CN111458429A - Preparation and application of chitosan modified magnetic nano material - Google Patents
Preparation and application of chitosan modified magnetic nano material Download PDFInfo
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- CN111458429A CN111458429A CN202010276515.XA CN202010276515A CN111458429A CN 111458429 A CN111458429 A CN 111458429A CN 202010276515 A CN202010276515 A CN 202010276515A CN 111458429 A CN111458429 A CN 111458429A
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Abstract
The invention relates to a method for enriching and extracting clenbuterol (clenbuterol) in a pork sample and simultaneously determining the content; in particular to a newType sulfhydryl modified chitosan magnetic graphene oxide nanocomposite (Fe)3O4@SiO2GO/CS/MPTS) and its use in the detection of terencromet in pork samples; in the invention, Fe is adopted3O4@SiO2The composite material can extract and enrich trace target detection substances under the interference of a sample matrix, and simultaneously still shows good adsorption performance in multiple recycling.
Description
Technical Field
The invention belongs to the technical field of food detection, relates to preparation of a novel magnetic nano composite material and application of the novel magnetic nano composite material in food detection, and particularly relates to application of a Magnetic Solid Phase Extraction (MSPE) technology in combination with ultra-high performance liquid chromatography tandem mass spectrometry (UP L C-MS/MS) to selective extraction and trace amount determination of clenbuterol hydrochloride in pork.
Background
Clenbuterol is β2-one of the families of adrenergic agonists. It is often used illegally in animal husbandry because of its ability to reduce fat levels and increase muscle protein anabolism in animals. Clenbuterol has a long half-life in animal blood and therefore is easily retained in animal tissues (e.g., liver, kidney, and muscle). Clenbuterol hydrochloride remaining in the animal body may be transferred to humans along the food chain, causing serious side effects such as muscle tremor, dizziness, headache, and the like. Therefore, the development of a simple, accurate and sensitive method for detecting clenbuterol hydrochloride in animal-derived food is of great significance.
Currently, there are many analytical methods for detecting clenbuterol hydrochloride, such as high performance liquid chromatography (HP L C), liquid chromatography-mass spectrometry (L C-MS), gas chromatography-mass spectrometry (GC-MS), electrochemical biosensors, enzyme-linked immunosorbent assay (E L ISA), colloidal gold nanoparticle immunochromatography (AuNPIA), etc. due to the rapid separation and high resolution of UP L C, ultra high performance liquid chromatography tandem mass spectrometry (UP L C-MS/MS) is one of the most effective methods, however, due to the complexity of the biological sample matrix and the trace level of clenbuterol hydrochloride in the actual sample, a sample pre-treatment procedure is usually required before instrumental analysis, classical methods of preconcentration and purification of clenbuterol hydrochloride in biological samples include liquid-liquid extraction (LL E), solid-phase extraction (SPE), matrix-solid-phase dispersion (MSPD) and solid-phase microextraction (SPME), however, these traditional pre-treatment methods do not have some drawbacks, such as time consuming, loss of analytes and organic contaminants, often lead to a decrease and to a decrease of magnetic field absorption in the sample, high efficiency of the magnetic field of the mineral absorbent, high absorption of the residual reagents in the sample, such as the mineral absorbent, mineral.
In MSPE, the selection of suitable magnetic nanomaterials is crucial to obtain high extraction yields. Graphene Oxide (GO) has abundant oxide groups, which makes GO well dispersed in water and easily modified by other compounds. However, GO is commonly used in combination with other materials as an adsorbent due to its easy agglomeration and single adsorption mechanism. Chitosan (CS) is a multifunctional polymer with hydroxyl and highly reactive amino groups, and has the characteristics of no toxicity, hydrophilicity, good biocompatibility, relatively low cost and easy degradation. Therefore, the CS grafted material is used as an adsorbent for purification and enrichment, and becomes a new choice. The CS-modified magnetic adsorbent has not only the ability to selectively recognize a target compound but also the ability to rapidly separate from a sample. But Fe3O4The particles are susceptible to oxidation during synthesis, especially in acidic solutions, thereby reducing adsorption capacity and magnetic properties. To avoid the above problems, it is necessary to use pure Fe3O4Is applied with a suitable protective coating. And silica coatingThe layer can improve oxidation resistance and prevent Fe3O4To (3) is performed. In addition, the magnetic silica particles can be easily modified with various silane coupling agents or compounds. In addition, thiol-functionalized adsorbents are reported to have high adsorption capacity for heavy metal ions and organic compounds. The method prepares a novel material (Fe) consisting of MPTS and CS modified magnetic graphene oxide3O4@SiO2/GO/CS/MPTS) and used as adsorbent for extraction of clenbuterol.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an economical, green and sensitive method for measuring clenbuterol hydrochloride in pork by a Magnetic Solid Phase Extraction (MSPE) technology. By adopting the method for enriching the clenbuterol hydrochloride in the pork, the sensitivity of an experiment can be improved, and the trace clenbuterol hydrochloride can be accurately and greenly determined.
