CN114324643B - Method for detecting macrolide antibiotics in organic fertilizer and sample treatment method thereof - Google Patents
Method for detecting macrolide antibiotics in organic fertilizer and sample treatment method thereof Download PDFInfo
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- CN114324643B CN114324643B CN202111596392.9A CN202111596392A CN114324643B CN 114324643 B CN114324643 B CN 114324643B CN 202111596392 A CN202111596392 A CN 202111596392A CN 114324643 B CN114324643 B CN 114324643B
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-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Fertilizers (AREA)
Abstract
The invention discloses a detection method of macrolide antibiotics in an organic fertilizer and a sample treatment method thereof. The sample processing method comprises the following steps: fe synthesized from manganese sulfate, zinc sulfate, thioacetamide, glycol, isopropyl alcohol and ferroferric oxide 3 O 4 @ZnO&And (3) taking MnO powder as an adsorption material, performing magnetic solid-phase extraction adsorption on the organic fertilizer in a buffer solution with pH of 4.0-7.0, desorbing by using an ammonia acetonitrile eluent, and drying the desorbed eluent to obtain a treated sample. The method for detecting the macrolide antibiotics in the organic fertilizer adopts the treated sample obtained by the sample treatment method as a test sample, and directly adopts one or more of the existing macrolide antibiotics detection methods for detection. The invention has the advantages of simple operation, time saving and quick speed, repeated utilization of the adsorption material, accurate detection result and wide popularization and application.
Description
Technical Field
The invention relates to the technical field of detection of antibiotics, in particular to a detection method of macrolide antibiotics in organic fertilizers and a sample treatment method thereof.
Background
Organic fertilizers, mainly derived from plants and/or animals, are applied to soil to provide plant nutrition as a carbonaceous material of its primary function. Is processed from biomass, animal and plant wastes and plant residues. The artificially synthesized antibiotics added into animal feed can remain in the feces, and the antibiotics can remain in the organic fertilizer after the feces are processed, and researches show that compared with the soil without the organic fertilizer, the content of tetracyclines and macrolide antibiotics in the soil with the feces organic fertilizer applied for a long time can be increased by ten times to tens times. Antibiotics in the organic fertilizer accumulate in soil, have a certain influence on crop growth, can diffuse to water body, cause surface water and groundwater pollution, and the influence and harm of the antibiotics on soil health at present are paid attention to, so that the problem of antibiotic residues in the organic fertilizer cannot be ignored.
Macrolide antibiotics (macrolides antibiotics, MA) are a generic term for a class of antibacterial drugs having a 12-16 carbon lactone ring in the molecular structure, which belong to the class of rapid bacteriostats by blocking the activity of peptide acyltransferase in the 50s ribosome to inhibit bacterial protein synthesis. Is mainly used for treating infections of aerobic gram-positive cocci and negative cocci, certain anaerobic bacteria, legionella, mycoplasma, chlamydia and the like. Research shows that macrolide antibiotics have other wide pharmacological actions besides antibacterial action. Commonly used drugs are erythromycin (EM/ERY), clarithromycin (CAM), roxithromycin (RM/ROX) and Azithromycin (Azithromycin, AZM).
The existing detection method of macrolide antibiotics mainly comprises a High Performance Liquid Chromatography (HPLC) method and a high performance liquid chromatography-mass spectrometry (HPLC-MS/LC-MS) detection method which are matched with a conventional detector such as a photodiode array detector (DAD) or an ultraviolet detector, and an applicable sample treatment method is generally adopted for different samples and detection targets so as to reduce interference of other substances in the samples on detection results of the detection targets. The pretreatment method of macrolide antibiotics in organic fertilizer, i.e. the sample treatment method, is mainly a solid phase extraction method, for example Ge Feng et al, establishes that sulfonamides and fluoroquinolones in the organic fertilizer sample,Solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry detection method (Ge Feng, guo Kun, tan Lichao, etc.) for total 18 antibiotic residues of tetracyclines and macrolides]Ecological and rural environmental school newspaper, 2012,028 (005): 587-594); the organic fertilizer sample is extracted by mixed solution of disodium ethylenediamine tetraacetate-acetonitrile (1:1, V/V), and is extracted and purified by a hydrophilic/lipophilic balance (HLB) solid phase extraction column, and is measured by a high performance liquid chromatography-tandem mass spectrometry-electrospray positive ion multi-reaction monitoring mode (MRM). Wu Dan et al use ultra-high performance liquid chromatography tandem mass spectrometry to determine 15 antibiotic residues in organic fertilizer (Wu Dan, hypersensitive, sun Yanmei, etc.. Ultra-high performance liquid chromatography tandem mass spectrometry to determine 15 antibiotic residues [ C ] in organic fertilizer]2017, the science and technology annual meeting discourse (third volume), the science and technology society of china, 2017); the sample adopts acetonitrile-Na 2 EDTA-McIlvaine buffer solution (1:1, V/V) ultrasonic extraction, purification by solid phase extraction column, and quantification by external standard method; the assay was separated by a Thermo HyspersilGOLD C18 column (100 mm. Times.2.1 mm,3 μm) to select for qualitative and quantitative analysis by reaction monitoring (SRM). Because the organic fertilizer has complex components, the solid phase extraction column of the traditional adsorption material is used for extraction, the solid phase extraction column is easy to be blocked in the purification process, and the quality of the sample is reduced and cannot reach the detection limit standard; and the solid phase extraction column has the technical problems of serious compound loss, poor repeatability of detection results, time and labor waste and higher cost.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a detection method of macrolide antibiotics in organic fertilizers, which is simple and convenient to operate and accurate in detection result, and a sample treatment method thereof.
A sample processing method for detecting macrolide antibiotics in organic fertilizer comprises the following steps:
(1)Fe 3 O 4 @ZnO&synthesis of MnO powder: manganese sulfate, thioacetamide, zinc sulfate, ethylene glycol and isopropanol are mixed uniformly, and nano Fe is added 3 O 4 Stirring and reacting for 60-72 hours at 30-40 ℃ after uniformly mixing; the reaction solution reacts at the constant temperature of 200 ℃ to 220 ℃ untilAfter the reaction liquid is cooled for 20 hours, washing the reaction liquid with water and ethanol for several times, and drying and grinding the product to obtain the magnetic material Fe 3 O 4 @ZnO&MnO powder;
(2) Magnetic solid phase extraction: taking an organic fertilizer sample, adding a magnetic material Fe 3 O 4 @ZnO&And (3) mixing MnO powder and a buffer solution with pH value of 4.0-7.0, vibrating, extracting and adsorbing, separating magnetic materials by using an external magnet, washing the separated magnetic materials with water, completely immersing the magnetic materials into an eluent consisting of ammonia water and acetonitrile for vibrating and desorbing, separating the magnetic materials and the eluent, and drying the separated eluent to obtain a treated sample.
