CN114235911A - Electrochemical sensor for choline detection and preparation method thereof - Google Patents
Electrochemical sensor for choline detection and preparation method thereof Download PDFInfo
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- CN114235911A CN114235911A CN202111587534.5A CN202111587534A CN114235911A CN 114235911 A CN114235911 A CN 114235911A CN 202111587534 A CN202111587534 A CN 202111587534A CN 114235911 A CN114235911 A CN 114235911A
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- 229960001231 choline Drugs 0.000 title claims abstract description 44
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- 238000001514 detection method Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
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- 229920000642 polymer Polymers 0.000 claims abstract description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 27
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 15
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- 229960004373 acetylcholine Drugs 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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Abstract
The invention discloses an electrochemical sensor for choline detection and a preparation method thereof, wherein the electrochemical sensor comprises a metal electrode layer, a polymer layer and a sensing layer which are sequentially stacked; the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm; the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm; the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers. The electrochemical sensor for choline detection has high sensitivity, low detection limit, fast response speed and excellent electrochemical interference resistance.
Description
Technical Field
The application relates to the field of biosensing, in particular to an electrochemical sensor for choline detection and a preparation method thereof.
Background
Choline, an important constituent of membrane phospholipids and also present in sphingomyelin, is a source of variable methyl groups in the body, a precursor of acetylcholine, one of the important brain chemicals involved in memory, and is present in the peripheral and central nervous systems as a neurotransmitter. Choline plays an important role in metabolism, information transmission, cell apoptosis regulation, fat metabolism promotion, cholesterol content reduction and normal cell function maintenance of a human body; meanwhile, the change of the choline level and the metabolic abnormality can also be used as diagnostic markers of various cancers such as acute coronary syndrome, brain glioma grading and the like. Therefore, the method has important biological significance for the detection of choline.
Since choline itself does not have electrochemical activity, the production of hydrogen peroxide by enzymatic choline catalysis is an important method for measuring choline. The current choline detection technology based on choline oxidase mainly comprises a colorimetric method, a liquid chromatography method, a fluorescence method, an electrochemical luminescence and chemiluminescence method, an electrochemical detection technology and the like. Among them, colorimetry can be read quickly with the naked eye and can be used as a tool for visual detection, but is easily interfered by the color of a colored sample in the examination of an actual sample, and the sensitivity of such biosensors is relatively low. Liquid chromatography often requires cumbersome pre-treatment steps and expensive instruments, and is not suitable for rapid in-situ detection. Fluorescence has the advantages of ease of application, wide response range and remote sensing, but fluorescence bioassays may also suffer from unstable optical signals and internal filtering effects. Compared with other choline detection methods, the electrochemical biosensor has the advantages of high specificity, low background noise, higher signal-to-noise ratio and the like in the biological identification process; when the measurement is carried out, only a small sample size is needed, the detection cost is low, and the system design structure is simple; the electrochemical technology has the most potential in commercialization and commercialization, is user-friendly and can realize portability, and at present, the electrochemical technology is successfully applied to the measurement of metabolites such as glucose and hormone, so that the application of the combination of the electrochemical technology and life science in clinical analysis has achieved unsophisticated achievement. However, the current electrochemical biosensor for choline detection also has some problems, such as: the sensor is easily interfered by electroactive substances, has small signals in amperometric detection and high detection limit, needs better materials to capture and fix enzyme and maintain enzyme activity, and is limited in application in practical application.
Therefore, the development of a biosensor with strong anti-interference capability, high sensitivity and low detection limit is urgently needed for improving the choline detection effect.
Disclosure of Invention
In view of the above problems, a first aspect of the present invention provides an electrochemical sensor for choline detection, including a metal electrode layer, a polymer layer, and a sensing layer, which are sequentially stacked;
the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm;
the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm;
the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers.
In one embodiment, the sensing layer further comprises magnetic nanoparticles, the average particle diameter of the magnetic nanoparticles is 75-100 nanometers, and the mass fraction of the magnetic nanoparticles in the sensing layer is 20-30%.
In one embodiment, the sensing layer further comprises metal nanoparticles selected from at least one of gold nanospheres, silver nanoflowers, gold nanoflowers and silver nanospheres, the average particle size of the metal nanoparticles is 10-20 nanometers, and the mass fraction of the metal nanoparticles in the sensing layer is 1-3%.
In one embodiment, the sensing layer further comprises functionalized carbon nanotubes, and the mass fraction of the functionalized carbon nanotubes in the sensing layer is 3-5%.