The purpose of the invention is realized as follows: a preparation method of a chitosan modified magnetic nano material is characterized by comprising the following steps:
(1) preparing magnetic ferroferric oxide from ferrous chloride tetrahydrate and ferric chloride hexahydrate in an alkaline solution by a chemical coprecipitation method;
(2) preparing magnetic ferroferric oxide wrapped by silicon dioxide with branched amino groups from the magnetic ferroferric oxide synthesized in the last step, ethyl orthosilicate and aminopropyl triethylsilane under the conditions of ethanol and alkalinity;
(3) magnetic ferroferric oxide wrapped by the silicon dioxide with the branched and linked amino groups synthesized in the last step and graphene oxide suspended in N-alkyl succinimide and N, N-dimethylformamide are stirred to prepare the magnetic graphene oxide.
(4) Preparing the magnetic graphene oxide modified by chitosan from the magnetic graphene oxide synthesized in the last step, chitosan and glutaraldehyde under the condition of acetic acid.
(5) And performing surface modification on the chitosan-modified magnetic graphene oxide synthesized in the last step by using a silane coupling agent KH590, and magnetically separating the chitosan-modified magnetic graphene oxide subjected to surface modification by using the silane coupling agent KH 590.
As a further preferable embodiment of the present invention, the mass ratio of the ferrous chloride tetrahydrate and the ferric chloride hexahydrate in step (1) is: 1.0: 2.5-5.0; the pH value of the alkaline solution of ferrous oxide tetrahydrate and ferric oxide hexahydrate in the step (1) is 10-12, and the pH value is adjusted by adding ammonia water.
As a further preferable scheme of the invention, the mass ratio of the magnetic ferroferric oxide, the ethyl orthosilicate and the aminopropyl triethylsilane in the step (2) is as follows: 1.0:3.0-6.0:0.4-0.8.
As a further preferable scheme of the invention, the mass ratio of the magnetic ferroferric oxide coated by the branched amino-group silica, the N-alkyl succinimide, the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, the graphene oxide and the N, N-dimethylformamide in the step (3) is 1.0:0.2-1.0:0.4-2.0:0.4-2.0: 96.0-100.0.
As a further preferable embodiment of the present invention, in the step (4), the mass ratio of the magnetic graphene oxide, the chitosan, and the glutaraldehyde is: 1.0:2.0-5.0:0.5-2.0.
In a further preferred embodiment of the present invention, the mass ratio of the chitosan-modified magnetic graphene oxide to the silane coupling agent KH590 in the step (5) is 1.0: 2.0-5.0.
The invention is further based on the application of the magnetic nano composite material in detecting clenbuterol hydrochloride in pork, and the method comprises the following steps:
(1) sample pretreatment
Pork is prepared by mixing pork sample with hydrochloric acid solution in polypropylene centrifuge tube, vortex pH for 1-2min, ultrasonic treating for 10-20min, centrifuging for 5-10min, collecting supernatant, adjusting with sodium hydroxide solution, centrifuging for 5-10min, discarding precipitate, and diluting the supernatant with ultrapure water to 10m L.
(2) Magnetic solid phase extraction, enrichment and concentration process
Adding a magnetic nano material into the uniformly mixed sample solution obtained in the step (1), carrying out vortex, carrying out magnetic adsorption to separate the sample solution, removing a supernatant to obtain a residue, adding an eluent into the residue, carrying out vortex, and separating to obtain a supernatant for later use;
(3) and (4) determining the content of the clenbuterol hydrochloride in the eluent by ultra performance liquid chromatography-tandem mass spectrometry (UHP L C-MS/MS).
In the step (1), the mass ratio of the pork to the hydrochloric acid solution is 1.0: 4.0-10.0; the pH value is 7-9.
In the step (2), the ratio of the adding amount of the magnetic nano material to the weight volume of the sample solution is 3.5-10.0 mg.m L-1Adding magnetic nanometer material, and performing vortex for 3-5 min; the eluent is ammonia-methanol mixed solution, wherein the volume ratio of ammonia water to acetonitrile is 10-70%.
As a further preferable scheme of the invention, in the step (1), the mass ratio of the pork to the hydrochloric acid solution is 1.0: 4.0-10.0; pH value: 7-9.
As a further preferable embodiment of the present invention, in the step (2), the ratio of the amount of the magnetic nanomaterial added to the weight volume of the sample solution is 3.5 to 10.0mg m L-1Adding magnetic nanometer material, and performing vortex for 3-5 min; the eluent is ammonia-methanol mixed solution, wherein the volume ratio of ammonia water to acetonitrile is 10-70%.
Compared with the prior art, the invention has the following beneficial effects:
1、Fe3O4@SiO2excellent adsorption capacity of/GO/CS/MPTS.
2. In pure Fe3O4To provide adsorptive and magnetic capabilities, by applying a suitable protective coating to the surface to prevent oxidation.
