CN114509479A - Magnetic core-shell molecular imprinting material, preparation and application thereof, electrochemical sensor and application thereof, and ketamine detection method - Google Patents
Magnetic core-shell molecular imprinting material, preparation and application thereof, electrochemical sensor and application thereof, and ketamine detection method Download PDFInfo
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Abstract
The invention provides a magnetic core-shell molecularly imprinted material, preparation and application thereof, an electrochemical sensor and application thereof, and a ketamine detection method, and belongs to the technical field of drug detection. The invention is provided withFe3O4As a carrier, Fe with uniform dispersion and uniform film coating can be synthesized3O4The @ MIPs has strong adsorption capacity, excellent selectivity and good recycling rate, and can be used for adsorbing the content of ketamine in domestic sewage (the adsorption capacity is 33.95mg g)‑1) And the electrochemical sensor with high sensitivity and high selectivity can be prepared, and the electrochemical sensor has high detection sensitivity, good stability, strong anti-interference capability and a linear range of 1 multiplied by 10‑12～4×10‑4mol·L‑1Detection limit is as low as 8.0X 10‑13mol·L‑1And the electrode preparation process is simple and reliable, the detection period is short, and the method is suitable for on-site rapid detection.
Description
Technical Field
The invention relates to the technical field of drug detection, in particular to a magnetic core-shell molecularly imprinted material, preparation and application thereof, an electrochemical sensor and application thereof, and a ketamine detection method.
Background
Ketamine (2-o-chlorophenyl-2-methylaminocyclohexanone, KT) is a derivative of pentachlorophenol (Chen et al, 2013), which is the main component of K powder. It is a well-known anesthetic and can also be used as a hallucinogen to cause hallucinations and schizophrenia. Clinical manifestations include slurred speech, dizziness, obnubilation, hyperactivity, hallucinations, vision, auditory hallucinations, motor dysfunction, depression, and bizarre dangerous behavior under drug action. Thus, many countries are restricting the use of KT and regulating it as a dangerous psychotropic drug. However, KT has also been developed to treat depression, which has increased the popularity and complexity of KT use in recent years. As such dangerous drugs enter the market, it is necessary to develop a new technology for rapidly and simply detecting KT.
Hitherto, the KT detection method includes liquid chromatography-mass spectrometry, gas chromatography, solid phase liquid chromatography-tandem mass spectrometry, high performance liquid chromatography-tandem mass spectrometry, solid phase extraction, spectrophotometry, and the like. However, the detection result is affected by interferents in the biological detection materials used in the methods, the detection period is long, and the rapid detection on site cannot be completed.
Disclosure of Invention
The invention aims to provide a magnetic core-shell molecular imprinting material, preparation and application thereof, an electrochemical sensor and application thereof, and a ketamine detection method, which are short in detection period and suitable for rapid field detection.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a magnetic core-shell molecularly imprinted material, which comprises the following steps:
mixing methacrylic acid, template molecules, ferroferric oxide, a cross-linking agent, an initiator and an organic solvent, and carrying out polymerization reaction under the microwave-assisted action to obtain a magnetic core-shell molecularly imprinted material; the template molecule is ketamine.
Preferably, the molar ratio of ketamine to methacrylic acid is 1 (2-8).
Preferably, the molar ratio of ketamine to ferroferric oxide is 1 (3-8).
Preferably, the crosslinking agent comprises ethylene glycol dimethacrylate; the molar ratio of the cross-linking agent to ketamine is (20-40) to 1; the initiator comprises azobisisobutyronitrile; the molar ratio of the initiator to the ketamine is (30-40): 1.
Preferably, the temperature of the polymerization reaction is 60-80 ℃, and the time is 2-12 h.
The invention provides the magnetic core-shell molecularly imprinted material prepared by the preparation method in the technical scheme.
The invention provides application of the magnetic core-shell molecularly imprinted material in the technical scheme in detection of ketamine in sewage.
