CN111735863A - Electrochemical sensor capable of rapidly detecting ciprofloxacin in water and detection method thereof - Google Patents

Electrochemical sensor capable of rapidly detecting ciprofloxacin in water and detection method thereof Download PDF

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CN111735863A
CN111735863A CN202010457060.1A CN202010457060A CN111735863A CN 111735863 A CN111735863 A CN 111735863A CN 202010457060 A CN202010457060 A CN 202010457060A CN 111735863 A CN111735863 A CN 111735863A
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ciprofloxacin
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polyimide film
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薛强
陈涛
李佳蔚
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China University of Geosciences Beijing
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Abstract

The embodiment of the invention discloses an electrochemical sensor capable of quickly detecting ciprofloxacin in water and a detection method thereof.

Description

Electrochemical sensor capable of rapidly detecting ciprofloxacin in water and detection method thereof
Technical Field
The embodiment of the invention relates to the technical field of water quality detection, in particular to an electrochemical sensor capable of quickly detecting ciprofloxacin in water and a detection method thereof.
Background
Ciprofloxacin (CFX), an artificially synthesized third-generation fluoroquinolone antibiotic, is one of the most widely used fluoroquinolone antibiotics at present because of its characteristics of broad-spectrum antibacterial activity, good bioavailability, few side effects, good tissue penetration and distribution in biological fluids. Ciprofloxacin enters water environments through domestic sewage, production and discharge of pharmaceutical factories, waste of solid wastes, livestock excrement, leaching of garbage fields and the like, and is frequently detected in various water environments.
With the aggravation of the problem of ciprofloxacin pollution in water environment, the detection method of ciprofloxacin is receiving more and more attention. So far, various detection means for ciprofloxacin have been available, and high performance liquid chromatography, immunoassay and spectrophotometry are commonly used. These methods have high sensitivity and low detection limit, and thus are widely used. However, these methods also have the disadvantages of high cost, complicated operation, long time consumption, etc., so that it is more necessary to develop a more convenient, rapid and accurate detection method. The electrochemical sensor detection method has the advantages of simplicity, portability, high sensitivity and low cost, so that a simple, rapid and good-selectivity method is developed to detect the antibiotics in the water environment, and the method has certain research significance.
At present, the electrochemical analysis detection method has the capabilities of simplicity, rapidness, high sensitivity, low consumption and in-situ on-line detection, and is also applied to the field of water quality detection. The working electrodes used to construct sensors in the past are mainly: glassy carbon electrodes, carbon paste electrodes, metal electrodes, and the like are modified and modified on the surfaces thereof to improve the performance of the electrodes, but the electrodes are expensive, and some electrodes still need complex modification materials and modification methods, which consumes time in the modification process. Therefore, there is a need to develop a simple, fast and low-cost modification method to effectively detect the residual CFX in the water environment.
Disclosure of Invention
Therefore, the embodiment of the invention provides an electrochemical sensor capable of rapidly detecting ciprofloxacin in water and a detection method thereof, and aims to solve the problems that an electrode of the existing electrochemical sensor is expensive, part of the electrode still needs complex modification materials and modification methods, and the modification process is time-consuming.
In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:
according to a first aspect of the embodiments of the present invention, an electrochemical sensor capable of rapidly detecting ciprofloxacin in water is provided, a working electrode of the electrochemical sensor is constructed as a laser-induced graphene electrode, and a preparation method of the laser-induced graphene electrode includes:
the preparation method comprises the steps of taking a polyimide film as a carbon source, taking high-temperature-resistant paper as a substrate, adhering the polyimide film to the substrate of the high-temperature-resistant paper, and irradiating the polyimide film by laser beams for laser induction to obtain the polyimide film.