3. The magnetic absorbent has the advantages of low consumption, high enrichment factor, high adsorption efficiency and easy separation under the action of an additional magnetic field.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the technical descriptions of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is Fe3O4、Fe3O4@SiO2、Fe3O4@SiO2/GO、Fe3O4@SiO2(GO/CS & Fe)3O4@SiO2Surface morphology and structural morphology diagrams and transmission electron microscopy diagrams of/GO/CS/MPTS;
FIG. 2 is Fe3O4、Fe3O4@SiO2、Fe3O4@SiO2/GO、Fe3O4@SiO2(GO/CS & Fe)3O4@SiO2Fourier transform infrared spectrogram of/GO/CS/MPTS;
FIG. 3 is Fe3O4、Fe3O4@SiO2A hysteresis loop diagram of/GO/CS/MPTS;
FIG. 4 is Fe3O4@SiO2X-ray photoelectron spectroscopy of/GO/CS/MPTS;
FIG. 5 is Fe3O4@SiO2The adsorption kinetics of/GO/CS/MPTS on clenbuterol hydrochloride;
FIG. 6 shows clenbuterol and Fe3O4@SiO2Adsorption isotherm of/GO/CS/MPTS;
FIG. 7 is a graph showing the effect of salt concentration in the MSPE extraction step;
FIG. 8 is Fe3O4@SiO2/GO、Fe3O4@SiO2(GO/CS & Fe)3O4@SiO2a/GO/CS/MPTS recovery histogram;
FIG. 9 is a response surface plot model for the MSPE extraction and elution step;
fig. 10 is an MRM chromatogram of clenbuterol hydrochloride in real samples.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without creative efforts, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a method for determining clenbuterol hydrochloride residue in pork, which comprises the following steps: the samples were lyophilized using a lyophilizer, and the pork samples were homogenized and sieved using a high speed food blender to obtain granules. And then performing selective extraction and trace determination on clenbuterol hydrochloride in pork by using magnetic solid-phase dispersion extraction and adopting an ultra-high-phase liquid chromatography tandem mass spectrum.
The magnetic nanocomposite material is prepared by the following method:
first, ferric chloride hexahydrate and ferrous chloride tetrahydrate were dissolved in deionized water at 50 ℃ under a nitrogen atmosphere. Then, ammonia was added dropwise to adjust the pH of the suspension. The suspension is continuously mechanically stirred at 80-90 deg.C for 30-40 min. Subsequently, the mixture was cooled to room temperature, and the magnetic material was collected with a magnet. Washing the obtained solid with ultrapure water and ethanol, and then carrying out vacuum drying on the solid at the temperature of 60-70 ℃ for 10-15h to obtain the magnetic ferroferric oxide nano-particles.
Dispersing magnetic ferroferric oxide nano particles in ethanol-water mixed solution, adding ammonia water, and stirring for 10-20min at 30-40 ℃. Then, ethyl orthosilicate is added dropwise to the mixture and stirred for 8-15h at 20-30 ℃. The resulting mixture particles were separated from the dispersion by an external magnetic field, washed with ethanol and water and dried to obtain silica-coated iron oxide.
Adding silica-coated iron oxide and 3-aminopropyltriethoxysilane into isopropanol, ultrasonic treating in nitrogen atmosphere for 30-40min, and stirring at 70-80 deg.C for 6-8 h. Washing with water and ethanol, and drying at 60-70 deg.C for 8-10h to obtain the magnetic ferroferric oxide coated with the generated silica with branched and linked amino groups.
Suspending graphene oxide in N-alkyl succinimide, N-dimethylformamide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, stirring at room temperature for 2-5h, adding magnetic ferroferric oxide coated by silica with branched and linked amino groups, keeping stirring until the mixture turns black, washing with water under an ultrasonic condition, and drying in vacuum at 70-80 ℃ to obtain the magnetic graphene oxide.
Dissolving chitosan powder in an acetic acid solution to prepare a chitosan solution, adding magnetic graphene oxide into the chitosan solution, stirring the mixture for 10-30min, adding glutaraldehyde, performing water bath at 65-80 ℃ for 6-10h, washing with water, and drying in vacuum to obtain the chitosan-modified magnetic graphite oxide.
Dispersing chitosan-modified magnetic graphene oxide in ultrapure water, dropwise adding a silane coupling agent KH590 while stirring, keeping the temperature at 60-70 ℃, stirring for 6-10h under nitrogen, magnetically separating to obtain the silane coupling agent KH590 surface-modified magnetic graphene oxide, washing with distilled water, and vacuum-drying at 40-60 ℃.
The chitosan-modified magnetic graphene oxide modified on the surface of the silane coupling agent KH590 prepared by the invention can be used as a magnetic solid phase extraction adsorbent, a pretreatment technology of pork samples, and an ultra-high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) as a detection tool for quantitative analysis of clenbuterol hydrochloride.
The invention discloses a method for detecting the content of clenbuterol hydrochloride in pork by taking chitosan-modified magnetic graphene oxide modified on the surface of a synthesized magnetic nano composite material silane coupling agent KH590 as a magnetic solid phase extraction adsorbent and combining with magnetic solid phase extraction, which comprises the following specific steps:
(1) pretreatment of samples
Mixing 0.5g pork sample with hydrochloric acid in a 20m L polypropylene centrifuge tube, vortexing for 1min, ultrasonically centrifuging, collecting supernatant, adjusting pH with sodium hydroxide, centrifuging the supernatant, removing precipitate, and diluting with ultrapure water to 10m L to obtain pork sample solution.