Aiming at the characteristics of the organic fertilizer, the magnetic material Fe with a specific structure prepared by the invention is utilized in a buffer solution with pH value of 4.0-7.0 in order to reduce or avoid the interference of other substances in the organic fertilizer on the detection result of macrolide antibiotics 3 O 4 @ZnO&MnO powder adsorbs macrolide antibiotics, and an eluent consisting of ammonia water and acetonitrile is adopted to lead the magnetic material Fe 3 O 4 @ZnO&And quickly eluting the macrolide antibiotics adsorbed in the MnO powder to finally obtain a treated sample suitable for the macrolide antibiotics detection method.
The magnetic material Fe prepared by adopting the specific preparation method of the invention 3 O 4 @ZnO&MnO powder is a nano material and has the following characteristics: fe (Fe) 3 O 4 @ZnO&The MnO composite magnetic material has the advantages of rough surface, developed gaps and large specific surface area, and the adsorption capacity of the MnO composite magnetic material serving as an adsorbent is remarkably improved; fe (Fe) 3 O 4 @ZnO&MnO material has a composition of Fe 3 O 4 The nano particles are cores and are made of Fe 3 O 4 Core-shell structure with ZnO and MnO layers covered on the surfaces of the nano particles to ensure that Fe 3 O 4 @ZnO&MnO materials have significantly lower Fe 3 O 4 Saturated magnetic moment values of the nanoparticles indicate Fe 3 O 4 ZnO and MnO coating on the surface of the nanoparticle influence the magnetic moment change in a magnetic field to ensure that Fe 3 O 4 @ZnO&MnO powder has certain magnetism and effectively reduces Fe 3 O 4 Nanometer particleThe particles are agglomerated. The invention discovers that the magnetic material Fe has the characteristics 3 O 4 @ZnO&The MnO powder has specific adsorption effect on macrolide antibiotics to be tested in the organic fertilizer sample, and can fully exert Fe 3 O 4 And ZnO&Synergistic effect of MnO on adsorption capacity of macrolide antibiotics in the organic fertilizer; meanwhile, the magnetic material Fe with the characteristics 3 O 4 @ZnO&The adsorbed macrolide antibiotics in MnO powder are easy to desorb, and can be quickly desorbed in eluent consisting of ammonia water and acetonitrile.
In order to achieve the better inventive effect, the following preferences are made:
in the step (1), the manganese sulfate, zinc sulfate, thioacetamide and ferroferric oxide (Fe 3 O 4 ) The mass ratio of (2) is 1:1:2.5:0.16-0.20. Research on Mn-doped ZnO samples shows that the samples with lower Mn doping concentration only have obvious ferromagnetism, and Mn ions with higher doping concentration have certain ferromagnetism ordering at low temperature, but can not form ferromagnetism ordering at normal temperature. The mass ratio of manganese sulfate to zinc sulfate is selected to be 1 in combination with the aim of the invention: 1. the thioacetamide is added to make the thioacetamide adsorbed on Fe 3 O 4 Surface, due to induction of positive charges, metal ion Mn 2+ 、Zn 2+ H released by gradual decomposition by heating or ultrasonic mixing with thioacetamide 2 S reacts to form ZnS, mnS and Fe 3 O 4 Surface nucleation and growth, and finally changing into ZnO and MnO at a high temperature of 200-220 ℃ to obtain the magnetic material Fe 3 O 4 @ZnO&MnO powder.
The ratio of the milliliters of ethylene glycol to the milliliters of isopropanol to the milligrams of ferroferric oxide is more than or equal to 0.4:0.4:1. Ethylene glycol and isopropanol are therefore optionally added in order to prevent agglomeration of the resulting material. The amount of ethylene glycol and isopropanol may be increased so that all the reactants can be completely immersed, and from the viewpoint of saving raw materials, it is further preferable that the ratio of the milliliters of ethylene glycol, the milliliters of isopropanol to the milligrams of ferroferric oxide is 0.4-4:0.4-4:1.
Magnetic nanomaterials refer to those materials whose dimensions of the constituent magnetic species are equal to or less than their phase coherence length and greater than the size of the atoms. The phase coherence length refers to the mean free path of inelastic scattering of charge carriers in the constituent materials, typically in the range of 1-100nm, so that the particular magnetic properties of the magnetic nanomaterial can be said to be nanomagnetic. Preferably, the nano Fe 3 O 4 The average particle diameter of (2) is below 100nm, and has nanometer magnetism.
In the step (2), the buffer solution with the pH value of=4.0-7.0 is used as an extracting agent, and disodium ethylenediamine tetraacetate-disodium hydrogen phosphate-citric acid (Na 2 EDTA-McIlvaine) buffer solution or from Na 2 EDTA-McIlvaine buffer solution and proper amount of one of phosphoric acid and alkali liquor. Preferably, the pH of the buffer solution is equal to or higher than 4 and lower than 7, more preferably, the pH of the buffer solution is=4 to 5, and most preferably, the pH of the buffer solution is=4. The alkali liquor can be one of common alkaline pH regulators, such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like. In specific operation, na 2 EDTA-McIlvaine buffer solution can be directly formulated into Na with various pH values of pH=4-7 2 EDTA-McIlvaine buffer solution (without adding proper amount of phosphoric acid and alkali solution to adjust pH); na may also be formulated at a pH 2 EDTA-McIlvaine buffer solution, pH is adjusted to 4-7 by adding proper amount of phosphoric acid and alkali liquor.
The amount of buffer solution at ph=4.0 to 7.0 is not particularly limited, and is generally at least that of the magnetic material Fe 3 O 4 @ZnO&The MnO powder and the organic fertilizer sample are completely immersed in the buffer solution to provide an extraction environment. Generally, the ratio of the milliliters of the buffer solution with the pH=4.0-7.0 to the gram of the organic fertilizer sample is at least 10:1, so that an extraction environment can be provided, the increase of the dosage of the buffer solution has no influence on the extraction effect, and from the viewpoint of saving cost, the ratio of the milliliters of the buffer solution to the gram of the organic fertilizer sample is preferably 10:1.
The magnetic material Fe 3 O 4 @ZnO&MnO powder is used as a magnetic adsorbent and has a mass ratio to an organic fertilizer sample of more than or equal to that of the organic fertilizer sample1:10, preferably 1 from the viewpoint of saving raw materials: 10.
the vibration extraction adsorption time is 10min-40min; further preferably 30min-40min; the operation time and the recovery rate are both considered to be most preferably 30min.
The oscillation desorption time is more than or equal to 5min, and the magnetic material Fe 3 O 4 @ZnO&Most of the macrolide antibiotics adsorbed in the MnO powder can be eluted; in order to shorten the pretreatment time of the sample, it is further preferable to be 5min to 20min; the operation time and the recovery rate are both considered to be most preferably 15min.