Further, the preparation method of the laser-induced graphene electrode specifically comprises the following steps:
firstly, cutting a polyimide film from an adhesive tape by using scissors, and sticking the polyimide film on specially-treated high-temperature-resistant paper to ensure flatness and smoothness; then wiping the surface of the polyimide film by using an alcohol cotton ball to remove impurities on the surface of the film, and airing in the air for later use; dividing the high-temperature-resistant paper into pieces with proper sizes so as to align the polyimide film on the surface for laser induction, fixing the polyimide film in a proper position, and enabling the horizontal plane of the polyimide film to be vertical to the angle of laser so as to ensure that the prepared laser-induced graphene electrode is uniform in texture; starting a laser transmitter, selecting a pattern to be printed, setting the laser power and the laser scanning speed of the instrument, adjusting the induction area of the instrument, and then performing laser induction.
Further, the preparation method of the laser-induced graphene electrode further comprises the following steps:
the prepared laser-induced graphene electrode is cut into a rectangle by scissors, a non-conductive blue film is used for tightly adhering, the reaction interface of the laser-induced graphene electrode is controlled while the waterproofness is increased, the reaction interface of the laser-induced graphene electrode is controlled to be a small circle with the diameter of 3mm, and finally the processed laser-induced graphene electrode is placed in a vacuum box for storage.
Further, the laser power is 90W, and the laser scanning speed is 5.
According to a second aspect of the embodiments of the present invention, there is provided a detection method of an electrochemical sensor capable of rapidly detecting ciprofloxacin in water, the detection method including:
the electrochemical sensor uses the laser-induced graphene electrode as a working electrode, the Ag/AgCl electrode and the Pt electrode are respectively used as a reference electrode and an auxiliary electrode, the reference electrode and the auxiliary electrode are connected to an electrochemical workstation, PBS buffer solution is used as background electrolyte, and a cyclic voltammetry method and a differential pulse voltammetry method are used for detecting ciprofloxacin in water.
Further, the detection method comprises the following steps:
the method comprises the steps of carrying out quantitative analysis on ciprofloxacin in water through a differential pulse voltammetry, specifically, testing differential pulse response curves of ciprofloxacin with different concentrations through the differential pulse voltammetry, drawing a linear regression curve according to the relation between peak current and ciprofloxacin concentration to obtain a linear regression equation and a detection limit, testing the differential pulse response curve of an actual water sample through the differential pulse voltammetry, and obtaining the concentration of ciprofloxacin in the actual water sample by combining the linear regression equation according to the peak current of the actual water sample.
Further, the detection method further comprises:
before the actual water sample is detected, the sample is filtered by using a polytetrafluoroethylene membrane to remove physical impurities.
Further, the pH of the PBS buffer solution is 3.
The embodiment of the invention has the following advantages:
according to the electrochemical sensor capable of rapidly detecting ciprofloxacin in water and the detection method thereof, the working electrode of the electrochemical sensor is constructed to be the laser-induced graphene electrode, the polyimide film is used as a carbon source, the high-temperature-resistant paper is used as a substrate, the polyimide film is adhered to the high-temperature-resistant paper substrate, and laser beams are used for irradiating the polyimide film to perform laser induction to obtain the electrochemical sensor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
Fig. 1 is a schematic diagram of a preparation process of an LIG electrode in an electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 2 is an SEM characterization diagram of an LIG electrode in the electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 3 is a raman characterization diagram of an LIG electrode in the electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 4 is a LIG electrode contact angle under different modification powers when the laser scanning speed is 5 in the electrochemical sensor capable of rapidly detecting ciprofloxacin in water provided in embodiment 1 of the present invention;
fig. 5 is an electrochemical impedance spectrum of an LIG electrode under different modification powers at a laser scanning speed of 5 in the electrochemical sensor capable of rapidly detecting ciprofloxacin in water provided in embodiment 1 of the present invention;
fig. 6 is a diagram illustrating an oxidation peak current value of CFX detected by an LIG electrode manufactured with different laser powers in an electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 7 is a linear regression curve of DPV response peak potentials of different PHs and LIG electrodes to CFX in the electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 8 shows Zeta potentials of LIG electrodes at different pH values in an electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 9 is a linear regression curve of CV response peak currents of different sweep rates and LIG electrodes to CFX in the electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 10 is a linear regression curve of CFX at different concentrations of an electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to embodiment 1 of the present invention;
fig. 11 is an anti-interference detection of an LIG electrode in an electrochemical sensor capable of rapidly detecting ciprofloxacin in water, provided by embodiment 1 of the present invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides an electrochemical sensor capable of rapidly detecting ciprofloxacin in water, and a working electrode for constructing the electrochemical sensor is a laser-induced graphene electrode.
