CN112816593A - Novel magnetic nano composite material, magnetic effervescent tablet, BPs detection method and application - Google Patents
Novel magnetic nano composite material, magnetic effervescent tablet, BPs detection method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of detection, and particularly relates to a novel magnetic nano composite material, a magnetic effervescent tablet, a method for detecting BPs and application. Wherein the novel magnetic nano composite material is g-C3N4Surface ofAttaching magnetic nanoparticles. The novel magnetic nano composite material provided by the invention can be mixed with the ionic liquid extractant to prepare an effervescent tablet, the prepared effervescent tablet can be used for separating and detecting BPs, and compared with the extraction efficiency of the ionic liquid extractant used alone, the extraction efficiency is greatly improved. The method for detecting the BPs avoids the use of the traditional organic dispersing solvent with the assistance of the special magnetic effervescent tablets, and the innovative micro-extraction technology completes the dispersing and recovering processes of the extracting agent in one step, thereby shortening the pretreatment time and ensuring that the method is more environment-friendly and efficient.
Description
Technical Field
The invention belongs to the technical field of detection, and particularly relates to a novel magnetic nano composite material, a magnetic effervescent tablet, a method for detecting BPs and application.
Background
Bisphenols (BPs) are a class of compounds that are frequently used in daily life. Bisphenol a (bpa) is a well-known environmental endocrine disrupter, primarily used as a raw material compound for the production of polycarbonate and epoxy resins plastics. Related studies have shown that bisphenol a can be detrimental to human health, such as reproductive diseases, cardiovascular diseases, breast cancer and congenital defects. With the increasing consumption of bisphenol a, low toxicity alternatives to bisphenol a have been widely used. Such alternatives to substituted bisphenol A include bisphenol F (BPF), bisphenol E (BPE) and bisphenol B (BPB), and the like. Currently, effective monitoring of BPs has become a worldwide concern. Therefore, there is an urgent need to develop a "green" method for determining the amount of trace amounts of BPs in complex matrices, such as human body fluids.
The currently available environmental monitoring schemes for BPs mainly include the following: solid Phase Extraction (SPE), Solid Phase Microextraction (SPME), stir bar adsorption extraction (SBSE) and dispersion liquid microextraction (DLLME). Wherein DLLME is a novel micro-extraction technology, and has the advantages of simple operation, high speed, low cost, high enrichment factor and the like. Therefore, DLLME has been successfully used for the determination of Polycyclic Aromatic Hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organophosphorus pesticides (OPPs), and Chlorobenzenes (CBs) in water samples. The subject group also successfully applied DLLME to the detection of PBDEs in water and food samples, methomyl in natural water, triazophos and carbaryl in water samples and fruit juice samples, four aromatic amines in water samples, polychlorinated biphenyl in soil and fish bodies, estrone and 17 beta-estradiol in water samples, and the like. Among these previously reported references, chlorinated solvents are the preferred extraction solvents. Although these conventional solvents have good recovery rates, they are flammable, volatile, and toxic. In order to overcome the disadvantages of the prior art methods, ionic liquids have recently been introduced as extraction solvents in the DLLME procedure. The ionic liquid is room temperature molten salt consisting of cations and anions, has the characteristics of high thermal stability, low vapor pressure, adjustable viscosity, good co-dissolution with water and organic solvents and the like, and is an attractive substitute for toxic extracting agents. During the past decade, several novel solvent-free dispersive microextraction techniques have been developed. The effervescent micro-extraction technique (ERME) was first proposed by Lasarte-Aragones et al in 2014. It produces a large amount of CO through acid-base reaction2The bubbles achieve solvent-free dispersion. CO 22The gas bubbles rising from the bottom to the top greatly increase the contact area between the extractant and the aqueous phase, thereby improving the extraction of the analyteAnd (4) recovering rate. However, this method still has a problem of being time-consuming due to the lack of a medium carrier capable of rapidly recovering and collecting the extractant.
In conclusion, the existing sample pretreatment technology has the defects of long time consumption, high cost, environmental pollution and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel magnetic nano composite material, a magnetic effervescent tablet, a method for detecting BPs and application.
In a first aspect of the invention, there is provided a novel magnetic nanocomposite material which is g-C3N4Surface-attached magnetic nanoparticles.
Preferably, the magnetic nanoparticles are prepared by hydrothermal method at g-C3N4And forming the surface of the nanometer material.
Preferably, the magnetic nanoparticles are NiFe2O4。
Preferably, in g-C3N4NiFe is formed on the surface of the nano material2O4The process of magnetic nanoparticles is as follows:
mixing nickel salt, iron salt and g-C3N4Placing the nano material in a reaction vessel, adding water, stirring, then adding urea, stirring, heating the reaction system to 170-190 ℃ under a closed condition, reacting for 11-13 h, cooling to room temperature after the reaction is finished, washing, separating by adopting a magnet to obtain a solid sample, and drying to obtain g-C3N4/NiFe2O4A magnetic nanocomposite material.
In a second aspect of the invention, there is provided a magnetic effervescent tablet comprising the novel magnetic nanocomposite material as described above, an effervescent precursor, and an ionic liquid extractant.
Preferably, the mass ratio of the effervescent precursor to the novel magnetic nanocomposite material is 452: 5-15.
Preferably, the ionic liquid extractant is [ C ]nMIM][PF6]。
In a third aspect of the present invention, there is provided a method for detecting BPs by using the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction (META-IL-DLLME) coupled technology as described above, comprising the following steps:
(1) placing the magnetic effervescent tablets in a water sample to be detected;
(2) when the magnetic effervescent tablets are completely disintegrated, separating the novel magnetic nano composite material coated with the ionic liquid and the object to be detected by magnetic attraction;
(3) eluting the novel magnetic nano composite material coated with the ionic liquid and the object to be detected by using an eluant;
(4) and (4) detecting the content of the BPs in the liquid obtained after elution.
In a fourth aspect of the invention, the application of the method for detecting the BPs by using the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction coupled technology for detecting the BPs in the urine sample is provided.
In a fifth aspect of the invention, the application of the method for detecting the BPs by using the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction combined technology in the detection of the BPs in blood samples is provided.
The invention has the following beneficial effects:
compared with the conventional dispersion liquid microextraction technology, the method for detecting the BPs has the advantages that the pretreatment technology is introduced into the dispersion liquid microextraction coupling technology to serve as an extracting agent, and can replace the traditional toxic chlorination reagent, so that the method becomes an environment-friendly pretreatment technology.
