CN111151222A - Preparation of magnetic composite adsorption material and application of magnetic composite adsorption material in detection of multiple pesticide residues in tea - Google Patents
Preparation of magnetic composite adsorption material and application of magnetic composite adsorption material in detection of multiple pesticide residues in tea Download PDFInfo
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Abstract
The invention discloses a preparation method of a magnetic composite adsorption material and application of the magnetic composite adsorption material in tea multi-pesticide residue detection. The magnetic composite adsorbing material is prepared by mixing nano Fe3O4After being mixed with graphitized carbon black, the product is prepared by taking absolute ethyl alcohol as a medium and carrying out ultrasonic magnetization, has good purification effect, can effectively remove matrix interference of a tea sample when being used for the pretreatment of the tea sample for purification, and is favorable for realizing the accurate detection of various pesticide residues in the tea.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and particularly relates to a method for preparing a magnetic composite adsorbing material by directly magnetizing absolute ethyl alcohol serving as a medium, and the obtained magnetic composite adsorbing material is successfully used for detecting various pesticide residues in tea.
Background
The problem of pesticide residue in tea leaves has been regarded as important, and various techniques for detecting the residue are also endless. However, the nature of the tea sample is complex and can cause a number of problems in performing the assay, such as signal interference, instrument contamination, etc. The content of pesticide residues is extremely micro, even trace and ultra trace levels, the possibility of direct analysis after sample collection is extremely low, and the sample generally needs to be concentrated, enriched and purified.
In recent years, methods such as Solid Phase Extraction (SPE) and Matrix Solid Phase Dispersion (MSPD) typified by QuEChERS have been used for tea leaf analysis. The Graphitized Carbon Black (GCB) is a regular polyhedron with a uniform graphitized surface, which is generated by calcining carbon black in inert gas at a high temperature of 2500-3000 ℃. Under the condition of high temperature, the large-gap structure of the carbon black is destroyed to form a smooth and non-porous graphite crystal structure. Therefore, SP is between carbon atoms on the GCB surface2Hybridization, single electron pair and active ion, and hexagonal microstructure. The GCB surface is hydrophobic in general and can adsorb nonpolar and weakly polar compounds; and secondly, the surface of the material has a plurality of polar sites, so that the material can adsorb polar compounds or be used as an anion exchanger, therefore, the material can adsorb both non-polar and weak-polar compounds and polar compounds, shows a wide adsorption spectrum for the compounds, and is particularly the first choice material in the purification of samples with high content of pigments such as tea leaves and the like.
Magnetic Solid Phase Extraction (MSPE) has gained much attention since its 1999. In recent years, many scientists combine magnetic nanoparticles with other materials in various ways to form a new functionalized magnetic nanomaterial for application in sample pretreatment. Compared with other materials, the magnetic adsorption material can be repeatedly used under certain conditions and only needs to be usedThe phase separation can be realized by an external magnetic field, and the operation is simple, time-saving and labor-saving. Quality of plum (quality of plum,' Fe)3O4Research on selective adsorption of nanoparticles to plant pigments in tea, "master academic thesis of university of Hunan, 2013) discusses Fe3O4The nanoparticles selectively adsorb plant pigment in tea, and can be expressed as Fe3O4The three fillers of 50mg of nano particles, 30mg of graphitized carbon black and 150mg of anhydrous magnesium sulfate are mixed in proportion and applied to the detection of 16 pesticide residues in the tea. The magnetic ferroferric oxide nano particle has the characteristics of superparamagnetism, large specific surface area, many adsorption sites and the like, is widely researched, but has poor stability, is easy to oxidize, is unstable under extreme acid and alkali conditions, and can be used for treating Fe3O4The magnetic material after functional modification has higher practical application value.