Laser-Induced Graphene (LIG) is a substance of Graphene prepared by an advanced Laser-Induced Graphene technology. The method takes a Polyimide (PI) film as a carbon source, instantaneous extremely high temperature is generated by laser to act on the surface of the PI film, and chemical substances on the surface of the PI film are heated and combusted by the laser, so that interconnected two-dimensional carbon structures are reserved. The polyimide film has a special porous layered fiber network structure, and can uniformly absorb the energy irradiated by laser, thereby greatly reducing the problems of structural deformation, sponginess, damage, defocusing and other material preparation caused by the graphitization process. The laser-induced graphene has excellent physical and chemical properties such as mechanics, electricity, piezoresistance, capacitance, super-hydrophobicity and the like. In the field of electrochemical sensors, the laser-induced graphene embodies certain advantages, such as simple preparation, low cost, good conductivity and stable physical structure, can be used for constructing flexible sensors, is not easy to fall off, and the like.
As shown in fig. 1, the preparation method of the laser-induced graphene electrode includes: the preparation method comprises the steps of taking a polyimide film as a carbon source, taking high-temperature-resistant paper as a substrate, adhering the polyimide film to the high-temperature-resistant paper substrate, and irradiating the polyimide film by laser beams for laser induction to obtain the polyimide film.
The method specifically comprises the following steps: firstly, cutting a polyimide film from an adhesive tape by using scissors, and sticking the polyimide film on specially-treated high-temperature-resistant paper to ensure flatness and smoothness; then wiping the surface of the polyimide film by using an alcohol cotton ball to remove impurities on the surface of the film, and airing in the air for later use; dividing the high-temperature-resistant paper into pieces with proper sizes so as to align the polyimide film on the surface for laser induction, fixing the polyimide film in a proper position, and enabling the horizontal plane of the polyimide film to be vertical to the angle of laser so as to ensure that the prepared laser-induced graphene electrode is uniform in texture; and starting a Nano Pro-III type laser transmitter, selecting a pattern to be printed, setting the laser power and the laser scanning speed of the instrument, adjusting the induction area of the instrument, and then performing laser induction.
Further, the preparation method of the laser-induced graphene electrode further comprises the following steps of pretreating the electrode: the prepared laser-induced graphene electrode is cut into a rectangle by scissors, a non-conductive blue film is used for tight adhesion, the reaction interface of the laser-induced graphene electrode is controlled while the waterproofness is increased, the reaction interface of the laser-induced graphene electrode is controlled to be a small circle with the diameter of 3mm, and finally the processed laser-induced graphene electrode is placed in a vacuum box for storage and standby application.
Electrode characterization test:
(1) SEM characterization
Fig. 2 is an SEM characterization diagram of the LIG electrode under different magnifications, and it can be seen from fig. 2(a) that the LIG electrode interface morphology is multi-layer and multi-fold, and fig. 2(C) (D) that under more microscopic characterization, the LIG electrode interface has a flocculent structure, which greatly increases the specific surface area of the electrode surface, provides more reaction sites for the electrochemical oxidation of CFX on the electrode surface, and thus improves the electrochemical response of the electrode.
(2) Raman characterization
Fig. 3 is a raman characterization diagram of the LIG electrode, and fig. 3 clearly shows a D-peak, a G-peak, and a 2D-peak, where the D-peak represents a defect of a crystal lattice, the presence of the 2D-peak indicates that the material generated after laser induction is graphene-like, and the D-peak is higher than the 2D-peak, indicating that the LIG material has many defects.