The invention discovers that the magnetic material Fe 3 O 4 @ZnO&The macrolide antibiotics adsorbed in the MnO powder are more easily eluted in a molecular form under the weak alkaline condition without dissociation, and therefore, the eluent is selected from the eluent consisting of ammonia water and acetonitrile. The ammonia water is ammonia water with the mass percentage concentration of 20-30%, and the volume of the ammonia water accounts for 5-10% of the volume of the eluent. Further preferably, the eluent consists of acetonitrile and 25% ammonia water in percentage by mass, wherein the volume of the 25% ammonia water in percentage by mass accounts for 5% -10% of the volume of the eluent; considering comprehensively, the eluent consisting of acetonitrile and 25% ammonia water with the mass percentage concentration is optimally selected, wherein the volume of the 25% ammonia water with the mass percentage concentration accounts for 5% of the volume of the eluent.
The amount of the eluent is not critical, and generally at least the magnetic material Fe is maintained 3 O 4 @ZnO&The MnO powder is completely immersed in the eluent, providing an eluting environment. The eluent is used in an amount of at least 1mL, preferably 1mL-8mL, more preferably 2mL-5mL, and the experimental time is increased in consideration of the fact that if 5mL of eluent is adopted, concentration is needed later, and the operation time and the recovery rate are both considered to be most preferably 2mL.
Preferably, the oscillation frequency is 800rpm-1000rpm. When the oscillation frequency is lower, the oscillation extraction adsorption time and the oscillation desorption time can be prolonged to ensure higher recovery rate.
The reaction solution may typically be cooled to ambient temperature.
The drying is preferably vacuum drying. The drying is preferably at 55 ℃ -65 ℃ (most preferably 60 ℃) for 6h-10h.
A method for detecting macrolide antibiotics in organic fertilizer adopts a treated sample obtained by the sample treatment method as a test sample, and directly adopts one or more of the existing macrolide antibiotics detection methods for detection. The detection method specifically comprises the following steps: taking a test sample, and directly detecting the macrolide antibiotics in the test sample by adopting a liquid chromatography (HPLC) detection method of the macrolide antibiotics or a liquid chromatography-mass spectrometry combined detection method of the macrolide antibiotics. The detection method of the macrolide antibiotics can be the detection method of the existing macrolide antibiotics, and can also be a detection method which simply adjusts parameters based on the detection method of the existing macrolide antibiotics.
The raw materials, reagents, instruments and the like used in the invention can be commercially available products.
The invention has the following beneficial effects:
the magnetic separation can rapidly and conveniently realize the separation of solid and liquid. Fe (Fe) 3 O 4 The magnetic nanomaterial has magnetic properties and a large active surface, and the strong interparticle interactions between the magnetic nanoparticles make it difficult to further use. The invention discovers that Fe 3 O 4 Specific coating encapsulation of magnetic nanoparticles is to stabilize Fe 3 O 4 Nanoparticles and a viable method of reducing agglomeration. Fe synthesized by the invention 3 O 4 @ZnO&MnO material has a composition of Fe 3 O 4 The nano particles are cores and are made of Fe 3 O 4 Core-shell structure with ZnO and MnO layers (shells) covered on surfaces of nano particles, and Fe in the core-shell structure 3 O 4 Is Fe (Fe) the ferromagnetic effect of 3 O 4 @ZnO&The MnO complexes can be easily separated and collected by external magnetic fields. The magnetism of the magnetic adsorption material increases the recycling convenience, and the recycling rate is not obviously reduced after the magnetic adsorption material is desorbed and recycled for 4 times, so that the magnetic adsorption material can be recycled and is economical to use.
Fe synthesized by the invention 3 O 4 @ZnO&MnO materialThe material has rough surface, developed gaps and large specific surface area, and the adsorption capacity of the material as an adsorbent is obviously improved; the organic fertilizer has specific adsorption effect on macrolide antibiotics in the organic fertilizer as an adsorption material, and can fully exert Fe 3 O 4 And ZnO&The MnO and the organic fertilizer have synergistic effect on the adsorption capacity of macrolide antibiotics in the organic fertilizer, and the recovery rate and RSD meet the requirements.
The sample treatment method is simple and convenient to operate, can not reduce the quality of the samples, can reach the detection limit standard, can perform pretreatment and detection on a large number of samples, is efficient and accurate in detection result, and can effectively overcome the interference of other substances in the organic fertilizer on detection of macrolide antibiotics.
Compared with the existing solid-phase extraction column filled with the extraction material, the sample processing method provided by the invention has the advantages that the blocking problem is avoided, the operation steps are greatly simplified, the method can be used for pretreatment and detection of a large number of samples, the time is saved, the speed is high, the efficiency is high, the adsorption material can be repeatedly utilized, the detection result is accurate, the popularization and the application can be widely realized, and the method has a great application prospect.
Drawings
FIG. 1 is a schematic diagram of a sample pretreatment operation flow, wherein four is an interferent (interferential compounds), o is a Target compound, o is a magnetic adsorbent (magnetica dsorbent), vortex is Vortex, and Magnet is Magnet;
FIG. 2 is a diagram of Fe according to the present invention 3 O 4 @ZnO&X-ray diffraction (XRD) patterns of MnO materials, with intensity on the ordinate;
FIGS. 3a and 3b show Fe according to the present invention 3 O 4 @ZnO&Scanning Electron Microscope (SEM) images of MnO materials;
FIG. 4 is Fe 3 O 4 Nanoparticles and Fe 3 O 4 @ZnO&Magnetization curve graph of MnO composite material; the abscissa Applied magnetic field is the externally Applied magnetic field, and the ordinate Magnetization is the Magnetization;
FIG. 5 is a graph showing the comparison of recovery of each target in samples treated with different eluents;
FIG. 6 is a graph showing the comparison of the recovery rate of each target in samples treated with different vibration extraction adsorption times;
FIG. 7 is a graph showing a comparison of recovery of each target in samples treated with different amounts of eluent;
FIG. 8 is a graph comparing the recovery of each target in samples treated at different elution times.
Detailed Description
The present invention is described in further detail below with reference to the drawings and specific embodiments so as to facilitate a better understanding of the technical solutions of the present invention by those skilled in the art.
EXAMPLE 1Fe 3 O 4 @ZnO&Synthesis of MnO powder
Adding manganese sulfate, thioacetamide, zinc sulfate, ethylene glycol and isopropanol into a three-neck flask, stirring for 20min, mixing uniformly, and adding nano Fe 3 O 4 (100 nm) of manganese sulfate, zinc sulfate, thioacetamide and Fe 3 O 4 The mass ratio of (2) Fe is 1:1:2.5:0.16 3 O 4 The ratio of milligrams to milliliters of glycol and milliliters of isopropanol is 1:0.4:0.4, and after being uniformly stirred, the mixture is heated to 35+/-5 ℃ and stirred and reacts for 3 days (72 h) at 35+/-5 ℃; the reaction solution is transferred into a hydrothermal kettle for reaction for 20 hours at the constant temperature of 200 ℃. After the reaction liquid is cooled to room temperature, washing the reaction liquid for a plurality of times by purified water and ethanol, vacuum drying the final product at 60 ℃ for 6 hours, and grinding the final product to obtain the magnetic material Fe 3 O 4 @ZnO&MnO powder.