Compared with the ionic liquid-based dispersion liquid microextraction technology, the method for detecting the BPs has the advantages that the pretreatment technology and the ionic liquid-based dispersion liquid microextraction technology are adopted, the effervescent tablet is introduced into the ionic liquid-based dispersion liquid microextraction combination technology, the traditional toxic dispersing agent such as methanol, acetonitrile, tetrahydrofuran and the like can be replaced, and the effervescent tablet is formed by pressing the extracting agent, the inorganic acid salt and the alkali salt2The bubble is from up rising down, and the effervescent tablet is disintegrated totally in 1min, and the extractant is by homodisperse in the water sample, meanwhile, also is the process that the determinand is simultaneously extracted respectively for this alling oneself with technology is simple high-efficient, green more.
Hair brushCompared with the effervescent tablet-ionic liquid based dispersion liquid microextraction technology, the novel magnetic nano composite material provided by the invention is introduced into the effervescent tablet-ionic liquid based dispersion liquid microextraction combined technology, so that the traditional tedious centrifugation time-consuming step can be replaced, and the magnetic nano composite material coated with the extractant and the object to be detected can be adsorbed at the bottom of a test tube by placing an external magnet at the bottom of the test tube. g-C prepared in specific examples of the invention compared to the extraction efficiency of the ionic liquid extractant alone3N4/NiFe2O4Contributes to the recovery rate of 32.02-43.10% in the micro-extraction process. By the pair g-C3N4/NiFe2O4A series of characterizations (XRD, SEM, hysteresis analysis, FT-IR, Zeta potential and N) were performed2Adsorption-desorption isotherms, etc.) to investigate the cause thereof. The result shows that the nano-particles have larger specific surface area (38.9 m)2 g-1) Pore volume and pore diameter (0.24 m)3 g-1And 23.4 nm), the extraction efficiency is greatly improved. It is believed that the high specific surface area and large pore size of the magnetic nanomaterial can greatly improve the adsorption efficiency of the magnetic nanomaterial on organic analytes. Here, the magnetic nanocomposite g-C3N4/NiFe2O4The method has double functions, and can be used for magnetic separation and high-efficiency adsorption.
The present invention provides a method for detecting BPs, one preferred embodiment of which is g-C3N4/NiFe2O4A magnetic effervescent tablet-ionic liquid based dispersion liquid-liquid microextraction combined technology, under the optimal single factor condition optimization, the substance to be detected is 0.05-100 mu g L-1The concentration range has good linearity, and the correlation coefficients are all larger than 0.9991. The enrichment factor is between 100 and 107. LODs based on BPs at S/N =3 are 0.006-0.031 mu g L-1LOQs at S/N =10 is 0.020-0.0.100 mu g L-1. Therefore, the method can meet the trace analysis requirements of high enrichment and low detection limit of the BPs. To examine the reproducibility and stability of the method, we performed a series of experiments to calculate the intra-day and inter-day precision of the methodAnd (4) degree. The RSD was calculated by averaging 6 replicates for each test. When the precision in the day is measured, the recovery rate of the same batch of samples is continuously detected for 6 times every 2 hours, and then the calculation is carried out; when the day precision is measured, the same type of sample is detected at a fixed time every day, and after 6 days of continuous measurement, the day precision and the day precision are respectively 1.92-3.90% and 2.93-5.88%, which are both less than 6%. The method has good stability and can completely meet the requirement of actual detection.
The applicability of the present invention is achieved by applying the combined technology to trace detection of BPs in human body fluids (male urine sample, female urine sample, pregnant urine sample and male blood sample, female blood sample, pregnant blood sample). The concentrations of BPA, BPF and BPA detected in a blank pregnant woman urine sample, a blank female blood sample and a blank pregnant woman blood sample are respectively 0.91 +/-3.32, 0.51 +/-3.08 and 0.95 +/-2.94 mu g L-1Whereas no BPs remained in the other blank samples. Three detection concentrations (1.0, 10.0, 100.0 mu g L) of low, medium and high were added to the actual sample-1) The standard of (1) has the relative recovery rates of the BPs in the male urine sample, the female urine sample, the pregnant urine sample and the male blood sample, the female blood sample and the pregnant blood sample in the ranges of 79.78-97.67%, 79.60-99.48%, 78.32-103.10%, 81.31-104.06%, 79.48-103.98% and 79.20-102.86 respectively. The data show that the established pretreatment coupling technology is simple, efficient and good in reproducibility, is very suitable for trace detection of BPs substances in human urine samples and blood samples, and belongs to the research field of green analytical chemistry.
The novel magnetic nano composite material provided by the invention can be mixed with the ionic liquid extractant to prepare an effervescent tablet, the prepared effervescent tablet can be used for separating and detecting BPs, and compared with the extraction efficiency of the ionic liquid extractant used alone, the extraction efficiency is greatly improved. The novel magnetic nano composite material provided by the invention can be used as conventional Fe3O4Magnetic separation of materials and a promising alternative to adsorbents. The method for detecting the BPs avoids the use of the traditional organic dispersing solvent with the assistance of the special magnetic effervescent tablets, and the innovative micro-extraction technology completes the dispersing and recovering processes of the extracting agent in one step,thereby shortening the pretreatment time and ensuring that the method is more environment-friendly and efficient. In general, the method is simple, sensitive, efficient and environment-friendly, and has great application value in human body fluid sample monitoring of trace BPs. In addition, the effervescent tablet can be easily prepared in advance and can be used according to needs, so that the effervescent tablet is suitable for field detection and is a new technology with potential application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art 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 within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1A is a synthesis g-C provided in an embodiment of the present invention3N4/NiFe2O4A method flowchart of (1); FIG. 1B is a schematic representation of a compressed effervescent tablet provided by an embodiment of the present invention; FIG. 1C is a schematic diagram of the procedure for the magnetic effervescent tablet-ionic liquid based dispersion liquid microextraction coupled technology provided by the embodiment of the present invention;
FIG. 2 is a graph of synthetic g-C provided in an example of the present invention3N4/NiFe2O4Characterization graph of (2): (A) SEM; (B) XRD, (C) hysteresis loop analysis; (D) FTIR; (E) zeta potential analysis; (F) n is a radical of2Adsorption-desorption isotherm analysis;
FIG. 3 is an optimization of various factors affecting the efficiency of the extraction of BPs provided by an embodiment of the present invention: (A) comparison of extraction efficiency whether effervescent tablets were compressed; (B) optimizing the proportion of a effervescent tablet precursor; (C) g-C3N4/NiFe2O4Selecting the addition amount; (D) selecting an extracting agent; (E) selecting the volume of the extractant; (F) selecting an eluent; (G) selecting the extraction temperature; (H) the salt effect; (I) selecting the pH value;
FIG. 4 shows a blank sample and a labeled human urine/blood sample (10) provided by an embodiment of the present invention.0 µg L-1BPs) high performance liquid chromatography typical chromatogram: blank (a) and labeled (b) male urine sample; blank (c) and spiked (d) female urine samples; blank (e) and labeling (f) a pregnant urine sample; blank (g) and labeled (h) male blood samples; blank (i) and spiked (j) female blood samples; blank (k) and spiked (l) maternal blood samples;
FIG. 5 is a graph of g-C provided by an embodiment of the present invention3N4/NiFe2O4Reproducibility of magnetic nanocomposites.