The invention provides a magnetic molecular imprinting electrochemical sensor, which comprises a glassy carbon electrode and a magnetic core-shell molecular imprinting material loaded on the surface of the glassy carbon electrode; the magnetic core-shell molecularly imprinted material is the magnetic core-shell molecularly imprinted material in the technical scheme.
The invention provides application of the magnetic molecularly imprinted electrochemical sensor in the technical scheme in detection of ketamine in sewage.
The invention provides a method for detecting ketamine in sewage, which comprises the following steps:
mixing a ketamine methanol solution with a magnetic core-shell molecular imprinting material, adsorbing, measuring the concentration of ketamine in supernatant obtained after adsorption, and calculating the content of ketamine in sewage; the magnetic core-shell molecularly imprinted material is the magnetic core-shell molecularly imprinted material in the technical scheme.
The invention provides a preparation method of a magnetic core-shell molecularly imprinted material, which comprises the following steps: mixing methacrylic acid, template molecules, ferroferric oxide, a cross-linking agent, an initiator and an organic solvent, and carrying out polymerization reaction under the microwave-assisted action to obtain a magnetic core-shell molecularly imprinted material; the template molecule is ketamine. Methacrylic acid (MAA) is used as a functional monomer, ketamine is used as a template molecule, the template molecule and the functional monomer are combined to form a hole cavity structure, after the template molecule is removed, a polymer forms a hole matched with the spatial configuration of the template molecule, and the hole can show specific identification property when the hole is acted with the template molecule and the like again. Thus, Fe prepared3O4The shape, size and functional group of the cavity with the same shape, size and functional group as those of the template molecule KT exist in the MIPs, so that the cavity can specifically adsorb ketamine KT, can be used as an adsorbent to enrich KT in domestic sewage, is applied to the surface of a magnetic electrode, is used as an electrochemical sensor to detect the content of KT in the domestic sewage, and can realize simultaneous adsorption and electrochemical detection of ketamine KT.
Fe prepared by the invention3O4The @ MIPs have a large specific surface area, and a large number of imprinting sites (cavities with the same functional groups as target molecules and having a specific recognition function on the target molecules) are distributed on the surface of the @ MIPs, and because of Fe3O4The @ MIPs core-shell structure is controllable, the monodispersity is high, the distribution of adsorption sites is uniform, the magnetic response is fast, and the template molecule ketamine KT can be quickly adsorbed.
In the invention, Fe3O4As a carrier, Fe with uniform dispersion and uniform film coating can be synthesized3O4The @ MIPs has strong adsorption capacity, excellent selectivity and good recycling rate, and can be used for adsorbing the content of ketamine in domestic sewage (the adsorption capacity is 33.95mg g)-1) And can also prepare high-sensitivity and high-selection electrochemicalA chemical sensor. The invention utilizes square wave voltammetry to measure ketamine drugs in buffer solution, and the result shows that the method has high detection sensitivity, good stability, strong anti-interference capability and linear range of 1 multiplied by 10-12～4×10-4mol·L-1Detection limit is as low as 8.0X 10-13mol L-1The electrode preparation process is simple and reliable, the detection period is short, the method is suitable for on-site rapid detection, the problems that in the existing detection method, the detection result is influenced by interferents in biological detection materials, the detection period is long, and on-site rapid detection cannot be completed can be solved, and the detection of Ketamine (KT) trace drugs in criminal investigation sewage can be solved.
The invention synthesizes the Fe with the nuclear shell structure under the assistance of microwave3O4@ MIPs, high energy in microwave-assisted synthesis propagates in the form of electromagnetic waves, enabling rapid synthesis of polymers. In addition, the polymer is uniformly heated in the polymerization process, so that the shape and the size of polymer particles are uniform, the embedding phenomenon of the imprinting cavities is reduced, and the imprinting cavities are uniformly distributed on the surface of the polymer.
