CN113945529A - Method for detecting and purifying methcathinone in sewage based on dual-function recyclable magnetic fluorescent sensor - Google Patents

Method for detecting and purifying methcathinone in sewage based on dual-function recyclable magnetic fluorescent sensor Download PDF

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CN113945529A
CN113945529A CN202111206483.7A CN202111206483A CN113945529A CN 113945529 A CN113945529 A CN 113945529A CN 202111206483 A CN202111206483 A CN 202111206483A CN 113945529 A CN113945529 A CN 113945529A
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methcathinone
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丁艳君
凌江
石坚
张文琦
成子佳
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Central South University
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Abstract

The invention discloses a method for detecting and purifying methcathinone in sewage based on a dual-function recyclable magnetic fluorescence sensor. Meanwhile, high-quality magnetic nano Fe serving as a fluorescent signal carrier and a magnetic collection functional group is synthesized by adopting a high-temperature coprecipitation method3O4And adding tetraethoxysilane to isolate Fe3O4. Then, respectively using 3-aminopropyl triethoxysilane, TEOS and ammonia water solution as functional monomer, cross-linking agent and catalyst, and making the template pass through the sol-gel polymerization methodMolecular methyl casitone and fluorescent signal molecules Si-CDs are uniformly imprinted on Fe3O4A surface. After the template is eluted, a cavity with high specificity and affinity to the methcathinone is exposed on the surface of the sensor, and the construction of the MFMIPs sensor is completed.

Description

Method for detecting and purifying methcathinone in sewage based on dual-function recyclable magnetic fluorescent sensor
Technical Field
The invention relates to a method for detecting and purifying methcathinone, in particular to a method for detecting and purifying methcathinone in sewage based on a dual-function recyclable magnetic fluorescent sensor. Belongs to the technical field of composite optical material preparation and forensic medicine drug (medicine) analysis and detection.
Background
At present, illegal drug abuse is still a serious global problem, and seriously threatens the stability and safety of the society. In 2009, 2.1 million people are estimated to use the methcathinone, accounting for 4.8% of the population of 15-64 years of age worldwide, and in 2018, 2.69 million people are estimated to use the methcathinone, accounting for 5.3% of the total population, of which the majority are the users abusing the methcathinone. The large scale of abuse, coupled with its concealment and diversity, undoubtedly increases the difficulty of monitoring.
Compared with traditional monitoring methods such as crime statistics, medical records and population surveys, the wastewater-based epidemiology (WBE) is an emerging and powerful tool and is more effective in monitoring drug circulation and consumption in a specific area. Generally, WBE is carried by measuring the levels of target drugs (or metabolites) and population markers in wastewater from centralized wastewater treatment plants, and the per-capita drug consumption rate in the region is inversely estimated by combining wastewater treatment capacity and population size. WBE has been widely used in drug abuse assessment worldwide for the past decade with its advantages of time saving, high accuracy, and the ability to effectively monitor certain high-incidence areas of drug abuse.
In fact, the analytical tools used to evaluate these targets during their application are mainly based on expensive instruments, which must be installed in the laboratory and operated by a skilled technician, such as liquid chromatography-tandem mass spectrometry (LC-MS/MS), for the detection of chemical substances or their metabolites with high sensitivity, high selectivity and high stability. However, the expensive requirements of the instruments and the limitations of laboratory analysis have limited the widespread use of these techniques. In recent years, biosensors using highly specific optical substances in combination with colorimetry, fluorescence and electrochemical biosensing platforms have become an effective alternative, showing the capability of trace sewage analysis and detection; however, these methods have only a single analytical function and most of them do not have the ability to be recycled and reused and purified. Therefore, a new method with double functions of recycling and purifying is provided, and the method has important application value and theoretical significance for accurate, efficient and low-cost detection of the methcathinone in the sewage.