The existing reports on magnetic materials mostly focus on enriching the compounds to be detected with magnetic materials, and the materials used include C18, graphene, carbon nanotubes, and the like. Most of these studies are based on the interaction between the target compound and a magnetic material to enrich the test compound and then desorb it for analysis. But the varieties of the adsorbable pesticides are limited and are not feasible for most pesticide analysis. And the prior art requires a more vigorous reaction. The preparation method of the magnetic composite adsorption material provided by the invention is simple and feasible, is harmless to human bodies and environment, and is suitable for purification of at least 378 pesticide residues in high-pigment samples such as tea leaves and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic composite adsorption material and application of the magnetic composite adsorption material in tea multi-pesticide residue detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparation method of magnetic composite adsorption materialMethod of mixing nano Fe3O4And mixing with Graphitized Carbon Black (GCB), adding absolute ethyl alcohol, whirling, uniformly mixing, performing ultrasonic treatment for 1 h at the power of 1000-2000W, taking out, standing for 2 h-4 h at room temperature, centrifuging for 1-3 min at 3000-5000 rpm, removing supernatant, placing the product at 80 ℃ for vacuum drying for 4h, crushing, and sieving with a 10-mesh sieve to obtain the magnetic composite adsorbing material.
The nano Fe3O4And the graphitized carbon black in a weight ratio of 1-3: 1. The nano Fe3O4The particle size of (A) is 10 to 50 nm.
The magnetic composite adsorption material prepared by the method can be applied to detection of multiple pesticide residues in tea, and the specific application method comprises the following steps: crushing a tea sample, adding 2g of the crushed tea sample into 3 mL of saturated saline solution, whirling for 30 s, standing for 10 min, adding 10 mL of acetonitrile, performing ultrasonic extraction for 10 min, adding 2g of anhydrous calcium chloride, whirling for 2min, centrifuging for 3 min at 4500rpm, transferring 3 mL of supernatant, adding 200-300 mg of the magnetic composite adsorption material, purifying by whirling for 30 s, adding a magnetic field for separation, and taking a purified solution for gas-mass spectrometry detection.
Compared with the prior art, the method has the obvious advantages that the method is simple and feasible, the magnetic composite adsorbing material can be efficiently constructed, the obtained magnetic composite adsorbing material is good in purifying effect, can be effectively separated from a liquid phase under an external magnetic field, is convenient and easily available in raw materials, non-toxic and harmless, simple and environment-friendly in operation process, free of excessive subsequent treatment, and time-saving and labor-saving.
The material is used for purification treatment of detection of various pesticide residues in tea, is quick and effective, has reliable result, can achieve good purification effect on tea samples with complex matrixes, and meets the requirements on accuracy and precision.
Drawings
FIG. 1 shows nano Fe3O4SEM images of the product obtained after mechanical shaking (A) and sonication (B) of the mixture with GCB in absolute ethanol, respectively.
FIG. 2 is a graph showing the separation effect of the product obtained after mechanical oscillation (A) and ultrasound (B) in acetonitrile solvent under the action of an applied magnetic field.
FIG. 3 shows GCB (A) and nano Fe3O4(B) And an SEM image of the magnetic composite adsorbent (C) of the present invention.
Fig. 4 is an SEM image of the magnetic composite adsorbent after the magnetic field (a) and the centrifugal separation (B) were applied.
FIG. 5 is a visible spectrum and a photograph of a sample purified with different materials (wherein A is black tea extract, B is black tea extract + nano Fe)3O4C, C: black tea extract + GCB, D: black tea extract + magnetic composite).
FIG. 6 is a full scan chromatogram of a sample purified with different materials (wherein A: 350 mg GCB and C: 200 mg magnetic composite adsorbent).
FIG. 7 is a graph showing the distribution of the range of recovery in the recovery experiment.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Preparation of
1.1 Experimental materials and Equipment
Nano ferroferric oxide, absolute ethyl alcohol and Graphitized Carbon Black (GCB).
Vortex oscillator, ultrasonic generator, centrifuge, electronic balance.