The second aspect of the present invention provides a method for preparing an electrochemical sensor for choline detection, comprising at least the following steps:
s1: providing a metal electrode layer, and depositing a polymer layer on one side of the metal electrode layer;
s2: forming a sensing layer on one side of the polymer layer far away from the metal electrode layer;
the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm;
the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm;
the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers.
The sensor is only composed of the metal electrode layer, the polymer layer and the sensing layer, is simple in structure and easy to prepare, and in the sensor, the H generated in the choline detection process is greatly amplified by adding the metal alkene MXene into the sensing layer2O2The sensitivity of the electrochemical sensor to choline detection is improved.
In one embodiment, the sensing layer further comprises magnetic nanoparticles prepared by:
s201: mixing ferric chloride and trisodium citrate dihydrate into ethylene glycol at room temperature, fully stirring and dissolving, adding sodium acetate trihydrate to obtain a mixed solution, transferring the mixed solution into a reaction container, reacting at the temperature of 180 ℃ and 230 ℃ for 6-24h to obtain a reaction solution, and carrying out magnetic separation to obtain the magnetic nanoparticles.
In one embodiment, the sensing layer further comprises metal nanoparticles, the metal particles being prepared by:
s202: and adding the metal precursor solution to boiling, adding trisodium citrate dihydrate, keeping boiling for 10-60min, and naturally cooling to room temperature to obtain the metal nanoparticles.
In one embodiment, the sensing layer further comprises functionalized carbon nanotubes, and the preparation method of the functionalized carbon nanotubes comprises the following steps:
s203 a: dispersing the carbon nano tube in the mixed acid solution, stirring and heating for 1-5h at 40-80 ℃ to obtain the carboxylated carbon nano tube.
In one embodiment, the method for preparing the functionalized carbon nanotube further comprises:
s203 b: adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the aqueous dispersion of the carboxylated carbon nano-tube, carrying out mixed reaction for 30-120 min at room temperature, then carrying out centrifugal washing to obtain the activated carboxylated carbon nano-tube, adding cysteamine into the activated carboxylated carbon nano-tube, and carrying out continuous reaction for 30-120 min at room temperature to obtain the thiolated carbon nano-tube.
In one embodiment, the manufacturing process of MXene in the sensing layer includes:
s204: providing acid solution, and then adding Ti at uniform speed3AlC2After the reaction is stable, the mixed solution is put at 30-50 ℃ for reaction for 12-36 hours.
The electrochemical sensor for choline detection prepared by the method is low in cost, high in sensitivity, wide in detection range, high in response speed, strong in anti-interference performance and good in application prospect.
Drawings
The following detailed description of embodiments of the invention is provided in conjunction with the appended drawings:
FIG. 1 shows a schematic diagram of an electrochemical sensor provided by an embodiment of the present invention;
FIG. 2 shows a schematic view of yet another electrochemical sensor embodiment provided by the present invention;
FIG. 3 shows a schematic view of another electrochemical sensor embodiment provided by the present invention;
FIG. 4 shows a schematic diagram of a preferred embodiment of an electrochemical sensor provided by the present invention;
FIG. 5 shows a corresponding velocity diagram for an electrochemical sensor provided by an embodiment of the invention;
FIG. 6 illustrates current response data for electrochemical sensors provided by embodiments of the present invention for different choline concentrations;
fig. 7 is a graph showing the linear relationship between the electrochemical sensor provided in example 2 of the present invention and the detection of choline at different concentrations.
Detailed Description
In order to clarify the invention in more detail, the technical solution of the invention is further elucidated below with reference to a preferred embodiment and the accompanying drawings.
In connection with fig. 1 to 4, in the present application, an electrochemical sensor for choline detection is proposed: the sensor comprises a metal electrode layer, a polymer layer and a sensing layer which are sequentially stacked; the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm; the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm; the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers.
The sensor is only composed of the metal electrode layer, the polymer layer and the sensing layer, is simple in structure and easy to prepare, and in the sensor, the H generated in the choline detection process is greatly amplified by adding the metal alkene MXene into the sensing layer2O2The sensitivity of the electrochemical sensor to choline detection is improved.
The preparation of the sensor at least comprises the following steps:
s1: providing a metal electrode layer, and depositing a polymer layer on one side of the metal electrode layer;
s2: forming a sensing layer on one side of the polymer layer far away from the metal electrode layer;
the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm;
the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm;
the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers.