(2) Magnetic solid phase extraction, enrichment and concentration process
Adding 35-100mg of magnetic nano material into the uniformly mixed sample solution obtained in the step (1), carrying out vortex for 3-5min, separating the material at the bottom of a centrifugal tube by using an external magnet, removing supernatant, adding 0.2-1.5m of L ammonia water methanol (10-70%) solution into residues, carrying out vortex for 3-10min, separating to obtain supernatant, carrying out blow drying, and carrying out redissolving by using an initial mobile phase, sampling and introducing into UHP L C-MS/MS for analysis.
(3) And (4) determining the content of the clenbuterol hydrochloride in the eluent by ultra performance liquid chromatography-tandem mass spectrometry (UHP L C-MS/MS).
Ultra high performance liquid chromatography separation
The chromatographic conditions are as follows, the chromatographic column is ACQUITY UHP L C
C18Chromatographic column (2.1mm × 100mm,1.7 μm), mobile phase A of 0.1% formic acid-water solution and B of methanol, and gradient elution procedure comprising 0min 60% B, 0-5min 60-80% B, 5-5.1min 80-60% B, 5.1-7min 60% B, flow rate 0.2m L. min-1The column temperature is 40 ℃, and the sample injection amount is 10 mu L;
mass spectrometric detection
The mass spectrum detection conditions comprise ion source electrospray ionization (ESI source), detection mode of positive ion mode, scanning mode of multiple reactive ion detection (MRM), ion source temperature of 110 deg.C, capillary voltage of 2.5kV, desolvation gas temperature of 400 deg.C, desolvation gas flow rate of 450L & H-1。
Compared with the traditional method for determining clenbuterol hydrochloride, the method has the following advantages:
to confirm Fe3O4@SiO2The results are summarized in Table 8 below the results clearly show that the MD L of the present invention is lower than all currently reviewed methods, which indicates the advantages (high sensitivity) of MSPE-UP L C-MS/MS, and furthermore, the method has higher accuracy and satisfactory recovery than other methods the comparison of the methods herein to the reported methods is shown in Table 1 below.
TABLE 1 comparison of Current methods with literature reported methods
EGC: ethylenediamine-connected graphene/carbon nanotube composite material
spMNBS: sulfonated polystyrene magnetic nano-bead
MIM: molecularly imprinted microspheres
PDMS: polydimethylsiloxane
MIP: molecularly imprinted polymers
PT-SPE: pipette tip solid phase extraction
MI-MSPD: solid phase dispersion of molecular engram substrate
DI-SPME: direct immersion solid phase microextraction
Example 2:
1 Instrument and reagent
1.1 Instrument:
mettler Toledo A L104 electronic balance (Mettler Torland Torledo, Switzerland), a constant temperature water bath (Shanghai Yangrong Biochemical instruments Co., Ltd.), kq5200 ultrasonic cleaner (Kunshan ultrasonic instruments Co., Ltd.), JJ-1 precision power-increasing electric stirrer (Jiangnan laboratory instruments Co., Ltd., Changzhou), JP200-24 type test tube nitrogen blowing concentrator (Shanghai Jingpai instruments Co., Ltd.), high speed centrifuge, XK-80A rapid mixer (Jiangsu Xinkang medical instruments Co., Ltd.), ACQUITY UP L CTMUltra high performance liquid chromatograph (Waters corporation, USA), Quattro microTMAn API triple quadrupole tandem mass spectrometer was equipped with an ESI source (Waters corporation, USA).
1.2 reagent:
clenbuterol hydrochloride (dydsite biotechnology limited), graphene oxide powder (Nanjing Ginko nanotechnology limited), ferric chloride hexahydrate, ferric chloride tetrahydrate (analytical purity, Erilan chemical technology limited), 3-aminopropyltriethoxysilane, N-hydroxysuccinimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (analytical purity, Shanghai Bigde pharmaceutical technology limited), glutaraldehyde (Fuchen chemical reagent limited), dimethylformamide (Fuyu Fine chemical Co., Ltd.), ethanol, isopropanol (chromatographic purity, Shandong Yuwang Mishi Kogyo Co., Ltd.), methanol (chromatographic purity, Sammer Feishi Tech technology limited), tetraethylorthosilicate, ammonia water (analytical purity, Tianjin optical recovery institute of Fine chemical engineering), MPTS (100-200 mPas), chitosan (Shanghai Ron chemical technology Co., Ltd.), and deionized water (Waha group Co., Ltd.).
1.3 preparation of magnetic nanomaterials
1.3.1 magnetic ferroferric oxide (Fe)3O4) The preparation of (1):
9.4g of ferric chloride hexahydrate and 3.5g of ferrous chloride tetrahydrate were dissolved in 160 m L deionized water under a nitrogen atmosphere at 50 ℃, 20m L of aqueous ammonia was added dropwise, after the pH of the suspension was adjusted to 10.0, the suspension was continuously mechanically stirred at 80 ℃ for 30min3O4And (3) nanoparticles.
1.3.2 silica-coated magnetic ferroferric oxide (Fe)3O4@SiO2) The preparation of (1):
0.6g of Fe3O4Nanoparticles were dispersed in 150m L ethanol-water mixed solution, then 2m L ammonia water was added, and stirred at 30 ℃ for 15min, after which 1.8m L of TEOS was added dropwise to the mixture, the reaction was carried out at room temperature under stirring for 8h, Fe was added by an external magnetic field3O4@SiO2The particles were separated from the dispersion, washed with ethanol and water, respectively, and dried for use.