Preparation method
Nano Fe with the grain diameter of 10-50 nm3O4And mixing the carbon-based magnetic nano adsorption material with Graphitized Carbon Black (GCB) according to a weight ratio of 1-3: 1, adding absolute ethyl alcohol with 5 times of solid weight, carrying out ultrasonic treatment for 1 h at a power of 1000-2000W after vortex uniformly mixing, taking out, standing at room temperature for more than 2 h, then centrifuging for 1-3 min at 3000-5000 rpm, removing supernatant, placing the product in a vacuum drier, carrying out vacuum drying for 4h at 80 ℃, taking out a centrifugal tube, crushing the obtained product, and sieving with a 10-mesh sieve to obtain the prepared carbon-based magnetic nano adsorption material.
Performance and application
2.1 Experimental materials and Equipment
378 pesticide standards were purchased from alta technologies ltd; acetonitrile, ethyl acetate, acetone, n-hexane; nano ferroferric oxide, N-propyl ethylenediamine (PSA), Graphitized Carbon Black (GCB) and C18 filler.
Scanning an electron microscope; gas chromatography-quadrupole/time-of-flight mass spectrometer; gas chromatography-triple quadrupole tandem mass spectrometer; an ultraviolet-visible spectrophotometer; a vortex oscillator; a high speed centrifuge; a multifunctional nitrogen blowing instrument; an ultra-pure water system; an electronic balance.
Determination of experimental conditions by direct magnetization method
2.2.1 magnetization mode
Ultrasound has now been applied to synthesize new materials. The mass transfer and heat transfer can be accelerated by using the auxiliary energy of the ultrasound, when the ultrasonic energy is high enough, the micro bubbles (cavitation nuclei) existing in the liquid collapse and close rapidly under the action of the ultrasonic energy, great energy is released, micro jet with strong impact force is generated, and local high temperature and high pressure are generated at the moment of rapid collapse. The cavitation effect of the ultrasonic waves can greatly improve the heterogeneous reaction rate and realize the uniform mixing of heterogeneous reaction substances.
The two magnetic assembly modes of mechanical oscillation and ultrasound were compared. FIG. 1 shows nano Fe3O4SEM images of products obtained after the mixture with GCB (1: 1, w/w) is mechanically shaken for 4h (A) and ultrasonically treated for 1 h (B) in absolute ethyl alcohol respectively. As can be seen in FIG. 1, under the action of ultrasound, nano Fe in an absolute ethanol medium3O4And the GCB is assembled into a uniform magnetic composite material.
GCB is easy to form suspension in water due to polar sites on the surface, has high recycling and enriching difficulty, and can become a new pollution source if being applied in large quantities. In organic solvents, fine particles are also dispersed in the solvent and centrifugation is required to complete the separation. FIG. 2 is a graph showing the separation effect of the product obtained after mechanical oscillation (A) and ultrasound (B) in acetonitrile solvent under the action of an applied magnetic field. As can be seen from FIG. 2, GCB + nano Fe after mechanical oscillation3O4In addition to the mixed materialUnder the action of the magnetic field, GCB still remains in the solvent, the magnetic composite adsorption material obtained by ultrasonic treatment is completely separated from the liquid phase under the external magnetic field, and all GCB in the solvent can be magnetically recovered.
Magnetized medium
To find a suitable medium for GCB magnetization, 6 solvents with different polarities, such as water, ethanol, acetonitrile, acetone, ethyl acetate, and n-hexane, were compared. As a result, it was found that GCB has a large surface tension in polar media such as water, ethanol and acetonitrile, while GCB tends to agglomerate more tightly in a less polar solvent such as ethyl acetate and n-hexane. This is probably because particles suspended in solution are generally subjected to van der waals forces, and GCB is small in size (about 10-20 nm) and is strongly subjected to van der waals forces, which easily cause agglomeration. But because SP is between carbon atoms on the surface of GCB2Hybridization is carried out, single electron pairs and active ions exist, polar sites exist, dipolar attraction exists between the polar sites and a polar solvent, and GCB is relatively dispersed in the polar solvent.
