CN114405476A - Magnetic nanoparticles and preparation method and application thereof - Google Patents
Magnetic nanoparticles and preparation method and application thereof Download PDFInfo
- Publication number
- CN114405476A CN114405476A CN202111657351.6A CN202111657351A CN114405476A CN 114405476 A CN114405476 A CN 114405476A CN 202111657351 A CN202111657351 A CN 202111657351A CN 114405476 A CN114405476 A CN 114405476A
- Authority
- CN
- China
- Prior art keywords
- magnetic
- adsorption
- optionally
- magnetic nanoparticles
- ppd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 94
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229930195730 Aflatoxin Natural products 0.000 claims description 38
- 239000005409 aflatoxin Substances 0.000 claims description 38
- 231100000765 toxin Toxicity 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 claims description 17
- 239000002105 nanoparticle Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KYERQSUZHFINIE-UHFFFAOYSA-N 4-[2,4,5-tris(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=C(C=2C=CC(C=O)=CC=2)C=C1C1=CC=C(C=O)C=C1 KYERQSUZHFINIE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000005389 magnetism Effects 0.000 abstract description 4
- 239000013310 covalent-organic framework Substances 0.000 description 21
- 239000011257 shell material Substances 0.000 description 18
- 239000000523 sample Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000000605 extraction Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000002086 nanomaterial Substances 0.000 description 9
- 235000013305 food Nutrition 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003131 biological toxin Substances 0.000 description 5
- 238000002470 solid-phase micro-extraction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- OQIQSTLJSLGHID-WNWIJWBNSA-N aflatoxin B1 Chemical compound C=1([C@@H]2C=CO[C@@H]2OC=1C=C(C1=2)OC)C=2OC(=O)C2=C1CCC2=O OQIQSTLJSLGHID-WNWIJWBNSA-N 0.000 description 2
- WWSYXEZEXMQWHT-WNWIJWBNSA-N aflatoxin B2 Chemical compound C=1([C@@H]2CCO[C@@H]2OC=1C=C(C1=2)OC)C=2OC(=O)C2=C1CCC2=O WWSYXEZEXMQWHT-WNWIJWBNSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 241000228197 Aspergillus flavus Species 0.000 description 1
- 241000228230 Aspergillus parasiticus Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002589 Fe-O-Fe Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 206010017999 Gastrointestinal pain Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- 231100000678 Mycotoxin Toxicity 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 231100000439 acute liver injury Toxicity 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010369 molecular cloning Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 239000002636 mycotoxin Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 pi-pi interactions Natural products 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a magnetic nanoparticle and a preparation method and application thereof, wherein the magnetic nanoparticle comprises the following components: a core body, wherein the core body is composed of superparamagnetic ferroferric oxide; and a shell overlying a surface of the core body, the shell being comprised of a repeating unit of formula I. The magnetic nanoparticles have excellent chemical and thermal stability, strong magnetism, good dispersibility in water, large specific surface area, strong adsorption capacity, high adsorption speed and reusability.
Description
Technical Field
The invention relates to the field of chemistry, in particular to magnetic nanoparticles and a preparation method and application thereof.
Background
The magnetic solid phase micro-extraction technology has the advantages of convenient operation, low organic solvent cost, high enrichment factor, high extraction efficiency and the like, and is concerned in sample pretreatment. The adsorption material is the core of the magnetic solid phase micro-extraction technology. In order to improve the extraction efficiency and the recovery rate, a large number of novel nano materials are developed and utilized as adsorption materials for magnetic solid phase microextraction, such as metal organic frameworks, metal oxide materials, carbon-based nano materials, hydrophilic materials, polydopamine derivative materials, molecularly imprinted monomers, polymers and the like. However, the above materials have problems of long extraction time, low adsorption capacity, and the like. Covalent organic frameworks are a new class of ordered crystalline porous polymers. The crystal has low density, large specific surface area, regular porosity, adjustable aperture and good thermal stability.
Biotoxins pose a serious threat to human health, with aflatoxin being one of the important biotoxins, a naturally occurring group of mycotoxins produced by aspergillus flavus and aspergillus parasiticus under appropriate temperature and humidity conditions. They are considered to be highly toxic substances, easily contaminate food products such as cereals, dairy products and the like, enter the food chain by directly ingesting or eating contaminated animal-derived products, and easily migrate to and accumulate in the animal's fresh milk liver, kidney and muscle tissue. Resulting in severe health damage such as gastrointestinal pain, edema, acute liver injury, and even death.
Due to the low content of aflatoxin in the food matrix, the purification and extraction of the target compound is the key to trace detection. Therefore, magnetic materials for purifying and extracting aflatoxin are under study.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, one object of the invention is to provide a magnetic nanoparticle which has a large specific surface area and a porous ordered crystal structure, is strong in adsorption capacity and short in adsorption time, can be used for efficiently enriching biotoxins, especially aflatoxins, in a complex sample, and is beneficial to carrying out trace detection on the biotoxins in the complex food sample.
According to one aspect of the present invention, there is provided a magnetic nanoparticle. According to an embodiment of the present invention, the magnetic nanoparticle comprises: a core body, wherein the core body is composed of superparamagnetic ferroferric oxide; and a shell overlying a surface of the core body, the shell being comprised of a repeating unit of formula I.
The magnetic nanoparticles provided by the embodiment of the invention have excellent chemical and thermal stability, strong magnetism, good dispersibility in water, large specific surface area, strong adsorption capacity, high adsorption speed and reusability.
In addition, the magnetic nanoparticles according to the above embodiments of the present invention may also have the following additional technical features:
according to an embodiment of the invention, the housing is a porous mesh structure.
According to an embodiment of the invention, the shell has an average adsorbent pore size of 1-3nm, preferably 2.2-2.9nm, and a thickness of 20-40 nm.