Drawings
FIG. 1 is Fe3O4(a) And Fe3O4TEM image of @ MIPs (b) and Fe before elution3O4@ MIPs (c) and Fe after elution3O4SEM picture of @ MIPs (d);
FIG. 2 shows Fe in example 13O4(a) And Fe3O4Hysteresis loop plot of @ mips (b);
FIG. 3 shows Fe at 25 ℃3O4@ MIPs and Fe3O4@ NIPs for KT (0.01-0.18 mg/mL) with different concentrations-1) Adsorption isotherm (a) of Fe3O4@ MIPs and Fe3O4Langmuir profile (b) and Freundlich profile (c) for @ NIPs;
FIG. 4 is Fe3O4@ MIPs and Fe3O4@ NIPs (5mg) vs. 5mLKT (0.07 mg. mL)-1) Adsorption kinetics curve (a), pseudo first order graph (b) and pseudo second order graph (c) at 25 ℃;
in FIG. 5, (a) is Fe at 25 ℃3O4@MIPs/Fe3O4@ NIPs (5mg) for KT and interferents Norketamine (NKT), 3, 4-methylenedioxymethamphetamine (MDMA), Methamphetamine (MA), Dopamine (DA), ascorbic acid (Vc) and Uric Acid (UA) (concentrations are all 0.07 mg. mL.)-1) The (b) is Fe3O4@ MIPs (5mg) vs. 5mL 0.07 mg. mL-1KT is repeated for 6 times to obtain an adsorption capacity effect graph;
FIG. 6 is Fe3O4@ MIPs/mGCE at 5.0 mmol.L-1K3[Fe(CN)6](containing 0.1mol L)-1KCl) for different concentrations of KT (mol L)-1) And a calibration graph (B) of the change in peak current (Δ i) versus the logarithm of KT concentration, error bars indicate the standard deviation of the results when n is 3.
Detailed Description
The invention provides a preparation method of a magnetic core-shell molecularly imprinted material, which comprises the following steps:
mixing methacrylic acid, template molecules, ferroferric oxide, a cross-linking agent, an initiator and an organic solvent, and carrying out polymerization reaction under the microwave-assisted action to obtain a magnetic core-shell molecularly imprinted material; the template molecule is ketamine.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
Mixing methacrylic acid (MAA), template molecules, ferroferric oxide, a cross-linking agent, an initiator and an organic solvent, and carrying out polymerization reaction under the microwave-assisted action to obtain a magnetic core-shell molecularly imprinted material; the template molecule is ketamine. In the invention, the molar ratio of ketamine to methacrylic acid is preferably 1 (2-8), and more preferably 1 (4-6); the molar ratio of ketamine to ferroferric oxide is 1 (3-8), and more preferably 1 (3-6); the diameter of the ferroferric oxide is preferably 150-300 nm.
In the present invention, the crosslinking agent preferably includes Ethylene Glycol Dimethacrylate (EGDMA); the molar ratio of the cross-linking agent to ketamine is preferably (20-40): 1, more preferably (25-30): 1; the initiator preferably comprises azobisisobutyronitrile; the molar ratio of the initiator to the ketamine is preferably (30-40): 1.
In the present invention, the organic solvent is preferably methanol; the invention has no special limit on the using amount of the methanol and can ensure that the reaction is carried out smoothly.
In the invention, the process of mixing methacrylic acid, template molecules, ferroferric oxide, a cross-linking agent, an initiator and an organic solvent is preferably to dissolve ketamine and methacrylic acid in the organic solvent, perform ultrasonic treatment for 10-30 min, and stir at room temperature for 1-2 h; adding Fe to the mixture3O4Stirring for 0.5-1.5 h (more preferably 1h) at 30-50 ℃ (more preferably 40 ℃), adding the cross-linking agent and the initiator respectively, and introducing nitrogen for 3-8 min, more preferably 5 min. The stirring rate is not particularly limited in the present invention, and the materials can be uniformly mixed according to a process well known in the art.