The rapid development of nanomaterial-related technologies offers tremendous opportunities to design selective and sensitive sensors for the detection of illegal drug analysis. In recent years, Carbon Dots (CDs) have received much attention due to their excellent optical, chemical and physical properties. Because the nano-carbon material has an ultra-small photoluminescence carbon nano structure and a plurality of surface functions, CDs are easy to functionalize, have an excellent optical sensing function, and are widely applied to the fields of biosensing, fluorescence imaging, biomedicine, chemical sensing and the like. Molecularly Imprinted Polymers (MIPs) are an emerging detection technology based on target recognition and analysis of modular molecular size, shape and functional group memory functions. Combining fluorescent signaling materials (e.g., CDs) with MIPs to achieve trace target detection based on fluorescent signal response is a currently popular approach. Since the target and the target have complementarity in size, shape and function, the recognition site formed on the MIPs can accurately recognize the target. In addition, under the signal response, the fluorescence intensity can linearly reflect the content of the target object. Magnetic nanoparticles, in particular Fe, on the other hand3O4NPs nanoparticles have been studied by researchers in the fields of targeted drug delivery and hyperthermia magnetic resonance imaging for cancer. One of the most important properties of magnetic nanoparticles is that they can be rapidly collected, separated and immobilized by an external magnetic field. Inspired by the above technology, combined with CDs, MIPs and Fe3O4NPs and WBE technologyA novel fluorescence sensor was developed which would be a multifunctional, recyclable Magnetic Fluorescence Molecular Imprinting Sensor (MFMIPs) for rapid detection and purification of methcathinone in sewage.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for detecting and purifying methcathinone in sewage based on a dual-function recyclable magnetic fluorescence sensor.
In order to achieve the purpose, the invention adopts the following technical scheme:
1. a preparation method of a dual-function recyclable magnetic fluorescence sensor comprises the following specific steps:
(1) firstly, preparing carbon-point CDs by using o-phenylenediamine as a raw material, and then carrying out silanization modification on the CDs by using 3-aminopropyltriethoxysilane to obtain Si-CDs;
(2) preparing nano ferroferric oxide by using ferric chloride hexahydrate and ferrous chloride tetrahydrate as raw materials in the presence of polyacrylic acid, and performing silanization treatment on the nano ferroferric oxide by using tetraethoxysilane to obtain silanized nano ferroferric oxide;
(3) and then uniformly dispersing silanized nano ferroferric oxide in absolute ethyl alcohol, adding methcathinone and Si-CDs, uniformly oscillating by ultrasonic waves, adding 3-aminopropyltriethoxysilane and tetraethoxysilane while stirring, finally adding ammonia water to initiate polymerization reaction, and performing post-treatment to obtain the sensor.
Preferably, in the step (1), the carbon dots CDs are prepared by the following method in parts by weight: dissolving 0.15-0.25 part of o-phenylenediamine in 20-40 parts of deionized water, adding 0.06-0.07 part of 65-70% nitric acid solution by mass, uniformly stirring, transferring into an autoclave, carrying out heat treatment at 160-240 ℃ for 12-48 hours, cooling, dialyzing, and freeze-drying to obtain the carbon dot CDs.
More preferably, the large particles are removed by using a 0.22 mu m polyethersulfone membrane, and then dialyzed for 12-48 hours by using a 500Da dialysis bag.
Preferably, in the step (1), the preparation method of Si-CDs comprises the following steps: dissolving 10-30 parts of CDs in 5-20 parts of absolute ethyl alcohol, adding 0.1-0.2 part of 3-Aminopropyltriethoxysilane (APTES), and stirring at room temperature for 24 hours to obtain the Si-CDs.
Preferably, in the step (2), the preparation method of the nano ferroferric oxide comprises the following steps: firstly, dissolving 5-20 parts of polyacrylic acid (PAA) in 15-60 parts of deionized water, transferring the solution into a three-necked bottle, purging the solution for 30-60 minutes in a nitrogen atmosphere, and then heating the solution to 75 ℃ to obtain a polymer solution; simultaneously, 0.584 part of FeCl3·6H2O and 0.222 part FeCl2·4H2Dissolving O in 1 part of 1mol/L hydrochloric acid solution to obtain a mixed iron solution; and then, under the nitrogen atmosphere and stirring, quickly injecting the mixed iron solution into the polymer solution, then adding 15 parts of ammonia water solution with the mass concentration of 28%, refluxing for 20-60 minutes at 50-100 ℃ after the solution turns black, and performing post-treatment to obtain the nano ferroferric oxide.
Further preferably, after the solution turns black, it is refluxed at 75 ℃ for 40 minutes.
Further preferably, the post-treatment comprises: centrifuging to obtain a precipitate to obtain a black product; and finally, alternately washing the black product by deionized water and absolute ethyl alcohol under the action of an external magnetic field for 3 times, and drying for 4 hours at 60 ℃.