Magnetic material Fe 3 O 4 @ZnO&XRD patterns of MnO are shown in FIG. 2, and SEM patterns are shown in FIG. 3a and FIG. 3b. Fig. 2 shows: fe (Fe) 3 O 4 6 classical diffraction peaks appear in 2 theta, namely 30.38 degrees, 35.73 degrees, 43.46 degrees, 53.70 degrees, 57.49 degrees and 62.97 degrees are respectively corresponding to Fe 3 O 4 Structural (220), (311), (400), (422), (511), (440), and Fe 3 O 4 Fe in Standard card (JCPDS card No. 19-0629) 3 O 4 Is kept consistent. Fe (Fe) 3 O 4 @ZnO&XRD patterns of MnO magnetic composites demonstrated the presence of Fe 3 O 4 Is matched with ZnO standard card JCCPDSNo. 36-1451, mnO standard card JCCPDS No.07-0230Since the diffraction peak and the diffraction peak of MnO are considered to be Fe 3 O 4 @ZnO&On MnO, fe is actually loaded 3 O 4 ZnO and MnO.
Fig. 3a and 3b show: when the operating voltage is an accelerating voltage (EHT) of 5.00kv, the operating distance "WD" of 6.0mm, the Spot size (Spot size) of the beam is generally 30, and Fe is obtained in the Signal mode of the operating mode 3 O 4 @ZnO&SEM image of MnO composite magnetic material, which is seen from the figure, shows that it has a magnetic structure of Fe 3 O 4 The nano particles are cores and are made of Fe 3 O 4 The surface of the nanoparticle is covered with a core-shell structure of ZnO and MnO layers, the surface is rough, the gap is developed, and Fe is added 3 O 4 @ZnO&The specific surface area of the MnO composite material can improve the adsorption capacity of the MnO composite material as an adsorbent. Core-shell structure enables Fe 3 O 4 @ZnO&MnO materials have significantly lower Fe 3 O 4 Saturated magnetic moment values of the nanoparticles (see FIG. 4), indicating Fe 3 O 4 ZnO and MnO coating on the surface of the nanoparticle influence the magnetic moment change in a magnetic field to ensure that Fe 3 O 4 @ZnO&MnO powder has certain magnetism and effectively reduces Fe 3 O 4 The nanoparticles agglomerate.
EXAMPLE 2Fe 3 O 4 @ZnO&Synthesis of MnO powder
Adding manganese sulfate, zinc sulfate, thioacetamide, ethylene glycol and isopropanol into a three-neck flask, stirring for 20min, mixing uniformly, and adding nano Fe 3 O 4 (100 nm) of manganese sulfate, zinc sulfate, thioacetamide, fe 3 O 4 The mass ratio of (2) Fe is 1:1:2.5:0.20 3 O 4 The ratio of milligrams of (2) to milliliters of glycol to milliliters of isopropanol is 1:4:4, and after uniform stirring, heating to 35+/-5 ℃, and stirring and reacting for 60 hours at 35+/-5 ℃; the reaction solution is transferred into a hydrothermal kettle for reaction for 25 hours at the constant temperature of 220 ℃. After the reaction liquid is cooled to room temperature, washing the reaction liquid for a plurality of times by purified water and ethanol, vacuum drying the final product at 60 ℃ for 6 hours, and grinding the final product to obtain the magnetic material Fe 3 O 4 @ZnO&MnO powder.
Magnetic material Fe 3 O 4 @ZnO&The XRD pattern of MnO is consistent with that in figure 2. Fe (Fe) 3 O 4 @ZnO&XRD patterns of MnO magnetic composite material exist and Fe exists 3 O 4 Fe matched with standard card JCPDS card No.19-0629 3 O 4 Diffraction peaks of ZnO matching with the ZnO standard card JCCPDSNo. 36-1451 and diffraction peaks of MnO matching with the MnO standard card JCCPDSNo. 07-0230, and therefore can be considered as Fe 3 O 4 @ZnO&On MnO, fe is actually loaded 3 O 4 ZnO and MnO.
Fe obtained in the Signal mode of the operation mode with an operation voltage EHT of 5.00kv and an operation distance "WD" of 6.0mm and a beam spot size of typically 30 3 O 4 @ZnO&SEM image of MnO composite magnetic material shows that it has a magnetic structure of Fe 3 O 4 The nano particles are cores and are made of Fe 3 O 4 The surface of the nanoparticle is covered with a core-shell structure of ZnO and MnO layers, the surface is rough, the gap is developed, and Fe is added 3 O 4 @ZnO&The specific surface area of the MnO composite material can improve the adsorption capacity of the MnO composite material as an adsorbent. Core-shell structure enables Fe 3 O 4 @ZnO&MnO materials have significantly lower Fe 3 O 4 Saturated magnetic moment values of the nanoparticles indicate Fe 3 O 4 ZnO and MnO coating on the surface of the nanoparticle influence the magnetic moment change in a magnetic field to ensure that Fe 3 O 4 @ZnO&MnO powder has certain magnetism and effectively reduces Fe 3 O 4 The nanoparticles agglomerate.
Example 3
Fe 3 O 4 @ZnO&Macrolide antibiotics in MnO Magnetic Solid Phase Extraction (MSPE) organic fertilizer:
1.0g of the organic fertilizer sample was accurately weighed into a 25mL clear glass sample bottle, and 100mg of the magnetic material Fe of example 1 was added 3 O 4 @ZnO&After addition of the MnO powder 10mL ph=7.0 Na 2 EDTA-McIlvaine buffer solution, vortex mixing, and vibration extraction and adsorption at 800rpm for 20min. Then the magnetic material is adsorbed by an external magnet, the solvent and the sample are poured and discarded, and the separated Fe 3 O 4 @ZnO&The MnO powder is washed by water and then is completely immersed into 5mL of ethanolAnd (3) vibrating and desorbing the nitrile and ammonia water with the mass percentage concentration of 25% in an eluent (wherein the mass percentage concentration of 25% ammonia water accounts for 5% of the volume of the eluent and is marked as 5% ammonia acetonitrile) at the frequency of 800rpm for 20min, adsorbing and separating the magnetic material by using an external magnet, and drying the eluent after passing through a 0.22 mu m filter membrane to obtain a treated sample.
Comparative example 1
The procedure of example 3 was repeated except that methanol was used instead of 5% aqueous ammonia acetonitrile as the eluent, thereby obtaining a treated sample.