According to an embodiment of the invention, the specific surface area of the housing is 50-160m2 g-1。
According to the embodiment of the invention, the magnetic strength of the magnetic nanoparticles is 40 emu/g.
According to the embodiment of the invention, the shell has crystal diffraction peaks at 2 theta of 30.4 degrees, 35.8 degrees, 43.4 degrees, 53.8 degrees, 57.3 degrees and 62.9 degrees in X-ray powder diffraction data.
According to the embodiment of the invention, the particle size of the inner core is 150-250 nm.
According to an embodiment of the present invention, the magnetic nanoparticles may be repeated more than 8 times.
According to another aspect of the present invention, the present invention provides a method for preparing the aforementioned magnetic nanoparticles. According to an embodiment of the invention, the method comprises: contacting superparamagnetic ferroferric oxide nanoparticles with p-phenylenediamine and carrying out first stirring to obtain a first mixture; and contacting the first mixture with 1,2,4, 5-tetrakis (4-formylphenyl) benzene and a catalyst and performing a second stirring to obtain the magnetic nanoparticles.
The preparation method provided by the embodiment of the invention has the advantages of mild synthesis conditions, simplicity in operation and high yield of the magnetic nanoparticles. In addition, the prepared magnetic nanoparticles have excellent chemical and thermal stability, large specific surface area, strong adsorption capacity and high adsorption speed.
According to the embodiment of the invention, the mass ratio of the superparamagnetic ferroferric oxide nanoparticles to the p-phenylenediamine is 1: (1-3), preferably, the mass ratio is: 1: 1.6.
according to the embodiment of the invention, the mass ratio of the p-phenylenediamine to the 1,2,4, 5-tetra (4-formylphenyl) benzene is 1: (1-3), preferably, the mass ratio is 1: 1.38.
according to an embodiment of the invention, the catalyst is acetic acid.
According to an embodiment of the invention, said first stirring is carried out in tetrahydrofuran.
According to an embodiment of the invention, the first stirring time is 20-40 minutes.
According to the embodiment of the invention, the time of the second stirring is 110-130 minutes.
According to an embodiment of the invention, the temperature of the first stirring and the second stirring are both 60-70 ℃, preferably 65 ℃; the rotation speed is 500-2000rpm, preferably 1000 rpm.
Further, according to yet another aspect of the present invention, there is provided a method of adsorbing a biotoxin. According to an embodiment of the present invention, the method is performed using the aforementioned magnetic nanoparticles. Therefore, the adsorption capacity to the biotoxin is strong, the speed is high, and the biotoxin in the sample can be extracted quickly and efficiently.
The method provided by the embodiment of the invention has strong adsorption capacity and high speed on the biotoxin, and is particularly suitable for adsorption and extraction of the biotoxin in a complex sample.
According to an embodiment of the invention, the biological toxin is aflatoxin.
According to an embodiment of the invention, the complex sample is a food product.
According to the embodiment of the invention, the adsorption capacity of the magnetic nanoparticles is 69.5-92.2 mg/g.
According to a further aspect of the invention, there is provided a kit. According to an embodiment of the present invention, the kit comprises the aforementioned magnetic nanoparticles. Therefore, the kit has strong adsorption capacity and high speed on the biotoxin, and is particularly suitable for adsorption and extraction of the biotoxin in complex samples.
Further, according to a further aspect of the invention, the invention provides the use of the aforementioned kit for adsorbing a biotoxin. Therefore, the kit has strong adsorption capacity and high speed on the biotoxin, and is particularly suitable for adsorption and extraction of the biotoxin in complex samples.
According to an embodiment of the invention, the biological toxin is aflatoxin.
The magnetic nanoparticles and the preparation method thereof according to the embodiment of the invention have at least one of the following advantages:
(1) the preparation method of the magnetic nanoparticles provided by the embodiment of the invention has mild reaction conditions, and the prepared magnetic covalent organic framework material has excellent chemical thermal stability, large specific surface area and good crystallization. In some embodiments, the mass loss of the shell material is less than 11.7% when the temperature reaches 500 ℃.
(2) The shell material of the magnetic nanoparticles provided by the embodiment of the invention can be prepared by reacting at 60-70 ℃ for 2-3 hours, and has mild reaction conditions and high reaction speed; the nanoparticles have a large specific surface area, in some embodiments up to 147.3m2Is superior to most of the existing magnetic nanoparticles in terms of the ratio of the magnetic nanoparticles to the magnetic nanoparticles.
(3) The magnetic nanoparticles provided by the embodiment of the invention are used for carrying out magnetic solid-phase microextraction on aflatoxin in a complex sample, the adsorption capacity is strong, the adsorption time is short, in some embodiments of the invention, the adsorption capacity reaches 69.5-92.2mg/g, and 50 microgram/mL aflatoxin can reach adsorption balance only in 30 minutes.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a schematic scanning electron microscope and a schematic transmission electron microscope of ferroferric oxide and magnetic nanoparticles according to an embodiment of the invention;
FIG. 2 shows XRD diffraction patterns of ferroferric oxide and magnetic nanoparticles according to one embodiment of the invention;
FIG. 3 shows an infrared spectrum (A) of ferroferric oxide and magnetic nanoparticles, and an infrared spectrum (B) of chemical stability analysis of the magnetic nanoparticles according to an embodiment of the present invention;
FIG. 4 shows a schematic diagram of the analysis of the specific surface area and pore size of magnetic nanoparticles according to one embodiment of the invention;
FIG. 5 shows a schematic diagram of the results of thermogravimetric analysis of magnetic nanoparticles according to one embodiment of the present invention;
FIG. 6 shows the result of magnetic measurements of ferroferric oxide and magnetic nanoparticles according to an embodiment of the present invention;
fig. 7 shows an adsorption equilibrium diagram of magnetic nanoparticles according to one embodiment of the invention;
fig. 8 shows a reusable diagram of magnetic nanoparticles according to one embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
It should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Further, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
According to one aspect of the present invention, there is provided a magnetic nanoparticle.