After the mixing is finished, the obtained mixture is transferred into a reaction kettle with a polytetrafluoroethylene lining for polymerization reaction; the microwave conditions are preferably provided by an atmospheric microwave reactor.
In the invention, the temperature of the polymerization reaction is preferably 60-80 ℃, and more preferably 70 ℃; the time is preferably 2 to 12 hours, and more preferably 5 to 10 hours.
After the polymerization reaction is finished, the obtained product is preferably sequentially eluted and dried to obtain the magnetic core-shell molecularly imprinted material (Fe)3O4@ MIPs); the reagent used for elution is preferably a mixed solution of methanol and acetic acid; the volume ratio of the methanol to the acetic acid is preferably (6-9) to (1-4), more preferably 7:3, and the elution time is preferably 2-4 h; the invention removes the template molecule, unreacted functional monomer MAA and cross-linking agent by elution. The drying process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The invention provides the magnetic core-shell molecularly imprinted material prepared by the preparation method in the technical scheme.
The invention provides application of the magnetic core-shell molecularly imprinted material in the technical scheme in detection of ketamine in sewage.
The invention provides a magnetic molecular imprinting electrochemical sensor, which comprises a glassy carbon electrode and a magnetic core-shell molecular imprinting material loaded on the surface of the glassy carbon electrode; the magnetic core-shell molecularly imprinted material is the magnetic core-shell molecularly imprinted material in the technical scheme. The glassy carbon electrode is not particularly limited in the present invention, and any commercially available glassy carbon electrode known in the art may be used.
In the present invention, the method for preparing the magnetic molecularly imprinted electrochemical sensor preferably comprises: and loading the dispersion liquid of the magnetic core-shell molecularly imprinted material on a glassy carbon electrode to obtain the magnetic molecularly imprinted electrochemical sensor.
In the invention, the dispersant used in the dispersion liquid of the magnetic core-shell molecularly imprinted material is preferably water, and the preparation process of the dispersion liquid is preferably to ultrasonically disperse the magnetic core-shell molecularly imprinted material in water for 20-50 min, more preferably 30min to obtain the dispersion liquid. In the invention, the concentration of the aqueous dispersion of the magnetic core-shell molecular imprinting material is preferably 1mg/mL, and the loading capacity of the aqueous dispersion of the magnetic core-shell molecular imprinting material on a glassy carbon electrode is preferably 15 muL.
In the invention, the loading process is preferably to drop the dispersion liquid on the surface of a glassy carbon electrode (mGCE), compound for 10-20 min, and load the magnetic core-shell molecularly imprinted material on the surface of the glassy carbon electrode through the action of electrostatic attraction. In an embodiment of the invention, the compounding is preferably performed under an infrared lamp.
The invention provides application of the magnetic molecularly imprinted electrochemical sensor in detection of ketamine in sewage.
The invention provides an electrochemical detection method of ketamine in sewage, which comprises the following steps:
mixing a ketamine methanol solution with a magnetic core-shell molecular imprinting material, adsorbing, measuring the concentration of ketamine in supernatant obtained after adsorption, and calculating the content of ketamine in sewage; the magnetic core-shell molecularly imprinted material is the magnetic core-shell molecularly imprinted material in the technical scheme.
The concentration of the ketamine methanol solution and the quality of the magnetic core-shell molecular imprinting material are not specially limited, and the concentration and the quality can be adjusted according to actual requirements. In the present example, ketamine methanol solutions were provided in a 5mL series of concentrations (0.01, 0.03, 0.05, 0.07, 0.09, 0.12, 0.15, 0.18) mg-mL-1Ketamine in methanol; the mass of the magnetic core-shell molecularly imprinted material is preferably 5 mg.