Comparative example 2
The procedure of example 3 was repeated except that acetonitrile was replaced with 5% aqueous ammonia as an eluent, thereby obtaining a treated sample.
Example 4
Fe 3 O 4 @ZnO&And MnO magnetic solid phase extraction of macrolide antibiotics in the organic fertilizer:
1.0g of the organic fertilizer sample was accurately weighed into a 25mL clear glass sample bottle, and 100mg of the magnetic material Fe of example 1 was added 3 O 4 @ZnO&After addition of the MnO powder 10mL ph=4.0 Na 2 EDTA-McIlvaine buffer (pH=7.0Na 2 And adding a proper amount of phosphoric acid into the EDTA-McIlvaine buffer solution, and vibrating, extracting and adsorbing for 20min at the frequency of 800rpm after vortex mixing uniformly. Then the magnetic material is adsorbed by an external magnet, the solvent and the sample are poured and discarded, and the separated Fe 3 O 4 @ZnO&The MnO powder is washed by water and then is completely immersed in 5mL of eluent consisting of acetonitrile and 25% ammonia water with the mass percentage concentration (wherein the volume of the 25% ammonia water with the mass percentage concentration accounts for 5% of the volume of the eluent and is recorded as 5% ammonia water acetonitrile), the eluent is subjected to vibration desorption for 20min at the frequency of 800rpm, the magnetic material is adsorbed and separated by an external magnet, and the eluent is dried after passing through a 0.22 mu m filter membrane, so that a treated sample is obtained.
Comparative example 3
The procedure of example 4 was repeated except that methanol was used instead of 5% aqueous ammonia acetonitrile as the eluent, thereby obtaining a treated sample.
Comparative example 4
The procedure of example 4 was repeated except that acetonitrile was replaced with 5% aqueous ammonia as an eluent, thereby obtaining a treated sample.
Example 5
The procedure of example 4 was repeated except that the eluent of 5% aqueous ammonia acetonitrile was replaced with an eluent composed of acetonitrile and 25% aqueous ammonia at a mass percentage concentration (wherein the volume of the aqueous ammonia at a mass percentage concentration of 25% was 10% based on the volume of the eluent, which was designated as 10% aqueous ammonia acetonitrile).
Comparative example 5
The procedure of example 4 was repeated except that the eluent of 5% aqueous ammonia acetonitrile was replaced with an eluent composed of acetonitrile and acetic acid (the volume of acetic acid in the eluent was 5% by volume of the eluent, which was denoted as 5% acetic acid acetonitrile).
Comparative example 6
The procedure of example 4 was repeated except that the eluent of 5% aqueous ammonia acetonitrile was replaced with an eluent of acetonitrile and acetic acid (the volume of acetic acid in the eluent was 10% by volume of the eluent, which was designated as 10% of acetic acid acetonitrile), to obtain a treated sample.
Example 6
The procedure of example 4 was repeated except that the vibration extraction adsorption was changed to the vibration extraction adsorption for 10min, to obtain a treated sample.
Example 7
Fe 3 O 4 @ZnO&And MnO magnetic solid phase extraction of macrolide antibiotics in the organic fertilizer: the procedure of example 4 was repeated except that the vibration extraction adsorption was replaced with the vibration extraction adsorption for 30min, and the procedure specifically included:
1.0g of the organic fertilizer sample was accurately weighed into a 25mL clear glass sample bottle, and 100mg of the magnetic material Fe of example 1 was added 3 O 4 @ZnO&After addition of the MnO powder 10mL ph=4.0 Na 2 EDTA-McIlvaine buffer (pH=7.0Na 2 And adding a proper amount of phosphoric acid into the EDTA-McIlvaine buffer solution, and vibrating, extracting and adsorbing for 30min at the frequency of 800rpm after vortex mixing uniformly. Then the magnetic material is adsorbed by an external magnet, the solvent and the sample are poured and discarded, and the separated Fe 3 O 4 @ZnO&The MnO powder is washed by water and then is completely immersed in 5mL of eluent consisting of acetonitrile and 25% ammonia water with the mass percentage concentration (wherein the volume of the 25% ammonia water with the mass percentage concentration accounts for 5% of the volume of the eluent and is recorded as 5% ammonia water acetonitrile), the eluent is subjected to vibration desorption for 20min at the frequency of 800rpm, the magnetic material is adsorbed and separated by an external magnet, and the eluent is dried after passing through a 0.22 mu m filter membrane, so that a treated sample is obtained.
Example 8
The procedure of example 4 was repeated except that the vibration extraction adsorption was changed to the vibration extraction adsorption for 40min, to obtain a treated sample.
Example 9
The procedure of example 7 was repeated except that the amount of 5mL of the eluent was changed to 1mL, to obtain a treated sample.
Example 10
The procedure of example 7 was repeated except that the amount of 5mL of the eluent was changed to 2mL, to obtain a treated sample.
Example 11
The procedure of example 7 was repeated except that the amount of 5mL of the eluent was changed to 8mL, to obtain a treated sample.
Example 12
Fe 3 O 4 @ZnO&And MnO magnetic solid phase extraction of macrolide antibiotics in the organic fertilizer:
1.0g of the organic fertilizer sample was accurately weighed into a 25mL clear glass sample bottle, and 100mg of the magnetic material Fe of example 1 was added 3 O 4 @ZnO&After addition of the MnO powder 10mL ph=4.0 Na 2 EDTA-McIlvaine buffer (pH=7.0Na 2 And adding a proper amount of phosphoric acid into the EDTA-McIlvaine buffer solution, and vibrating, extracting and adsorbing for 30min at the frequency of 800rpm after vortex mixing uniformly. Then the magnetic material is adsorbed by an external magnet, the solvent and the sample are poured and discarded, and the separated Fe 3 O 4 @ZnO&The MnO powder is washed by water and then is completely immersed in 2mL of eluent consisting of acetonitrile and 25 percent ammonia water (wherein the volume of the 25 percent ammonia water is 5 percent of the volume of the eluent and is recorded as 5 percent ammonia acetonitrile) at the frequency of 80And (3) vibrating and desorbing for 5min at 0rpm, adsorbing and separating the magnetic material by using an external magnet, and drying the eluent after passing through a 0.22 mu m filter membrane to obtain a treated sample.
Example 13
The procedure of example 12 was repeated except that the vibration desorption was performed for 5 minutes instead of 10 minutes, to obtain a treated sample.
Example 14
The procedure of example 12 was repeated except that the vibration desorption was performed for 15min instead of 5min, to obtain a treated sample.