The magnetic nanoparticles provided by the embodiment of the invention have excellent chemical and thermal stability, strong magnetism, good dispersibility in water, large specific surface area, strong adsorption capacity, high adsorption speed and reusability.
The magnetic nanoparticles of the embodiments of the present invention have large specific surface areas, in some embodiments up to 147.3m2Is superior to most of the existing magnetic nanoparticles in terms of the ratio of the magnetic nanoparticles to the magnetic nanoparticles.
According to the embodiment of the invention, the magnetic nanoparticles provided by the embodiment of the invention are used for carrying out magnetic solid-phase microextraction on aflatoxin in a complex sample, so that the adsorption capacity is strong, the adsorption time is short, in some embodiments of the invention, the adsorption capacity reaches 69.5-92.2mg/g, 50 mu g/mL of aflatoxin can reach adsorption balance in only 30 minutes, and the enrichment capacity on trace biotoxins (such as aflatoxin) in a complex matrix, such as a food matrix, is strong.
The magnetic nanoparticles of the embodiment of the invention can be used as a magnetic solid phase extraction adsorbent to be applied to the efficient and green enrichment of aflatoxin in a complex sample, greatly simplifies the synthesis steps of the existing magnetic covalent organic framework nanoparticles, and has mild preparation conditions and high reaction speed.
To facilitate understanding of the magnetic nanoparticles of the embodiments of the present invention, the magnetic nanoparticles are explained herein, and according to the embodiments of the present invention, the magnetic nanoparticles include: a core body and a shell. According to the embodiment of the invention, the core body is composed of superparamagnetic ferroferric oxide; according to an embodiment of the invention, the shell overlies the surface of the core body, the shell being formed from a repeating unit of formula I.
According to an embodiment of the invention, the housing is a porous mesh structure. Therefore, the crystal form is large in specific surface area, strong in adsorption capacity, stable in crystal form, rich in adsorption functional groups and good in dispersibility in water.
According to an embodiment of the invention, the shell has an average adsorbent pore size of 1-3nm, preferably 2.2-2.9nm, and a thickness of 20-40 nm. Therefore, the adsorption effect on biological toxins such as aflatoxin and the like is good, wherein the adsorption pore diameter is larger than the molecular diameter of the target object when being 2.2-2.9nm, a space embedding effect can be formed between the adsorption pore diameter and the target object, and the adsorption effect is better.
According to an embodiment of the invention, the specific surface area of the housing is 50-160m2 g-1. This results in a large specific surface area and a high adsorption capacity.
According to an embodiment of the invention, the shell is in X-ray powder diffraction data, Fe3O4And Fe3O4Crystal diffraction peaks were present at @ COF (PPD-TFPB) at 2 θ at 30.4 °, 35.8 °, 43.4 °, 53.8 °, 57.3 ° and 62.9 °. The results show that the synthesized Fe3O4@ COF (PPD-TFPB) retains Fe3O4Characteristic crystal peak of (1). The above crystal diffraction peak and Fe having spinel structure3O4Match, and thus demonstrate Fe3O4The successful synthesis of @ COF (PPD-TFPB) and the maintenance of the original crystal structure.
According to the embodiment of the invention, the particle size of the inner core is 150-250 nm. Therefore, the magnetic nanoparticles have large specific surface area and strong adsorption capacity.
According to the embodiment of the invention, the magnetic strength of the magnetic nanoparticles is 40 emu/g. Under the condition, the magnetic nanoparticles can generate strong reaction to an external magnetic field, and provide a foundation for the rapid magnetic solid-phase extraction. Therefore, the rapid separation of the magnetic nanoparticles and the sample matrix is realized, the operation time is shortened, and meanwhile, the magnetic nanoparticles have shorter analyte diffusion distance in the sample solution, so that the adsorption efficiency can be improved.
According to the embodiment of the invention, the magnetic nanoparticles can be reused for more than 8 times. Therefore, the magnetic nanoparticles can be repeatedly utilized for many times, and the cost is reduced.
According to another aspect of the present invention, the present invention provides a method for preparing the aforementioned magnetic nanoparticles. According to the preparation method provided by the embodiment of the invention, ferroferric oxide, 1,2,4, 5-tetra (4-formylphenyl) benzene and p-phenylenediamine are subjected to template-mediated precipitation polymerization reaction to obtain the magnetic nanoparticles, the synthesis conditions are mild, the operation is simple, the yield of the magnetic nanoparticles is high, almost no other byproducts are generated, the method belongs to atom economy reaction, and the prepared magnetic nanoparticles have excellent chemical and thermal stability, large specific surface area, strong adsorption capacity and high adsorption speed.
In order to facilitate understanding of the method for preparing the aforementioned magnetic nanoparticles, the method is explained according to an embodiment of the present invention, and includes:
s100 first stirring
According to the embodiment of the invention, superparamagnetic ferroferric oxide nanoparticles are contacted with p-phenylenediamine and subjected to first stirring to obtain a first mixture. Thus, p-phenylenediamine is preferentially anchored to ferroferric oxide to obtain p-phenylenediamine (PPD) -functionalized magnetic nanoparticles (Fe)3O4@PPD)。
S200 second stirring
According to an embodiment of the present invention, the first mixture is contacted with 1,2,4, 5-tetrakis (4-formylphenyl) benzene and a catalyst and subjected to second stirring, so as to obtain the magnetic nanoparticles. Thereby utilizing Fe3O4@ PPD as bridge, p-phenylenediamine (PPD) and 1,2,4, 5-tetra (4-formylphenyl) benzene (TFPB) as functional monomers, and Fe through Schiff base reaction3O4The surface obtains covalent organic framework material with larger specific surface area and ordered porous structure.