1.3.3 magnetic graphene oxide (Fe)3O4@SiO2Preparation of/GO):
0.5g of Fe3O4@SiO2And 0.25m L APTES to 125m L isopropanol, sonicating the mixture for 30min under nitrogen and stirring continuously at 70 ℃ for 6h, cleaning the product with water and ethanol, drying under vacuum at 60 ℃ for 8h to give the resulting Fe3O4@SiO2-NH2Then 0.2g GO was suspended in 50m L DMF containing 0.1g NHS and 0.2g EDC and then stirred at room temperature for 2h to activate the carboxyl groups of GO next 0.5g Fe3O4@SiO2-NH2Adding into the above obtained solution, and keeping stirring overnight, and ultrasonic treatingAfter washing with water, it was dried in vacuo at 70 ℃. 1.3.4 magnetic graphene oxide (Fe) modified with chitosan3O4@SiO2Preparation of/GO/CS):
first, a CS solution (w/v) was prepared by dissolving 0.2g of CS powder in 40m L of acetic acid solution (v/v)3O4@SiO2Add/GO to CS solution, stir mixture for 10min, add 50 μ L glutaraldehyde to reaction flask, keep in 80 deg.C water bath for 6h, then obtain Fe3O4@SiO2the/GO/CS was washed with water and dried in vacuo.
1.3.5MPTS modified chitosan modified magnetic graphene oxide (Fe)3O4@SiO2Preparation of/GO/CS/MPTS):
100mg of Fe3O4@SiO2dispersing/GO/CS in 100m L ultrapure water, dropwise adding 0.2m L MPTS while stirring, and continuously stirring for 6h at 60 ℃ under nitrogen3O4@SiO2/GO/CS/MPTS, and washed with distilled water, then dried under vacuum at 40 ℃.
1.4 pretreatment of the samples
Mixing 0.5g pork sample with 5.0m L0.01.01 mol L-1Mixing HCl in 20m L polypropylene centrifuge tube, vortexing for 1min, ultrasonic treating for 10min, and processing at 10000 r.min-1Centrifuging at high speed for 5min, collecting supernatant, adjusting pH to neutral with NaOH solution, and centrifuging at 12000r min-1Then, the resultant was centrifuged again for 5min to discard the precipitate, and the resultant supernatant was diluted with ultrapure water to 10m L to prepare a sample solution.
1.5MPSE Pre-treatment Process
The sample solution under 1.4 was taken, 32mg of magnetic adsorbent under "1.3.5" was added, vortexed vigorously for 4min, the nanocomposite was separated from the solution using a magnet, the supernatant was discarded methanol containing 10% ammonia solution (v/v) at 2.0m L as the elution solvent was added to the tube, vortexed vigorously for 3min, clenbuterol hydrochloride was eluted from the nanocomposite surface after desorption, nanocomposite was separated at the bottom of the centrifuge tube using an external magnet, the desorbed solution was evaporated to dryness in a gentle stream of air at 50 ℃, then redissolved with 200 μ L initial mobile phase, passed through a 0.45 μm organic filter, and the subsequent filtrate was taken for subsequent analysis.
2 optimization of Material Properties and extraction Process
2.1 pairs of Fe3O4@SiO2Characterization of/GO/CS/MPTS nanomaterials
Magnetic nanocomposite Fe by Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Fourier transform Infrared Spectroscopy (FT-IR), Vibrating Sample Magnetometer (VSM) and X-ray photoelectron Spectroscopy (XPS)3O4@SiO2the/GO/CS/MPTS characteristics.
For the purpose of studying the morphological characteristics of the nanocomposite, for Fe3O4、Fe3O4@SiO2、Fe3O4@SiO2/GO， Fe3O4@SiO2SEM study of/GO/CS and Fe3O4@SiO2SEM and TEM studies were performed on/GO/CS/MPTS as shown in FIG. 1. From FIG. 1a, the synthesized Fe can be seen3O4The particles are spherical or ellipsoidal and there is very severe agglomeration between particles. FIG. 1b shows that the aggregation disappears and the size of the nanoparticles becomes larger, indicating that silica has been successfully coated on Fe3O4Above, it shows Fe3O4@SiO2And (4) successfully synthesizing. As shown in fig. 1c, a flake structure with a large surface area was observed, and a large number of particles were tightly attached to the flake surface, indicating that GO has successfully reacted with Fe3O4@SiO2-NH2Are assembled together. While in fig. 1d a high surface area and a very thin transparent film with a typical layered structure in the form of wrinkles is observed. Therefore, the above is especially 400-4000cm-1In the range of (1), Fe3O4，Fe3O4@SiO2，Fe3O4@SiO2/GO，Fe3O4@SiO2(GO/CS & Fe)3O4@SiO2The FT-IR spectrum of/GO/CS/MPTS is shown in FIG. 2. Fe3O4(FIG. 2a) shows a depth of 541cm-1Characteristic peak of (A), which is attributed to the tensile vibration of Fe-O-FeAnd (6) moving. FIG. 2b shows a cross section at 1066cm-1A strong absorption band at (A), which can be attributed to Si-O-Si symmetric and asymmetric vibrations, indicating Fe3O4Has been successfully coated with SiO2And (6) covering. As shown in FIG. 2c, the carboxyl group was observed at 1733cm-1C ═ O tensile vibration and vibration at 1611cm-1The peaks in (A) were attributed to N-H bending vibration and C-C stretching vibration, thereby confirming successful synthesis of Fe3O4@SiO2and/GO. In FIG. 2d, the peak intensity and peak area of the N-H bending vibration is 1611cm compared to Fe3O4@ SiO2/GO-1Is significantly increased due to the-NH-on the CS chain2Reaction of groups with-COOH groups of GO. At the same time, at 1395cm-1Typical C-H/O-H bending vibrations of CS were observed, indicating an increase in oxygen-containing groups. 2559cm in FIG. 2e-1The absorption peak at (A) is due to S-H tensile vibration of MPTS, indicating that MPTS and Fe3O4@SiO2Successful combination of/GO/CS. Thus, the results of FTIR analysis confirmed the formation of nanoparticles.