Example 15
Fe 3 O 4 @ZnO&And MnO magnetic solid phase extraction of macrolide antibiotics in the organic fertilizer:
1.0g of the organic fertilizer sample was accurately weighed into a 25mL clear glass sample bottle, and 100mg of the magnetic material Fe of example 2 was added 3 O 4 @ZnO&After addition of the MnO powder 10mL ph=5.0 Na 2 EDTA-McIlvaine buffer solution, vortex mixing, and vibration extraction and adsorption at 1000rpm for 20min. Then the magnetic material is adsorbed by an external magnet, the solvent and the sample are poured and discarded, and the separated Fe 3 O 4 @ZnO&The MnO powder is washed by water and then is completely immersed in 5mL of eluent consisting of acetonitrile and 25% ammonia water with the mass percentage concentration (wherein the volume of the 25% ammonia water with the mass percentage concentration accounts for 5% of the volume of the eluent and is recorded as 5% ammonia water acetonitrile), the eluent is subjected to vibration desorption for 20min at the frequency of 1000rpm, the magnetic material is adsorbed and separated by an external magnet, and the eluent is dried after passing through a 0.22 mu m filter membrane, so that a treated sample is obtained.
Comparative example 7
Except for the magnetic material Fe of example 1 3 O 4 @ZnO&Substitution of MnO powder to nano Fe 3 O 4 The procedure of example 4 was repeated except for (100 nm) to obtain a treated sample.
Comparative example 8
Accurately weigh 1.0g of organic fertilizer sample in 25mL of clear glass sample bottle, add 100mg of nano ZnO (100 nm) and add 10mL of ph=4.0 Na 2 EDTA-McIlvaine buffer (pH=7.0Na 2 EDTA-McIlvaine, adding a proper amount of phosphoric acid into the buffer solution, and vibrating, extracting and adsorbing for 20min at the frequency of 800rpm after vortex mixing uniformly. And then carrying out high-speed centrifugal separation, discarding liquid, washing the separated solid with water, completely immersing the solid into 5mL of eluent consisting of acetonitrile and 25% ammonia water in percentage by mass (wherein the volume of the 25% ammonia water in percentage by mass is 5% of the volume of the eluent, and the eluent is marked as 5% ammonia water acetonitrile), carrying out vibration desorption for 20min at a frequency of 800rpm, carrying out high-speed centrifugal separation, and drying the eluent after passing through a 0.22 mu m filter membrane to obtain a treated sample.
Comparative example 9
Accurately weigh 1.0g of organic fertilizer sample in 25mL of clear glass sample bottle, add 100mg of nano MnO (100 nm) and then add 10mL of ph=4.0 Na 2 EDTA-McIlvaine buffer (pH=7.0Na 2 And adding a proper amount of phosphoric acid into the EDTA-McIlvaine buffer solution, and vibrating, extracting and adsorbing for 20min at the frequency of 800rpm after vortex mixing uniformly. And then carrying out high-speed centrifugal separation, discarding liquid, washing the separated solid with water, completely immersing the solid into 5mL of eluent consisting of acetonitrile and 25% ammonia water in percentage by mass (wherein the volume of the 25% ammonia water in percentage by mass is 5% of the volume of the eluent, and the eluent is marked as 5% ammonia water acetonitrile), carrying out vibration desorption for 20min at a frequency of 800rpm, carrying out high-speed centrifugal separation, and drying the eluent after passing through a 0.22 mu m filter membrane to obtain a treated sample.
Comparative example 10
Adding thioacetamide, zinc sulfate, ethylene glycol and isopropanol into a three-neck flask, stirring for 20min, mixing uniformly, and adding nano Fe 3 O 4 (100 nm) of zinc sulfate, thioacetamide and Fe 3 O 4 The mass ratio of (2) to (0.16) is 1:2.5:0.16, fe 3 O 4 The ratio of milligrams to milliliters of glycol and milliliters of isopropanol is 1:0.4:0.4, and after being uniformly stirred, the mixture is heated to 35+/-5 ℃ and stirred and reacts for 3 days (72 h) at 35+/-5 ℃; the reaction solution is transferred into a hydrothermal kettle for reaction for 20 hours at the constant temperature of 200 ℃. After the reaction liquid is cooled to room temperature, washing the reaction liquid for a plurality of times by purified water and ethanol, vacuum drying the final product at 60 ℃ for 6 hours, and grinding the final product to obtain Fe 3 O 4 @ ZnO powder.
Fe 3 O 4 XRD pattern of @ ZnO powderFe 3 O 4 Fe matched with standard card JCPDS card No.19-0629 3 O 4 Diffraction peaks of (C) and ZnO matched with ZnO standard card JCPDS No.36-1451, indicating Fe 3 O 4 On ZnO, fe is actually loaded 3 O 4 And ZnO.
Except for the magnetic material Fe of example 1 3 O 4 @ZnO&Substitution of MnO powder for Fe 3 O 4 The procedure of example 4 was repeated except that the @ ZnO powder was used to obtain a treated sample.
Comparative example 11
Adding manganese sulfate, thioacetamide, ethylene glycol and isopropanol into a three-neck flask, stirring for 20min, mixing uniformly, and adding nano Fe 3 O 4 (100 nm) of manganese sulfate, thioacetamide and Fe 3 O 4 The mass ratio of (2) to (0.16) is 1:2.5:0.16, fe 3 O 4 The ratio of milligrams to milliliters of glycol and milliliters of isopropanol is 1:0.4:0.4, and after being uniformly stirred, the mixture is heated to 35+/-5 ℃ and stirred and reacts for 3 days (72 h) at 35+/-5 ℃; the reaction solution is transferred into a hydrothermal kettle for reaction for 20 hours at the constant temperature of 200 ℃. After the reaction liquid is cooled to room temperature, washing the reaction liquid for a plurality of times by purified water and ethanol, vacuum drying the final product at 60 ℃ for 6 hours, and grinding the final product to obtain Fe 3 O 4 @ MnO powder.
Fe 3 O 4 XRD pattern of @ MnO powder present with Fe 3 O 4 Fe matched with standard card JCPDS card No.19-0629 3 O 4 Diffraction peaks of (2) and MnO matched with MnO standard card JCPSDSNo. 07-0230, indicate Fe 3 O 4 On MnO, fe is actually loaded 3 O 4 And MnO.
Except for the magnetic material Fe of example 1 3 O 4 @ZnO&Substitution of MnO powder for Fe 3 O 4 Except for @ MnO powder, the procedure of example 4 was followed to obtain a treated sample.
Example 16
The treated samples of examples 3 to 15 and comparative examples 1 to 11 were taken, respectively, and the macrolide antibiotics were measured by the UPLC-MS/MS method.
Chromatographic conditions:
chromatographic column: ACQUITY UPLC BEH-C 18 Chromatographic column (2.1 mm. Times.100 mm,1.7 μm);
mobile phase: phase A-methanol, phase B-containing 0.1% by mass of HCOOH and 2 mmol.L -1 HCOONH 4 The gradients are shown in table 1;
flow rate: 0.30mL/min;
column temperature: 40 ℃;
sample injection amount: 5. Mu.L.
