CN113295795B - Method and kit for detecting zearalenone mycotoxins and application thereof - Google Patents

Method and kit for detecting zearalenone mycotoxins and application thereof Download PDF

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CN113295795B
CN113295795B CN202110568454.9A CN202110568454A CN113295795B CN 113295795 B CN113295795 B CN 113295795B CN 202110568454 A CN202110568454 A CN 202110568454A CN 113295795 B CN113295795 B CN 113295795B
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zearalenone
elution
acetonitrile
solution
mycotoxins
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CN113295795A (en
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刘通
张峰
王秀娟
王友法
李银龙
母国栋
杨敏莉
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Chinese Academy of Inspection and Quarantine CAIQ
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/36—Control of physical parameters of the fluid carrier in high pressure liquid systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N2030/062—Preparation extracting sample from raw material

Abstract

The invention discloses a method for detecting zearalenone mycotoxin, a kit and application thereof, wherein the method for detecting zearalenone mycotoxin comprises the following steps: contacting a sample to be detected with an extraction solvent, and performing extraction treatment to obtain an extracting solution; adsorbing the extracting solution by using magnetic nanoparticles, and then adding an eluent to obtain an eluent; and carrying out ultra performance liquid chromatography tandem mass spectrometry detection on the eluent so as to obtain the content of the zearalenone mycotoxins. The method utilizes the magnetic covalent organic framework material to adsorb the zearalenone mycotoxin in the sample to be detected, and the detection method is rapid, accurate, efficient and high in sensitivity.

Description

Method and kit for detecting zearalenone mycotoxins and application thereof
Technical Field
The invention relates to the field of analytical chemistry, in particular to a method for detecting zearalenone mycotoxin, a kit and application of the kit in detecting content of the zearalenone mycotoxin.
Background
Zearalenone mycotoxins (ZEAs), which are representative of mycotoxins, are widely distributed in various food and animal products and pose serious hazards to human health and the development of the economic society. Currently, ZEAs commonly found in food products mainly include Zearalenone (ZEA), α -zearalenol (α -ZAL), β -zearalenol (β -ZAL), α -zeaenol (α -ZEL), β -zeaenol (β -ZEL), and the like. These compounds are stable in nature, readily associate with food matrix ingredients, do not degrade even at high temperatures, and are therefore not readily detectable and degradable during food manufacturing processes, and readily migrate and accumulate in the food chain. It has been reported that ingestion of foods contaminated with ZEAs can cause serious damage to the human reproductive system and even cause cancer. In order to ensure food safety, strict limit standards are set in countries of the world including china.
Therefore, there is a need to develop a method for detecting zearalenone mycotoxins.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, an object of the present invention is to provide a method for detecting zearalenone mycotoxins, which has the advantages of fast detection speed and high sensitivity, and is particularly suitable for detecting zearalenone mycotoxins in food.
Thus, according to one aspect of the invention, there is provided a method of detecting zearalenone mycotoxins. According to an embodiment of the present invention, the method comprises a method for detecting zearalenone mycotoxins comprising: contacting a sample to be detected with an extraction solvent, and performing extraction treatment to obtain an extracting solution; carrying out adsorption treatment on the extracting solution and the magnetic nanoparticles so as to obtain adsorbed nanoparticles; eluting the adsorbed nanoparticles by using an elution solvent so as to obtain an eluted solution; and performing ultra performance liquid chromatography tandem mass spectrometry detection on the eluted solution so as to obtain the content of the zearalenone mycotoxin, wherein the magnetic nanoparticles comprise: a core body, wherein the core body is composed of superparamagnetic ferroferric oxide; a shell overlying the surface of the core, the shell being comprised of repeating units of formula I.
Figure BDA0003081047560000021
According to the method for detecting the zearalenone mycotoxins, magnetic nanoparticles are used for adsorbing the zearalenone mycotoxins in a sample to be detected, the magnetic nanoparticles have large specific surface area and a porous ordered crystal structure, and the zearalenone mycotoxins in the sample to be detected can be quickly and efficiently adsorbed. Meanwhile, the detection is carried out by using the ultra-high performance liquid chromatography tandem mass spectrometry, and the detection accuracy and sensitivity are high. Therefore, the method provided by the embodiment of the invention can be used for detecting the zearalenone mycotoxins quickly, accurately, efficiently and sensitively, is particularly suitable for detecting the zearalenone mycotoxins in complex samples such as food and the like, and in some embodiments, the detection limit can reach 0.003-0.018 mu g/kg.
In addition, the zearalenone mycotoxins according to the above embodiment of the present invention may have the following additional technical features:
according to the embodiment of the invention, the ratio of the extracting solution to the magnetic nanoparticles is 10mL:1-5.0mg, preferably 10mL:3.0mg.
According to an embodiment of the present invention, the elution solvent is at least one selected from the group consisting of ethanol, methanol, ethyl acetate, acetonitrile, an acetonitrile solution containing 0.5% formic acid and an acetonitrile solution containing 0.5% ammonia water, and preferably, acetonitrile.