The electrochemical sensor for choline detection prepared by the method is low in cost, high in sensitivity, wide in detection range, high in response speed, strong in anti-interference performance and good in application prospect.
It should be noted that, in the preparation process of the sensor, step S1 further includes performing a pretreatment on the metal electrode, where the pretreatment step includes one or more of mechanical polishing and electrochemical polishing, so that the polymer layer on the electrode and the sensing layer can form a uniform film layer on the surface of the electrode.
In the above sensor, the polymer layer is preferably at least one of poly (m-phenylenediamine), poly (p-phenylenediamine), poly (o-phenylenediamine), such as poly (m-phenylenediamine), which limits diffusion across the sensor surface of macromolecules and allows only hydrogen peroxide to selectively pass through during detection, thereby eliminating interference from electroactive chemicals. Preferably, the poly-m-phenylenediamine is obtainable by cyclic voltammetry for the deposition of m-phenylenediamine or by galvanostatic deposition for the deposition of m-phenylenediamine.
In some preferred embodiments, the sensing layer further comprises magnetic nanoparticles, specifically, the magnetic nanoparticles may be ferroferric oxide particles having an average particle size of between 75nm and 100nm, as shown in fig. 2. The magnetic particles have peroxidase-like activity, are used as enzyme carriers in the sensor, improve the enzyme loading rate, and simultaneously can enhance the electron transfer speed and the electrocatalytic activity in the sensing detection process, thereby enhancing the electrochemical signal of the sensor and further improving the response speed of the electrochemical sensor. Preferably, the mass fraction of magnetic nanoparticles in the sensing layer is 20-30%. Preferably, the magnetic nanoparticles are Fe3O4Magnetic nanoparticles.
Preferably, Fe3O4The preparation of the magnetic nanoparticles includes step S201: mixing ferric chloride and trisodium citrate dihydrate into ethylene glycol at room temperature, fully stirring and dissolving, adding sodium acetate trihydrate to obtain a mixed solution, transferring the mixed solution into a reaction container, reacting at the temperature of 180 ℃ and 230 ℃ for 6-24h to obtain a reaction solution, and carrying out magnetic separation to obtain the magnetic nanoparticles.
Specifically, Fe used in the examples that follow the present application3O4The nanoparticles are obtained by the following steps:
to 40mL of ethylene glycol were added 1.35g of ferric chloride hexahydrate and 0.5582g of dihydrateAnd mixing trisodium citrate, performing ultrasonic dispersion to fully dissolve the trisodium citrate, stirring for 1h at normal temperature, adding 3.98136g of sodium acetate trihydrate, performing ultrasonic dispersion, stirring for 0.5h at normal temperature, transferring the solution into an autoclave liner, and placing the autoclave liner in a 200 ℃ oven to react for 12.5 h. After the reaction is finished, performing magnetic separation on the product, washing the product with pure water for multiple times, washing the product with absolute ethyl alcohol for multiple times, finally washing the product with pure water for multiple times, and freeze-drying the product by using a freeze dryer to obtain Fe3O4Magnetic nanoparticles.
As shown in fig. 3, in some preferred embodiments, the sensor can further include metal nanoparticles, which can be selected from at least one of gold nanoparticles, gold nanoflowers, and silver nanoflowers, having an average particle size of 10nm to 20 nm. Taking gold nanoparticles as an example, the gold nanoparticles have stable electrochemical performance and high catalytic activity, can accelerate electron transfer between protein and an electrode, and in addition, the gold nanoparticles show good compatibility with the protein, so the gold nanoparticles can also play a certain role in maintaining biological activity in a sensor. Preferably, the mass fraction of the metal nanoparticles in the sensing layer is 1-3%.
Preferably, the metal particles are prepared by:
s202: and adding the metal precursor solution to boiling, adding trisodium citrate dihydrate, keeping boiling for 10-60min, and naturally cooling to room temperature to obtain the metal nanoparticles.
Specifically, gold nanoparticles (GNps) mentioned in subsequent examples in the present application were prepared by the following procedure:
50mL of pure water was added to the vessel, and 0.5mL of 1% HAuCl was added4Condensing and refluxing the gold nanoparticles by using a 30cm spherical condenser tube, stirring and heating the gold nanoparticles in a magnetic heating sleeve until the gold nanoparticles are boiled, adding 2.5mL of trisodium citrate dihydrate with the concentration of 1 percent, keeping the boiling state for 20min, and naturally cooling the gold nanoparticles to room temperature to obtain the gold nanoparticles.