Mass spectrometry conditions:
spray voltage: 5500V;
ionization source mode: electrospray ionization ESI (+);
ion source temperature: 500 ℃;
curtain air (CUR) pressure: 40psi;
scanning mode: monitoring multiple reactions;
assist Gas (Gas 2) pressure: 50psi;
atomization Gas (Gas 1) pressure: 55psi.
The macrolide antibiotics comprise one or more of tilmicosin, hypocrellin, tylosin, roxithromycin, erythromycin, kitasamycin, and cisamycin. The optimal mass spectral parameters for each test are shown in table 2.
Table 1 liquid chromatography gradient elution procedure
Table 2 mass spectral parameters after target optimization
Table 2 represents the quantitative ion.
Table 3 results of the tests of examples and comparative examples
Observing the effect of the extraction agent on the recovery rate of the target substances of buffer solutions with different pH values in examples 3-4 and comparative examples 1-2, it is found that: the Fe synthesized by the invention is under neutral condition or acid condition 3 O 4 @ZnO&The MnO magnetic material can absorb 7 macrolide antibiotics in the organic fertilizer. Acetonitrile as an eluent is easier to elute the target substance than methanol as an eluent at the same pH. And the recovery rate of the target object is higher than that of the vibration extraction adsorption under the neutral condition. Therefore, the extractant of the present invention may be selected from buffer solutions with ph=4 to 7, preferably acidic (pH 4 or more and less than 7), more preferably buffer solutions with ph=4 to 5, and most preferably Na with ph=4 2 EDTA-McIlvaine buffer solution or Na 2 EDTA-McIlvaine buffer solution and proper amount of one of phosphoric acid and alkali solution.
In the observation of examples 4 to 5 and comparative examples 4 to 6, the target was eluted as molecules as possible without dissociation by adjusting the type of the eluent. Target recovery as shown in fig. 5, most of the target is eluted more easily in molecular form without dissociation under weakly alkaline conditions. For most targets, the eluent used was 5% aqueous acetonitrile and 10% aqueous acetonitrile, with little difference, but with reduced recovery of tilmicosin, cisamycin and erythromycin. Therefore, the eluent is composed of acetonitrile and ammonia water; preferably, the mass percentage concentration of the ammonia water is 20-30%, and the volume of the ammonia water accounts for 5-10% of the volume of the eluent; further preferably, the eluent consists of acetonitrile and 25% ammonia water in percentage by mass, wherein the volume of the 25% ammonia water in percentage by mass accounts for 5% -10% of the volume of the eluent; considering comprehensively, 5% ammonia acetonitrile is optimally selected as eluent for pretreatment.
The influence of different vibration extraction adsorption times of 10min, 20min, 30min and 40min in the example 4 and the examples 6-8 on the recovery rate of each target in the treated sample is observed, and the result is shown in fig. 6. As can be seen from FIG. 6, the recovery rate of each target in the sample after the treatment of different vibration extraction adsorption times of 10min, 20min, 30min and 40min is 57.4-109.8%; as the shake extraction adsorption time increases, the recovery rates of the target substances OLE, TYL and JOS gradually increase; the recovery rate of the target substance TIL, KIT, ERY and ROX increases and then gradually decreases, which may be due to the fact that the target substance TIL, KIT, ERY and ROX and impurities exhibit a dynamic competitive adsorption during the whole extraction process, and more impurities will be extracted with the increase of time. Therefore, the invention selects the vibration extraction adsorption time to be 10min-40min, preferably 30min-40min, and combines the operation time and the recovery rate to be most preferably 30min.
The effect of the different eluent amounts of 1mL, 2mL, 5mL and 8mL in example 7 and examples 9-11 on the recovery rate of each target in the treated samples was observed, and the results are shown in FIG. 7. FIG. 7 shows that the recovery rate of each target in the samples treated by 1mL, 2mL, 5mL and 8mL of different eluents is 63.1% -109.8%; wherein, the recovery rate of OLE, TYL, ERY and JOS is not changed greatly when the eluent is used for 2mL, 5mL and 8mL, and the recovery rate is the best when the eluent is used for 2 mL; the recovery rate of KIT is not changed greatly when the eluent is used for 1mL, 5mL and 8mL, and the recovery rate is the best when the eluent is used for 2 mL; the recovery rate of TIL is the best when the eluent is used for 2 mL; the recovery of ROX was best at an eluent level of 5 mL. Therefore, the use amount of the eluent is at least 1mL, preferably 1mL-8mL, more preferably 2mL-5mL, and the experimental time is increased in consideration of the fact that the concentration is needed to be carried out after the concentration is needed when 5mL of eluent is adopted, and the operation time and the recovery rate are both the most preferably 2mL.
The effect of different shake desorption times (i.e., elution times) of 5min, 10min, 15min and 20min in example 10 and examples 12 to 14 on the recovery rate of each target in the treated sample was observed, and the results are shown in FIG. 8. Fig. 8 shows that the recovery rates of OLE, TYL, KIT and ROX increased with increasing elution time, the recovery rates of TIL, ERY and JOS increased with increasing elution time, and decreased slightly at 20min, with little decrease in amplitude. Therefore, the method selects the oscillation desorption time to be more than or equal to 5min, preferably 5min-20min for shortening the pretreatment time of the sample, and the operation time and the recovery rate are most preferably 15min.
Under the optimal conditions, the recovery rate, precision, linear range, matrix effect, linear equation, correlation coefficient (r), qualitative detection Limit (LOD), quantitative detection Limit (LOQ) and the like of the method are examined. Preparing solvent standard solution and matrix matching standard solution with the same concentration gradient respectively by adopting pure solvent and blank organic fertilizer matrix solution, and obtaining the concentration C (mug.L) of each target compound -1 ) And (3) respectively manufacturing linear regression curves by taking the quantitative ion peak area as an abscissa and taking the quantitative ion peak area as an ordinate to obtain a linear correlation equation. As a result, it was found that the concentration of the surfactant was 0.5 to 200. Mu.g.L -1 In a linear relationship, the linear correlation coefficient (r) is 0.9992-1.0000 (see Table 4). Comparing the slopes of the two curves, the ratio of the slopes of the matrix matching standard solution and the solvent standard solution is found to be 40% -106%, which indicates that the matrix has a matrix effect on the determination of the target object and has a higher matrix inhibition effect on kitasamycin and erythromycin. Therefore, the matrix matching calibration curve is used for quantification to reduce the influence of matrix interference on the detection result. The quantitative Limit (LOQ) and the detection Limit (LOD) of the method are respectively based on the lowest standard concentration (25 mug.kg) -1 ) The signal-to-noise ratios of 3 and 10 times thereof were estimated (S: n=3, s: n=10), LOD is 0.8-2.5 μg kg -1 LOQ is 2.1-8.4 mug.kg -1 。
TABLE 4 Linear correlation equation, detection limit and quantification limit
The recovery rate of the method is obtained by adopting the optimal conditions (namely the conditions in example 14) of the invention after different concentrations of standard samples are added to blank organic fertilizer samples, and the recovery rate is shown in Table 5.7 macrolide antibiotics 25. Mu.g.kg -1 ，50μg·kg -1 And 100. Mu.g.kg -1 The recovery rate under the third-gear concentration is 73.7% -102.6%,78.3% -106.5% and 82.0% -101.4%, the RSD is 2.0% -12.8%, and the repeatability is good.