In the invention, the adsorption temperature is preferably 20-50 ℃, the time is preferably 2-4 h, and more preferably 2.5 h; the adsorption is preferably carried out in a constant temperature shaker. The present invention does not specifically limit the oscillating rate, and the oscillating may be performed according to a process well known in the art.
After the adsorption is completed, the invention preferably utilizes a magnet to adsorb the magnetic molecularly imprinted polymer in the obtained product, takes out the supernatant, measures the concentration of ketamine in the supernatant, and calculates the content of ketamine in the sewage. The invention preferably utilizes an ultraviolet spectrophotometer to measure the concentration of ketamine in the supernatant; the process of the measurement and calculation is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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
Dissolving 0.05mmol KT and 0.2mmol MAA in 8mL methanol, sonicating for 30min, stirring in a room temperature round bottom flask for 2h, adding 70mg Fe to the resulting mixture3O4Stirring at 40 deg.C for 1h, adding 2.0mmol of cross-linking agent (EGDMA) and 2mmol of initiator (AIBN), introducing N2Transferring the obtained mixture into a reaction kettle lined with polytetrafluoroethylene at 70 deg.C for 5min, reacting in a microwave reactor at normal pressure for 2 hr, polymerizing, and adding methanol to acetic acid (volume ratio)Is 7:3), the solution is eluted for 2h, and is dried overnight to obtain the core-shell molecularly imprinted material which is marked as Fe3O4@MIPs。
Comparative example 1
The only difference from example 1 is: omitting the process of adding KT, and marking the prepared magnetic material as Fe3O4@NIPs。
Characterization and Performance testing
1) For Fe in example 13O4And Fe3O4TEM examination of @ MIPs with Fe before and after elution in example 13O4@ MIPs SEM test, the results are shown in FIG. 1; FIG. 1 is Fe3O4(a) And Fe3O4TEM image of @ MIPs (b) and Fe before elution3O4@ MIPs (c) and Fe after elution3O4@ MIPs (d) SEM picture. As can be seen from FIG. 1 (a), magnetic Fe3O4The spherical particles were uniform, and as can be seen from FIG. 1 (b), Fe3O4@ MIPs is of a core-shell structure, and the molecularly imprinted polymer uniformly transfers magnetic Fe3O4Wrapped inside. As can be seen from (c) and (d) in FIG. 1, the surface of the polymer before elution is relatively uniform, and after the template molecule KT is eluted, rough imprinted pores are left on the surface of the polymer.
2) FIG. 2 shows Fe in example 13O4(a) And Fe3O4Hysteresis loop of @ MIPs (b), with Fe in the absence and presence of applied magnetic field3O4The dispersion and separation of @ MIPs solutions. As seen from FIG. 2, Fe3O4Has a saturation magnetization value greater than Fe3O4@ MIPs because of Fe3O4The outer surface of @ MIPs is coated with a layer of imprinted polymer, resulting in a reduction of its magnetization value. The inset shows that the polymer material is able to rapidly collect near the magnet within 30 s.
3) 5mL of KT solutions (0.01, 0.03, 0.05, 0.07, 0.09, 0.12, 0.15, 0.18) mg/mL were prepared in different concentrations-1) Several portions of 5mg of Fe prepared in example 1 were added3O4@ MIPs and Fe prepared in comparative example 13O4@ NIPs, mixtures obtainedPlacing the material in a 25mL conical flask, oscillating and adsorbing for 150min in a constant-temperature oscillator, adsorbing the magnetic molecularly imprinted polymer in the obtained product by using a magnet, taking out the supernatant, and measuring the concentration of KT in the supernatant by using an ultraviolet spectrophotometer to obtain an adsorption kinetics curve of KT. FIG. 3 shows Fe at 25 ℃3O4@ MIPs and Fe3O4@ NIPs for KT (0.01-0.18 mg. mL) with different concentrations-1) Adsorption isotherm (a) of Fe3O4@ MIPs and Fe3O4Langmuir profile (b) and Freundlich profile (c) for @ NIPs; as can be seen from a in FIG. 3, the amount of KT adsorbed by the adsorbent is 0.01 to 0.18 mg/mL-1. In this range, Fe3O4The adsorption capacity of @ MIPs to KT is far higher than that of Fe3O4@ NIPs. As the KT concentration increases, the adsorption capacity increases. When the concentration is 0.18 mg/mL-1Of (i) Fe3O4The adsorption amount of @ MIPs on KT reaches saturation, and the calculated adsorption amount is 33.95mg g-1,Fe3O4The adsorption amount of @ MIPs is Fe3O4@NIPs(13.9mg·g-1) 2.44 times higher. This demonstrates Fe3O4@ MIPs contain a large number of specific KT molecule recognition sites. KT is Fe3O4Adsorption on @ NIPs is primarily due to non-specific recognition sites.
