE with a diameter of 2mm was first polished on a polishing cloth to a mirror surface with 0.3mm and 0.05mm alumina slurries, respectively, and then ultrasonically cleaned with ethanol/distilled water and distilled water at a volume ratio of 1:1 for 5min, respectively.
(6) And (3) preparing a P-TP/GO/GCE electrode, namely dripping 5 mu L of the P-TP/GO dispersion liquid prepared in the step (4) on the surface of the GCE treated in the step (5), and drying in argon flow for 5 minutes to prepare the working electrode P-TP/GO/GCE.
(7) Preparation of P-TP/rGO/GCE electrode: performing cyclic voltammetry on the P-TP/GO/GCE electrode prepared in the step (6) at a potential of-1.0-0.2V and at a scanning rate of 50mVs-1And circularly scanning for 20 circles in 0.2M PBS solution to prepare a working electrode P-TP/rGO/GCE of the reproducible electrochemical sensor.
Example 2
The electrochemical sensor P-TP/rGO/GCE prepared in example 1 was used to analyze and detect samples of epinephrine and uric acid by differential pulse voltammetry, and at the same time, to detect electrochemical regeneration and self-cleaning signals of the modified electrode.
Preparing Adrenaline (AD) and Uric Acid (UA) solutions:
adrenaline (AD) and Uric Acid (UA) are weighed by an electronic balance to be dissolved in water of 2m L, and Adrenaline (AD) and Uric Acid (UA) solutions of 0.001 mol/L are prepared and are diluted step by step to the required concentration according to the experimental requirements.
Simultaneous determination of epinephrine (AD) and Uric Acid (UA):
by using an electrochemical sensor P-TP/rGO/GCE as a working electrode, a saturated calomel electrode as a reference electrode and a platinum wire electrode as a counter electrode, and simultaneously measuring a 2 mu mol/L solution of epinephrine and uric acid in a 0.2M PBS (pH 7.4) solution by adopting differential pulse voltammetry, the current response is shown in figure 3, and according to the graph, no obvious peak current exists on the naked GCE, while the corresponding peak currents of two target analytes are observed for the P-TP/rGO/GCE.
The simultaneous measurement of different concentrations of epinephrine and uric acid by the electrochemical sensor P-TP/rGO/GCE is examined by the same method as shown in FIG. 4, and according to the graph, the corresponding peak currents of two target analytes are increased along with the increase of the analyte concentration, and the peak currents show good linear relation along with the change of the concentration.
The current response (I) is related to the concentration of epinephrine and uric acid (C) by Ipa (μ a) ═ 0.001+0.067C (μ M) (R2 ═ 0.996) and Ipa (μ a) ═ 0.292+0.026C (μ M) (R2 ═ 0.990), with the concentration of epinephrine and uric acid measured in the range of 0.05-100 μ M. The detection limits for epinephrine and uric acid were calculated from the working curves to be 4.54nM and 3.01nM, respectively (S/N-3).
The P-TP/GO/GCE electrode subjected to multiple tests is subjected to cyclic voltammetry again at a potential of-1.0-0.2V and at a scanning rate of 50mVs-1And circularly scanning for 20 circles in 0.2M PBS (phosphate buffer solution) to reflect the regeneration and self-cleaning effects of the electrochemical sensor (namely the electrode surface), wherein the electrochemical regeneration and self-cleaning effects are shown in FIG. 5, as can be seen from the graph, after multiple tests, the peak current drops (curve c) of AD and UA are 75% of the original (curve b), and after electrochemical reduction again, the peak currents (curve d) of AD and UA are recovered.
Example 3
The electrochemical sensor P-TP/rGO/GCE prepared in example 1 was used to measure the concentration of epinephrine (AD) and Uric Acid (UA) in human serum.
The detection method comprises the following steps: taking a practical serum sample of a healthy human body as a detection sample;
the specific test conditions were:
measurement Medium: PBS buffer solution with pH7.4;
detection potential range: -0.2V-0.6V;
differential pulse conditions: the amplitude is 0.05V, the pulse period is 0.5s, and the pulse width is 0.05 s;
the specific detection method comprises the steps of adding 20 mu L of human serum into PBS (phosphate buffer solution) containing 0,2 mu M,5 mu M and 10 mu M of epinephrine and uric acid respectively, as shown in figure 6, wherein uric acid can be detected when standard analytes are not added, and then the peak current is correspondingly increased along with the addition of the standard analytes, so that the simultaneous determination of epinephrine and uric acid in the serum can be realized.
Example 4
The repeatability and reproducibility of the electrochemical sensor for measuring epinephrine (AD) and Uric Acid (UA) was measured by differential pulse voltammetry using the electrochemical sensor P-TP/rGO/GCE prepared in example 1.