Detailed Description
A novel magnetic nanocomposite material which is g-C3N4Surface-attached magnetic nanoparticles.
Wherein g-C3N4Either commercially available or by all preparations known in the art3N4The method of (1).
In one embodiment of the invention, g-C is prepared by high temperature calcination of urea in a tube furnace3N4The prepared novel magnetic nano composite material is verified to have better adsorption performance.
Wherein the magnetic nanoparticles may be ferrite particles, such as gamma-Fe2O3、Me Fe2O4(Me = Co, Ni, Mn) and Fe3O4Particles, etc., and may also be metal type particles, such as Fe, Co, Ni and alloy particles thereof, and may also be iron nitride particles, such as FeN, Fe2N、ε-Fe2N、Fe16N2And the like.
In one embodiment of the present invention, the magnetic nanoparticles are prepared by hydrothermal method at g-C3N4And forming the surface of the nanometer material.
In one embodiment of the invention, success is at g-C3N4NiFe is formed on the surface of the nano material2O4Magnetic nanoparticles, which are proven to have superior magnetic and adsorptive properties.
In g-C3N4NiFe is formed on the surface of the nano material2O4The process of magnetic nanoparticles is as follows:
mixing nickel salt, iron salt and g-C3N4Placing the nano material in a reaction vessel, adding water, stirring, then adding urea, stirring, heating the reaction system to 170-190 ℃ under a closed condition, reacting for 11-13 h, cooling to room temperature after the reaction is finished, washing, separating by adopting a magnet to obtain a solid sample, and drying to obtain g-C3N4/NiFe2O4A magnetic nanocomposite material.
A magnetic effervescent tablet comprises the novel magnetic nano composite material, an effervescent precursor and an ionic liquid extractant.
The effervescent precursor is a special disintegrant special for effervescent tablets, carbonate, acid or acid salt and basic salt form acid-base pairing, and carbon dioxide gas is continuously generated when the effervescent precursor meets water, so that the tablets are rapidly disintegrated within minutes. Effervescent precursors can be selected from: citric acid and NaHCO3(ii) a Tartaric acid and NaHCO3(ii) a Citric acid and Na2CO3(ii) a Tartaric acid and Na2CO3(ii) a Citric acid, tartaric acid and NaHCO3(ii) a Citric acid, tartaric acid and Na2CO3(ii) a Sodium dihydrogen phosphate and Na2CO3And so on for a plurality of series.
Preferably, the mass ratio of the effervescent precursor to the novel magnetic nanocomposite material is 452: 5-15.
The ionic liquid is a salt which is in a liquid state at or near room temperature and is completely composed of anions and cations, and is also called low-temperature molten salt. The main reason why the ionic liquid is used as an ionic compound and has a low melting point is that ions cannot be regularly accumulated into crystals due to the asymmetry of certain substituents in the structure of the ionic liquid. The anion ion exchange resin is generally composed of organic cations and inorganic or organic anions, wherein common cations comprise quaternary ammonium salt ions, quaternary phosphonium salt ions, imidazolium salt ions, pyrrole salt ions and the like, and anions comprise halogen ions, tetrafluoroborate ions, hexafluorophosphate ions and the like. In one embodiment of the invention, the ionic liquid extractant used is [ C ]nMIM][PF6]Verification of better extraction effect。
A method for detecting BPs by using a magnetic effervescent tablet auxiliary ionic liquid-based dispersion liquid microextraction combined technology comprises the following steps:
(1) placing the magnetic effervescent tablets in a water sample to be detected;
(2) when the magnetic effervescent tablets are completely disintegrated, separating the novel magnetic nano composite material coated with the ionic liquid and the object to be detected by magnetic attraction;
(3) eluting the novel magnetic nano composite material coated with the ionic liquid and the object to be detected by using an eluant;
(4) and (4) detecting the content of the BPs in the liquid obtained after elution.
The application of the method for detecting the BPs in the urine sample by using the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction combined technology is disclosed.
The application of the method for detecting the BPs in the blood sample by using the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction combined technology is disclosed.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The application of the principles of the present invention will now be described in detail with reference to the accompanying drawings, in which:
example 1: magnetic nanocomposite g-C3N4/NiFe2O4Preparation and characterization of
Step 1: magnetic nanocomposite g-C3N4/NiFe2O4Preparation of (see FIG. 1A)
(1) Weighing 15-25 g of urea, placing the urea into a porcelain boat, paving the urea, placing the urea into a tubular furnace, setting a program for heating the urea to 500-fold sand 600 ℃ from room temperature within 115 min at a speed of 4-6 ℃/min, keeping the temperature for 1.5-2.5 h, naturally cooling the urea to the room temperature, washing the urea for 3 times respectively by using ultrapure water and ethanol, and placing the obtained solid sample into a vacuum drying box for heating for 5-7 h at a temperature of 50-70 ℃. After the sample is naturally cooled to room temperature in a vacuum drying oven, collecting, grinding and weighing for later use, and finally calibratingIs marked as g-C3N4And (3) nano materials.
(2) Weighing about 0.23-0.24 g NiCl2·6H2O、0.50-0.55 g FeCl3·6H2O、0.3-0.5g g-C3N4Pouring into a reaction kettle, adding 45-55 mL of ultrapure water, and magnetically stirring for 15-25 min. After stirring, 0.7-0.9g of urea is weighed and poured into the water sample, and magnetic stirring is carried out again for 15-20 min. After the completion, the reaction kettle which is assembled is placed into an electric heating constant temperature air blast drying box, the setting condition is 170-190 ℃, and the reaction kettle is heated for 11-13 h. And after the reaction is finished, naturally cooling to room temperature, collecting a solid product after the reaction, washing for 3 times respectively by using deionized water and ethanol, then carrying out magnet separation, and putting the obtained solid sample into a vacuum drying oven to heat for 5-7 h at the temperature of 55-65 ℃. After the sample is naturally cooled to room temperature in a vacuum drying oven, collecting, grinding and weighing for later use, and finally marking as g-C3N4/NiFe2O4A magnetic nanocomposite material.