As shown in fig. 4, the sensor may further include a carbon nanotube, and preferably, the carbon nanotube is a functionalized carbon nanotube for supporting the metal nanoparticle, and since the functionalized carbon nanotube has both metallic and semiconductor properties, electron transfer can be promoted, and the corresponding speed and sensitivity of the sensor can be further improved, and meanwhile, the functionalized carbon nanotube is easily compatible with a biomolecule, and biological activity can be maintained during the choline detection process of the sensor. More preferably, the functionalized carbon nanotubes are carboxylated carbon nanotubes and/or thiolated carbon nanotubes. The functionalized carbon nano-tube is combined with the gold nano-particles through gold-sulfur bonds. Preferably, the mass fraction of the functionalized carbon nanotubes in the sensing layer is 3-5%.
The preparation process of the functionalized carbon nanotube may include step S203 a: dispersing the carbon nano tube in the mixed acid solution, stirring and heating for 1-5h at 40-80 ℃ to obtain the carboxylated carbon nano tube. Further, the preparation process of the thiolated carbon nanotube further includes, on the basis of step S203 a: step S203 b: adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the aqueous dispersion of the carboxylated carbon nano-tube, carrying out mixed reaction for 30-120 min at room temperature, then carrying out centrifugal washing to obtain the activated carboxylated carbon nano-tube, adding cysteamine into the activated carboxylated carbon nano-tube, and carrying out continuous reaction for 30-120 min at room temperature to obtain the thiolated carbon nano-tube.
Specifically, the functionalized carbon nanotubes used in the subsequent examples of the present invention were prepared by the following steps:
adding 500 mu L of multi-walled carbon nanotube (MWCNT) water dispersion into a mixed solution of concentrated sulfuric acid and nitric acid, wherein the concentrated sulfuric acid is 9mL, the nitric acid is 3mL, the rotating speed is as follows: 900 rpm. Heating with magnetic heating sleeve, condensing, refluxing and heating at 60 deg.C for 3 hr to obtain carboxylated carbon nanotube (MWCNT-COOH), dialyzing the reaction solution in dialysis bag until pH is neutral, and taking out.
Next, activating carboxyl groups on the carbon nanotubes: 2mL of MWCNT-COOH aqueous dispersion was put in a test tube, 1mL of 2mg/mL 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 1mL of 1mg/mL N-hydroxysuccinimide (NHS) were added, the mixture was reacted at 200rpm in a shaker for 1 hour, and then removed therefrom, and the reaction mixture was washed with pure water by centrifugation at 14000rpm for 1 hour. After washing, the solution is made to be 1mL by pure water, and the activated MWCNT-COOH is obtained for later use.
Subsequently, 1mL of cysteamine having a concentration of 5mg/mL was added to the test tube, reacted at 180rpm in a shaker for 1 hour, and then removed, and washed with pure water by centrifugation at 14000rpm for 45min for a plurality of times. After washing, the solution is subjected to volume fixing to 1mL by pure water, and the multi-walled carbon nanotube (MWCNT-SH) modified by sulfydryl is obtained for later use.
In some preferred embodiments, the functionalized carbon nanotubes and the functionalized gold nanoparticles are combined through gold-sulfur bonds, so that the enzyme loading amount in the sensor can be further increased, and meanwhile, the electrochemical signal is greatly enhanced through the gold nanoparticles. The specific synthesis steps are as follows:
adding 1mL of the gold nanoparticles prepared in the previous step into the MWCNT-SH, reacting for 1h at room temperature in a shaking table at 180rpm, taking down, and centrifuging and washing the gold nanoparticles for 30min for many times by pure water at 14000 rpm. After completion of the washing, the solution was made up to 200. mu.L with pure water to obtain MWCNT-GNps hybrid.
In some preferred embodiments, the sensing layer may also include film forming agents, adhesives, and other substances. The film forming agent can be a glycerin aqueous solution, and preferably, the concentration of glycerin in the glycerin aqueous solution is 5% -20%, so that the overall film forming effect of the sensing layer is improved. The adhesive may be glutaraldehyde, which allows the enzyme to be stably immobilized on the surface of the electrochemical sensor. In addition, the sensing layer can further comprise one or more of Polyethyleneimine (PEI) and Bovine Serum Albumin (BSA) for synergistically improving the sensitivity of the sensor.