To understand KT in Fe3O4The adsorption mechanism on @ MIPs adopts Langmuir and Freundlich isothermal adsorption models to describe Fe3O4Adsorption equilibrium of @ MIPs. Isothermal curves constructed by Langmuir and Freundlich adsorption isothermal models correspond to (b) and (c) in FIG. 3, respectively, and the parameters are shown in Table 1.
TABLE 1 Fe3O4Langmuir and Freundlich isothermal adsorption model parameters for absorbing KT by @ MIPs
The correlation coefficients of the fitted curves in Table 1 indicate that the Langmuir model (R)20.97107) vs Freundlich model (R)20.95029) is more suitable for describing Fe3O4Adsorption of KT by @ MIPs. Thus, Fe3O4The adsorption of @ MIPs to KT belongs to monomolecular adsorption. The results show that KT adsorbs to Fe3O4The @ MIPs adsorbent has uniform surface and uniform energy distribution in the surface active area of the adsorbent.
4) The prepared 5mL of the solution was 0.07 mg/mL-1KT methanol solution of (1) was added in a quantity of 5mg each of Fe prepared in example 13O4@ MIPs, placing the obtained mixture in a 25mL conical flask, oscillating for a specific time in a constant-temperature oscillator, adsorbing the magnetic molecularly imprinted polymer in the obtained product by using a magnet, taking out the supernatant, and sampling and measuring the concentration of KT in the supernatant within a specific time (25, 50, 75, 100, 125, 150) min by using an ultraviolet spectrophotometer to obtain an adsorption kinetics curve of KT. FIG. 4 is Fe3O4@ MIPs and Fe3O4@ NIPs (5mg) vs. 5mLKT (0.07 mg. mL)-1) Adsorption kinetics curve (a), pseudo first order graph (b) and pseudo second order graph (c) at 25 ℃; as can be seen from a in FIG. 4, Fe3O4The KT adsorption of @ MIPs increases with time and tends to be stable in a certain time. And Fe3O4The increase of KT adsorption by @ NIPs is not large, which indicates that Fe3O4The affinity of @ MIPs to KT is stronger than that of Fe3O4@NIPs。Fe3O4The adsorption quantity of @ MIPs to KT reaches the adsorption balance within 125 min. Fe3O4Variation tendency of @ NIPs and Fe3O4@ MIPs are approximately the same. However, due to Fe3O4The surfaces of the @ NIPs are not provided with structural cavities matched with ketamine, and KT and Fe are absorbed by nonspecific binding sites formed by the action of hydrophilic groups3O4The equilibrium adsorption amount generated by @ NIPs is small, and the state can reach a saturated state in a short time.
To analyze Fe3O4The adsorption kinetics of @ MIPs, the adsorption data are fitted by adopting a quasi-primary and a quasi-secondary kinetic model, and relevant parameters of the two kinetic models are shown in a table 2.