Step 2: magnetic nanocomposite g-C3N4/NiFe2O4Characterization of (1A)
Scanning Electron microscope analysis (SEM)
Scanning electron microscope pair of prepared g-C3N4/NiFe2O4The surface of the composite material was characterized, and the results are shown in FIG. 2A, and it can be clearly seen that the granular material, g-C, was attached to the sheet-like object at a magnification of 3 ten thousand times3N4Generally in the form of flakes, NiFe2O4Present as particulate matter.
X-ray diffraction analysis
g-C3N4、NiFe2O4And g-C3N4/NiFe2O4The characterization pattern of X-ray powder diffraction (XRD) and NiFe2O4As shown in fig. 2B. The values of the characteristic 2 theta angle of 18.40 degrees, 30.34 degrees, 35.70 degrees, 37.33 degrees, 43.33 degrees, 53.78 degrees, 57.31 degrees, 63.03 degrees and 74.54 degrees can respectively correspond to NiFe2O4(111), (220), (311), (222), (400), (422), (511), (440) and (533) The crystal planes, consistent with the reference magnetonickelite report (joint committee for powder diffraction standards (JCPDS) 10-325), have broad and sharp XRD diffraction peaks consistent with the small-size crystals and high crystallinity of the magnetonickelite. Further, the 2 θ angle values of 13 ° and 27.4 ° may be indexed as g-C3N4The (100) and (002) crystal planes of (a). It is clear that g-C3N4And NiFe2O4The peak value of (A) is not transferred, so that the chemical adsorption process has no influence on the crystal structure, and the peak value of (A) is in g-C3N4/NiFe2O4In the composite material, g-C appears at the angle value of 27.4 DEG of 2 theta3N4The diffraction peak of (a) shows that the experiment successfully synthesizes the g-C3N4/NiFe2O4A composite material.
Analysis of hysteresis curves
Prepared NiFe2O4And g-C3N4/NiFe2O4The magnetic properties of the composite materials were measured at room temperature by a sample vibration magnetometer, as shown in FIG. 2C, and the maximum magnetic susceptibility, remanence, and coercive force were 46.6 emu/g, 3.6 emu/g, 19.9 Oe, 29.1 emu/g, 2.8 emu/g, and 20.0 Oe, respectively, indicating NiFe2O4Attached to g-C3N4The magnetic property is reduced after the extraction, but the requirement of magnetic separation in the extraction process is met. As is clear from the experiments of the inset, it was found that g-C dispersed in an aqueous solution was obtained by using a magnet 5s3N4/NiFe2O4The magnetic nanocomposite is rapidly adsorbed on the tube wall to facilitate separation, which is of great significance in practical applications, avoiding lengthy centrifugation steps.
Fourier transform infrared spectroscopy
The FT-IR spectra in fig. 2D are respectively: (a) NiFe2O4；（b）g-C3N4；（c）g-C3N4/NiFe2O4；（d）[C8MIM][PF6]；（e）g-C3N4/NiFe2O4And [ C8MIM][PF6]And (3) extracting BPs substances in the water sample. Compare curves a, c and e in FIG. 2D, 605 cm-1And 426 cm-1Is NiFe2O4Two absorption peaks of the infrared spectrum, because of each O2-Shared by one tetrahedral cation and three octahedral cations, so that O2-All vibrations of (2) are related to tetrahedrons and octahedrons. 605 cm-1The absorption peak of (A) is generally ascribed to Ni in tetrahedron2+-O2-Vibration of key 426 cm-1The absorption peak of (A) is generally ascribed to Fe in octahedron3+-O2-The vibration of the key. Compare curves b, c and e, 804 cm in FIG. 2D-1 g-C3N4Bending vibration of medium C-N, 1203--1A series of peaks in the range are attributed to C-N stretching vibration characteristic peak, 3158 cm-1The position is an N-H stretching vibration characteristic peak. Compare curves D and e, 836 cm in FIG. 2D-1Is [ C ]8MIM][PF6]Vibration absorption peak of middle P-F, 1171 cm -11382 cm generated for in-plane deformation vibration of fragrance-1Peak value corresponds to alkyl-CH on imidazole ring3Absorption characteristic of stretching vibration of 1571 cm-1Is C = N vibration absorption peak, 2965 cm-1，2938 cm-1，2877 cm-1Is the vibration absorption peak of C-H on an alkyl substituent on an imidazole ring, and is 3163 cm-1，3123 cm-1Is the C-H shock absorption peak on the imidazole ring. Curve e in fig. 2D, is the synthesized material g-C3N4/NiFe2O4As magnetic separating and extracting agent [ C ]8MIM][PF6]After the auxiliary adsorbent is used for extracting BPs in a water sample, the material is directly dried without elution, and then infrared characterization is carried out to obtain the auxiliary adsorbent. From the curve e in FIG. 2D, 1000 cm-1Is a characteristic absorption peak of-C-O-bond in the BPs-like substances of 1450 cm-1Is a characteristic absorption peak of-C = C-double bond on benzene ring, and is also one of the mark peaks for identifying the presence or absence of benzene ring. In summary, [ C ] is described8MIM][PF6]And the enriched BPs to be detected are successfully adsorbed on the g-C3N4/NiFe2O4The surface of the composite magnetic nano composite material.
Zeta potential analysis
To further demonstrate g-C3N4/NiFe2O4The composite magnetic nano material has charge difference on the surface, and Zeta potentials of the material under different pH conditions are respectively measured. As can be seen in FIG. 2E, g-C3N4/NiFe2O4Isoelectric point pH = 7.48 of composite magnetic nanomaterial, indicating when pH of solution is<At 7.48, the surface of the material is positively charged and the pH value of the solution is>7.48, the surface of the material is in negative charge distribution.