According to the embodiment of the invention, the mass ratio of the superparamagnetic ferroferric oxide nanoparticles to the p-phenylenediamine is 1: (1-3), preferably, the mass ratio is: 1: 1.6. therefore, p-phenylenediamine can be better coated on the surface of carboxyl functionalized ferroferric oxide under the proportion, and a bridge for preparing the magnetic covalent organic framework material is formed.
According to the embodiment of the invention, the mass ratio of the p-phenylenediamine to the 1,2,4, 5-tetra (4-formylphenyl) benzene is 1: (1-3), preferably, the mass ratio is 1: 1.38. the covalent organic framework material formed under the proportion has a better core-shell structure and relatively higher yield.
According to an embodiment of the invention, the catalyst is acetic acid. Therefore, the catalytic effect is good, and the reaction rate is high.
According to an embodiment of the invention, said first stirring is carried out in tetrahydrofuran. Tetrahydrofuran is used as a reaction solvent, and carboxyl functionalized ferroferric oxide and two monomers have good dispersion phases in the tetrahydrofuran, so that the full contact of a reaction system is ensured, and a good reaction effect can be obtained.
According to an embodiment of the invention, the first stirring time is 20-40 minutes. According to the embodiment of the invention, the time of the second stirring is 110-130 minutes. Therefore, the method is favorable for the full reaction and has high product yield.
According to an embodiment of the invention, the temperature of the first stirring and the second stirring are both 60-70 ℃, preferably 65 ℃; the rotation speed is 500-2000rpm, preferably 1000 rpm. Thus, the reaction conditions are mild, and the COF can be successfully coated on Fe rapidly3O4A surface.
In particular, according to an embodiment of the invention, the shell material is Fe3O4The synthesis method of @ COF (PPD-TFPB) comprises the following steps: in a 50mL two-necked round bottom flask, 100mg of Fe3O4And 116mg of PPD were added to 22mL of THF and sonicated for 20 minutes. Secondly, the mixture is mechanically stirred at 60-70 ℃ for 20-40 minutes, so that part of the PPD is first anchored uniformly to Fe by hydrogen bonds3O4A surface. Then, 60mg of TFPB is uniformly dispersed into 8mL of THF, and is dropwise added into the reaction system with 1mL of acetic acid under stirring, after the dropwise addition is finished, the reaction is carried out for 2-3 hours, and the imine covalent organic framework-coated magnetic Fe is obtained3O4。
Further, according to yet another aspect of the present invention, there is provided a method of adsorbing a biotoxin. According to an embodiment of the present invention, the method is performed using the aforementioned magnetic nanoparticles. Therefore, the adsorption capacity to the biotoxin is strong, the speed is high, and the biotoxin in the sample can be extracted quickly and efficiently.
The method provided by the embodiment of the invention has strong adsorption capacity and high speed on the biotoxin, and is particularly suitable for adsorption and extraction of the biotoxin in a complex sample.
According to an embodiment of the invention, the biological toxin is aflatoxin. According to an embodiment of the invention, the complex sample is a food product. Therefore, the magnetic nanoparticles are particularly suitable for adsorption and extraction of aflatoxin in complex matrixes such as food and the like.
According to the embodiment of the invention, the adsorption capacity of the magnetic nanoparticles is 69.5-92.2 mg/g. Therefore, the magnetic nanoparticles have strong adsorption capacity to biotoxins, and are particularly suitable for adsorption and extraction of biotoxins in complex samples.
According to a further aspect of the invention, there is provided a kit. According to an embodiment of the present invention, the kit comprises the aforementioned magnetic nanoparticles. Therefore, the kit has strong adsorption capacity and high speed on the biotoxin, and is particularly suitable for adsorption and extraction of the biotoxin in complex samples.
Further, according to a further aspect of the invention, the invention provides the use of the aforementioned kit for adsorbing a biotoxin. Therefore, the kit has strong adsorption capacity and high speed on the biotoxin, and is particularly suitable for adsorption and extraction of the biotoxin in complex samples.
According to an embodiment of the invention, the biological toxin is aflatoxin.
The present invention is described below with reference to specific examples, which are intended to be illustrative only and are not to be construed as limiting the invention.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are carried out according to techniques or conditions described in literature in the art (for example, refer to molecular cloning, a laboratory Manual, third edition, scientific Press, written by J. SammBruke et al, Huang Petang et al) or according to product instructions. The reagents or apparatus used are not indicated by the manufacturer, but are conventional products available commercially, for example from Illumina.
Example 1
According to the method provided by the embodiment of the invention, ferroferric oxide is used as a magnetic core, p-phenylenediamine (PPD) and 1,2,4, 5-tetra (4-formylphenyl) benzene (TFPB) are used as functional monomers to synthesize the magnetic covalent organic framework nanoparticles, and the preparation process comprises the following steps:
(a) in a 50mL two-necked round bottom flask, 100mg ferroferric oxide and 116mg p-phenylenediamine were added to 22mL tetrahydrofuran and sonicated for 20 minutes.
(b) And mechanically stirring the mixture for 20-40 minutes at 60-70 ℃ to ensure that part of p-phenylenediamine is firstly anchored on the surface of ferroferric oxide through hydrogen bonds to form a bridge action.