(3) Contact Angle Characterisation (CA)
Fig. 4 shows the contact angle of the LIG electrode at different modification powers at a laser scanning speed of 5, and fig. 4(a) shows the contact angle of the electrode at an induced power of 60W, θ being 84.2 °; fig. 4(B) shows the contact angle of the electrode at an induction power of 70W, θ being 72.1 °; fig. 4(C) shows the contact angle of the electrode at an induction power of 80W, θ being 65.1 °; fig. 4(D) shows the contact angle of the electrode when the induced power is equal to 90W, and θ is 46.4 °. Fig. 4(a) - (D) show that the contact angle of the LIG electrode gradually decreases during the gradual increase of the induction power by 3, which may be due to the fact that the LIG electrode is not graphitized to a high degree at a lower induction power, some polyimide is not completely converted into graphene, and polyimide is poor in hydrophilicity, resulting in poor hydrophilicity of the electrode; the polyimide can be fully graphitized by higher induction power, and oxygen-containing functional groups exist on the surface of the LIG, so that the hydrophilicity of the electrode is better.
Electrode electrochemical behavior test:
by adjusting different laser powers and laser scanning speeds, the electrochemical performance difference of the LIG electrode under different laser powers and laser scanning speeds is researched, and the result shows that: the laser power is 90W, the laser scanning speed is 5, the pH of the electrolyte solution is 3, and the scanning rate of the cyclic voltammetry is 200 mV.s-1The LIG electrode exhibits good electrochemical performance.
(1) Electrochemical characteristics of electrodes under different laser scanning speeds and powers
To evaluate the electrochemical activity of the LIG electrodes induced by different laser powers (70W, 80W, 90W, 100W) and scan speeds (1, 5, 10), different electrodes were scanned using Cyclic Voltammetry (CV). The experiment was carried out in a medium containing 5mM K3[Fe(CN)6]In 1M KCl solution. The result shows that the LIG electrode has better electrochemical performance when the laser scanning speed is 5.
The electron transport resistance of the LIG electrode was studied by Electrochemical Impedance Spectroscopy (EIS) in the presence of 5mM K3[Fe(CN)6]In 1M KCl solution, using a frequency range of 1Hz to 100 kHz. Fig. 5 shows an EIS diagram of the LIG electrode under different laser power modifications at a laser scanning speed of 5, and it can be seen that the electrochemical impedance of the LIG electrode is smaller as the power is increased; under the same laser scanning speed, along with the increase of the laser power, the electrochemical impedance of the LIG electrode is gradually reduced, and the reduction value is decreased progressively, which shows that the electrochemical impedance of the LIG electrode is greatly influenced by the change of the laser power under low power; fig. 5 shows that the LIG electrode has better ability to transfer electrons under the condition of higher laser power.
(2) Optimization of trim power
As shown in fig. 6, when the laser power is increased from 60W to 90W, the oxidation peak current value of CFX is gradually increased, when 90W is increased to 100W, the oxidation peak current value of CFX is decreased, and when the laser power is 90W, the oxidation peak current value of CFX is the highest. The reason is that when the laser power is increased from 60W to 90W, the laser induces the polyimide surface to promote the polyimide surface to generate graphene, the polyimide is not sufficiently induced into graphene at low power, and the polyimide is completely converted into graphene along with the increase of the power, so that the electrochemical performance of the LIG is continuously increased; as the laser power continues to increase to 100W, the thickness of the LIG becomes larger due to the power being too high, and the background current at which the LIG detects CFX increases, resulting in a decrease in its electrochemical response. Therefore, 90W was selected as the optimum laser power for this experiment.