⑥N2Adsorption-desorption isotherm analysis
To determine g-C3N4/NiFe2O4The specific surface area and pore structure of the magnetic nanocomposite material were determined, and the N of the material was determined2Adsorption-desorption isotherms. As shown in FIG. 2F, g-C3N4/NiFe2O4N of (A)2The adsorption-desorption isotherm shows a typical type IV, at medium pressure (0.1)< P/P0 <1) Has obvious capillary condensation phenomenon, which indicates the formation of mesopores in the material. g-C can be calculated from the isotherm at a pressure of 77K3N4/NiFe2O4Has a specific surface area of 38.9 m2 g-1. g-C was calculated from Barrett-Joyner-Halenda (BJH) model3N4/NiFe2O4Respectively pore volume and pore diameter of 0.24 m3 g-1And 23.4 nm (as shown by the inset in FIG. 2F). Are all greater than Fe3O4The specific surface area, pore volume and pore diameter of (2) were respectively 9.6 m2 g-1、0.02 m3 g-1Compared with 1.9 nm. Furthermore, g-C3N4/NiFe2O4The larger the specific surface area is, the larger the pore diameter is, the ion diffusion degree is obviously shortened, more sites are provided for the transfer of organic compounds, and the possibility of greatly enhancing the object to be detected and the g-C3N4/NiFe2O4The interaction between them. It is believed that the high specific surface area and large pore size of the magnetic nanomaterial can greatly improve the adsorption efficiency of the magnetic nanomaterial on organic analytes.
Example 2: pressing of magnetic effervescent tablet (see figure 1B)
Anhydrous sodium carbonate and sodium dihydrogen phosphate are used as effervescent precursors, dried in a 90 ℃ oven for 3h and then stored in a dryer for later use. First, 0.452 g of effervescent precursor (0.212 g of sodium carbonate and 0.24 g of sodium dihydrogen phosphate), 10 mg of-C were added in each portion3N4/NiFe2O4Magnetic composite material and 10. mu.L of [ C ]nMIM][PF6](n =4, 6, 8) mixed grinding. The homogeneous powder consisting of the above three parts is then compressed within 1min into a magnetic effervescent tablet (8 mm diameter, 2 mm thickness) using a 0.4T tablet press. The obtained tablet is placed in a sealed bag and then placed in a dryer for use.
Example 3: based on g-C3N4/NiFe2O4The magnetic effervescent tablet assists the ionic liquid-based dispersion liquid and liquid microextraction combined technology (see figure 1C)
The method for detecting BPs using this technique comprises the steps of: 1) first, 5.0 mL of each sample (15 mL centrifuge tube containing the test substance) was placed in a water bath at 30 ℃; 2) the magnetic effervescent tablet is put into a centrifuge tube, and a large amount of CO is formed instantly due to the effervescence reaction2Rising bubbles from bottom to top, disintegrating effervescent tablet completely within 1min, and extracting agent ([ C)nMIM][PF6]) And magnetic composite material (g-C)3N4/NiFe2O4) Is uniformly dispersed in water sample, and simultaneously the substances to be detected are respectively extracted into [ C ]nMIM] [PF6]And g-C3N4/NiFe2O4The process of (2); 3) without centrifugation, the coated [ C ] can be placed at the bottom end of the test tube by using an Nd magnetnMIM][PF6]And g-C of the analyte3N4/NiFe2O4Adsorbing the solution on the bottom of the test tube; 4) discarding the supernatant, eluting the magnetic nanocomposite precipitated at the bottom with 500 μ L, 300 μ L and 200 μ L acetonitrile respectively, separating the magnetic nanocomposite and the acetonitrile eluate containing the analyte with Nd magnet each time, mixing the three acetonitrile eluates, and filtering with 0.22- μm filter membrane; 5) drying the filtered acetonitrile elution liquid nitrogen, adding 100 mu L acetonitrile for redissolving, and transferring to brown containing an inner cannulaAnd (4) placing the sample into a sample bottle, and then placing the sample into an HPLC/FLD system for sample injection and determination.
Based on g-C3N4/NiFe2O4Optimization of factors in the extraction of META-IL-DLLME
Comparison of extraction efficiency of effervescent tablets
The effervescent tablet is prepared by pressing an extracting agent, a disintegrating agent and a magnetic nano composite material. The effervescent tablet works on the principle that a compressed tablet is put into an aqueous solution, and after the compressed tablet is contacted with water, acid-base neutralization reaction is rapidly carried out to generate a large amount of CO2The gas, the gas driving force produced by the rapid disintegration, disperses the extractant rapidly and uniformly, thereby fully extracting the substance to be detected. The extraction efficiency after compression into effervescent tablets was about 17.20% to 23.04% higher than that obtained by sprinkling the material prepared in example 1 directly into a water sample (see fig. 3A). The effervescent tablet is disintegrated by uniformly dispersing the extracting agent in water, so that the extracting agent has larger contact area with an object to be detected, and better extraction efficiency is obtained. Therefore, the experiments all used compressed effervescent tablets to assist the whole micro-extraction process.
② optimization of effervescent precursor proportion
Sodium bicarbonate, sodium carbonate and sodium dihydrogen phosphate may all be selected as effervescent precursors. When sodium bicarbonate is used in the effervescence reaction, the carbon dioxide is produced too rapidly and too short a dispersion time may result in a reduction of the extraction efficiency. Thus, sodium carbonate and sodium dihydrogen phosphate were ultimately selected as effervescent precursors. Sodium carbonate and sodium dihydrogen phosphate react according to the following chemical equation:
2H2PO4 -+CO3 2-→2HPO4 2-+CO2+H2O （1）
H2PO4 -+CO3 2-→PO4 3-+CO2+H2O （2）
according to the chemical equations (1) and (2), the molar ratio of the two effervescent precursors, sodium carbonate and sodium dihydrogen phosphate, is an important parameter for measuring the extraction efficiency, and the quality of the effervescent precursors also influences the extraction efficiency. Adding more effervescent precursor to a water sample can create more bubbles, accelerate the dispersion of the extraction solvent, but also increase the ionic strength and viscosity of the solution and can reduce extraction efficiency due to its viscous drag effect. According to the principle of stoichiometry, the effect of different molar ratios (1: 1 and 1: 2) of sodium carbonate and sodium dihydrogen phosphate on the extraction efficiency was investigated. As is apparent from fig. 3B, in the ratio of 1: at 1, the extraction efficiency of the BPs is higher than that of the BPs with the ratio of 1: and (2). However, excess amounts of reagents may increase the ionic strength and viscosity of the solution and affect extraction efficiency. Because the isoelectric point of the material is neutral, the precursor proportion is 1: the neutral environment after the acid-base reaction can better promote the extraction of the nano material in 1 hour. Therefore, the most preferred molar ratio is 1: 1 sodium carbonate and sodium dihydrogen phosphate as effervescent precursors.