According to an embodiment of the present invention, the extraction treatment is performed using an extraction solvent, wherein the extraction solvent is a mixed solution of acetonitrile, acetic acid, and water.
According to the embodiment of the invention, the volume ratio of the acetonitrile to the acetic acid to the water is 70-90:1:18-22.
According to the embodiment of the invention, the chromatographic detection conditions of the ultra performance liquid chromatography tandem mass spectrometry are as follows:
column temperature: 35 ℃; and (3) chromatographic column: c18 chromatographic column with specification of 2.1mm × 100mm and 3.5 μm; sample introduction volume: 5 mu L of the solution; flow rate: 0.4000mL/min.
According to the embodiment of the invention, the mass spectrum conditions of the ultra performance liquid chromatography tandem mass spectrometry detection are as follows: ionization mode: ESI; detection mode: multiple reaction monitoring (MRM mode); ion source temperature: 550 ℃; electrospray voltage:-4500V；GS1(N 2 )，GS2(N 2 ) Air curtain pressure (N) 2 ) 55, 50 and 30psi, respectively; collision cell exit voltage: -10V; residence time (DT): 100ms.
According to the embodiment of the invention, the mobile phase of the chromatography of the ultra performance liquid chromatography tandem mass spectrometry detection is as follows: a: acetonitrile, B: an aqueous solution.
According to an embodiment of the invention, the elution conditions of the chromatography are gradient elution.
According to an embodiment of the present invention, the gradient elution has an elution gradient of 0min,85% B;5min,20% by weight B;6min,20% B;6.2min,5% by weight of B;9min,5% of B;9.2min,85% B.
According to another aspect of the invention, a kit is provided. According to an embodiment of the invention, the kit comprises: the magnetic nanoparticles, the extraction solvent and the elution solvent are described above. Therefore, the kit can be used for detecting the zearalenone mycotoxin quickly, accurately, efficiently and highly sensitively, and is particularly suitable for detecting the zearalenone mycotoxin in complex substances such as food and the like.
Furthermore, the kit also comprises reagents, consumables and instruments for the method for detecting zearalenone mycotoxins, which are not illustrated herein. Furthermore, the kit also has the technical characteristics and technical effects of the method for detecting the zearalenone mycotoxins, and the details are not repeated here.
According to another aspect of the invention, the invention provides the application of the kit in detecting the content of the zearalenone mycotoxins. Therefore, the kit can be used for detecting the zearalenone mycotoxin in complex substances such as food and the like, and has the advantages of high detection speed, high accuracy and high sensitivity.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a schematic representation of the effect of different experimental conditions on experimental results according to one embodiment of the present invention;
fig. 2 shows a schematic diagram of the results of the test of the regeneration performance and the batch reusability of the adsorbent according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
It should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Further, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
According to one aspect of the invention, the invention provides a method for detecting zearalenone mycotoxins. According to an embodiment of the present invention, the method comprises a method for detecting zearalenone mycotoxins comprising: contacting a sample to be detected with an extraction solvent, and performing extraction treatment to obtain an extracting solution; carrying out adsorption treatment on the extracting solution and the magnetic nanoparticles so as to obtain adsorbed nanoparticles; eluting the adsorbed nanoparticles by using an elution solvent so as to obtain an eluted liquid; and carrying out ultra performance liquid chromatography tandem mass spectrometry detection on the eluted solution so as to obtain the content of the zearalenone mycotoxin.
According to the method for detecting the zearalenone mycotoxin, disclosed by the embodiment of the invention, the magnetic nanoparticles are used for adsorbing the zearalenone mycotoxin in a sample to be detected, and the magnetic nanoparticles have large specific surface area and a porous ordered crystal structure, so that the zearalenone mycotoxin in the sample to be detected can be quickly and efficiently adsorbed. Meanwhile, the detection is carried out by using the ultra-high performance liquid chromatography tandem mass spectrometry, and the detection accuracy and sensitivity are high. Therefore, the method provided by the embodiment of the invention can be used for detecting the zearalenone mycotoxins in complex samples such as food in a rapid, accurate, efficient and high-sensitivity manner, and is especially suitable for detecting the zearalenone mycotoxins in complex samples such as food, and in some embodiments, the detection limit can reach 0.003-0.018 mu g/kg.
According to an embodiment of the present invention, the magnetic nanoparticle comprises: the magnetic core comprises a core body and a shell, wherein the core body is composed of superparamagnetic ferroferric oxide; the shell is covered on the surface of the shell, and the shell is formed by the repeating unit shown in the formula I. The magnetic nanoparticles provided by the embodiment of the invention have excellent chemical and thermal stability, and are large in specific surface area, strong in adsorption capacity and high in adsorption speed.
Figure BDA0003081047560000041
According to an embodiment of the invention, the shell is a porous network structure, further a porous ordered crystal structure. Therefore, the specific surface area is large, the adsorption capacity is strong, and the crystal form is stable.