Preferably, in the step (2), the preparation method of the silanized nano ferroferric oxide comprises the following steps in parts by weight: dissolving 20 parts of nano ferroferric oxide in 15 parts of 80% ethanol solution with volume concentration, performing ultrasonic treatment for 20 minutes, adding 0.1 part of 28% ammonia water with mass concentration of 28% and 0.3 part of Tetraethoxysilane (TEOS), performing ultrasonic oscillation at room temperature for 12-24 hours, and performing post-treatment to obtain silanized nano ferroferric oxide Fe3O4NPs@SiO2。
Further preferably, the post-treatment comprises: centrifuging to obtain a precipitate, alternately washing the precipitate for 2-3 times by using 1mol/L hydrochloric acid solution, absolute ethyl alcohol and ultrapure water under the action of an external magnetic field, and drying the precipitate for 4 hours at the temperature of 60 ℃.
Preferably, the specific method of step (3) is as follows, in parts by weight: firstly, 10 parts of Fe3O4NPs@SiO210 parts by volume of 8And (2) carrying out ultrasonic oscillation treatment for 20 minutes in 0% ethanol solution, then adding 10 parts of methcathinone and 0.5 part of Si-CDs, continuing the ultrasonic oscillation treatment for 20 minutes, then adding 0.04 part of APTES and 0.2 part of TEOS while stirring, then adding 0.1 part of ammonia water solution with the mass concentration of 28% to initiate polymerization reaction, carrying out polymerization reaction for 12 hours, and carrying out post-treatment to obtain the sensor.
Further preferably, the post-treatment comprises: the volume ratio of 9: 1, washing the mixed solution of ethanol and acetic acid for multiple times by ultrasound, detecting by using an ultraviolet-visible spectrophotometer until no methcathinone exists in the washing solvent, and drying for 4 hours at 60 ℃.
2. The difunctional recyclable magnetic fluorescent sensor is obtained by the preparation method.
3. The magnetic fluorescence sensor is applied to the detection of the methcathinone in the sewage.
4. The method for detecting the methcathinone in the sewage based on the dual-function recyclable magnetic fluorescent sensor comprises the following specific steps:
(A) firstly, dispersing the sensor in absolute ethyl alcohol by ultrasonic waves to obtain a working solution, then uniformly mixing the working solution and a standard solution of the methcathinone, recording the fluorescent response of the sensor to the addition of the methcathinone, and drawing a standard curve;
(B) and (D) magnetically separating and recovering the sensor, fully washing, dispersing the sensor in a sewage sample by ultrasonic waves to obtain a sample solution, detecting the fluorescence intensity, and determining the content of the methcathinone in the sewage according to the standard curve in the step (A).
5. The magnetic fluorescent sensor is applied to purifying the methcathinone in the sewage.
6. The method for purifying the methcathinone in the sewage based on the dual-function recyclable magnetic fluorescent sensor comprises the following specific steps:
(a) firstly, uniformly dispersing the sensors in water to prepare an aqueous solution, then injecting the aqueous solution into an annular diversion hose, and uniformly fixing the sensors at the bottom of the hose by virtue of an external magnetic field to form a purification device;
(b) then, injecting the sewage sample into a purification device, and realizing the purification of the methcathinone in the sewage through the adsorption effect of a sensor at the bottom of a hose.
The invention has the beneficial effects that:
the invention synthesizes fluorescent carbon dots by using o-phenylenediamine as a carbon source, and then silane functionalization is carried out by using APTES to obtain silanized carbon dots (Si-CDs). Meanwhile, high-quality magnetic nano Fe serving as a fluorescent signal carrier and a magnetic collection functional group is synthesized by adopting a high-temperature coprecipitation method3O4And adding tetraethyl orthosilicate (TEOS) to isolate Fe3O4. Then, respectively taking 3-aminopropyltriethoxysilane, TEOS and 28% ammonia water solution as functional monomers, a cross-linking agent and a catalyst, and uniformly imprinting template molecules of methylcardienone and fluorescent signal molecules of Si-CDs on Fe by a sol-gel polymerization method3O4A surface. After the template is eluted, a cavity with high specificity and affinity to the methcathinone is exposed on the surface of the sensor, and the construction of the MFMIPs sensor is completed.
During the sensing process, the Si-CDs embedded in the imprinted layer during imprinted polymerization is considered as a stable fluorescent signal indicator. The recognition cavity on the surface of the MFMIPs sensor can be specifically combined with the methcathinone, and the fluorescence after quenching of the CDs is obtained through Photoinduced Electron Transfer (PET) between hydroxyl on the surface of the CDs and primary amino of the methcathinone. In addition, the difunctional MFMIPs surface cavity has strong adsorption capacity to the methcathinone, can purify sewage and can be recycled under an external magnetic field.
The method has great potential for detecting and purifying the methcathinone in the sewage, monitors the drug prevalence and consumption condition of a certain community based on WBE, and has the unique advantages of rapidness, simple operation, no need of expensive instruments and the like.
The specific analysis is as follows:
(1) the invention utilizes molecular imprinting technology to identify and combine with the methcathinone to form a specific cavity, is not influenced by other molecules and has extremely high specificity to the methcathinone.
(2) The invention uses magnetic nano Fe3O4As fluorescent signal carrier and magnetic collection functional group, so that MFThe MIPs sensor achieves effective recovery and reuse for at least 5 times under the action of an external magnetic field.
(3) The magnetic fluorescence sensor MFMIPs developed by the invention has excellent correlation to the cassidone within the concentration range of 0.5-100nM, the detection limit reaches 0.2nM, and the trace detection of the cassidone in the sewage is realized.
(4) The dual-function based recyclable magnetic fluorescence sensor designed by the invention only needs a fluorescence spectrometer, has low cost and can be widely popularized.
(5) The dual-function recyclable magnetic fluorescent sensor fluorescent probe for the methcathinone detection and purification has the advantages of easily controlled conditions, simple operation, low energy consumption, clean production process and batch production.
(6) The difunctional recyclable magnetic fluorescent sensor fluorescent probe for the methcathinone detection and purification is safe, nontoxic, environment-friendly, pollution-free and widely applicable.
(7) The method has the advantages of fewer types of used reagents, simple operation, quickness and low cost; the material has good stability, can be stored for a long time, and can ensure the determination effect.
(8) The method for measuring the methcathinone provided by the invention can be used for measuring the concentration of the methcathinone in body fluids such as blood, urine, vitreous humor and the like in human bodies and animals, can also be used for measuring the concentration of the methcathinone in other samples such as water quality and the like, and is wide in application.
(9) The method for determining the concentration of the methcathinone in the sewage can quickly and accurately determine the concentration of the methcathinone, applies a fluorescence technology to judicial identification for the first time, and provides a method for monitoring abused substances in the sewage.
(10) The MFMIPs magnetic material developed by the invention can realize the adsorption and purification of the methcathinone in the sewage, and the purification capacity of the MFMIPs magnetic material reaches 0.27 mg/g; has quite important application potential in the aspect of sewage treatment.
Drawings
FIG. 1 is the preparation of nano Fe according to the present invention3O4(A) And TEM images (B) of MFMIPs;
FIG. 2 is an infrared diagram of the present invention for preparing MFMIPs;
FIG. 3 is a magnetic investigation diagram of the present invention for preparing MFMIPs; under the action of an external magnetic field, MFMIPs dissolved in water can be rapidly concentrated on one side close to the magnet;
FIG. 4 is a graph showing the measurement of fluorescence intensity at 520nm of a wastewater containing methcathinone according to a standard curve of the present invention; as shown by the direction of the arrow in the figure, when the amount of added methcathinone was slowly increased from 0 to 100nM, the fluorescence intensity of MFMIPs was decreased from 7100a.u. to 5431a.u. in turn.
FIG. 5 is a standard graph obtained from FIG. 4;
FIG. 6 is a selective study of MFMIPs prepared in accordance with the present invention on mecamylamine-like abuse substances, including methamphetamine, cocaine, ketamine, morphine, codeine, amphetamine, etc.;
FIG. 7 is a schematic view of the homemade apparatus for purifying methcathinone of the present invention;
fig. 8 is a graph of the number of reuses of MFMIPs sensors prepared by the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1:
the MFMIPs sensor is synthesized by the following specific steps:
(1) preparation of silanized fluorescent carbon dots Si-CDs: 0.15g of o-phenylenediamine is dissolved in 20mL of deionized water, 0.06g of a 65% nitric acid solution is added, and the mixture is stirred uniformly. The resulting solution was transferred to a Teflon-lined autoclave (50 ml) lined with Teflon at 160 ℃ for 8 h. The reaction product was cooled and large particles removed using a 0.22 μm polyethersulfone membrane and dialyzed in a 500Da dialysis bag for 12 h. The resulting solution of CDs was lyophilized. Si-CDs: 10mg of CDs was dissolved in 5mL of ethanol, and 0.1mL of 3-Aminopropyltriethoxysilane (APTES) was added thereto, followed by stirring at room temperature overnight. Thus obtaining the Si-CDs.
(2)Fe3O4Synthesizing: dissolving 5mg polyacrylic acid (PAA) in 15ml deionized water, and standingIn a 200ml three-necked flask, nitrogen was blown for 30min and then heated to 75 ℃. At the same time, 0.584g FeCl3·6H2O and 0.222g FeCl2·4H2O was dissolved in 1mL of dilute hydrochloric acid (1M). Under nitrogen atmosphere and stirring, the mixed iron precursor was then rapidly injected into the polymer solution, followed by addition of 15ml of 28% by mass aqueous ammonia solution, and refluxing at 75 ℃ for 20 minutes after the solution became black. And (3) cooling the black product, washing the black product for 3 times by using deionized water and ethanol under the action of an external magnetic field, and drying the black product for 4 hours at the temperature of 60 ℃ to obtain the nano ferroferric oxide (A in the figure 1).
(3) Silanized Fe3O4: 20mg of Fe3O4Dissolved in a mixture of 12mL of ethanol and 3mL of water, sonicated for 20min, and then 0.1mL of a 28% by mass aqueous ammonia solution having a mass concentration of 28% and 0.3mL of Tetraethylorthosilicate (TEOS) were added and vibrated at room temperature for 12 hours. The obtained Fe3O4NPs@SiO2Washing with hydrochloric acid (1M), ethanol and ultrapure water under external magnetic action, removing excessive reactant, and drying at 60 deg.C for 4 hr.
(4) Synthesis of MFMIPs sensor: 10mg Fe3O4NPs@SiO2Dissolve in 10mL ethanol/water (v, v,4:1) for 20min with sonication. Then 10mg of methcathinone and 0.5mL of Si-CDs were added to the above solution and sonication continued for 20 minutes. Thereafter, 40. mu.L of APTES and 200. mu.L of TEOS were added to the solution with constant stirring. Then 0.1mL of ammonia water solution with mass concentration of 28% and ammonia water solution with mass concentration of 28% are added to initiate polymerization reaction, after polymerization for 12 hours, ethanol/acetic acid (90:10, v/v) is used for ultrasonic multiple washing, and an ultraviolet-visible spectrophotometer is used for detecting until no methcathinone template exists in a washing solvent. And drying in an oven at 60 ℃ for 4h to obtain the MFMIPs sensor.
Example 2:
the MFMIPs sensor comprises the following specific steps:
(1) preparation of silanized fluorescent carbon dots Si-CDs: 0.25g of o-phenylenediamine is dissolved in 40mL of deionized water, 0.07g of nitric acid solution with the mass concentration of 70% is added, and the mixture is stirred uniformly. The resulting solution was transferred to a Teflon-lined autoclave (50 ml) lined with Teflon at 240 ℃ for 12 h. The reaction product was cooled and large particles removed using a 0.22 μm polyethersulfone membrane and dialyzed in a 500Da dialysis bag for 48 h. The resulting solution of CDs was lyophilized. Si-CDs: 30mg of CDs was dissolved in 20mL of ethanol, and 0.2mL of 3-Aminopropyltriethoxysilane (APTES) was added thereto, followed by stirring at room temperature overnight. Thus obtaining the Si-CDs.
(2)Fe3O4Synthesizing: 20mg of polyacrylic acid (PAA) were dissolved in 60ml of deionized water, placed in a 200ml three-necked flask, purged with nitrogen for 60min, and then heated to 75 ℃. At the same time, 0.584g FeCl3·6H2O and 0.222g FeCl2·4H2O was dissolved in 1mL of dilute hydrochloric acid (1M). Under nitrogen atmosphere and stirring, the mixed iron precursor is then rapidly injected into the polymer solution, then 15ml of 28% ammonia solution by mass concentration is added, and the solution is refluxed for 20-60 minutes at 75 ℃ after being blackened. And (3) cooling the black product, washing the black product for 5 times by using deionized water and ethanol under the action of an external magnetic field, and drying the black product for 4 hours at the temperature of 60 ℃ to obtain the nano ferroferric oxide.
(3) Silanized Fe3O4: 20mg of Fe3O4Dissolved in a mixture of 12mL of ethanol and 3mL of water, sonicated for 20min, then 0.1mL of 28% strength by mass aqueous ammonia and 0.3mL of Tetraethylorthosilicate (TEOS) were added and shaken at room temperature for 24 h. The obtained Fe3O4NPs@SiO2Washing with hydrochloric acid (1M), ethanol and ultrapure water under external magnetic action, removing excessive reactant, and drying at 60 deg.C for 4 hr.
(4) Synthesis of MFMIPs sensor: 10mg Fe3O4NPs@SiO2Dissolve in 10mL ethanol/water (v, v,4:1) for 20min with sonication. Then 10mg of methcathinone and 0.5mL of Si-CDs were added to the above solution and sonication continued for 20 minutes. Thereafter, 40. mu.L of APTES and 200. mu.L of TEOS were added to the solution with constant stirring. Then 0.1mL of ammonia water solution with the mass concentration of 28% is added to initiate polymerization reaction, after 24 hours of polymerization, ethanol/acetic acid (90:10, v/v) is used for ultrasonic multiple washing, and an ultraviolet-visible spectrophotometer is used for detecting until the washing solvent has no methcathinone template. And drying in an oven at 60 ℃ for 4h to obtain the MFMIPs sensor.
Example 3:
a method for detecting and purifying methcathinone in sewage by using a dual-function recyclable magnetic fluorescent sensor is carried out according to the following steps:
(1) preparation of silanized fluorescent carbon dots Si-CDs: 0.2g of o-phenylenediamine is dissolved in 30mL of deionized water, 0.065g of a 68% nitric acid solution is added, and the mixture is stirred uniformly. The resulting solution was transferred to a Teflon-lined autoclave (50 ml) lined with Teflon and heat treated at 200 ℃ for 10 h. The reaction product was cooled and large particles removed using a 0.22 μm polyethersulfone membrane and dialyzed in a 500Da dialysis bag for 24 h. The resulting solution of CDs was lyophilized. Si-CDs: 20mg of CDs was dissolved in 5-20mL of ethanol, and 0.15mL of 3-Aminopropyltriethoxysilane (APTES) was added thereto, followed by stirring at room temperature overnight. Thus obtaining the Si-CDs.
(2)Fe3O4Synthesizing: 10mg of polyacrylic acid (PAA) were dissolved in 30ml of deionized water, placed in a 200ml three-necked flask, purged with nitrogen for 45min, and then heated to 75 ℃. At the same time, 0.584g FeCl3·6H2O and 0.222g FeCl2·4H2O was dissolved in 1mL of dilute hydrochloric acid (1M). The mixed iron precursor was then rapidly injected into the polymer solution under nitrogen with stirring, followed by addition of 15ml of 28% strength by mass aqueous ammonia (28%), and refluxing at 75 ℃ for 40 minutes after the solution became black. And (3) cooling the black product, washing the black product for 4 times by using deionized water and ethanol under the action of an external magnetic field, and drying the black product for 4 hours at the temperature of 60 ℃ to obtain the nano ferroferric oxide (A in the figure 1).
(3) Silanized Fe3O4: 20mg of Fe3O4Dissolved in a mixture of 12mL of ethanol and 3mL of water, sonicated for 20min, then 0.1mL of 28% strength by mass aqueous ammonia and 0.3mL of Tetraethylorthosilicate (TEOS) were added and shaken at room temperature for 20 h. The obtained Fe3O4NPs@SiO2Washing with hydrochloric acid (1M), ethanol and ultrapure water under external magnetic action, removing excessive reactant, and drying at 60 deg.C for 4 hr.
(4) Synthesis of MFMIPs sensor: 10mg Fe3O4NPs@SiO2Dissolve in 10mL ethanol/water (v, v,4:1) for 20min with sonication. Then 10mg of methcathinone and 0.5mL of Si-CDs were added to the above solution and sonication continued for 20 minutes. Thereafter, 40. mu.L of APTES and 200. mu.L of TEOS were added to the solution with constant stirring. Then 0.1mL of ammonia water solution with the mass concentration of 28% is added to initiate polymerization reaction, and after polymerization for 18h, the mixture is usedEthanol/acetic acid (90:10, v/v) was washed with ultrasound for several times and detected by uv-vis spectrophotometer until there was no methcathinone template in the wash solvent. MFMIPs (B in figure 1, figure 2, figure 3) are obtained after drying in an oven at 60 ℃ for 4 h.
(5) And (3) detecting the methcathinone: the obtained MFMIPs sensor was dispersed in ethanol under ultrasound to ensure uniform dispersion, and a fresh working solution (0.25mg/mL) was prepared. Mixing 500 mu L of the prepared MFMIPs working solution with 500 mu L of the methcathinone standard solution with the final concentration in the range of 0.5-200 nM, shaking for about 10min, recording the fluorescence response of the sensor to the addition of the methcathinone (figure 4), and drawing a calibration curve (figure 5).
(6) Selectivity of MFMIPs sensors to methcathinone: referring to step (5), the fluorescence response of 0.25mg/mL MFMIPs to various interferents in wastewater, including methamphetamine, ketamine, cathinone, morphine, cocaine and amphetamine, was examined to evaluate the selectivity of the fluorescence sensor for the detection of mecamylamine (fig. 6). 500. mu.L of MFMIPs working solution prepared above was mixed with 500. mu.L of an interfering substance (both interferent addition concentrations were 100nM), shaken for about 10min, and the fluorescence response of the sensor was recorded. As shown in FIG. 6, the fluorescence change of MFNIPs to interfering substances is significantly similar to that of methylcardinone in wastewater, indicating that MFNIPs cannot specifically recognize and bind to methylcardinone. However, MFMIPs respond much more to methcathinone than interfering substances, indicating that MFMIPs can bind selectively to the target molecule. These results indicate that MFMIPs can be used for the selective detection of methcathinone in wastewater.
(7) Purifying the methcathinone in the sewage: 20mL of MFMIPs (0.25mg/mL) solution is injected into a 10-meter long annular diversion hose and is uniformly fixed at the bottom of the hose by virtue of an external magnetic field to form a self-made purification device (figure 7). After the sewage sample is subjected to centrifugation and pH adjustment pretreatment, the sewage sample is injected into a self-made device from a water inlet, and is purified through the MFMIPs adsorption action on the wall of a hose. And then, analyzing the concentration of the methcathinone in the sewage collected by the inlet water and the outlet water by adopting LC-MS-MS respectively, and verifying the purifying capacity of MFMIPs on the methcathinone in the sewage.
(8) Analyzing the sewage sample by adopting the prepared MFMIPs sensor according to the steps, and calculating to obtain that the concentration of the methcathinone in the sewage to be detected is 45.3 nM; the adsorption capacity for methcathinone was 0.31 mg/g.
FIG. 8 is a graph of the number of reuses of MFMIPs sensors prepared in accordance with the present invention (MFMIPs fluorescence intensity vs. 5 reuses), the upper and lower rows of dots representing the fluorescence intensity of MFMIPs before and after binding to the target methcathinone, respectively; it can be seen that: when the first assay is complete, MFMIPs fluorescence intensity decreases from 7100a.u. to about 5431 a.u.; the MFMIPs fluorescence is basically recovered to 7100a.u. after elution, and the late fluorescence of the combined target is reduced to 5400a.u. again; thus, the product can be reused at least 5 times.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, the scope of the present invention is not limited thereto, and various modifications and variations which do not require inventive efforts and which are made by those skilled in the art are within the scope of the present invention.

Claims (10)

1. A preparation method of a dual-function recyclable magnetic fluorescence sensor is characterized by comprising the following specific steps:
(1) firstly, preparing carbon-point CDs by using o-phenylenediamine as a raw material, and then carrying out silanization modification on the CDs by using 3-aminopropyltriethoxysilane to obtain Si-CDs;
(2) preparing nano ferroferric oxide by using ferric chloride hexahydrate and ferrous chloride tetrahydrate as raw materials in the presence of polyacrylic acid, and performing silanization treatment on the nano ferroferric oxide by using tetraethoxysilane to obtain silanized nano ferroferric oxide;
(3) and then uniformly dispersing silanized nano ferroferric oxide in absolute ethyl alcohol, adding methcathinone and Si-CDs, uniformly oscillating by ultrasonic waves, adding 3-aminopropyltriethoxysilane and tetraethoxysilane while stirring, finally adding ammonia water to initiate polymerization reaction, and performing post-treatment to obtain the sensor.
2. The method according to claim 1, wherein in the step (1), the carbon dots CDs are prepared by the following method in parts by weight: dissolving 0.15-0.25 part of o-phenylenediamine in 20-40 parts of deionized water, adding 0.06-0.07 part of 65-70% nitric acid solution by mass, uniformly stirring, transferring into an autoclave, carrying out heat treatment at 160-240 ℃ for 12-48 hours, cooling, dialyzing, and freeze-drying to obtain the carbon dot CDs.
3. The method according to claim 1, wherein in the step (1), the Si-CDs are prepared by the following method in parts by weight: firstly, dissolving 10-30 parts of CDs in 5-20 parts of absolute ethyl alcohol, then adding 0.1-0.2 part of 3-aminopropyltriethoxysilane, and stirring at room temperature for 24 hours to obtain Si-CDs.
4. The preparation method according to claim 1, characterized in that in the step (2), the preparation method of the silanized nano ferroferric oxide comprises the following steps in parts by weight: dissolving 20 parts of nano ferroferric oxide in 15 parts of 80% ethanol solution with volume concentration, performing ultrasonic treatment for 20 minutes, adding 0.1 part of 28% ammonia water with mass concentration of 28% and 0.3 part of ethyl orthosilicate, performing ultrasonic oscillation at room temperature for 12-24 hours, and performing post-treatment to obtain silanized nano ferroferric oxide Fe3O4NPs@SiO2。
5. The preparation method according to claim 1, wherein the specific method of step (3) is as follows, in parts by weight: firstly, 10 parts of Fe3O4NPs@SiO2Adding the mixture into 10 parts of 80% ethanol solution with volume concentration, carrying out ultrasonic oscillation treatment for 20 minutes, then adding 10 parts of methcathinone and 0.5 part of Si-CDs, continuing ultrasonic oscillation treatment for 20 minutes, then adding 0.04 part of APTES and 0.2 part of TEOS while stirring, then adding 0.1 part of 28% ammonia water solution with mass concentration to initiate polymerization reaction, carrying out polymerization reaction for 12 hours, and carrying out post-treatment to obtain the sensor.
6. A bifunctional recyclable magnetic fluorescence sensor obtained by the preparation method of any one of claims 1 to 5.
7. Use of the magnetic fluorescence sensor according to claim 6 for the detection of methcathinone in wastewater.
8. The method for detecting the methcathinone in the sewage based on the magnetic fluorescence sensor of claim 6 is characterized by comprising the following specific steps:
(A) dispersing the sensor of claim 6 in absolute ethyl alcohol by ultrasonic waves to obtain a working solution, then uniformly mixing the working solution and a standard solution of the methcathinone, recording the fluorescence response of the sensor to the addition of the methcathinone, and drawing a standard curve;
(B) and (D) magnetically separating and recovering the sensor, fully washing, dispersing the sensor in a sewage sample by ultrasonic waves to obtain a sample solution, detecting the fluorescence intensity, and determining the content of the methcathinone in the sewage according to the standard curve in the step (A).
9. Use of the magnetic fluorescence sensor according to claim 6 for purifying methcathinone in sewage.
10. The method for purifying the methcathinone in the sewage based on the magnetic fluorescence sensor of claim 6 is characterized by comprising the following specific steps:
(a) uniformly dispersing the sensor of claim 6 in water to prepare an aqueous solution, then injecting the aqueous solution into an annular diversion hose, and uniformly fixing the sensor at the bottom of the hose by virtue of an external magnetic field to form a purification device;
(b) then, injecting the sewage sample into a purification device, and realizing the purification of the methcathinone in the sewage through the adsorption effect of a sensor at the bottom of a hose.
CN202111206483.7A 2021-10-16 2021-10-16 Method for detecting and purifying methcathinone in sewage based on dual-function recyclable magnetic fluorescent sensor Pending CN113945529A (en)

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