③g-C3N4/NiFe2O4Selection of the amount to be added
In the process of magnetic vesicant tablet auxiliary ion liquid-based dispersion liquid microextraction, the magnetic nano composite material g-C3N4/NiFe2O4Plays an important role as a magnetic separating agent and an auxiliary adsorbent. To screen for different masses of g-C3N4/NiFe2O4Influence on the extraction efficiency, g-C of 0 mg, 10 mg, 20 mg and 30 mg were chosen3N4/NiFe2O4The experiment was performed, as shown in FIG. 3C, with 10 mg g-C3N4/NiFe2O4The extraction efficiency of the four BPs is optimal. The excessive nano materials can make the ionic liquid which is adsorbed on the surface and extracts the object to be detected difficult to completely elute, and the extraction efficiency is reduced. When no nano material is added in the extraction process, the extraction rate (58.28% -69.72%) of the four BPs is the contribution rate of the ionic liquid of the extractant, and the contribution rate of the nano material is the extraction recovery rate of the four BPs when the volume of the extractant is 0 muL. Thus, 10 mg of g-C3N4/NiFe2O4For subsequent experiments.
Selection of extractant
The selection of the extractant is very critical, and a good extractant needs to have several basic conditions: the property of the extractant needs to be matched with that of the analyte to ensure that the extractant has stronger extraction and enrichment capacity on the analyte; less volatile, less water soluble and denser than water (indeed, by improving the extraction process so far, some extractants less dense than water can also be used in the micro-extraction procedure); can be uniformly dispersed in a water phase under the action of a dispersing agent or a medium with a dispersing function, and has good chromatographic performance. Ionic Liquids (ILs) have the characteristics of low vapor pressure, high viscosity, good thermal stability, good co-solubility with water and organic solvents, and the like, and have good extraction capacity for most organic compounds, so the Ionic liquids are selected as the extractant in the experiment.
In this study, three ionic liquids [ C ] were selected4MIM][PF6](Density 1.37 g/mL) and [ C ]6MIM][PF6](density 1.30 g/mL) and [ C8MIM][PF6](density 1.23 g/mL) to extract BPs. Changes in carbon chain length, water solubility and viscosity all affect extraction efficiency. When [ C ] is added, as shown in FIG. 3D8MIM][PF6]The recovery rate of the four kinds of BPs is the highest (82.50% -99.90%), which is probably because the stronger hydrophobicity is when the imidazole ring of the ionic liquid is connected with a longer alkyl chain, and the stronger action between the imidazole ring of the ionic liquid and the BPs substance is pi-pi is also. Thus, [ C ] was selected in this experiment8MIM][PF6]As an optimal extractant.
Selection of volume of extractant
The volume of the extractant directly affects the enrichment efficiency of the dispersion liquid microextraction process. To evaluate the effect of extractant volume on extraction efficiency, different volumes of extractant [ C ] were used in this experiment8MIM][PF6](0, 10, 20, 30, 40, 50 μ L) was mixed with the magnetic nanocomposite and the effervescent precursor and tabletted, and in addition, the ionic liquid also played a role as a binder during the tabletting process. As shown in FIG. 3E, it is apparent that when [ C ] is present8MIM][PF6]When the volume of (2) is from 10 to 50. mu.L, the extraction efficiency of the four BPs gradually decreases and the amount of the excessC8MIM][PF6]Volume when compressed into effervescent tablets, the extraction efficiency is reduced by losing more because of too much stickiness, [ C ]8MIM][PF6]When the volume of the effervescent tablet is less than 10 mu L, the effervescent tablet is difficult to be pressed into tablets, and the extraction efficiency is indirectly influenced; when not adding [ C8MIM][PF6]Then, the extraction efficiency of four kinds of BPs is 32.02% -43.10%, under the condition, the magnetic nano composite material g-C is obtained3N4/NiFe2O4Contribution to the efficiency of BPs extraction, so g-C3N4/NiFe2O4Is an auxiliary adsorbent for ionic liquids, and an extractant [ C8MIM][PF6]Is the main contributor to the efficiency of the extraction of BPs. Therefore, the extractant [ C ] is optimally selected8MIM][PF6]The optimal volume of (a) is 10 muL.
Selection of eluent
Due to the inclusion of [ C ] of the analyte8MIM][PF6]Quilt g-C3N4/NiFe2O4The magnetic nanocomposite material is adsorbed on its surface and then separated from the aqueous phase with a magnet, so that the analyte is separated from g-C using a suitable eluent3N4/NiFe2O4The surface elution is a key factor affecting the resolution efficiency. Acetonitrile, methanol and acetonitrile are respectively selected: methanol (1: 1) and 0.2% NaOH-acetonitrile as eluents. As can be seen from FIG. 3F, acetonitrile extracted the analyte with the highest efficiency. One possible reason why acetonitrile is superior to other eluents is that ionic liquid has higher solubility in acetonitrile, and in the experimental process, due to the good dispersibility of acetonitrile, when the nanomaterial is eluted, the nanomaterial is not easily adhered to a centrifuge tube, so that the operation is convenient, and the loss is reduced. Methanol is not a suitable eluent because it does not have good dispersibility, resulting in the adhesion of most of the nanomaterial to the wall of the centrifuge tube during elution, indirectly reducing the extraction efficiency. Compared with the latter three eluents, acetonitrile has better solubility and dispersibility, higher recovery rate and lower toxicity, so that acetonitrile is selected as the best eluent in the next experiment.
Seventhly, selection of extraction temperature
The ionic liquid is very sensitive to temperature change, and the proper temperature can enable the ionic liquid to be better dispersed in the water phase, so that the contact area between the water phase and the ionic liquid phase can be increased, and an object to be detected can be extracted more quickly. The experiment examines the influence of the temperature ranging from-20 ℃ to 50 ℃ on the extraction efficiency of the object to be detected. As can be seen from fig. 3G, the extraction efficiency gradually increased as the temperature increased from-20 ℃ to 40 ℃, while the extraction efficiency significantly decreased as the temperature increased from 40 ℃ to 50 ℃. Lower temperatures will slow down CO2The formation rate of (A) results in a decrease in the effect of disintegration and dispersion, but too high a temperature enhances mass transfer based on Brownian motion, resulting in a decrease in the partition coefficient of the analyte into the extractant. Therefore, 40 ℃ was chosen as the optimum extraction temperature.