The shell of the embodiment of the invention is a porous net structure, and the thicker the thickness is, the more layers between the frame materials added together are, and the larger the adsorption capacity is. According to an embodiment of the invention, the shell has an average adsorbent pore size of 2.2-2.5nm, preferably 2.3-2.4nm, and a thickness of 30-50nm. Therefore, the adsorption effect on the zearalenone fungal toxin is better, wherein the mesoporous aperture of 2.3-2.4nm is larger than the molecular diameter of a target object, and the spatial embedding effect can be formed between the mesoporous aperture and the target object.
According to an embodiment of the invention, the magnetic strength of the housing is 20-25emu/g, preferably 23emu/g, and the contact angle with a water droplet is 50-55 °, preferably 52.8 °. Therefore, the magnetic response is appropriate, the rapid separation of the magnetic nanoparticles and the sample matrix can be realized, the operation time is shortened, and meanwhile, the magnetic nanoparticles have shorter analyte diffusion distance in the sample solution, so that the adsorption efficiency can be improved. Herein, the term "contact angle" as used herein refers to an angle between a tangent to a liquid/gas-interface shape profile of a liquid at a point (three-phase contact boundary, 3 PCP) of contact with a solid surface and the solid surface (including a liquid phase side) when the liquid is in contact with the solid surface. The value of this angle marks the wettability of the liquid on the solid surface: when the wettability is good, the liquid can be completely spread on the solid surface, and the contact angle value of 0 degree is presented; when the wettability is poor, the liquid can not spread on the solid surface at all, but can only gather together to form a lump, and the contact angle value is 180 degrees; when the wettability is between good and poor, the liquid spreads out on the solid surface with a limited degree, forming a contact angle between 0 and 180 °. Therefore, the magnetic nanoparticles have good hydrophilicity, can be better dispersed in a sample solution, further enlarge the contact range between the material and a target object, and are favorable for fully adsorbing the zearalenone fungal toxins in the sample.
According to an embodiment of the invention, the specific surface area of the housing is 50-170m 2 g -1 . Thereby having large specific surface area and strong adsorption capacity
According to an embodiment of the present invention, the housing is located at 2 of 2.74 ° in the X-ray powder diffraction data θ There is a diffraction peak. The diffraction peak is different from the characteristic peak of carboxyl functionalized ferroferric oxide and is the characteristic crystal peak of the shell, which indicates that the shell is successfully prepared and coated on the carboxyl functionalized ferroferric oxide. According to an embodiment of the present invention, in the X-ray powder diffraction data, 2 located at 4.82 °, 5.60 °, 30.16 °, 35.54 °, 43.46 °, 53.66 °, 57.12 ° and 62.49 ° is included θ Crystal diffraction peaks are present at all. The characteristic peaks and Fe with spinel structure 3 O 4 Match, and thus demonstrate Fe 3 O 4 Successful synthesis of and Fe 3 O 4 The original crystal structure is still kept after the shell is coated. Therefore, the magnetic nanoparticles have ferroferric oxide and magnetism at the same timeStable crystalline forms of covalent organic framework materials.
According to an embodiment of the invention, the particle size of the inner core is 180-400nm. Therefore, the magnetic nanoparticles have large specific surface area and strong adsorption capacity.
According to the embodiment of the invention, the ratio of the extracting solution to the magnetic nanoparticles is 10mL: 1.0-3.0mg, preferably 10mL:3.0mg. When the amount of the magnetic nanoparticles is 1.0-3.0mg, the experimental recovery rate is increased along with the increase of the mass of the adsorbent, the amount of the magnetic nanoparticles is more than 3.0mg, the increase of the recovery rate is not obviously changed, and the balance is achieved.
The inventors have found that, as the amount of salt ions increases, the viscosity of the solution increases during the adsorption treatment, and the target substance is prevented from diffusing to the surface of the adsorbent, thereby affecting the adsorption effect. In addition, the presence of a large amount of salt ions may occupy the adsorption sites of the target substance, and may also result in poor adsorption effect. Therefore, no salt ions were added to the MSPE solution. Further, the extraction is performed using an organic solvent, which is a mixed solution of acetonitrile, acetic acid, and water according to an embodiment of the present invention. According to the embodiment of the invention, the volume ratio of the acetonitrile to the acetic acid to the water is 70-90:1:18-22. Therefore, cation interference is avoided, and the adsorption efficiency is high.
After adsorption of the target, the use of the correct elution solvent is one of the key factors for increasing the recovery rate of the experiment. According to an embodiment of the present invention, the elution solvent is at least one selected from the group consisting of ethanol, methanol, ethyl acetate, acetonitrile, an acetonitrile solution containing 0.5% formic acid and an acetonitrile solution containing 0.5% ammonia water. Therefore, the recovery rate of the zearalenone mycotoxin is high. According to the preferred embodiment of the invention, the elution solvent is acetonitrile, and the recovery rate can reach more than 80%.