Table 5 recovery and precision (n=6) of the process of the invention
Example 17
30 commercial organic fertilizer samples were selected for testing. Wherein 8 samples detect tilmicosin, and the detected concentration range is 10.2-30.8 mug.kg -1 Tylosin was detected in 2 samples at a concentration of 12.1. Mu.g.kg, respectively -1 And 17.5. Mu.g.kg -1 The detection results are shown in Table 6. The remaining targets were not detected in the 30 samples tested. The detection results are consistent with those of the method for detecting 15 antibiotics in the organic fertilizer by adopting the existing method such as Wu Dan and the like by adopting an ultra-high performance liquid chromatography tandem mass spectrometry method, namely tilmicosin is detected in 8 samples (chicken manure organic fertilizers 8 and 10 and pig manure organic fertilizers 2, 7, 10, 11 and 15), tylosin is detected in 2 samples (chicken manure organic fertilizers 1 and 10), and the rest targets are not detected in 30 samples.
TABLE 6 actual sample detection conditions
| Sample numbering | Detecting a substance | Detected concentration μg kg -1 |
| Chicken manure organic fertilizer 1 | Tylosin | 12.1 |
| Chicken manure |
Tilmicosin | 16.4 |
| Chicken manure |
Tylosin | 17.5 |
| Chicken manure |
Tilmicosin | 20.7 |
| Pig manure |
Tilmicosin | 30.8 |
| Pig manure organic fertilizer 7 | Tilmicosin | 18.4 |
| Pig manure |
Tilmicosin | 22.9 |
| Pig manure organic fertilizer 11 | Tilmicosin | 29.6 |
| Pig manure |
Tilmicosin | 10.2 |
The invention synthesizes a novel Fe 3 O 4 @ZnO&The MnO magnetic material establishes a magnetic solid phase extraction method-a detection method for measuring 7 macrolide antibiotics residues in the organic fertilizer by a high performance liquid chromatography mass spectrometry method based on the novel magnetic material. Sample warp Fe 3 O 4 @ZnO&And (3) after MnO adsorption and ammoniated acetonitrile elution, separating by using a BEH-C18 chromatographic column, and then measuring by using a UPLC-MS/MS machine. The experiment optimizes parameters which may influence the pretreatment effect of the sample, such as extractant, eluent, oscillation extraction adsorption time, eluent dosage, elution time (namely oscillation desorption time) and the like. Under the best optimized condition, the average recovery rate of the antibiotic is 73.7% -106.5%, and the relative standard deviation is 2.0% -12.8%. Fe synthesized by the invention 3 O 4 @ZnO&The MnO composite material can be reused for at least 4 times, the recovery rate after the repeated use for 4 times is basically equivalent to that of the primary use (the amplitude reduction is kept within 5 percent), the obvious reduction is not seen, and the experiment cost is greatly saved. At the same time Fe 3 O 4 @ZnO&The addition of MnO makes the solid phase extraction process more rapid and convenient. Thus, as Fe 3 O 4 @ZnO&The UPLC-MS/MS method using MnO as the magnetic adsorbent is a convenient and quick analysis means for 7 macrolide antibiotics in the organic fertilizer, saves time and is efficient, can provide technical support for the detection of the antibiotics in the organic fertilizer, and can also provide a reference method for the analysis and research of the organic fertilizer products.
Claims (8)
1. The sample processing method for detecting macrolide antibiotics in organic fertilizer is characterized by comprising the following steps:
（1）Fe 3 O 4 @ZnO&synthesis of MnO powder: manganese sulfate, thioacetamide, zinc sulfate, ethylene glycol and isopropanol are mixed uniformly, and nano Fe is added 3 O 4 Uniformly mixing, stirring and reacting at 30-40 ℃ for 60-72 hoursWhen in use; reacting the reaction solution at the constant temperature of 200-220 ℃ for at least 20 hours, washing the reaction solution with water and ethanol for several times after the reaction solution is cooled, and drying and grinding the product to obtain the magnetic material Fe 3 O 4 @ZnO&MnO powder;
(2) Magnetic solid phase extraction: taking an organic fertilizer sample, adding a magnetic material Fe 3 O 4 @ZnO&Mixing MnO powder and a buffer solution with pH value of 4.0-7.0, vibrating, extracting and adsorbing, separating magnetic materials by using an external magnet, washing the separated magnetic materials with water, completely immersing the magnetic materials into an eluent consisting of ammonia water and acetonitrile for vibrating and desorbing, separating the magnetic materials and the eluent, and drying the separated eluent to obtain a treated sample;
the macrolide antibiotics comprise one or more of tilmicosin, hypocrellin, tylosin, kitasamycin, erythromycin, josamycin and roxithromycin;
the ammonia water in the eluent is ammonia water with the mass percentage concentration of 20% -30%, and the volume of the ammonia water accounts for 5% of the volume of the eluent; the dosage of the eluent is 2mL-5mL;
the vibration extraction adsorption time is 30-40 min; and the oscillation desorption time is more than or equal to 15min.
2. The method according to claim 1, wherein in the step (1), the mass ratio of manganese sulfate, zinc sulfate, thioacetamide, and ferroferric oxide is 1:1:2.5:0.16-0.20.
3. The method according to claim 1 or 2, wherein in the step (1), the ratio of the milliliters of ethylene glycol, the milliliters of isopropyl alcohol to the milligrams of ferroferric oxide is 0.4:0.4:1 or more.
4. The method according to claim 1, wherein in the step (2), the buffer solution with ph=4.0-7.0 is selected from disodium ethylenediamine tetraacetate-disodium hydrogen phosphate-citric acid buffer solution or consists of disodium ethylenediamine tetraacetate-disodium hydrogen phosphate-citric acid buffer solution and an appropriate amount of one of phosphoric acid and alkali solution.
5. The method of claim 4, wherein the buffer solution has a ph=4-5.
6. The method according to claim 1, wherein in the step (2), the magnetic material Fe 3 O 4 @ZnO&Mass ratio of MnO powder to organic fertilizer sample is greater than or equal to 1:10.
7. a method for detecting macrolide antibiotics in organic fertilizers, characterized in that a treated sample obtained by the sample treatment method according to any one of claims 1 to 6 is used as a test sample.
8. The method according to claim 7, wherein the macrolide antibiotics in the test sample is detected directly by liquid chromatography detection of the macrolide antibiotics or liquid chromatography-mass spectrometry combination detection of the macrolide antibiotics.
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