TABLE 2 Fe3O4Kinetic parameter for absorbing KT by @ MIPs/mGCE
As can be seen from Table 2, the quasi-second order kinetic model (R)20.97859) is greater than the first order kinetic model (R)20.9485). At the same time, with the theory Q of quasi-first order kineticsc1(47.857mg·g-1) In contrast, theory Q of quasi-second order kineticsc2(24.096mg·g-1) More approximate to the experimental value of 23.9mg g-1. Apparently, the pseudo-second order kinetic model is more suitable for describing the adsorption of KT.
5) At 25 deg.C, Fe3O4@ MIPs and Fe3O4@ NIPs as adsorbents for respectively carrying out adsorption measurement on KT and interferents NKT, MDMA, MA, DA, Vc and UA, wherein the dosage of the adsorbents is 5mg, the adsorption time is 150min, and the concentrations of the KT and the interferents in methanol solution are both 0.07 mg/mL-1The results of the test of the amount of the KT and the interferent adsorbed by the adsorbent are shown in FIG. 5 (a), and Norketamine (NKT) is an analogue of KT and has a molecular structure similar to that of KT. Due to Fe3O4The @ MIPs have cavities with the same shape and size as the KT of the template molecule, namely cavities with the structure similar to that of NKT, so that Fe3O4The amount of NKT adsorbed by @ MIPs is similar to KT. For MDMA, MA, DA, Vc and UA, Fe3O4@ MIPs and Fe3O4The @ NIPs have similar adsorption capacities for them, mainly Fe3O4@ MIPs on MDMA, MA, DA, VCUA is a non-specific binding site, with Fe3O4The adsorption principle of @ NIPs is similar.
Verification of Fe3O4The repeatability and stability of the adsorption of @ MIPs to KT: using Fe3O4@ MIPs elution-adsorption cycle experiments on KT were performed continuously for 6 cycles (n ═ 1, 2, 3,4, 5, 6); in which Fe3O4The dosage of @ MIPs is 5mThe concentration of the methanol solution of g and KT is 0.07 mg/mL-1Each adsorption time is 150 min; after adsorption, recording the concentration of KT in the supernatant in balance by using an ultraviolet spectrophotometer; then using a methanol-acetic acid (volume ratio of 9:1) mixed solution as an eluent to Fe3O4@ MIPs eluted for 1 h; repeated measurement of Fe after each elution-adsorption cycle experiment3O4The amount of KT adsorbed by @ MIPs is shown in FIG. 5 (b). As shown in FIG. 5 (b), after six adsorption cycle experiments, Fe was observed3O4The adsorption efficiency of @ MIPs is only reduced by 10.96%. The reason for the reduced adsorption efficiency may be due to decomposition or clogging of the binding sites. The above results show that the Fe prepared by the invention3O4@ MIPs have relatively good repeatability.
Application example 1
Fe prepared in example 13O4Ultrasonic dispersing for 30min in deionized water at @ MIPs to obtain dispersion (1 mg. mL)-1) Dripping 10 mu L of dispersion liquid on the surface of the polished glassy carbon electrode, and drying for 15min under an infrared lamp to obtain the magnetic molecular imprinting electrochemical sensor (Fe)3O4@MIPs/mGCE)。
1) The Fe prepared in application example 1 was measured by using square wave voltammetry SWV (potential range of-0.2V to 0.6V, amplitude of 0.025V, frequency of 15Hz)3O4Electrochemical response and calibration curve of @ MIPs/mGCE to KT, solution selection 5.0 mmol.L-1K3[Fe(CN)6](containing 0.1 mol. L)-1KCl) solution, Fe prepared3O4@ MIPs/mGCE at different concentrations KT (mol. L)-1The concentration of KT is a:0, b: 1X 10-12，c:6×10-12，d:2×10-11，e:4×10-10，f:8×10-10，g:2×10-9，h:1×10-8，i:1×10-7，j:1×10-6，k:1×10-5，l:4×10-4Corresponding to the concentrations of the curves from the top to the bottom), the results are shown in fig. 6.