According to an embodiment of the present invention, the adsorption treatment is performed at a pH of 6.0 to 8.0, preferably at a pH of 6.0 to 7.0. The inventors found that at pH values above 8.0, the magnetic nanoparticle adsorption efficiency drops rapidly and avoids ionization of the ZEAs that the environment might cause, impairing the hydrophobic interaction between the analyte and the magnetic nanoparticles.
Further, the inventors have found that the elution efficiency of 5 kinds of ZEAs at 1min is as high as 80% or more, and further, according to the embodiment of the present invention, under the above-mentioned optimum adsorbent dosage condition, the elution solvent is 1-5mL, preferably 2mL, and the recovery rate is higher than 80%. Therefore, the elution time of the elution solvent with the dosage is short, the recovery rate is high, the elution equilibrium is reached at 2min, and 2min can be taken as the elution time.
According to the embodiment of the invention, the chromatographic detection conditions of the ultra performance liquid chromatography tandem mass spectrometry are as follows: column temperature: 35 ℃; a chromatographic column: c18 chromatographic column with specification of 2.1mm × 100mm and 3.5 μm; sample introduction volume: 5 mu L of the solution; flow rate: 0.4mL/min. Therefore, the separation effect of the zearalenone mycotoxin is good, and the sensitivity and the accuracy of detection can be improved.
According to the embodiment of the invention, the mass spectrum conditions of the ultra performance liquid chromatography tandem mass spectrometry detection are as follows: ionization mode: ESI; detection mode: multiple reaction monitoring (MRM mode); ion source temperature: 550 ℃; electrospray voltage: -4500V; GS1 (N) 2 )，GS2(N 2 ) Air curtain pressure (N) 2 ) 55, 50 and 30psi, respectively; collision cell exit voltage: -10V; residence time (DT): 100ms. Therefore, the detection condition is suitable for detecting the zearalenone mycotoxin, and the detection sensitivity and accuracy are high.
According to the embodiment of the invention, the mobile phase of the chromatogram of the ultra performance liquid chromatography tandem mass spectrometry detection is as follows: a: acetonitrile, B: an aqueous solution. According to an embodiment of the invention, the elution conditions of the chromatography are gradient elution. According to an embodiment of the present invention, the gradient elution has an elution gradient of 0min,85% B;5min,20% by weight of B;6min,20% B;6.2min,5% by weight of B;9min,5% of B;9.2min,85% by weight B. Therefore, the elution time is appropriate, the sufficient separation of the zearalenone mycotoxins is facilitated, and the detection accuracy and sensitivity are high.
To facilitate an understanding of the foregoing methods for detecting zearalenone mycotoxins, a general method for detecting zearalenone mycotoxins is provided herein, as follows:
(1) A certain mass of food sample is put into a centrifuge tube, and an extraction solvent is added. And (3) performing vortex oscillation and ultrasonic treatment, centrifuging, absorbing a certain amount of supernatant, drying by blowing with nitrogen, and diluting to 10mL by using a deionized water solution containing 5% acetonitrile for magnetic solid-phase extraction.
(2) Adding magnetic nanoparticles, and oscillating and adsorbing on a multi-tube vortex mixer.
(3) Eluting the adsorbed magnetic nanoparticles, blowing nitrogen, redissolving, and filtering with 0.22 μm filter membrane to obtain the solution.
(4) And (4) injecting the upper machine solution obtained in the step (3) into an ultra-high performance liquid chromatography tandem mass spectrum for detection so as to obtain the content of the zearalenone mycotoxins.
Kit and application thereof
According to another aspect of the invention, the invention provides a kit. According to an embodiment of the invention, the kit comprises: the magnetic nanoparticles, the extraction solvent and the elution solvent are described above. Therefore, the kit can be used for detecting the zearalenone mycotoxin quickly, accurately, efficiently and highly sensitively, and is particularly suitable for detecting the zearalenone mycotoxin in complex substances such as food and the like.
Furthermore, the kit also comprises reagents, consumables and instruments used in the method for detecting the zearalenone mycotoxin, which are not illustrated herein. Furthermore, the kit also has the technical characteristics and technical effects of the method for detecting the zearalenone mycotoxins, and the details are not repeated herein.
According to another aspect of the invention, the invention provides the application of the kit in detecting the content of the zearalenone mycotoxins. Therefore, the kit can be used for detecting the zearalenone mycotoxins in complex substances such as food and the like, and has the advantages of high detection speed, high accuracy and high sensitivity.
According to still another aspect of the invention, the kit is used for detecting the content of zearalenone mycotoxins.
According to an embodiment of the present invention, the zearalenone type mycotoxin is at least one selected from the group consisting of Zearalenone (ZEA), α -zearalenol (α -ZAL), β -zearalenol (β -ZAL), α -zeaenol (α -ZEL) and β -zeaenol (β -ZEL).
The present invention is described below with reference to specific examples, which are intended to be illustrative only and are not to be construed as limiting the invention.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or apparatus used are conventional products which are commercially available, e.g. from Sigma, without reference to the manufacturer.