(3) Electrolyte solution pH optimization
To determine the optimal pH for detection of CFX, the pH of the electrolyte solution (3-9) was optimized experimentally. The results show that both the oxidation peak current and oxidation peak potential of CFX are different at different pH, as shown in fig. 7, the electrochemical response of CFX oxidation peak gradually decreases as pH increases from 3 to 9, which is probably due to the coulomb electrostatic force and other forces existing between CFX and LIG at different pH, so that the electrochemical response of LIG to CFX is maximum at pH 3, and therefore, PBS buffer solution with pH 3 is finally selected as the best supporting electrolyte for the experiment. Meanwhile, as shown in FIG. 8, oxidation peak potential of CFX is dependent on pHIncreasing and moving negatively in the range of 2-9. The linear regression equation between oxidation potential (Ep) and pH is: epa (V) ═ 1.3133(V) -0.0621 · pH (correlation coefficient, R)2＝0.9932)。
(4) Optimization of sweeping speed
To explore the electrochemical behavior of CFX on LIG, different scan rates (25, 50, 75, 100, 125, 150, 175, 200 mV. s) were studied using cyclic voltammetry-1) the lower LIG measures the electrochemical response generated by CFX for a 5X 10 solution-5mol·L-1CFX, pH of the electrolyte solution was 3. The results show that as the scan rate increases, the peak current value also gradually increases, while the background current signal also increases significantly. As shown in fig. 9, the peak current (Ipa) and the scan rate are linearly related, and the linear equation can be expressed as follows: ipa (μ a) ═ 0.3559v (mV · s)-1) +10.985 (correlation coefficient, R)20.9836), the results indicate that the oxidation process of CFX on LIG is an adsorption-controlled process.
The detection method of the electrochemical sensor capable of rapidly detecting ciprofloxacin in water, which is provided by the embodiment, comprises the following steps:
the electrochemical sensor uses a laser-induced graphene electrode as a working electrode, an Ag/AgCl electrode and a Pt electrode are respectively used as a reference electrode and an auxiliary electrode and connected to an electrochemical workstation, a PBS (phosphate buffer solution) is used as a background electrolyte, and a cyclic voltammetry method and a differential pulse voltammetry method are used for detecting ciprofloxacin in water.
Under the optimal conditions, ciprofloxacin in water was quantitatively analyzed by differential pulse voltammetry:
specifically, a differential pulse voltammetry is used for testing differential pulse response curves of ciprofloxacin with different concentrations, a linear regression curve is drawn according to the relation between peak current and ciprofloxacin concentration, a linear regression equation and a detection limit are obtained, the differential pulse response curve of an actual water sample is tested through the differential pulse voltammetry, and the concentration of ciprofloxacin in the actual water sample is obtained by combining the linear regression equation according to the peak current of the actual water sample.
In order to obtain higher sensitivity and electrochemical response signal, the method adoptsa stock solution of 1mM CFX was prepared in 0.2M PBS solution (pH 3) as a background electrolyte, and CFX was prepared at various concentrations by adding the stock solution to the background electrolyte, as shown in fig. 10, the concentration of CFX and the resulting peak current were 1 × 10-6—1×10- 4mol·L-1Has a good linear relationship, the linear regression equation can be described as Ipa (μ a) ═ 0.0782CCFX(μM)+0.2951(R20.996) and a detection limit LOD of 7 × 10-7mol·L-1。
In order to verify the practicability of the prepared LIG electrode in practical application, the LIG electrode is used for measuring actual water samples obtained from Taohuajiang and Qingshi pool reservoirs in Guilin, Guangxi province.
And calculating the relative standard deviation (R.S.D.) and recovery rate by adding CFX solutions of different concentrations to the water sample according to a standard addition method and sequentially measuring the CFX concentration in the water solution under similar conditions, the results are shown in Table 1, the recovery rate of ciprofloxacin in the lake water sample is 118.36%, and the recovery rate of R.S.D. is 10.73%; in the reservoir sample, the recovery rate of ciprofloxacin was 108.88%, and the r.s.d. was 8.63%, so that the electrochemical sensor developed in this example was effective and reliable in the determination of CFX in a water sample.
TABLE 1 detection of CFX in real water samples
Figure BDA0002509754600000091
Further, the detection method further comprises the following steps:
before the actual water sample was examined, the sample was filtered using a 0.45 μm teflon membrane to remove physical impurities.