The electrode has good repeatability and reproducibility as shown in figure 7, wherein the Relative Standard Deviation (RSD) of the electrode is less than 3% as shown in a graph, and the electrode is prepared by using 6 parallel electrochemical sensors P-TP/rGO/GCE as a working electrode, adopting differential pulse voltammetry to measure a solution of 2 mu mol/L of adrenaline and uric acid in a solution of 0.2MPBS (pH is 7.4) and simultaneously using the same electrochemical sensor P-TP/rGO/GCE to measure a solution of 2 mu mol/L of adrenaline and uric acid in parallel 6 times under the same conditions.
Claims (10)
1. A reproducible electrochemical sensor for simultaneously detecting epinephrine and uric acid is characterized by being P-TP/rGO/GCE and formed by modifying a porphyrin-based conjugated polymer P-TP-reduced graphene oxide rGO composite material on the surface of a glassy carbon electrode GCE.
2. The method for preparing the renewable electrochemical sensor for simultaneously detecting epinephrine and uric acid according to claim 1, comprising the steps of:
(1) preparation of P-TP/GO material: mixing porphyrin-based conjugated polymer P-TP and graphene oxide GO in DMF, and performing ultrasonic treatment to form a uniform dispersion; heating for reaction, centrifuging to remove supernatant, washing and drying to obtain P-TP/GO brown powder;
(2) dispersing and pretreating a P-TP/GO material: dissolving and dispersing P-TP/GO brown powder in absolute ethyl alcohol and a Nafion solvent to obtain a P-TP/GO dispersed suspension;
(3) preparation of P-TP/GO/GCE: grinding and polishing a glassy carbon electrode GCE, cleaning and drying, then dripping the dispersed suspension liquid of the P-TP/GO in the step (2) on the surface of the glassy carbon electrode GCE, and drying to obtain the P-TP/GO/GCE;
(4) and (4) carrying out electrochemical reduction on the P-TP/GO/GCE obtained in the step (3) to obtain the renewable electrochemical sensor P-TP/rGO/GCE.
3. The method according to claim 2, wherein the preparation of the porphyrin-based conjugated polymer P-TP in step (1) comprises the steps of:
1) preparation of TP: dissolving 4-alkynylbenzaldehyde in a mixture of nitrobenzene and propionic acid, heating to 120 ℃, and adding fresh pyrrole; stirring at 120 deg.C for 2h, cooling to room temperature, standing overnight, filtering the mixture to obtain dark brown crystals, washing with methanol until the filtrate is colorless, and recrystallizing to purify the crystals to obtain purple solid TP;
2) preparation of P-TP: TP and CuCl were dissolved in TMEDA and 1% pyridine/dichloromethane; stirring the mixed solution for 36h at 30 ℃ in an air atmosphere, cooling to room temperature, filtering and washing precipitates with water, chloroform, methanol and acetone to remove unreacted monomers and catalysts, and performing Soxhlet extraction for 48h with water, methanol and tetrahydrofuran to further purify the target polymer; the target product is dried for 24h at 100 ℃ to obtain the P-TP.
4. The method according to claim 3, wherein the molar ratio of 4-alkynylbenzaldehyde to pyrrole in step 1) is 1:1, and the molar ratio of TP to CuCl in step 2) is 1: 4.
5. The preparation method according to claim 2, wherein in the step (1), the mass ratio of the P-TP to GO is 5-10: 1.
6. The method according to claim 2, wherein in the step (2), the concentration of the P-TP/GO dispersed suspension is 0.5-2mg/m L.
7. The preparation method according to claim 2, wherein in the step (3), the glassy carbon electrode GCE has a diameter of 2mm, and the amount of the suspension dropped on the surface of the glassy carbon electrode is 5-10 μ L.
8. The method according to claim 2, wherein in the step (4), the electrochemical reduction is performed by cyclic voltammetry at a potential of-1.0 to 0.2V and a scan rate of 30 to 80mVs-1And circularly scanning for 20-40 circles in 0.1-0.5M PBS solution.
9. Use of the electrochemical sensor according to claim 1 for simultaneous detection of epinephrine and uric acid.
10. The application according to claim 9, characterized in that it comprises the following steps: the electrochemical sensor P-TP/rGO/GCE is used as a working electrode, the working electrode, a counter electrode and a reference electrode are placed in a PBS (phosphate buffer solution) with the pH value of 7.40.2M, the scanning potential is set to be-0.2-0.6V, and the differential pulse condition is as follows: the amplitude is 0.05V, the pulse period is 0.5s, the pulse width is 0.05s, differential pulse voltammetry curves of adrenaline and uric acid with different concentrations on a P-TP/rGO/GCE electrode are recorded, a linear relation graph of the concentrations of the adrenaline and the uric acid and the current is obtained, different human serum samples are respectively added into a measuring medium, the differential pulse voltammetry curves of the P-TP/rGO/GCE electrodes with the different human serum samples are collected, the detection concentration of the sensor is obtained, and the detection concentration is obtained through calculation by a standard adding recovery method.
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