Example 1
According to the method provided by the embodiment of the invention, the magnetic nanoparticles with the magnetic covalent organic framework synthesized by taking carboxyl functionalized ferroferric oxide as a magnetic core and 1,3, 5-tri (4-aminophenyl) benzene and 1,3, 5-triacyl phloroglucinol as functional monomers are prepared, and the preparation process is as follows:
(a) In a 50mL two-necked round bottom flask, 50.0mg of carboxy-functionalized ferroferric oxide and 80.0mg of 1,3, 5-tris (4-aminophenyl) benzene were added to 11mL of tetrahydrofuran and sonicated for 20min.
(b) Mechanically stirring the mixture of the product obtained in the step (a) at 65 ℃ for 30min to ensure that part of 1,3, 5-tri (4-aminophenyl) benzene is firstly anchored on the surface of carboxyl functionalized ferroferric oxide through hydrogen bonds to form a bridge action, thus obtaining the magnetic nano material (Fe) 3 O 4 @TAPB)。
(c) Uniformly dispersing 60.0mg of 1,3, 5-triacyl phloroglucinol into 4mL of tetrahydrofuran, dropwise adding the tetrahydrofuran and 200 mu L of acetic acid into the reaction system in the step (b) under stirring, and after dropwise adding, reacting for 2h to obtain magnetic nanoparticles (Fe) 3 O 4 @TAPB-Tp)。
Example 2
In this example, the Fe prepared in example 1 was used 3 O 4 The @ TAPB-Tp magnetic nanoparticles are used for extracting and detecting the zearalenone mycotoxins in the sample to be detected, and analyzing and comparing different detection conditions.
1. Preparation of sample liquid
(1) The samples were purchased from different local supermarkets and the specific preparation steps were as follows:
(2) A certain mass of food sample is put into a centrifuge tube, and a certain volume of extraction solvent is added.
(3) The mixed system was vortexed and sonicated for extraction.
(4) Centrifuging under certain conditions by using a centrifuge, sucking a certain amount of supernatant into a white glass vial, drying by blowing nitrogen, and diluting to 10mL by using deionized water solution containing 5% acetonitrile for Magnetic Solid Phase Extraction (MSPE) experiment application.
2. Reagent and standard solution
The various test ZEAs standards were purchased from ROOM corporation, and all standards were stored as per the recommendations of the certificate and formulated with acetonitrile into 1.0mg/mL standard stock solutions to obtain working solutions by diluting the stock solutions to the appropriate concentrations. Acetonitrile and formic acid were both chromatographically pure, all other reagents were at least analytical reagent grade.
3. Instrument
The UHPLC-MS/MS analysis was performed using LC-30AD UHPLC (Shimadzu) with QTRAP 6500+ triple quadrupole rod tandem spectrometer (AB SCIEX, USA). Chromatography was carried out at 35 ℃ using a C18 column (2.1 mm. Times.100mm, 3.5 μm) with a sample injection volume of 5 μ L and a flow rate of 0.4000mL/min. The mobile phase consisted of acetonitrile (a) and water (B). Gradient elution was performed under the following conditions: 0min,85% by volume B;5min,20% by weight B;6min,20% B;6.2min,5% by weight of B;9min,5% of B;9.2min,85% by weight B; the post run time was 2.8min.
The mass spectrometer parameters were as follows: ionization mode, ESI - (ii) a Detection mode, multiple Reaction Monitoring (MRM); ion source temperature, 550 ℃; electrospray voltage, -4500V; GS1 (N2)) GS2 (N2), gas curtain pressure (N2) 55, 50 and 30psi, respectively; the voltage at the outlet of the collision pool is-10V; residence time (DT): 100ms. Table 1 lists the MRM parameters of ZEAs.
TABLE 1 MRM parameters of 15 ZEAs
Figure BDA0003081047560000081
4. Magnetic solid phase extraction procedure
The magnetic solid phase extraction comprises the following specific steps:
(1)3.0mg Fe 3 O 4 @ TAPB-Tp was added to the vial containing the sample extract solution, and the vial was then shaken on a shaker for 2min.
(2) Decanting the supernatant obtained in step (1) with the aid of a magnet and keeping it in Fe 3 O 4 @ TAPB-Tp was rinsed with 2mL of deionized water.
(3) After discarding the deionized water with the help of a magnet, the analytes were ultrasonically eluted with 2mL of acetonitrile for 2min, and the collected eluates were transferred to a clean tube and evaporated to dryness under a stream of nitrogen.
(4) Before UHPLC-MS/MS analysis, the residue was dissolved in 1mL of the initial mobile phase and filtered through a 0.22 μm filter.
5. Influence of different reaction conditions on the results of the experiment
(1) Influence of adsorbent dosage and adsorption time
To obtain the optimal experimental conditions for simultaneous quantitative adsorption of 5 ZEAs, fe was studied 3 O 4 The amount of @ TAPB-Tp and the adsorption time.