(c) Uniformly dispersing 160mg of 1,2,4, 5-tetra (4-formylphenyl) benzene (TFPB) into 8mL of tetrahydrofuran, dropwise adding the mixture and 1mL of acetic acid into the reaction system under stirring, and after dropwise addition, reacting for 2-3 hours to obtain magnetic nanoparticles, wherein the nanoparticles are imine covalent organic framework coated magnetic Fe3O4(Fe3O4@COF(PPD-TFPB))。
Example 2
Magnetic covalent organic framework nanomaterial (Fe) prepared for example 13O4@ COF (PPD-TFPB)) detailed characterization experiments were performed to demonstrate the successful preparation and superior physicochemical properties of the magnetic nanoparticles. The method comprises the following specific steps:
1. for ferroferric oxide (Fe)3O4) And carrying out analysis on the magnetic covalent organic framework nano material by a scanning electron microscope and a transmission electron microscope. The results are shown in FIG. 1, from Fe3O4(FIG. 1(A)) and Fe3O4SEM image of @ COF (PPD-TFPB) (FIG. 1(B)) shows Fe of example 13O4And Fe3O4@ COF (PPD-TFPB) has a regular octahedral morphology and good dispersibility. Compared with Fe3O4，Fe3O4The surface morphology of the @ COF (PPD-TFPB) is obviously changed, which indicates that the COF shell is successfully wrapped in Fe3O4A surface. Fe3O4(C) And Fe3O4TEM images of @ COF (PPD-TFPB) further demonstrate successful encapsulation of the COF shell in Fe3O4Surface, and a shell thickness of about 20-40nm (FIG. 1 (D)).
2. Fe by powder XRD diffraction experiment3O4And Fe3O4The crystal structure of @ COF (PPD-TFPB) was analyzed, and the results are shown in FIG. 2. As can be seen from FIG. 2, Fe3O4And Fe3O4The XRD patterns of the @ COF (PPD-TFPB) nanoparticles all have diffraction peaks at 2 theta of 30.4 degrees, 35.8 degrees, 43.4 degrees, 53.8 degrees, 57.3 degrees and 62.9 degrees, which is in contrast to Fe with spinel structure3O4Match, and thus demonstrate Fe3O4Successful synthesis of and Fe3O4The original crystal structure is still kept after COF coating.
3. Fourier transform infrared spectroscopy is adopted for Fe3O4And magnetic nanomaterial Fe3O4The surface functionality and chemical stability of @ COF (PPD-TFPB) were analyzed. From Fe3O4And Fe3O4As can be clearly seen on the infrared spectrum (FIG. 3A) of @ COF (PPD-TFPB), the two magnetic nanoparticles were at 588cm–1All the parts have characteristic absorption peaks which are the vibration absorption peaks of Fe-O-Fe; and Fe3O4In the infrared spectrum of @ COF (PPD-TFPB), at 1700cm-1The absorption peak appearing there can be attributed to C ═ N shock absorption, indicating Fe3O4The surface presents a COF (PPD-TFPB) shell. To further study Fe3O4Chemical stability of @ COF (PPD-TFPB), this example Fe prepared in example 13O4Separately soaking the @ COF (PPD-TFPB) nanoparticles in H2O, ACN, HCl (1mol/L) and NaOH (1mol/L) for 24 hours, and then the changes in the surface functional groups were observed using infrared spectroscopy. As shown in FIG. 3(B), through H2Fe treated with O, ACN, HCl (1mol/L) and NaOH (1mol/L)3O4@COF(PPD-TFPB) infrared spectrogram has no obvious change, which shows that the prepared Fe3O4And the @ COF (PPD-TFPB) has better chemical stability.
4. By using N2Adsorption desorption isothermal line pair Fe3O4And magnetic nanomaterial Fe3O4Specific surface area and porosity of @ COF (PPD-TFPB) were analyzed, and the results are shown in FIG. 4(A), Fe3O4N of @ COF (PPD-TFPB)2Adsorption and desorption isotherms indicating Fe3O4@ COF (PPD-TFPB) presents a mesoporous structure. By aperture analyzer for Fe3O4The pore size on @ COF (PPD-TFPB) was analyzed and the results indicated Fe3O4The average pore diameter of @ COF (PPD-TFPB) was about 2.7nm (FIG. 4 (B)). The specific surface areas of Fe3O4 and Fe3O4@ COF (PPD-TFPB) were measured to be 6.5m, respectively, by a BET specific surface area analyzer2G and 147.3m2/g。Fe3O4The specific surface area of @ COF (PPD-TFPB) is significantly higher than that of Fe3O4It is further demonstrated that the COF (PPD-TFPB) shell is in Fe3O4The successful synthesis of Fe also shows3O4And the @ COF (PPD-TFPB) has better adsorption performance.
5. Adopting thermogravimetric analyzer to prepare magnetic nano material Fe3O4The thermal stability of @ COF (PPD-TFPB) was analyzed. As can be seen from FIG. 5, Fe is present at 25-750 deg.C3O4The weight loss of the @ COF (PPD-TFPB) magnetic nanoparticles was 11.7% and 25%, respectively. Furthermore, before 500 ℃, Fe3O4The weight loss of @ COF (PPD-TFPB) was only 11.7%, which was attributable to the loss of moisture contained in the COF (PPD-TFPB) shell, indicating that Fe was produced3O4@ COF (PPD-TFPB) has better thermal stability.