The magnetic properties of the material were studied by VSM at room temperature. According to curves 1, 2 in FIG. 3, Fe3O4、 Fe3O4@SiO2The saturation magnetizations of/GO/CS/MPTS are 58.49 and 43.21emu g-1This is sufficient to separate the material from the sample solution with an external magnetic field. With pure Fe3O4In contrast, Fe3O4@SiO2The magnetization of/GO/CS/MPTS is reduced by 15.23emu g-1This is due to the modification of Fe3O4A non-magnetic silicon shell on the surface. As can be seen from fig. 3, the adsorbent was easily dispersed into the sample solution by shaking. When an external magnetic field is used to separate the adsorbents, the magnetic material will quickly attract to the walls of the container.
By XPS on Fe3O4@SiO2The chemical composition of/GO/CS/MPTS was further studied, as shown in FIG. 4. Fe3O4@SiO2Wide scan XPS spectra of/GO/CS/MPTS show that the material is composed primarily of Fe, O, N, C, S and Si. As can be seen from FIG. 4A (a), the Fe2p peak is deconvoluted into two typical characteristic peaks of 711.3eV and 725.0eVRespectively assigned as Fe2p3/2And Fe2p1/2Shows that Fe3O4The successful synthesis of the compound. A peak of Si 2p of about 102.0eV was also observed, indicating that Fe3O4Successfully coated with silica. For fig. 4a (b), the N1 s spectrum was fitted by introducing two peaks at 399.5eV and 402.2 eV. The peak at 402.2eV is assigned as-NH2While the peak at 399.5eV is assigned as-NH-CO-, indicating that Fe3O4@SiO2-NH2And CS was successfully grafted onto GO by acylation. -NH2Indicates Fe3O4@SiO2Some of the amino groups on the surface do not participate in the acylation reaction due to steric effects. The XPS spectrum of C1 s (fig. 4B) can be deconvoluted into six peaks with binding energies of 283.3eV (C-Si), 284.2eV (C-C/C-H), 284.7 eV (C-OH/C-O-Si/C-N), 285.1eV (O-C), 286.2eV (C ═ O) and 288.0eV (O-C ═ O), respectively. For O1 s (fig. 4C), the characteristic peaks for 530.2, 531.25, 531.85, 532.45 and 533.3eV are assigned to Fe-O, O-C ═ O, Si-O-Si and C-OH/C-O-Si, respectively. The C1 s and O1 s spectra show that Fe3O4@SiO2CS and MPTS successfully attached to GO surfaces by reacting terminal amine or silane groups, respectively, with the oxidized groups of GO surfaces. In addition, the S2 p signal at 163.2eV further demonstrates the presence of MPTS. Thus, the results of XPS spectroscopy clearly demonstrate that this work successfully synthesized Fe3O4@SiO2/GO/CS/MPTS。
2.2 optimization of Magnetic Solid Phase Extraction (MSPE) conditions
The MSPE process was optimized using Design-Expert 11.0 statistical software program Box-Behnken Design (BBD). The model contained three levels (low, medium and high, coded as-1, 0 and +1, respectively), and a total of 15 experimental runs (3 repetitions of the center point) were performed to optimize the variables in the extraction and desorption steps, according to our study, the range and levels of independent variables are recorded in Table 2, and the resulting response curve model is shown in FIG. 9 with the optimal conditions of pH 7, adsorbent usage 32mg, adsorption time 6min, eluent volume 2.0m L, ammonia eluent concentration 12%, and elution time 3.7 min.
TABLE 2 ranges and levels of independent variables for BBD
2.3 adsorption kinetics and adsorption isotherm study
Predicting the rate of absorption of analytes during adsorption is a major factor in designing adsorption systems. To study Fe3O4@SiO2The absorption kinetics of/GO/CS/MPTS to clenbuterol hydrochloride adopts a first-order simulation kinetic model and a second-order simulation kinetic model. FIG. 5 depicts adsorption data fitted to these models, with the rate constants and determination coefficients (R) for each model2) Recorded in table 3. The results show that the adsorption of clenbuterol is best described by a pseudo-secondary kinetic model, indicating that chemisorption is the rate-limiting step.