The amount of the adsorbent was varied according to the above experimental method, and as a result, as shown in FIG. 1 (A), when the amount of the adsorbent was from 1.0 to 3.0mg, the experimental recovery rate increased with the increase in the mass of the adsorbent, and when Fe was used 3 O 4 At @ TAPB-Tp levels exceeding 3.0mg, the experimental recovery remained nearly constant as the mass of the adsorbent increased, which is likely when Fe 3 O 4 When the amount of @ TAPB-Tp is 3.0mg, the target substance in the solution is almost completely adsorbed, and the adsorption is in kinetic equilibrium. Thus, it is possible to provideIn this experiment, 3.0mg of Fe was finally selected 3 O 4 @ TAPB-Tp is a preferred amount of adsorbent in MSPE.
3.0mg of Fe was selected according to the above experimental method 3 O 4 @ TAPB-Tp was used as an adsorbent in MSPE, and the adsorption time was changed, as shown in FIG. 1 (B), and as a result, when the extraction time was 0.5min, the recovery rate of 5 ZEAs was 70% or more, and the adsorption equilibrium was reached at 2min. This indicates that Fe was produced 3 O 4 @ TAPB-Tp has a rapid adsorption process for 5 ZEAs. Furthermore, it can also be seen from FIG. 1 (B) that the adsorption rate is slowed at 0.5-2min, which may be Fe 3 O 4 Immediately after the addition of @ TAPB-Tp, the amount of adsorption sites and target was large, and the food base was Fe 3 O 4 The effect of @ TAPB-Tp on the adsorption of 5 ZEAs is small, and the matrix solution has a remarkably reduced effect on Fe along with the target in the adsorption solution 3 O 4 The effect of adsorbing 5 ZEAs is increased at @ TAPB-Tp. Therefore, 2min was selected as the preferred adsorption time for the process of this example.
(2) Influence of the pH value and ion concentration of the sample solution
In order to obtain the optimal experimental conditions for simultaneous quantitative adsorption of 5 ZEAs, the pH value and ion concentration of MSPE standard solution on Fe were studied 3 O 4 The effect of the extraction effect of @ TAPB-Tp.
The pH of the MSPE standard solution was changed according to the above experimental method, and the results are shown in FIG. 1 (C), and it is preferable that the pH of the MSPE standard solution is 6.0-7.0, and Fe is contained when the pH of the MSPE standard solution is higher than 8.0 3 O 4 The adsorption efficiency of @ TAPB-Tp for adsorbing 5 ZEAs is rapidly reduced. This is because ZEAs contain phenolic hydroxyl functional groups, are weak acid compounds, and have large pKa values (pKa = 7.58-8.68). Thus, changing the sample pH may result in target protonation and deprotonation, which is detrimental to Fe 3 O 4 And @ TAPB-Tp adsorption of 5 ZEAs. And 5 ZEAs are stable in weak acid or neutral environment, thereby being beneficial to Fe 3 O 4 Adsorption of 5 ZEAs @ TAPB-Tp. Furthermore, the alkaline environment may cause the ZEAs to be in an ionized state, which may weaken the hydrophobic interaction between the analyte and the adsorbent. Therefore, due toThe pH value of the prepared MSPE standard solution is in the optimal pH range, and the experiment does not adjust the pH value of the prepared MSPE standard solution in consideration of the convenience of the experiment.
According to the experimental method, the influence of salt ions in the MSPE standard solution on the experimental result is researched. Different concentrations of NaCl were added to the MSPE standard solution, and as a result, as shown in fig. 1 (D), the experimental recovery rate of 5 ZEAs began to decrease significantly when the salt ion (NaCl) concentration in the MSPE standard solution exceeded 0.2 mol/L. This may be due to Na + And Cl - Competition for Fe with the target 3 O 4 Due to adsorption sites on @ TAPB-Tp, when Na + And Cl - Will occupy Fe when present in excess 3 O 4 A large number of adsorption sites on @ Tp-TAPB, affecting Fe 3 O 4 @ TAPB-Tp adsorption of a target. In addition, as the NaCl content increases, the viscosity of the adsorption solution increases, which results in the decrease of the diffusion rate of the target in the MSPE standard solution, thereby preventing the transfer of 5 ZEAs from the MSPE standard solution to Fe 3 O 4 @ TAPB-Tp. Therefore, in view of the convenience of the experiment, fe 3 O 4 When @ TAPB-Tp is applied to detection of 5 ZEAs in food, salt ions are not added into the MSPE solution.
(3) Influence of elution solvent
After adsorbing the target, using the correct elution solution is one of the key factors for improving the experimental recovery. In order to obtain the preferred elution efficiency, the present example first selects four organic solvents commonly used in the laboratory as Fe 3 O 4 The results of experiments conducted under the above conditions with respect to the elution solutions of 5 kinds of ZEAs on @ TAPB-Tp, namely Ethanol (EA), methanol (MA), ethyl Acetate (EAC) and Acetonitrile (ACN) are shown in FIG. 1 (E), and among the four desorption solutions, when ACN was used as the elution solution, the elution efficiency of 5 kinds of ZEAs was the best, and the recovery rate was 80% or more. Meanwhile, since the pKa values of 5 ZEAs were between 7.58 and 8.68, the change in experimental recovery was investigated when the elution solution was weak acid or weak alkaline. This example was prepared with 0.5% acetic acid (HAC) in acetonitrile and 0.5% ammonia (NH) 4 OH) as desorption solution. From FIG. 1(E) It can also be seen that the elution solution is weak acid or weak alkaline, which has little effect on the experimental recovery rate and slightly reduces the experimental recovery rate. Therefore, ACN was chosen as Fe in this experiment 3 O 4 @ TAPB-Tp elution solutions of 5 ZEAs.