And (3) detecting the interference resistance of the electrode:
the LIG paper-based sensor is mainly prepared for enriching detection means of CFX in domestic water environment, substances coexisting in the water environment generally interfere the sensor, particularly other antibiotics easily interfere the sensor, and a timing current method (i-t) is used for evaluating the anti-interference performance of the LIG paper-based sensor on other antibiotics in the process of detecting CFX by LIGtests show that four concentrations are respectively selected and all the four concentrations are 1 multiplied by 10-4mol·L-1The antibiotic of (1): tetracyclines (aureomycin), quinolones (enoxacin), macrolides (lincomycin) and sulfonamides (sulfapyridine) to investigate their effect on CFX detection. As shown in fig. 11, after ciprofloxacin is added within 400-500 s, the peak current is obviously improved; after aureomycin is added in 500-600 s, the peak current is not obviously changed; in 500-600 s, the peak current is obviously improved by adding the enoxacin, the peak current is not obviously changed after the lincomycin is added, in 700-800 s, the peak current is not obviously changed after the sulfapyridine is added, and the peak current is obviously and greatly improved after the ciprofloxacin is added again; the main reason why the enoxacin has the largest influence on the detection of ciprofloxacin is that the moxifloxacin and the ciprofloxacin are both quinolone antibiotics and have similar structures, so that the detection of CFX is greatly influenced. In general, different antibiotics have limited influence on LIG detection of CFX, and the prepared LIG electrode shows good selectivity on CFX.
Repeatability and reproducibility test of the electrode:
to examine the reproducibility of the modified electrode, 1X 10 concentration was measured 10 times in succession using 1 electrode-4mol·L-1the CFX solution of (1) showed a relative standard deviation (R.S.D.) of 8.94%, indicating that the electrode has good reproducibility, and 5 LIG electrodes were prepared in the same manner and under the same conditions, using 5 LIG electrodes at a concentration of 1X 10 to verify the reproducibility of the electrode-4mol·L-1The r.s.d. of the current response value is 7.68%, which indicates that the sensor prepared based on the LIG electrode has higher reproducibility.
According to the electrochemical sensor capable of rapidly detecting ciprofloxacin in water, a working electrode for constructing the electrochemical sensor is a laser-induced graphene electrode, a polyimide film is used as a carbon source, high-temperature-resistant paper is used as a substrate, the polyimide film is adhered to the base of the high-temperature-resistant paper, and laser induction is performed on the polyimide film through laser beam irradiation. The electrochemical sensor is low in cost and simple to prepare, and can effectively and quickly detect ciprofloxacin in water. LIG has good conductivity, stable physical structure and is not easy to fall off. The LIG electrode has good hydrophilicity, shows a wide linear concentration range for effective detection of CFX in water, has a detection limit of 0.7 mu M, and the LIG sensor has good anti-interference capability for non-target detection objects (such as aureomycin, enoxacin, lincomycin and sulfapyridine), and also has good repeatability and reproducibility, and can determine the content of CFX in a real water environment.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (8)

1. An electrochemical sensor capable of rapidly detecting ciprofloxacin in water is characterized in that a working electrode for constructing the electrochemical sensor is a laser-induced graphene electrode, and a preparation method of the laser-induced graphene electrode comprises the following steps:
the preparation method comprises the steps of taking a polyimide film as a carbon source, taking high-temperature-resistant paper as a substrate, adhering the polyimide film to the substrate of the high-temperature-resistant paper, and irradiating the polyimide film by laser beams for laser induction to obtain the polyimide film.
2. The electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to claim 1, wherein the preparation method of the laser-induced graphene electrode specifically comprises:
firstly, cutting a polyimide film from an adhesive tape by using scissors, and sticking the polyimide film on specially-treated high-temperature-resistant paper to ensure flatness and smoothness; then wiping the surface of the polyimide film by using an alcohol cotton ball to remove impurities on the surface of the film, and airing in the air for later use; dividing the high-temperature-resistant paper into pieces with proper sizes so as to align the polyimide film on the surface for laser induction, fixing the polyimide film in a proper position, and enabling the horizontal plane of the polyimide film to be vertical to the angle of laser so as to ensure that the prepared laser-induced graphene electrode is uniform in texture; starting a laser transmitter, selecting a pattern to be printed, setting the laser power and the laser scanning speed of the instrument, adjusting the induction area of the instrument, and then performing laser induction.