Further comparing GCB with nano Fe in water, ethanol and acetonitrile medium3O4The magnetization reaction of (2). The results show that under the action of ultrasonic wave, GCB in three media can be combined with nano Fe3O4The homogeneous phase is formed, but the subsequent operation of removing the solvent is time-consuming and labor-consuming when water is used as a medium, and ethanol is more economical and environment-friendly than acetonitrile, so that ethanol is selected as a reaction solvent medium.
Characterization of the Properties of the magnetic composite adsorbent Material
FIG. 3 shows GCB (A) and nano Fe3O4(B) And an SEM image of the magnetic composite adsorbent (C) of the present invention. As can be seen from the figure, GCB is magnetized by ultrasonic and then reacts with nano Fe3O4The composite material with a flat surface is formed. Upon separation from the solvent medium, the phase remains homogeneous, whether by separation with an applied magnetic field or by centrifugation (5500 rpm) (FIG. 4).
Purifying effect of magnetic composite adsorbing material
Weighing 4 parts of pulverized black tea sample, 2g each, placing in a 50 mL centrifuge tube, adding 3 mL saturated saline solution, and vortexing for 30 sStanding for 10 min, adding 10 mL acetonitrile, ultrasonic extracting for 10 min, adding 2g anhydrous calcium chloride, vortexing for 2min, centrifuging at 4500rpm for 3 min, respectively transferring 3 mL supernatant, and adding 200 mg nanometer Fe into 3 parts of the supernatant3O4The GCB and the magnetic composite adsorbing material prepared by the invention are whirled for 30 s, a magnetic field is applied or the centrifugal separation is carried out at 4500rpm, and the supernatant is taken to be scanned in the ultraviolet visible spectrophotometer for the wavelength, and the result is shown in figure 5. As can be seen from fig. 5, the magnetic composite adsorbing material has a good purifying effect, and the background absorption of the matrix is significantly reduced.
Weighing 2 parts of crushed black tea sample, placing 2g of the crushed black tea sample into a 50 mL centrifuge tube, adding 3 mL of saturated saline solution, whirling for 30 s, standing for 10 min, adding 10 mL of acetonitrile, performing ultrasonic extraction for 10 min, adding 2g of anhydrous calcium chloride, whirling for 2min, centrifuging at 4500rpm for 3 min, respectively transferring 3 mL of supernate, adding 200 mg of the magnetic composite adsorption material prepared by the invention and 350 mg of GCB, and performing gas chromatography-triple quadrupole mass spectrometry full scan analysis, wherein the result is shown in figure 6. The experimental results of fig. 6 show that the background of the substrate purified by the magnetic composite adsorbing material is relatively simple, the purifying effect is good, and if GCB is used for treatment, a larger amount of GCB is needed to obtain the same depigmenting effect as the magnetic composite adsorbing material.
Application example
2.5.1 apparatus conditions
Chromatographic conditions are as follows: a chromatographic column: VF-1701 MS capillary column (30.0 m.times.0.25 mm.times.0.25 μm); temperature rising procedure: keeping the temperature at 40 ℃ for 1 min, then heating to 130 ℃ at 30 ℃/min, heating to 250 ℃ at the speed of 5 ℃/min, heating to 280 ℃ at the speed of 10 ℃/min, and keeping the temperature for 2 min. Flow rate: 1.4 mL/min; sample introduction amount: 1 mu L of the solution; and (3) sample introduction mode: no shunt sampling; carrier gas: helium with purity more than or equal to 99.999%; sample inlet temperature: 280 ℃; the retention time was adjusted with epoxy heptachloride.
Mass spectrum conditions: electron impact ion source (EI); electron energy: 70 eV; emission current: 45 muA; ion source temperature: 230 ℃; transmission line temperature: 280 ℃; solvent retardation: 5 min; first-order mass spectrum mass scanning range: m/z is 50-600; mass scan range of secondary mass spectrum: m/z is 50-400; acquisition rate: 2 spectra/s; collecting time: 200 ms/span.