(4) Influence of eluent dosage and elution time
In order to obtain the preferred experimental conditions for simultaneous quantitative adsorption of 5 ZEAs, the influence of the amount of elution solution and elution time was investigated. Experimental methods as described above, the amounts of eluents were varied, and the results are shown in fig. 1 (F), where the elution efficiency of the experiment was rapidly increased when the amount of the elution solution was 1-2mL, and reached a balance at 2mL, and the recovery rate was 85% or more. Furthermore, when 2mL of ACN was used again for the first elution of Fe with 2mL of ACN 3 O 4 @ TAPB-Tp elution was found to give less than 3% recovery from the experiment, indicating that 2mL of ACN was sufficient. Thus, 2mL of ACN was used as the volume of elution solution in the subsequent MSPE.
Experimental method as described above, the elution times were changed, and as a result, as shown in fig. 1 (H), the elution efficiency of 5 ZEAs was as high as 80% or more at 1min and the elution equilibrium was reached at 2min. This indicates the eluent pair Fe 3 O 4 The elution procedure for 5 ZEAs on @ TAPB-Tp is also a rapid process, with Fe above 1min 3 O 4 The 5 ZEAs on @ TAPB-Tp were mostly eluted, so the experimental recovery increased less. And when the elution time exceeds 2min, fe 3 O 4 @ TAPB-Tp 5 ZEAs were completely eluted, so the experimental recovery was not increasing. Finally, the elution time of 2min was chosen as the elution time for the target in this experiment.
(5) Regeneration performance and batch reusability of adsorbents
Regeneration performance and batch reusability are among the key factors for evaluating adsorbents. The adsorbent was recovered and the extraction experiment repeated as described above. By repeating the extraction experiment on the adsorption material, the results show that: prepared Fe 3 O 4 @ TAPB-Tp can be reused at least 10 times, and the sample recovery rate is still kept above 85%, indicating thatThe prepared magnetic nano material Fe 3 O 4 @ TAPB-Tp has good reusability, and is shown in figure 2 in detail. In addition, different batches of prepared Fe 3 O 4 The @ TAPB-Tp has no significant influence on the recovery rate of the sample, and the relative standard deviation (RSD,%) is between.01 and 3.73 percent, which indicates that the prepared magnetic nano material Fe 3 O 4 @ TAPB-Tp has better batch repeatability, as detailed in Table 2.
Fe prepared in Table 2 3 O 4 Batch repeatability research result of @ TAPB-Tp
Figure BDA0003081047560000101
Figure BDA0003081047560000111
(6) Analysis of Performance
Based on the above studies, the optimum conditions for the MSPE of the 5 ZEAs were determined as follows; the volume of the standard solution for magnetic solid phase extraction is 10mL, the dosage of the adsorbent is 3.0mg, the adsorption time is 2min, the sample solution is not subjected to pH value adjustment treatment and salt ions (NaCl) are not added, the elution solvent of 5 ZEAs on the adsorbent is acetonitrile, the dosage is 2mL, and the elution time is 2min.
Under the preferred conditions, the established MSPE-UHPLC-MS/MS method was evaluated for analytical performance, and the results are shown in Table 3, which show that:
(1) The ZEA, alpha-ZEL, beta-ZEL, alpha-ZAL and beta-ZAL have good linearity (R2 > 0.9990) in the linear range of 0.01-50 mug L-1;
(2) The detection limit of 5 ZEAs in milk, eggs and corns is lower than 0.02 mug kg-1, which shows that the established method has higher detection sensitivity;
(3) The limit of quantification of 5 ZEAs in milk, eggs and corn is 0.012-0.050 mug kg -1 The established method can completely meet the requirements of each country on the detection of ZEAs in food;
(4) The relative standard deviation (RSD,%) between day and day was between 2.37-10.40%, indicating good reproducibility and reproducibility of the established method.
TABLE 3 validation results of 5 ZEAs in food
Figure BDA0003081047560000112
The results, compared to the reported methods, are shown in table 4, indicating that:
(1) Compared with other solid-phase extraction materials, the magnetic solid-phase extraction material mentioned in the embodiment 1 is not only relatively simple and rapid in preparation method, but also has the advantages of less dosage, higher extraction speed and the like;
(2) Compared with other methods based on other magnetic solid phase extraction materials, the method has higher detection sensitivity (detection limit: 0.003-0.018 mu g kg) -1 ) These results indicate that the established Fe-based alloy is based on Fe 3 O 4 An MSPE-UHPLC-MS/MS detection method of @ TAPB-Tp is a more efficient analysis method aiming at ZEAs.