Example 1:
providing a metal platinum disk electrode, and pretreating the electrode: mechanically polishing, homogenizing with commercially available alumina powder and chamois leather, polishing to obtain mirror surface according to particle size from coarse to fine (1 μm, 0.3 μm, 0.05 μm), and soaking in chromic acid lotion for 30 min; finally, electrochemical polishing is carried out, and the working electrode is inserted into H with the concentration of less than 0.5M2SO4In the potential range of-0.15-1.3V vs Ag/AgCl reference electrode, scanning by Cyclic Voltammetry (CV), setting the scanning speed to be 0.1V/s,until the curve no longer changes.
After pretreatment of the platinum disk electrode, a m-phenylenediamine film was deposited on the platinum disk electrode using cyclic voltammetry: the pretreated platinum disk working electrode, platinum wire counter electrode, Ag/AgCl reference electrode were immersed in a solution of 5mM m-phenylenediamine dissolved in 1 XPBS at pH 7.4. Receiving 10-15 CV graphs without stirring. The film was dried after deposition on a platinum disk electrode and stored at 4 ℃ for at least 3 hours. Electrochemical workstation parameter setting: initial potential: 0V; final potential: + 0.9V; scanning speed: 20 mV/s; sampling interval: 5 mV; number of scanning segments: 20-30 sections; initial scanning direction: and (4) a positive direction.
Then 4. mu.L of MXene with the concentration of 7.7mg/mL, 1.3. mu.L of MWCNT-GNps with the concentration of 1mg/mL and 4. mu.L of Fe with the concentration of 3mg/mL are sequentially dripped on the surface of the platinum disk electrode modified with the m-phenylenediamine film3O4Magnetic nanoparticles, 4. mu.L choline oxidase (ChOx) at a concentration of 100U/mL (in pbs buffer), 1. mu.L Bovine Serum Albumin (BSA) at a concentration of 4%, 1. mu.L aqueous glycerol at a concentration of 10%, 1. mu.L polyethyleneimine PEI at a concentration of 2% and a molecular weight of 750K, 1. mu.L glutaraldehyde at a concentration of 1.6%, were dried at 37 ℃ for 20 min. After the reaction is finished, the electrode is cooled to room temperature, the unbound components of the biological selective membrane are washed by 1 XPBS, dried for 40 minutes in a dark place at room temperature, and then stored in a refrigerator at 4 ℃ in 1 XPBS buffer.
Example 2:
this example differs from example 1 only in that Fe was not added3O4Magnetic nanoparticles.
Comparative example 1:
the comparative example differs from example 1 only in that Fe was not added3O4Magnetic nanoparticles and MXene.
Comparative example 2:
the comparative example differs from example 1 only in that MWCNT-GNps and Fe were not added3O4Magnetic nanoparticles and MXene.
The electrochemical sensors obtained in example 1, example 2, comparative example 1 and comparative example 2 were used to perform a choline electrochemical response test in artificial cerebrospinal fluid:
the current-time curve is measured by using artificial cerebrospinal fluid to prepare choline solutions with different concentrations, during testing, 2mL of artificial cerebrospinal fluid is added into an electrolytic cell firstly, the test is started, the working voltage is set to be 0.6V, after a base line is leveled, the choline solutions are added in sequence from low to high according to the concentrations, and the current response is tested under different concentrations.
Referring to fig. 5, it can be seen that the corresponding time of the electrochemical sensor added with MXene is 17s, the response speed is faster, and Fe is further added3O4The response time of the electrochemical sensor is better, and the response speed can reach 5 s.
As can be seen in fig. 6, the sensitivity of the electrochemical sensor doped with MXene is significantly improved over that of the electrochemical sensor undoped with MXene. And Fe3O4The addition of the magnetic nanoparticles does not have a significant effect on the sensitivity of the electrode.
Finally, the chemical sensors obtained in example 2 were used to determine the linear equation obtained for choline concentrations of 0. mu.M, 0.02. mu.M, 0.033. mu.M, 0.071. mu.M, 0.125. mu.M, 0.56. mu.M, 1. mu.M, 4.52. mu.M, 8.33. mu.M, 38.46. mu.M, 71.43. mu.M, 133.33. mu.M, 588.24. mu.M and 1111.11. mu.M. As shown in FIG. 7, the current values were linearly related in the range of 0.033 to 133.33. mu.M by linear fitting, and the detection range was wide. The resulting fit equation is: 1.78E-9+8.80E-9[ Choline concentration ]](μM)(R20.9991). The detection limit of choline was 0.022 μ M at a signal-to-noise ratio of 3.