Salt effect
The effect of different ionic strengths on the extraction efficiency was investigated by adding 0-80% (w/v) NaCl to the sample solution. As can be seen from fig. 3H, the extraction efficiency gradually increased as the salt concentration increased from 20% to 60%, and decreased when it was more than 60%. Generally, an increase in ionic strength may decrease the solubility of the target analyte in solution, thereby facilitating extraction of the target. However, the enhancement of ionic strength in solution can reduce mass transport by altering the physical properties of the Nerst diffusion layer, thereby reducing the surface diffusion rate of the target to the extractant or adsorbent, resulting in a reduction in target analyte extraction efficiency. Therefore, the optimal extraction conditions of 60% NaCl (W/V) were chosen.
Ninthly selection of pH
An appropriate pH is important to reduce the matrix effect for the extraction of the target. Under the condition that other extraction conditions are not changed, the pH value of the solution is adjusted from 4.0 to 9.0 by selecting a sodium hydroxide solution and a hydrochloric acid solution. As shown in fig. 3I, the extraction efficiency gradually increased with increasing pH; when the pH is 7.0, the extraction efficiency of each BPs is maximum; the recovery rate showed a downward trend as the pH increased from 7.0 to 9.0. The experimental phenomenon can explain the low pH value condition from the aspect of changing the property of the magnetic nano material by the pH value of the sample solutionBPs in g-C3N4/NiFe2O4The above fact that the adsorption efficiency is low. According to literature reports that Fe dissolved on the surface of the magnetic nano material under acidic conditions3+Adsorption of the target analyte thereon is inhibited, thereby reducing extraction recovery. We speculate that under acidic conditions, the flakes g-C3N4NiFe supported thereon2O4The nanoparticles may be dissolved, or Fe3+ May dissolve from the surface of the nanoparticles, resulting in a decrease in adsorption efficiency. Therefore, in order to achieve quantitative recovery and maintain the stability of the magnetic nanomaterial, the pH of the aqueous solution is adjusted to 7.0 for optimum pH for subsequent experiments.
Example 4: based on g-C3N4/NiFe2O4Evaluation of Performance of the-META-IL-DLLME method
In order to carry out method evaluation on the established new combination technology, a series of standard solutions with different concentrations are prepared by diluting a stock solution under the optimal extraction conditions, extraction is carried out according to the optimal extraction conditions, and the Linear Range (LR) and the correlation coefficient (R) of the standard solutions are subjected to2) Analytical performance parameters such as Enrichment Factor (EFs), detection Limits (LODs), and quantitation Limits (LOQs) were rigorously studied and the results are shown in Table 1. As can be seen from the table, the analyte is 0.05-100 mu g L-1The concentration range has good linearity, and the correlation coefficients are all larger than 0.9991. The enrichment factor is between 100 and 107. LODs based on BPs at S/N =3 are 0.006-0.031 mu g L-1LOQs of 0.02-0.10 mu g L at S/N =10-1. Therefore, the method can meet the trace analysis requirements of high enrichment and low detection limit of the BPs.
To investigate the reproducibility and stability of the method, we performed a series of experiments to calculate the intra-day and inter-day precision of the method. The RSD was calculated by averaging 6 replicates for each test. When the precision in the day is measured, the recovery rate of the same batch of samples is continuously detected for 6 times every 2 hours, and then the calculation is carried out; the precision of the day is measured by detecting the same type of sample every day for a fixed time, and calculating after continuously measuring for 6 days. The specific results are shown in table 1, wherein the daily precision and the daytime precision are respectively 1.92% -3.90% and 2.93% -5.88%, and both are less than 6%. The method has good stability and can completely meet the requirement of actual detection.
Example 5: analysis of actual samples
The plasma and urine samples collected were provided by healthy volunteers from the subsidiary hospital of the university of medical Wenzhou, and the volunteers had not used products containing the BPs class within 3 months, and the samples collected in this study were in compliance with the provisions of the ethical Committee of the university of medical Wenzhou. When the plasma is collected, the anticoagulant EDTA-2Na is quickly added, and then the plasma is centrifuged for 10 min at the rotating speed of 12,000 rpm in a low-temperature environment at 4 ℃ (part of impurities in the blood are precipitated at the bottom of a centrifugal tube). The clarified solutions appearing in the upper layers of the blood and urine samples after the low-temperature centrifugation treatment were removed and filtered through 0.45 μm filter membranes, and then they were respectively transferred to glass test tubes and stored in a refrigerator at-80 ℃ for later use. Before the extraction process, the serum and urine samples are taken out of the refrigerator and naturally thawed to room temperature before subsequent pretreatment. Pretreatment of serum: adding 3 mL of frozen methanol into 1 mL of collected serum, performing vortex for 5 min, centrifuging at 10,000 rpm for 30 min after protein precipitation, filtering supernatant with 0.45μm filter membrane, adding NaCl to supersaturated state, discarding upper methanol phase and lower salting-out layer phase, taking purified serum phase of middle layer, and performing mild N filtration2The residual methanol phase was evaporated by running down and subsequently filtered with a 0.22 μm filter for future use. Pretreatment of a urine sample: the thawed urine sample was filtered directly through a 0.22 μm filter for further use.
For evaluation based on g-C3N4/NiFe2O4The applicability of the META-IL-DLLME method is applied to trace detection of BPs in actual samples of male urine sample, female urine sample, pregnant urine sample and male blood sample, female blood sample and pregnant blood sample. FIG. 4 shows blank and superscript (10 μ g L)-1) Typical chromatograms of human urine/blood samples (a, c, e, g, i, k and b, d, f, h, j, lBlank and labeled chromatogram maps of a male urine sample, a female urine sample, a pregnant urine sample, a male blood sample, a female blood sample and a pregnant blood sample respectively). As can be seen from Table 2, the concentrations of BPA, BPF and BPA detected in the urine sample of the pregnant woman blank, the blood sample of the female blank and the blood sample of the pregnant woman blank are respectively 0.91 + -3.32, 0.51 + -3.08 and 0.95 + -2.94 mu g L-1Whereas no BPs remained in the other blank samples. Three detection concentrations (1.0, 10.0, 100.0 mu g L) of low, medium and high were added to the actual sample-1) The standard of (1) has the relative recovery rates of the BPs in the male urine sample, the female urine sample, the pregnant urine sample and the male blood sample, the female blood sample and the pregnant blood sample in the ranges of 79.78-97.67%, 79.60-99.48%, 78.32-103.10%, 81.31-104.06%, 79.48-103.98% and 79.20-102.86 respectively. The data show that the established pretreatment coupling technology is simple, efficient and good in reproducibility, and is very suitable for trace detection of the BPs substances in human urine samples and blood samples.