TABLE 4 comparative analysis results with the existing methods
Figure BDA0003081047560000121
a Fe 3 O 4 @ pDA: polydopamine Magnetic nanoparticles (Magnetic nanoparticles of polyadopamine)
b rGO/Au: composite of reduced graphene oxide and gold nanoparticles
c Fe 3 O 4 @ MWCNTs: multi-walled carbon nanotube magnetic nanoparticles (Maguetic nanoparticles of Multi walled carbon nanotubes)
d SPMIPs: magnetic surface pseudo molecular imprinted polymer (Magnetic surface pseudo molecular imprinted polymer)
e AuNPs @ Aptamer: gold nanoparticle @ aptamer hybrid materialMaterial (Gold nanoparticles @ aptamer hybrid materials)
The results of the actual sample analysis, which are shown in tables 5 and 6, indicate that:
(1) The actual sample tests of milk, egg and corn are carried out, a small amount of corn samples have the problem of mildew, and low concentrations of ZEA, alpha-ZEL and beta-ZEL (0.11-10.50 mu g kg) are detected in the corn samples -1 )
(2) To verify the accuracy of the developed method, milk, egg and corn samples were spiked to obtain three different concentrations (0, 1, 10 and 100. Mu.g L) -1 ) The recovery rates of the sample solution and five ZEAs (detailed in Table 6) are respectively as follows: the results of 81.4-90.26% of milk sample, 81.27-89.93% of egg sample and 83.13-90.20% of corn sample show that the detection method of the embodiment of the invention is accurate and efficient.
TABLE 5 actual sample test results
Figure BDA0003081047560000122
Figure BDA0003081047560000131
TABLE 6 actual sample standard recovery experiment
Figure BDA0003081047560000132
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims (7)

1. A method for detecting zearalenone mycotoxins, which is characterized by comprising the following steps:
contacting a sample to be detected with an extraction solvent, and carrying out extraction treatment to obtain an extraction solution, wherein the extraction solvent is a mixed solution of acetonitrile, acetic acid and water;
adsorbing an extracting solution by using magnetic nanoparticles, and adding an eluting solvent to obtain an eluent, wherein the eluting solvent is at least one selected from ethanol, methanol, ethyl acetate, acetonitrile, an acetonitrile solution containing 0.5% of formic acid and an acetonitrile solution containing 0.5% of ammonia water, and the ratio of the extracting solution to the magnetic nanoparticles is 10mL:1-5.0mg; and
performing ultra performance liquid chromatography tandem mass spectrometry detection on the eluent so as to obtain the content of the zearalenone mycotoxins,
wherein the magnetic nanoparticles comprise:
a core body, wherein the core body is composed of superparamagnetic ferroferric oxide;
a shell overlying the surface of the core body, the shell being comprised of a repeating unit of formula I,
Figure FDA0004049351690000011
the chromatographic detection conditions of the ultra performance liquid chromatography tandem mass spectrometry detection are as follows:
column temperature: 35 ℃;
and (3) chromatographic column: c18 chromatographic column with specification of 2.1mm × 100mm,3.5 μm;
sample introduction volume: 5 mu L of the solution;
flow rate: 0.4mL/min of the water-soluble polymer,
the mass spectrum conditions of the ultra performance liquid chromatography tandem mass spectrometry detection are as follows:
ionization mode: ESI － ；
Detection mode: monitoring multiple reactions;
ion source temperature: 550 ℃;
electrospray voltage: -4500V;
GS1, GS2, gas curtain pressure 55, 50 and 30psi respectively;
collision cell exit voltage: -10V;
residence time (DT): the time period of 100ms is shorter than the time period of 100ms,
the mobile phase of the chromatogram detected by the ultra performance liquid chromatography tandem mass spectrometry is as follows: a: acetonitrile, B: an aqueous solution;
the elution conditions of the chromatogram were gradient elution, the gradient elution having an elution gradient of 0min,85% by volume B;5min,20% by weight B;6min,20% B;6.2min,5% by weight of B;9min,5% of B;9.2min,85% B.
2. The method according to claim 1, wherein the ratio of the extracting solution to the magnetic nanoparticles is 10mL:3.0mg.
3. The method of claim 1, wherein the elution solvent is acetonitrile.
4. The method of claim 1,
in the extraction solvent, the volume ratio of the acetonitrile to the acetic acid to the water is 70-90.
5. A kit, comprising:
magnetic nanoparticles according to any one of claims 1 to 4;
the extraction solvent of any one of claims 1 to 4; and
the elution solvent according to any one of claims 1 to 4.
6. Use of the kit of claim 5 for detecting zearalenone mycotoxin levels.
7. The use according to claim 6, wherein the zearalenone fungal toxin is at least one selected from the group consisting of Zearalenone (ZEA), α -zearalenol (α -ZAL), β -zearalenol (β -ZAL), α -zeaenol (α -ZEL) and β -zeaenol (β -ZEL).
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