6. Magnetic Strength (VSM) analysis on Fe by vibration sample3O4And magnetic nanomaterial Fe3O4The magnetic properties of @ COF (PPD-TFPB) were analyzed. The results are shown in FIG. 6, Fe3O4And Fe3O4The hysteresis curve of @ COF (PPD-TFPB) shows that both materials exhibit superparamagnetism without hysteresis. COF (PP)Encapsulation of D-TFPB) results in Fe3O4The saturation magnetization of the alloy is obviously reduced, but can still reach 40emu/g, which is enough to satisfy Fe3O4The requirement for separation of @ COF (PPD-TFPB) from the sample matrix solution. As can be seen from the inset in FIG. 5, Fe was produced3O4@ COF (PPD-TFPB) can be well dispersed in the sample solution when Fe is attracted by magnet3O4At @ COF (PPD-TFPB), Fe can be achieved within 30 seconds3O4Complete separation of @ COF (PPD-TFPB) from the sample matrix solution.
Example 3
Magnetic covalent organic framework nanomaterial (Fe) prepared using example 13O4@ COF (PPD-TFPB)) investigated its feasibility for adsorption of Aflatoxins (AFs) in complex samples, as follows:
fe is researched by adsorption static adsorption and dynamic adsorption experiments3O4Adsorption Performance of @ COF (PPD-TFPB) on 4 AFs. Briefly, 2mL of standard solutions of each target at concentrations of 5mg/L, 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L and 60mg/L were prepared, and 1.0mg of Fe was added to each of the standard solutions3O4@ COF (PPD-TFPB) adsorption with shaking for 120 min. Fe was calculated by the following formula (1)3O4Maximum adsorption capacity of @ COF (PPD-TFPB) for 4 AFs.
Wherein Q is the maximum adsorption capacity (mg/g), C0Initial concentration (. mu.g/mL) of the adsorption solution, Cs target concentration (. mu.g/mL) at which adsorption equilibrium is reached, and m is Fe3O4Mass (mg) of @ COF (PPD-TFPB), v is volume of adsorption solution (mL).
For adsorption kinetics experiments, 1mg of Fe was added3O4@ COF (PPD-TFPB) was added to 2mL of a mixed solution of 4 AFs (50. mu.g/mL) and adsorbed with shaking for various times (2min, 5min, 10min, 20min, 30min, 60min, 90min and 120 min). The experimental result still calculates Fe through the formula (1)3O4@COF(PPD-TFPB) maximum adsorption capacity for 4 AFs.
At different initial concentrations, Fe was studied by static equilibrium experiments3O4The adsorption capacity of @ COF (PPD-TFPB) as adsorbent for 4 AFs. Since 4 AFs have low solubility in aqueous solutions, the concentration of each target in the standard solution should be within the solubility range. At different adsorption times, Fe3O4The adsorption curves of @ COF (PPD-TFPB) for 4 AFs are shown in FIG. 7(A), and it can be seen from FIG. 7(A) that Fe3O4Adsorption of the 4 AFs by @ COF (PPD-TFPB) is a fast adsorption process and reaches adsorption equilibrium in 30 minutes. This can be attributed to the large specific surface area (147.3 m) of the magnetic COF2(g) — NH), various adsorptive functional groups (C ═ N, -NH)2) And abundant adsorption sites. These adsorptive groups can form various interactions with 4 AFs such as pi-pi interactions, hydrogen bonds, hydrophobic interactions, and the like. Thus, Fe prepared in example 13O4The adsorption of the @ COF (PPD-TFPB) nanoparticle to 4 AFs shows a rapid kinetic process, which indicates that Fe3O4And the @ COF (PPD-TFPB) has better adsorption performance on 4 AFs.
Example 4
The Fe prepared in example 1 was further investigated by Langmuir and Freundlich isotherm models on the basis of example 33O4The adsorption mechanism of the @ COF (PPD-TFPB) nanoparticle on 4 AFs. The Langmuir isotherm is based on the assumption that the target is covered by a single layer on the outer surface of the adsorbent. The linear form expression of the Langmuir isotherm is:
another characteristic parameter of a Langmuir isotherm is the dimensionless factor R related to the shape of the isothermL(separation factor). 0<RL<1 denotes that adsorption is advantageous, RL>1 indicates that adsorption is unfavorable, R L0 represents irreversible adsorption. RLThe calculation formula of (2) is as follows:
wherein Ce (μ g/mL) is the equilibrium concentration, Qe (mg/g) is the equilibrium adsorption amount, Qs (mg/g) is the theoretical saturation adsorption amount, Kl(L/mg) is the Langmuir constant. C0(μ g/mL) is the highest concentration of the target.
The Freundlich isotherm is based on multi-layer adsorption of heterogeneous surfaces. The linear form of the Freundlich equation is:
wherein, KFAnd n is Freundlich constant and Fe, respectively3O4The affinity constant for the adsorption of 4 AFs is @ COF (PPD-TFPB).
According to equation (3), AFB1,AFB2,AFG1,AFG2R of (A) to (B)LThe values were calculated as 0.8492,0.7794,0.5165,0.6551, respectively, indicating Fe in the high concentration range3O4The adsorption of the @ COF (PPD-TFPB) on 4 AFs is advantageous. Freundlich isotherms have better linear fit linear coefficients (R)2) Are all superior to the linear coefficient of Langmuir isotherms. According to equation (4), AFB1,AFB2,AFG1,AFG2The values of n of (a) are calculated as 1.051,1.077,1.264 and 1.192, respectively. The values of n are all greater than 1, indicating that 4 AFs are readily prepared Fe in the low concentration range3O4@ COF (PPD-TFPB) adsorption.
Example 5
Magnetic covalent organic framework nanoparticles (Fe) prepared for example 13O4@ COF (PPD-TFPB)) repeated use studies were performed as follows:
dispersing 2mg of magnetic nanoparticles in 5mL of aqueous solution of a target substance, oscillating for adsorption, discarding supernatant, eluting the target substance adsorbed on the magnetic nanoparticles with acetonitrile, blowing nitrogen, redissolving, passing through a membrane, and detecting by a computer. Washing the magnetic nanoparticles with acetonitrile for multiple times until the magnetic nanoparticles are washed clean; the above experimental procedure was repeated 7 times.