TABLE 3Fe3O4@SiO2Kinetic parameters of/GO/CS/MPTS for adsorbing clenbuterol hydrochloride
To study clenbuterol with Fe3O4@SiO2The adsorption mechanism of/GO/CS/MPTS in the adsorption process is fitted to the adsorption equilibrium data using L angmuir and Freundlich isothermal models, the results are shown in FIG. 6, and the fitting parameters of the adsorption isotherm of clenbuterol are shown in Table 4. as shown in Table 4, the L angmuir adsorption constant is more suitable for the adsorption process, indicating that monolayer absorption is the dominant process.
TABLE 4 parameters of 4L angMuir and Freundlich isotherm models
2.4 Effect of salt concentration on recovery
In this experiment, the effect of salinity on extraction efficiency was investigated by adding NaCl to the extraction solvent at a concentration of 0-35% (w/v). As shown in fig. 7, when NaCl was added, the recovery of clenbuterol decreased, since the presence of salt may occupy Fe3O4@SiO2Certain binding sites on/GO/CS/MPTS and interfere with the electrostatic interaction between the magnetic material and the protonated clenbuterol hydrochloride.
3 detection method and verification
3.1 use of Waters AcquityTMUltra-high liquid chromatography and Micromass Quattro MicrTMAPI mass spectrometry system for measuring content of clenbuterol hydrochloride in pork
A chromatographic column:
BEH C18chromatography column (2.1mm × 100mm,1.7 μm)
Mobile phase: a: 0.1% formic acid-water, B: methanol
Gradient elution procedure: 0 min: 60% of B; 0-5 min: 60-80% B; 5-5.1 min: 80-60% B; 5.1-7 min: 60% of B
Flow rate of 0.2m L & min-1
Column temperature: 40 deg.C
The sample injection amount is 10 mu L;
an ion source: electrospray ionization source (ESI source)
The detection mode is as follows: positive ion mode
The scanning mode is as follows: multiple reactive ion detection (MRM)
Ion source temperature: 110 deg.C
Capillary voltage: 2.5kV
Desolventizing gas temperature: 400 deg.C
Desolventizing gas flow rate 450L. H-1
3.1.1 matrix Effect
In this invention, matrix effects are evaluated by obtaining a calibration chart with three sample sets.
Recovery of sample pretreatment method (% RE):
overall process efficiency (% PE):
table 5 shows ME, RE and PE for the MSPE process in different matrices. It can be seen that the MSPE method can effectively purify pork samples, reduce the interference of matrix components and improve the accuracy of the method.
TABLE 5 clenbuterol hydrochloride ME, RE and PE in pork samples
3.1.2 methodological validation
The linearity of the method was tested by preparing a calibration curve with a standard addition, and the clenbuterol hydrochloride concentration range tested was 1-500 ng g-1Clenbuterol was obtained by injecting a separate standard solution for UP L C-MS/MS instrumental limit of detection (ID L) and instrumental limit of quantitation (IQ L). ID L and IQ L are clenbuterol hydrochloride concentrations with signal-to-noise ratios (S/N) of 3 and 10, respectively.md L and MQ L for analytes in different pork matrices were calculated using the following formulas:
MDL＝(V×IDL×100)/(m×PE×CF) (6)
MQL＝(V×IQL×100)/(m×PE×CF) (7)
where V is the volume of initial solvent (m L), m is the mass of the pork sample (g), and CF is the concentration coefficient between the initial volume (10m L) and the final volume (200 μ L), thus CF 50.
As shown in Table 6, the results show that R2The values are 0.9903-0.9942, and the ID L and IQ L of the analyte are 0.3 and 1 ng.m L respectively-1Correspondingly, in three different matrices, the MD L and MQ L of clenbuterol hydrochloride are 0.036-0.136ng g-1And 0.122-0.456ng g-1. In addition, the recovery rate of clenbuterol hydrochloride in the marked pork sample is between 84.7 and 101.1 percent, and the RSD is not more than 9.3 percent. Shows that the matrix matching standard curve of clenbuterol hydrochloride in different freeze-dried pork matrixes is 1-500 ng g-1Shows good linearity in the range, and the quantitative limit of the method is lower than 10 ng.kg-1Thus, the method has high sensitivity.
TABLE 6 Linear Range, correlation coefficient, instrumental detection and quantitation limits for clenbuterol hydrochloride in samples and methodological detection and quantitation limits for analytes
Three concentrations (10, 200 and 400 ng g) of the spiked lyophilized pork samples were determined in three replicate samples of the day-1) To assess the accuracy (repeatability) and precision over the day. Daytime accuracy and precision were calculated by determining the same samples for three consecutive days. Accuracy is expressed as the percentage of the Relative Standard Deviation (RSD) of the repeated measurements. Accuracy is expressed as a percentage of recovery. As shown in Table 6, the in-day precision and the in-day precision are in the range of 2.5-9.3% and 4.2-8.7%, respectively, and the method verification result shows that the proposed analysis method is stable and reliable, and has good repeatability and reproducibility.