Matrix effect investigation
The matrix effect of pesticide analysis refers to the influence of other matrix components in a sample besides the analyte on the measured value of the analyte. The matrix effect of 378 pesticide residues is evaluated by adopting the magnetic composite adsorption material. The method comprises the following steps:
weighing 2g of crushed black tea sample, placing the crushed black tea sample in a 50 mL centrifuge tube, adding 3 mL of saturated saline solution, whirling for 30 s, standing for 10 min, adding 10 mL of acetonitrile, carrying out ultrasonic extraction for 10 min, adding 2g of anhydrous calcium chloride, whirling for 2min, centrifuging for 3 min at 4500rpm, transferring 3 mL of supernatant, adding 300 mg of magnetic composite adsorbing material, whirling for 30 s for purification, separating by an external magnetic field, adding purified solution 378 into standard solution of pesticide compounds to make the concentrations of the pesticide compounds 20 ng/mL, comparing the standard solution with the standard solution of pure solvent (ethyl acetate) with the same concentration, operating the instrument condition according to 2.5.1, and calculating the matrix effect according to the following formula:
matrix effect ME (%) = (A2-A1)/A1 × 100%,
wherein A1 is the response value of the pesticide in the ethyl acetate solution, and A2 is the response value of the pesticide in the tea blank sample solution. The results are shown in Table 1.
Table 1 matrix effect investigation
The matrix effect is 0-20% of weak matrix effect, 20-50% of medium matrix effect and more than 50% of strong matrix effect, and as can be seen from table 1, the matrix interference of the tea sample can be effectively removed by adopting the magnetic composite adsorbing material for pretreatment.
Recovery and precision results
Weighing 2g of crushed black tea sample, placing the black tea sample in a 50 mL centrifuge tube, adding 3 mL of saturated saline solution, whirling for 30 s, standing for 10 min, adding 10 mL of acetonitrile, carrying out ultrasonic extraction for 10 min, adding 2g of anhydrous calcium chloride, whirling for 2min, centrifuging for 3 min at 4500rpm, accurately transferring 3 mL of supernatant, adding 10 muL of pesticide compound standard solution with the concentration of 20 ng/muL to enable the concentration of each pesticide compound in the sample to be 50 ng/mL, adding 300 mg of magnetic composite material, whirling for 30 s for purification, separating by an external magnetic field, taking purified liquid, and carrying out mechanical analysis on the purified liquid. The instrument conditions were as per 2.5.1. Table 2 shows the results of 3 replicates and fig. 7 is a recovery range profile.
Table 2 recovery and precision (n = 3)
As can be seen from Table 2, the recovery rate of 349 compounds is between 70 and 120 percent, and the relative standard deviation of 3 times of repeated experiments of 370 compounds is less than 10 percent, so that the effect is satisfactory.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (6)
1. A preparation method of a magnetic composite adsorption material is characterized by comprising the following steps: mixing nano Fe3O4And mixing with graphitized carbon black, adding absolute ethyl alcohol, whirling, uniformly mixing, performing ultrasonic treatment for 1 h at the power of 1000-2000W, taking out, standing for 2 h-4 h at room temperature, centrifuging to remove supernatant, drying the product, crushing, and sieving with a 10-mesh sieve to obtain the magnetic composite adsorbing material.
2. The method for preparing a magnetic composite adsorption material according to claim 1, wherein: the nano Fe3O4And the graphitized carbon black in a weight ratio of 1-3: 1.
3. The method for preparing a magnetic composite adsorbent material according to claim 1 or 2, wherein: the nano Fe3O4The particle size of (A) is 10 to 50 nm.
4. The method for preparing a magnetic composite adsorption material according to claim 1, wherein: the rotating speed of the centrifugation is 3000-5000 rpm, and the time is 1-3 min.
5. The method for preparing a magnetic composite adsorption material according to claim 1, wherein: the drying temperature is 80 ℃ and the drying time is 4 h.
6. The application of the magnetic composite adsorbing material prepared by the method of claim 1 in tea multi-pesticide residue detection.
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