Finally, it should be noted that: the above-mentioned embodiments are merely preferred examples for clearly illustrating the invention, but are not limited to the embodiments of the invention, and it should be understood by those skilled in the art that the technical features in the above-mentioned embodiments can be combined arbitrarily, and other modifications in different forms or equivalent replacements of part of the technical features can be made on the basis of the above-mentioned embodiments, and not all embodiments can be exhaustive, so that any modifications, improvements, equivalents and the like which are included in the technical solution of the present invention are within the technical scope of the claims of the present invention.
Claims (10)
1. An electrochemical sensor for choline detection is characterized by comprising a metal electrode layer, a polymer layer and a sensing layer which are sequentially stacked;
the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm;
the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm;
the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers.
2. The electrochemical sensor for choline detection according to claim 1, wherein the sensing layer further comprises magnetic nanoparticles, the magnetic nanoparticles have an average particle diameter of 75-100 nm, and the mass fraction of the magnetic nanoparticles in the sensing layer is 20-30%.
3. The electrochemical sensor for choline detection according to claim 1, wherein the sensing layer further comprises metal nanoparticles selected from at least one of gold nanospheres, silver nanoflowers, gold nanoflowers, and silver nanoparticles, the metal nanoparticles have an average particle size of 10-20 nm, and the mass fraction of the metal nanoparticles in the sensing layer is 1-3%.
4. The electrochemical sensor for choline detection according to claim 1, wherein the sensing layer further comprises functionalized carbon nanotubes, and the mass fraction of the functionalized carbon nanotubes in the sensing layer is 3-5%.
5. The method for preparing an electrochemical sensor for the detection of choline according to any one of claims 1 to 4, comprising at least the steps of:
s1: providing a metal electrode layer, and depositing a polymer layer on one side of the metal electrode layer;
s2: forming a sensing layer on one side of the polymer layer far away from the metal electrode layer;
the metal electrode layer is at least one of platinum, gold and silver, and the thickness of the metal electrode layer is 1000-2000 nm;
the polymer layer is at least one of poly (m-phenylenediamine), poly (p-phenylenediamine) and poly (o-phenylenediamine), and the thickness of the polymer layer is 300-500 nm;
the sensing layer comprises MXene, and the thickness of the sensing layer is 14000-18000 nanometers.
6. The method of preparing an electrochemical sensor for choline detection according to claim 5, wherein the sensing layer further comprises magnetic nanoparticles, the magnetic nanoparticles being prepared by:
s201: mixing ferric chloride and trisodium citrate dihydrate into ethylene glycol at room temperature, fully stirring and dissolving, adding sodium acetate trihydrate to obtain a mixed solution, transferring the mixed solution into a reaction container, reacting at the temperature of 180 ℃ and 230 ℃ for 6-24h to obtain a reaction solution, and carrying out magnetic separation to obtain the magnetic nanoparticles.
7. The method of preparing an electrochemical sensor for choline detection according to claim 5, wherein the sensing layer further comprises metal nanoparticles, the metal particles being prepared by:
s202: and adding the metal precursor solution to boiling, adding trisodium citrate dihydrate, keeping boiling for 10-60min, and naturally cooling to room temperature to obtain the metal nanoparticles.
8. The method of preparing an electrochemical sensor for choline detection according to claim 5, wherein the sensing layer further comprises functionalized carbon nanotubes, and the method of preparing the functionalized carbon nanotubes comprises:
s203 a: dispersing the carbon nano tube in the mixed acid solution, stirring and heating for 1-5h at 40-80 ℃ to obtain the carboxylated carbon nano tube.
9. The method of preparing an electrochemical sensor for choline detection according to claim 8, wherein the method of preparing the functionalized carbon nanotube further comprises:
s203 b: adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the aqueous dispersion of the carboxylated carbon nano-tube, carrying out mixed reaction for 30-120 min at room temperature, then carrying out centrifugal washing to obtain the activated carboxylated carbon nano-tube, adding cysteamine into the activated carboxylated carbon nano-tube, and carrying out continuous reaction for 30-120 min at room temperature to obtain the thiolated carbon nano-tube.
10. The method for preparing an electrochemical sensor for choline detection according to claim 5, wherein the MXene in the sensing layer is prepared by the following steps:
s204: providing acid solution, and then adding Ti at uniform speed3AlC2After the reaction is stable, the mixed solution is put at 30-50 ℃ for reaction for 12-36 hours.
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