Accuracy and precision of clenbuterol hydrochloride measurement method in samples of table 7
3.2 actual sample detection
Determination of residual content of clenbuterol hydrochloride in real pork sample MRM chromatogram of real pork sample extracted with the proposed method is shown in fig. 10. Table 8 lists the results for clenbuterol hydrochloride in real pork samples. Clenbuterol was detected in all muscle samples, especially in one of the muscle samples with clenbuterol hydrochloride residue up to 187.53 ng g-1And no analyte is detected in the cardiac sample. The result shows that the established method is suitable for analyzing the clenbuterol hydrochloride in the pork sample.
TABLE 8 determination of clenbuterol hydrochloride in real pork samples
ND: not found out
The experimental results show that: the established method is successfully applied to determination of clenbuterol hydrochloride in pork samples.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A method for preparing a magnetic nanocomposite material, characterized in that the method comprises the following steps:
(1) preparing magnetic ferroferric oxide from ferrous chloride tetrahydrate and ferric chloride hexahydrate in an alkaline solution by a chemical coprecipitation method;
(2) preparing magnetic ferroferric oxide wrapped by silicon dioxide with branched amino groups from the magnetic ferroferric oxide synthesized in the last step, ethyl orthosilicate and aminopropyl triethylsilane under the conditions of ethanol and alkalinity;
(3) magnetic ferroferric oxide wrapped by the silicon dioxide with the branched and linked amino groups synthesized in the last step and graphene oxide suspended in N-alkyl succinimide and N, N-dimethylformamide are stirred to prepare the magnetic graphene oxide.
(4) Preparing the magnetic graphene oxide modified by chitosan from the magnetic graphene oxide synthesized in the last step, chitosan and glutaraldehyde under the condition of acetic acid.
(5) And performing surface modification on the chitosan-modified magnetic graphene oxide synthesized in the last step by using a silane coupling agent KH590, and magnetically separating the chitosan-modified magnetic graphene oxide subjected to surface modification by using the silane coupling agent KH 590.
2. The method of claim 1, wherein the step of preparing the magnetic nanocomposite material comprises: in the step (1), the mass ratio of ferrous chloride tetrahydrate to ferric chloride hexahydrate is as follows: 1.0: 2.5-5.0; the pH value of the alkaline solution of ferrous oxide tetrahydrate and ferric oxide hexahydrate in the step (1) is 10-12, and the pH value is adjusted by adding ammonia water.
3. The method of claim 1, wherein the step of preparing the magnetic nanocomposite material comprises: the mass ratio of the magnetic iron oxide, the ethyl orthosilicate and the aminopropyl triethylsilane in the step (2) is as follows: 1.0:3.0-6.0:0.4-0.8.
4. The method of claim 1, wherein the step of preparing the magnetic nanocomposite material comprises: the mass ratio of the magnetic ferroferric oxide wrapped by the amino-branched silicon dioxide, the N-alkyl succinimide, the 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride, the graphene oxide and the N, N-dimethylformamide in the step (3) is 1.0:0.2-1.0:0.4-2.0:0.4-2.0: 96.0-100.0.
5. The method of claim 1, wherein the step of preparing the magnetic nanocomposite material comprises: the mass ratio of the magnetic graphene oxide to the chitosan to the glutaraldehyde in the step (4) is as follows: 1.0:2.0-5.0:0.5-2.0.
6. The method of claim 1, wherein the step of preparing the magnetic nanocomposite material comprises: the mass ratio of the chitosan-modified magnetic graphene oxide to the silane coupling agent KH590 in the step (5) is 1.0: 2.0-5.0.
7. Use of a magnetic nanocomposite material prepared according to any one of claims 1 to 6 for detecting clenbuterol hydrochloride in pork.
8. The use of the magnetic nanocomposite material according to claim 7 for detecting clenbuterol hydrochloride in pork, comprising the steps of:
(1) sample pretreatment
Pork is prepared by mixing pork sample with hydrochloric acid solution in polypropylene centrifuge tube, vortex for 1-2min, ultrasonic treating for 10-20min, centrifuging for 5-10min, collecting supernatant, adjusting with sodium hydroxide solution to pH., centrifuging for 5-10min, discarding precipitate, and diluting the supernatant with ultrapure water to 10m L to obtain pork sample solution.
(2) Magnetic solid phase extraction, enrichment and concentration process
Adding a magnetic nano material into the uniformly mixed sample solution obtained in the step (1), carrying out vortex, carrying out magnetic adsorption to separate the sample solution, removing a supernatant to obtain a residue, adding an eluent into the residue, carrying out vortex, and separating to obtain a supernatant for later use;
(3) and (4) determining the content of the clenbuterol hydrochloride in the eluent by ultra performance liquid chromatography-tandem mass spectrometry (UHP L C-MS/MS).
9. Use of the magnetic nanocomposite material according to claim 7 for detecting clenbuterol hydrochloride in pork, wherein: in the step (1), the mass ratio of the pork to the hydrochloric acid solution is 1.0: 4.0-10.0; pH value: 7-9.
10. The use of the magnetic nanocomposite material of claim 7 for detecting clenbuterol hydrochloride in pork, wherein in the step (2), the ratio of the added amount of the magnetic nanocomposite material to the weight volume of the sample solution is 3.5-10.0 mg-m L-1Adding magnetic nanometer material, and performing vortex for 3-5 min; the eluent is ammonia-methanol mixed solution, wherein the volume ratio of ammonia water to acetonitrile is 10-70%.
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