3. The electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to claim 2, wherein the preparation method of the laser-induced graphene electrode further comprises the following steps:
the prepared laser-induced graphene electrode is cut into a rectangle by scissors, a non-conductive blue film is used for tightly adhering, the reaction interface of the laser-induced graphene electrode is controlled while the waterproofness is increased, the reaction interface of the laser-induced graphene electrode is controlled to be a small circle with the diameter of 3mm, and finally the processed laser-induced graphene electrode is placed in a vacuum box for storage.
4. The electrochemical sensor capable of rapidly detecting ciprofloxacin in water according to claim 2, wherein the laser power is 90W, and the laser scanning speed is 5.
5. The method for detecting the electrochemical sensor capable of rapidly detecting the ciprofloxacin in the water according to any one of claims 1 to 4, wherein the method for detecting the ciprofloxacin comprises the following steps:
the electrochemical sensor uses the laser-induced graphene electrode as a working electrode, the Ag/AgCl electrode and the Pt electrode are respectively used as a reference electrode and an auxiliary electrode, the reference electrode and the auxiliary electrode are connected to an electrochemical workstation, PBS buffer solution is used as background electrolyte, and a cyclic voltammetry method and a differential pulse voltammetry method are used for detecting ciprofloxacin in water.
6. The method for detecting the electrochemical sensor capable of rapidly detecting the ciprofloxacin in the water according to claim 5, wherein the method for detecting the ciprofloxacin comprises the following steps:
the method comprises the steps of carrying out quantitative analysis on ciprofloxacin in water through a differential pulse voltammetry, specifically, testing differential pulse response curves of ciprofloxacin with different concentrations through the differential pulse voltammetry, drawing a linear regression curve according to the relation between peak current and ciprofloxacin concentration to obtain a linear regression equation and a detection limit, testing the differential pulse response curve of an actual water sample through the differential pulse voltammetry, and obtaining the concentration of ciprofloxacin in the actual water sample by combining the linear regression equation according to the peak current of the actual water sample.
7. The method for detecting the electrochemical sensor capable of rapidly detecting the ciprofloxacin in the water according to claim 6, wherein the method further comprises the following steps:
before the actual water sample is detected, the sample is filtered by using a polytetrafluoroethylene membrane to remove physical impurities.
8. The method as claimed in claim 5, wherein the PBS buffer solution has a pH of 3.
CN202010457060.1A 2020-05-26 2020-05-26 Electrochemical sensor capable of rapidly detecting ciprofloxacin in water and detection method thereof Pending CN111735863A (en)

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CN113328101A (en) * 2021-08-03 2021-08-31 首都师范大学 Zinc/graphene three-dimensional composite structure cathode for zinc battery and preparation method thereof
CN114323852A (en) * 2021-12-27 2022-04-12 山东大学 Preparation method and application of laser-induced graphene without pinning effect
CN115096482A (en) * 2022-06-24 2022-09-23 山东大学 Flexible deformation pressure sensor and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112903773A (en) * 2021-01-19 2021-06-04 江西农业大学 Preparation method and application of hollow gold nanoshell modified flexible laser-induced graphene electrode
CN112903768A (en) * 2021-01-21 2021-06-04 江苏集萃微纳自动化系统与装备技术研究所有限公司 Preparation method of electrochemical immunosensor based on laser-induced graphene
CN113311044A (en) * 2021-06-19 2021-08-27 中国地质大学（北京） Sensor capable of rapidly detecting nitrite in water environment and detection method
CN113328101A (en) * 2021-08-03 2021-08-31 首都师范大学 Zinc/graphene three-dimensional composite structure cathode for zinc battery and preparation method thereof
CN114323852A (en) * 2021-12-27 2022-04-12 山东大学 Preparation method and application of laser-induced graphene without pinning effect
CN114323852B (en) * 2021-12-27 2023-08-29 山东大学 Preparation method and application of laser-induced graphene without pinning effect
CN115096482A (en) * 2022-06-24 2022-09-23 山东大学 Flexible deformation pressure sensor and preparation method thereof
CN115096482B (en) * 2022-06-24 2024-03-12 山东大学 Flexible pressure sensor and preparation method thereof

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