The use times are plotted as abscissa and the recovery rate is plotted as ordinate, and the result is shown in fig. 8, and the recovery rate does not change much after 8 times of repeated use, which indicates that the magnetic nanoparticles can be repeatedly used at least 8 times.
The above results indicate that Fe3O4@ COF (PPD-TFPB) exhibits a similar adsorption process for 4 AFs. Fe3O4The adsorption of @ COF (PPD-TFPB) to 4 AFs is more consistent with the Freundlich isotherm model. This phenomenon may be explained as: fe3O4And multilayer adsorption caused by hydrophobic interaction, hydrogen bonding, pi-pi stacking force and the like of @ COF (PPD-TFPB) and a target. The results show that the magnetic nanoparticles of the embodiment of the invention can be used as high-efficiency adsorption materials of 4 AFs in a complex sample.
In conclusion, the magnetic nanoparticles of the embodiments of the present invention have excellent chemical and thermal stability, strong magnetism, good dispersibility in water, large specific surface area, strong adsorption capacity, fast adsorption speed, and reusability.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A magnetic nanoparticle, comprising:
a core body, wherein the core body is composed of superparamagnetic ferroferric oxide;
a shell overlying the surface of the core, the shell being comprised of repeating units of formula I.
2. The magnetic nanoparticle according to claim 1, wherein the shell is a porous network structure,
optionally, the shell has an average adsorbent pore size of 1-3nm, preferably 2.2-2.9nm, a thickness of 20-40nm,
optionally, the specific surface area of the shell is 50-160m2g-1，
Optionally, the magnetic strength of the magnetic nanoparticle is 40 emu/g.
3. The magnetic nanoparticle according to claim 1, wherein the shell has crystalline diffraction peaks at 2 θ at 30.4 °, 35.8 °, 43.4 °, 53.8 °, 57.3 ° and 62.9 ° in X-ray powder diffraction data.
4. The magnetic nanoparticle according to claim 1, wherein the particle size of the inner core is 150-250nm,
optionally, the magnetic nanoparticles can be reused more than 8 times.
5. A method of preparing a magnetic nanoparticle according to any one of claims 1 to 4, comprising:
contacting superparamagnetic ferroferric oxide nanoparticles with p-phenylenediamine and carrying out first stirring to obtain a first mixture; and
contacting the first mixture with 1,2,4, 5-tetrakis (4-formylphenyl) benzene and a catalyst and performing a second stirring to obtain the magnetic nanoparticles.
6. The method according to claim 5, wherein the mass ratio of the superparamagnetic ferroferric oxide nanoparticles to the p-phenylenediamine is 1: (1-3), preferably, the mass ratio is: 1: 1.6,
optionally, the mass ratio of the p-phenylenediamine to the 1,2,4, 5-tetrakis (4-formylphenyl) benzene is 1: (1-3), preferably, the mass ratio is 1: 1.38.
7. the process of claim 5, wherein the catalyst is acetic acid,
optionally, the first stirring is carried out in tetrahydrofuran,
optionally, the first stirring time is 20 to 40 minutes,
optionally, the time of the second stirring is 110-130 minutes,
optionally, the temperature of the first stirring and the second stirring are both 60-70 ℃, preferably 65 ℃; the rotation speed is 500-2000rpm, preferably 1000 rpm.
8. A method for adsorbing biotoxin, wherein the method is carried out by using the magnetic nanoparticles as claimed in any one of claims 1 to 4, and preferably, the biotoxin is aflatoxin;
optionally, the magnetic nanoparticles have an adsorption capacity of 69.5-92.2 mg/g.
9. A kit comprising the magnetic nanoparticle of any one of claims 1-4.
10. Use of the kit according to claim 9 for adsorbing a biotoxin, preferably wherein the biotoxin is aflatoxin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111657351.6A CN114405476B (en) | 2021-12-30 | 2021-12-30 | Magnetic nanoparticle, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111657351.6A CN114405476B (en) | 2021-12-30 | 2021-12-30 | Magnetic nanoparticle, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114405476A true CN114405476A (en) | 2022-04-29 |
| CN114405476B CN114405476B (en) | 2024-03-12 |
Family
ID=81269153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111657351.6A Active CN114405476B (en) | 2021-12-30 | 2021-12-30 | Magnetic nanoparticle, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114405476B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532243A (en) * | 2022-10-25 | 2022-12-30 | 中国检验检疫科学研究院 | Magnetic nanoparticles and preparation method and application thereof |
| CN116272880A (en) * | 2023-03-01 | 2023-06-23 | 中国检验检疫科学研究院 | Ureido functional group modified magnetic nanoparticle as well as preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170130349A1 (en) * | 2015-11-10 | 2017-05-11 | Indian Educational and Research Institute | Covalent organic frameworks as porous supports for non-noble metal based water splitting electrocatalysts |
| CN110314669A (en) * | 2019-07-08 | 2019-10-11 | 浙江省农业科学院 | A kind of magnetic COF-TbPa and its preparation method and application for being enriched with triazole pesticide |
| CN110586052A (en) * | 2019-09-25 | 2019-12-20 | 南开大学 | Preparation and application of magnetic composite porous network adsorption material |
| CN111450803A (en) * | 2020-03-16 | 2020-07-28 | 哈尔滨工业大学 | Preparation method and application of magnetic covalent organic framework compound for adsorbing triphenylmethane dyes |
| CN111715197A (en) * | 2020-07-03 | 2020-09-29 | 中国检验检疫科学研究院 | Urea functional group modified magnetic nanoparticle and preparation method thereof |