As shown in fig. 6 a, the peak current decreases with increasing concentration of KT; from B in FIG. 6, the logarithm of the concentration of KT and the change Δ i of the peak currentLinear range of 1 × 10-12～4×10-4mol L-1. Equation is Δ i-3.88992 lgCKT(μmol L-1)+26.4674(R2＝0.99188)。Δi＝i0-icWherein i0And icKT concentration was 0 and c. mu. mol-1The current of time. Limit of detection (LOD) by 3SbThe value of/m is 8X 10-13mol L-1In which S isbThe standard deviation of the blank amount is shown, and m is the slope of the calibration curve; illustrating that the detection method of the present invention exhibits a relatively low LOD and a good dynamic range.
2) Fe prepared in application example 13O4The @ MIPs/mGCE is used for detecting KT in domestic sewage (No. 5 southern park building domestic sewage in dormitory district of Yunnan university): collecting 10mL domestic sewage, storing in a refrigerator at 4 deg.C for 24h, centrifuging, collecting 1mL supernatant, and adding 5.0 mmol.L-1K3[Fe(CN)6](containing 0.1 mol. L)-1KCl) the domestic sewage was diluted 5 times and subjected to electrochemical analysis. A series of fixed concentration KT methanol solutions (0.05. mu. mol L) were added using standard addition methods-1、0.25μmol L-1、0.5μmol L-1、1μmol L-1And 5. mu. mol L-1) The concentration of KT was measured by adding it to a domestic sewage sample, and the analysis results are shown in Table 3.
TABLE 3 Fe3O4@ MIPs/mGCE determination of KT content in domestic sewage sample (n ═ 3)
As can be seen from Table 3, the recovery rate was 98.4 to 110% and the RSD was < 2.9%. The result shows that the sensor can be used for reliably measuring KT in an actual water sample.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a magnetic core-shell molecularly imprinted material is characterized by comprising the following steps:
mixing methacrylic acid, template molecules, ferroferric oxide, a cross-linking agent, an initiator and an organic solvent, and carrying out polymerization reaction under the microwave-assisted action to obtain a magnetic core-shell molecularly imprinted material; the template molecule is ketamine.
2. The preparation method according to claim 1, wherein the molar ratio of ketamine to methacrylic acid is 1 (2-8).
3. The preparation method according to claim 1, wherein the molar ratio of ketamine to ferroferric oxide is 1 (3-8).
4. The method of claim 1, wherein the cross-linking agent comprises ethylene glycol dimethacrylate; the molar ratio of the cross-linking agent to ketamine is (20-40) to 1; the initiator comprises azobisisobutyronitrile; the molar ratio of the initiator to the ketamine is (30-40): 1.
5. The method according to claim 1, wherein the polymerization reaction is carried out at a temperature of 60 to 80 ℃ for 2 to 12 hours.
6. The magnetic core-shell molecularly imprinted material prepared by the preparation method of any one of claims 1 to 5.
7. The application of the magnetic core-shell molecularly imprinted material of claim 6 in the detection of ketamine in sewage.
8. A magnetic molecular imprinting electrochemical sensor is characterized by comprising a glassy carbon electrode and a magnetic core-shell molecular imprinting material loaded on the surface of the glassy carbon electrode; the magnetic core-shell molecularly imprinted material is the magnetic core-shell molecularly imprinted material of claim 6.
9. The use of the magnetic molecularly imprinted electrochemical sensor of claim 8 for the detection of ketamine in wastewater.
10. A method for detecting ketamine in sewage is characterized by comprising the following steps:
mixing a ketamine methanol solution with a magnetic core-shell molecular imprinting material, adsorbing, measuring the concentration of ketamine in supernatant obtained after adsorption, and calculating the content of ketamine in sewage; the magnetic core-shell molecularly imprinted material is the magnetic core-shell molecularly imprinted material of claim 6.
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