Example 6: method Performance comparison
The newly established combination technology of the invention is based on g-C3N4/NiFe2O4The META-IL-DLLME/HPLC-FLD is applied to trace analysis of BPs in urine samples and serum in human body fluid, and is compared with SPE, SPME, MSPE, DMSPE, DSPE, MDME and other methods in the aspects of adsorbent and dosage, to-be-detected substances, detection sample types, LR, LODs, RSD, ERs, extraction time and the like. As shown in table 3, the method is advantageous in the following aspects: (1) inorganic acid salt, alkali salt (Na)2CO3、NaH2PO4) By producing large quantities of CO2The bubbles can quickly disperse the extractant and the adsorbent, and the use of traditional organic toxic dispersion solvents (methanol, acetonitrile, acetone and the like) is avoided; (2) the prepared novel nano composite material reaches a good detection range (0.05-100 mu g L) under the condition of less usage amount (10 mg)-1) The lowest detection limit (0.006-0.031 mu g L)-1) Good repeatability (1.92% -5.88%); (3) using g-C3N4/NiFe2O4The magnetism of the magnetic nano composite material can be quickly separated by an external magnet, and the traditional complex and time-consuming centrifugation is replacedA step of; (4) the method has very short time (less than 1 min) for reaching extraction equilibrium, which should be one of the reasons for good repeatability of the method. Furthermore, the process does not involve expensive equipment, hazardous chlorinated extraction solvents and complex operations, green solvents and recyclable magnetic nanocomposites, making the process more environmentally friendly. Therefore, the method is simple, rapid, economic, environment-friendly and efficient, and has great potential in the trace monitoring of BPs-like pollutants in complex human body fluid.
Example 7: g-C3N4/NiFe2O4Repeatability of (A)
g-C prepared herein3N4/NiFe2O4The number of repeated uses of the magnetic nanocomposite material plays an important role in practical applications. Used g-C for investigation3N4/NiFe2O4The g-C can be repeatedly used, and after 3 times of washing by acetonitrile and ultrapure water respectively, the analyte to be detected is not detected3N4/NiFe2O4And circulating in the next extraction process. As shown in FIG. 5, g-C3N4/NiFe2O4The loss of extraction recovery of the magnetic nanocomposite was less than 14% after at least 6 repetitions, demonstrating that the g-C produced3N4/NiFe2O4The magnetic nanocomposite material has good repeatability, which is of great significance in practical application.
In summary, the present invention proposes an attractive g-C-based solution3N4/NiFe2O4Novel method for combining META-IL-DLLME with HPLC/FLD and successfully applying method to urine sample in human body fluid and trace amount of BPs in serumAnd (5) trace analysis. g-C compares to the extraction efficiency of the ionic liquid extractant alone3N4/NiFe2O4Contributes to the recovery rate of 32.02-43.10% in the micro-extraction process, and has larger specific surface area (38.9 m)2 g-1) Pore volume and pore diameter (0.24 m)3 g-1And 23.4 nm), the extraction efficiency is greatly improved. Thus, g-C3N4/NiFe2O4Can be taken as conventional Fe3O4Magnetic separation of materials and a promising alternative to adsorbents. Newly developed g-C-based3N4/NiFe2O4The META-IL-DLLME method avoids the use of traditional organic dispersing solvent with the assistance of special magnetic effervescent tablets, and the innovative micro-extraction technology completes the dispersing and recovering processes of the extracting agent in one step, thereby shortening the pretreatment time and ensuring that the method is more environment-friendly and efficient. In addition, the method has high precision (1.92% -5.88%) and low detection limit (0.006-0.031 mu g L)-1) And satisfactory recovery (78.3% -104.1%). In general, the method is simple, sensitive, efficient and environment-friendly, and has great application value in human body fluid sample monitoring of trace BPs. In addition, the effervescent tablet can be easily prepared in advance and can be used according to needs, so that the effervescent tablet is suitable for field detection and is a new technology with potential application value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A novel magnetic nanocomposite characterized by: it is g-C3N4Surface-attached magnetic nanoparticles.
2. The magnetic nanocomposite material of claim 1, wherein the magnetic nanoparticles are produced at g-C by hydrothermal method3N4Nano material meterAnd (4) forming a surface.
3. The novel magnetic nanocomposite material according to claim 1, wherein: the magnetic nano particles are NiFe2O4。
4. The novel magnetic nanocomposite material according to claim 3, wherein: in g-C3N4NiFe is formed on the surface of the nano material2O4The process of magnetic nanoparticles is as follows:
mixing nickel salt, iron salt and g-C3N4Placing the nano material in a reaction vessel, adding water, stirring, then adding urea, stirring, heating the reaction system to 170-190 ℃ under a closed condition, reacting for 11-13 h, cooling to room temperature after the reaction is finished, washing, separating by adopting a magnet to obtain a solid sample, and drying to obtain g-C3N4/NiFe2O4A magnetic nanocomposite material.
5. A magnetic effervescent tablet, characterized in that: comprising the novel magnetic nanocomposite material according to claim 1, an effervescent precursor, an ionic liquid extractant.
6. A magnetic effervescent tablet according to claim 5, wherein: the mass ratio of the effervescent precursor to the novel magnetic nanocomposite material is 452: 5-15.
7. A magnetic effervescent tablet according to claim 5, wherein: the ionic liquid extractant is [ C ]nMIM][PF6]。
8. A method for detecting BPs by using the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction combined technology according to any one of claims 5-7, which is characterized by comprising the following steps:
(1) placing the magnetic effervescent tablets in a water sample to be detected;
(2) when the magnetic effervescent tablets are completely disintegrated, separating the novel magnetic nano composite material coated with the ionic liquid extractant and the object to be detected by magnetic attraction;
(3) eluting the magnetic nano composite material coated with the ionic liquid and the object to be detected by using an eluant;
(4) and (4) detecting the content of the BPs in the liquid obtained after elution.
9. Use of the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction coupled technology of claim 8 for detecting BPs in urine sample.
10. The use of the magnetic effervescent tablet assisted ionic liquid-based dispersion liquid microextraction combination technology according to claim 8 for detecting the BPs in the blood sample.
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