| US20200316562A1 (en) * | 2017-12-18 | 2020-10-08 | Nanjing University | Magnetic polymer adsorption material, preparation method therefor and application thereof |
| CN113274981A (en) * | 2021-05-24 | 2021-08-20 | 中国检验检疫科学研究院 | Magnetic nanoparticles and preparation method thereof |
-
2021
- 2021-12-30 CN CN202111657351.6A patent/CN114405476B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170130349A1 (en) * | 2015-11-10 | 2017-05-11 | Indian Educational and Research Institute | Covalent organic frameworks as porous supports for non-noble metal based water splitting electrocatalysts |
| US20200316562A1 (en) * | 2017-12-18 | 2020-10-08 | Nanjing University | Magnetic polymer adsorption material, preparation method therefor and application thereof |
| CN110314669A (en) * | 2019-07-08 | 2019-10-11 | 浙江省农业科学院 | A kind of magnetic COF-TbPa and its preparation method and application for being enriched with triazole pesticide |
| CN110586052A (en) * | 2019-09-25 | 2019-12-20 | 南开大学 | Preparation and application of magnetic composite porous network adsorption material |
| CN111450803A (en) * | 2020-03-16 | 2020-07-28 | 哈尔滨工业大学 | Preparation method and application of magnetic covalent organic framework compound for adsorbing triphenylmethane dyes |
| CN111715197A (en) * | 2020-07-03 | 2020-09-29 | 中国检验检疫科学研究院 | Urea functional group modified magnetic nanoparticle and preparation method thereof |
| CN113274981A (en) * | 2021-05-24 | 2021-08-20 | 中国检验检疫科学研究院 | Magnetic nanoparticles and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 安连财;韩久放;章应辉;卜显和;: "多孔有机聚合物吸附分离水体系中有机污染物研究和应用进展", 应用化学, no. 09, pages 52 - 58 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532243A (en) * | 2022-10-25 | 2022-12-30 | 中国检验检疫科学研究院 | Magnetic nanoparticles and preparation method and application thereof |
| CN116272880A (en) * | 2023-03-01 | 2023-06-23 | 中国检验检疫科学研究院 | Ureido functional group modified magnetic nanoparticle as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114405476B (en) | 2024-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113274981B (en) | Magnetic nanoparticle and preparation method thereof | |
| Arica et al. | Magnetic MCM-41 silica particles grafted with poly (glycidylmethacrylate) brush: modification and application for removal of direct dyes | |
| CN114405476B (en) | Magnetic nanoparticle, and preparation method and application thereof | |
| Vojoudi et al. | A new nano-sorbent for fast and efficient removal of heavy metals from aqueous solutions based on modification of magnetic mesoporous silica nanospheres | |
| Jian et al. | Click chemistry: a new facile and efficient strategy for the preparation of Fe 3 O 4 nanoparticles covalently functionalized with IDA-Cu and their application in the depletion of abundant protein in blood samples | |
| Aghayi‐Anaraki et al. | Fe3O4@ MOF magnetic nanocomposites: Synthesis and applications | |
| Mahdavi et al. | Fabrication and characterization of SiO 2/(3-aminopropyl) triethoxysilane-coated magnetite nanoparticles for lead (II) removal from aqueous solution | |
| Song et al. | Removal and recovery of mercury from aqueous solution using magnetic silica nanocomposites | |
| Gao et al. | Preparation and characterization of uniformly sized molecularly imprinted polymers functionalized with core–shell magnetic nanoparticles for the recognition and enrichment of protein | |
| Lu et al. | Synthesis and adsorption properties investigation of Fe3O4@ ZnAl-LDH@ MIL-53 (Al) for azole fungicides removal from environmental water | |
| Yang et al. | pH-Responsive magnetic metal–organic framework nanocomposites for selective capture and release of glycoproteins | |
| Jiang et al. | Facile synthesis of magnetic hybrid Fe3O4/MIL-101 via heterogeneous coprecipitation assembly for efficient adsorption of anionic dyes | |
| Gong et al. | Effective adsorption of phenolic pollutants from water using β-cyclodextrin polymer functionalized Fe 3 O 4 magnetic nanoparticles | |
| CN108273471B (en) | Carbon nanotube metal organic framework magnetic composite material and preparation method thereof | |
| Yao et al. | Janus-like boronate affinity magnetic molecularly imprinted nanobottles for specific adsorption and fast separation of luteolin | |
| CN106853363B (en) | A kind of cyclodextrin supermolecule polymer/Fe3O4Magnetic nano-particle complex | |
| Wei et al. | Ionic liquid modified magnetic microspheres for isolation of heme protein with high binding capacity | |
| Liang et al. | Metal affinity-carboxymethyl cellulose functionalized magnetic graphene composite for highly selective isolation of histidine-rich proteins | |
| Hu et al. | Magnetic nanoparticle sorbents | |
| Banaei et al. | Synthesis and characterization of new modified silica coated magnetite nanoparticles with bisaldehyde as selective adsorbents of Ag (I) from aqueous samples | |
| Shafizadeh et al. | Preparation of a novel magnetic Pd (II) ion-imprinted polymer for the fast and selective adsorption of palladium ions from aqueous solutions | |
| Setoodehkhah et al. | Water soluble schiff base functinalized Fe 3 O 4 magnetic nano-particles as a novel adsorbent for the removal of Pb (II) and Cu (II) metal ions from aqueous solutions | |
| Icten et al. | Magnetite doped metal–organic framework nanocomposites: an efficient adsorbent for removal of bisphenol-A pollutant | |
| Beyki et al. | Melamine-based dendronized magnetic polymer in the adsorption of Pb (ΙΙ) and preconcentration of rhodamine B | |
| CN113976082B (en) | Magnetic nanoparticle as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |