CN112439394B - Novel magnetic nano functional material and application thereof - Google Patents

Novel magnetic nano functional material and application thereof Download PDF

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CN112439394B
CN112439394B CN202011279148.5A CN202011279148A CN112439394B CN 112439394 B CN112439394 B CN 112439394B CN 202011279148 A CN202011279148 A CN 202011279148A CN 112439394 B CN112439394 B CN 112439394B
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functional material
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blood
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CN112439394A (en
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邹伟
向佳
游兰
陈立义
郑汶江
刘波
颜杰
李慧
李颜利
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Sichuan University of Science and Engineering
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Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Sichuan University of Science and Engineering
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Abstract

The invention discloses a novel magnetic nano functional material and application thereof, wherein the novel magnetic nano functional material is used for removing fluorocarbon surfactant in human blood, superparamagnetic magnetic nano particles are selected as a substrate material, an inert protective layer is coated on the surface of the substrate material, and then a fluorine carbon bond and a polyethylene glycol bond are modified on the inert protective layer to prepare the magnetic nano functional material. The invention adopts the ferromagnetic magnetic nano-particles as the substrate material, the substrate material can be quickly separated from the solution by a very simple mode, in addition, the magnetic nano-particles have better biocompatibility, and the modified perfluoropolyether chain is non-toxic and degradable, and the functional nano-material can efficiently, safely and quickly remove the fluorocarbon surfactant in the blood of a human body.

Description

Novel magnetic nano functional material and application thereof
Technical Field
The invention relates to the technical field of nano materials, in particular to a novel magnetic nano functional material and application thereof, which can be used for removing fluorocarbon surfactant in human blood.
Background
Fluorocarbon surfactants such as perfluorooctanoic acid (PFOA), perfluorooctylsulfonic acid (PFOS), perfluoro-2-propoxypropionic acid ammonium (GenX), etc. are used in large amounts in chemical production due to their excellent properties, but a large number of studies have shown that perfluoroalkyl substances present a great potential safety hazard to organisms. Because the fluorocarbon surfactant has extremely low surface energy and fluorocarbon bonds are extremely stable, the traditional degradation modes such as adsorption, photocatalysis, catalytic oxidation and the like are not ideal for the treatment effect of the fluorocarbon surfactant, and some degradation modes even have no selectivity. The fluorocarbon surfactant has bioaccumulation and persistence, and a large number of related documents report that the presence of the fluorocarbon surfactant in human blood has been detected, but at present, no good countermeasure is provided for how to treat the fluorocarbon surfactant in the blood. Although harmful small molecules in blood can be separated out of the body through the membrane technology, the membrane technology has no selectivity for the fluorocarbon surfactant and cannot effectively remove the fluorocarbon surfactant in the blood. From the data presented by the 3M company, the blood concentration of workers in long-term contact with PFOA can reach 5.2ppm, with the concentration of fluorocarbon surfactant in the blood of ordinary US persons being about 4 ppb. PFOA, PFOS, GenX can induce various diseases such as cancer, liver disease, reproductive disease, etc. For human body, the fluorocarbon surfactant is difficult to metabolize outside the body, the half-life period of PFOA is 3-4 years, and the half-life period of PFOS is about 5 years, so that the fluorocarbon surfactant has great health risks for human body. At present, no relevant literature report and a reasonable solution are available for a method for degrading the fluorocarbon surfactant in the human blood, so that the design of a material capable of removing the fluorocarbon surfactant in the human blood has very important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a magnetic nano functional material for removing fluorocarbon surfactant in human blood and application thereof, so as to solve the problem that the fluorocarbon surfactant in human blood cannot be removed in the prior art.
In order to solve the technical problem, the invention adopts the following technical scheme:
a novel magnetic nano functional material can be used for removing fluorocarbon surfactant in human blood and is prepared by the following method:
1) modification: selecting strong magnetic MnFe 2 O 4 The preparation method comprises the following steps of (1) taking nano particles as a substrate material, putting the magnetic nano particles into an organic solvent, then adding dopamine hydrochloric acid, reacting under a light-tight condition to obtain magnetic nano particles, separating the obtained magnetic nano particles by using a neodymium magnet, and removing particles suspended in a solution to obtain modified magnetic nano particles;
2) coating: adding the modified magnetic nanoparticles and dopamine hydrochloric acid into a reactor filled with a Tris-buffer solution, and stirring for a period of time at room temperature to obtain a polydopamine-coated magnetic nanoparticle material;
3) hydrophilic modification: adding the polydopamine-coated magnetic nanoparticle material obtained in the step 2) into a reactor filled with a Tris-buffer solution, adding a hydrophilic group, starting reaction at the temperature of 20-30 ℃, and washing the product with ethanol for multiple times to obtain the hydrophilic group-modified magnetic nanoparticle material;
4) and (3) fluorocarbon modification: adding the magnetic nano-particle material modified with the hydrophilic group obtained in the step 3) into an organic solvent for ultrasonic dispersion, then adding a perfluoroalkyl polyether substance and pyridine, stirring, heating, reacting for a period of time, washing with an ethanol solution for multiple times, and drying to obtain the novel magnetic nano-functional material modified with fluorocarbon bonds.
Preferably, the MnFe 2 O 4 The magnetic nanoparticles have a particle size of 5-100 nm and a magnetic property of 70-150 emu g -1 。
Preferably, the inert protective layer comprises polydopamine, polystyrene, SiO 2 One or more of (a).
Preferably, the hydrophilic group comprises polyethylene glycol and the perfluoroalkylpolyether species comprises one or more of perfluoropolyether carboxylic acids (d, k, y, z type), perfluoropolyether acid chlorides (d, k, y, z type), perfluoropolyether acid fluorides (d, k, y, z type), perfluoropolyether amides (d, k, y, z type), perfluoropolyether alcohols (d, k, y, z type), perfluoropolyether propylene ethers, perfluoropolyether acrylates, trimethoxyperfluoropolyether silanes, triethoxyperfluoropolyether silanes.
Preferably, the mass ratio of the dopamine hydrochloride to the magnetic nanoparticles in the step 1) is 1-10: 1.
Preferably, the mass ratio of the dopamine hydrochloride to the magnetic nanoparticles in the step 2) is 1-10: 1.
Preferably, the mass ratio of the magnetic nanoparticles to the hydrophilic groups in the step 3) is 1: 2.
Preferably, the mass ratio of the polydopamine-coated magnetic nanoparticle material, the perfluoroalkyl polyether substance and the pyridine in the step 4) is 1:4: 5.
The application of the novel magnetic nano functional material in removing simulated blood is characterized in that the novel magnetic nano functional material is obtained by the preparation method, and the preparation method specifically comprises the following steps:
adding bovine serum albumin solution containing fluorocarbon surfactant into a sample bottle, then putting the novel magnetic nano functional material, sealing, putting the novel magnetic nano functional material into a constant-temperature oscillator, oscillating and capturing the novel magnetic nano functional material for a period of time at 0-20 ℃, then putting the novel magnetic nano functional material on a neodymium magnet for standing, taking supernatant, putting the supernatant into a dialysis bag for dialysis, then filtering the supernatant by using a filter membrane, and determining the removal rate of the fluorocarbon surfactant.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, magnetic nanoparticles with strong magnetism and good biocompatibility are selected as a substrate material, the material is a superparamagnetic material, has good coercive force, and can achieve good separation effect under a magnetic field; the selected superparamagnetic material is spherical, has small particle size, can provide larger specific surface area, can coat polydopamine on the surface, is an ideal modifying material because the polydopamine can provide a plurality of active sites and has good biocompatibility, and can modify a polyethylene glycol chain on the polydopamine through simple chemical reaction, thereby not only improving the biocompatibility of the magnetic nanoparticles again, but also enhancing the hydrophilicity of the magnetic nanoparticles and leading the magnetic nanoparticles to be better dispersed in a blood system; the poly dopamine can be modified with fluorine-carbon bonds which are specifically identified for the fluorocarbon surfactant as much as possible, more fluorocarbon surfactant can be captured, the capturing capability of the fluorocarbon surfactant is improved, and a non-toxic, non-bioaccumulation and easily-degradable perfluoropolyether chain is selected as an identification group in the invention.
2. The magnetic nano functional material prepared by the invention can be well dispersed in a blood system through the polydopamine coated on the surface of the magnetic nano functional material and the polyethylene glycol chain modified on the polydopamine, so that fluorine-carbon bonds modified on the polydopamine can be rapidly identified with fluorocarbon surfactant in blood and adsorbed on the surface of the magnetic nano functional material, and then the magnetic material is removed from the blood through a strong magnetic field, so that the fluorocarbon surfactant in the blood can be effectively removed.
Drawings
FIG. 1 is a TEM image of a magnetic nanoparticle synthesized according to the present invention.
Fig. 2 is an infrared spectrum of the magnetic nano-functional material synthesized in example 1 in the method for synthesizing a magnetic nano-functional material for removing fluorocarbon surfactant from human blood according to the present invention.
Fig. 3 is an XPS chart of the magnetic nano-functional material synthesized in example 1 in the method for synthesizing a magnetic nano-functional material for removing fluorocarbon surfactant from human blood according to the present invention.
FIG. 4 is a diagram of the effect of example 1 on PFOA removal of different modified perfluoropolyether chain magnetic nano-functional materials, wherein the amounts of the added perfluoropolyether carboxylic acid are 0.1mmol, 0.2mmol, 0.5mmol, 1mmol and 2mmol in sequence.
Figure 5 is a graph of the PFOA removal rate for different amounts of added magnetic nano-functional material in example 1.
Fig. 6 is a graph of the removal rate of the magnetic nano-functional material for PFOA at different capture times and a corresponding graph of the residual concentration of PFOA in example 1.
FIG. 7 is a graph showing the removal rates of PFHxA, PFOA, PFOS and GenX of the magnetic nanomaterial of example 1.
FIG. 8 is a cytotoxicity test chart of the magnetic nano-functional material in example 1.
Fig. 9 is a schematic diagram of an experimental device in an animal simulation experiment designed by the invention.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Preparation method of novel magnetic nano functional material
1) Modification: selecting ferromagnetic MnFe 2 O 4 The preparation method comprises the following steps of (1) taking nano particles as a substrate material, putting the magnetic nano particles into an organic solvent, sequentially adding N, N-dimethylformamide and dopamine hydrochloric acid, reacting for 1-12 hours at 50-100 ℃ in a dark place, washing for multiple times by using absolute ethyl alcohol to obtain the magnetic nano particles, separating the obtained magnetic nano particles by using a neodymium magnet, and removing particles suspended in a solution to obtain modified magnetic nano particles; wherein the organic solvent is chloroform, the mass ratio of the dopamine hydrochloric acid to the magnetic nanoparticles in the step 1) is 1-10: 1, and the modified magnetic nanoparticles are stored at the temperature of-10 ℃. Meanwhile, the magnetic nanoparticles are screened, so that the magnetic functional nano material after screening has good magnetic property and good biocompatibility, and the capture of the fluorocarbon surfactant in blood is more reliable and efficient.
2) Coating: adding the modified magnetic nanoparticles and dopamine hydrochloric acid into a reactor filled with a Tris-buffer solution, and stirring for a period of time at room temperature to obtain a polydopamine-coated magnetic nanoparticle material; stirring for 5 hours at 25 ℃, wherein the mass ratio of the dopamine hydrochloric acid to the magnetic nanoparticles in the step 2) is 1-10: 1.
3) Hydrophilic modification: adding the polydopamine-coated magnetic nanoparticle material obtained in the step 2) into a reactor filled with Tris-buffer solution, adding hydrophilic groups, starting reaction at 20-30 ℃, and washing the product with ethanol for multiple times to obtain the hydrophilic group-modified magnetic nanoparticle material; wherein the mass ratio of the magnetic nanoparticles to the hydrophilic groups in the step 3) is 1: 2.
4) And (3) fluorocarbon modification: adding the magnetic nano-particle material modified with the hydrophilic group obtained in the step 3) into an organic solvent for ultrasonic dispersion, then adding a perfluoroalkyl polyether substance and pyridine, stirring, heating, reacting for a period of time, washing with an ethanol solution for multiple times, and drying to obtain the novel magnetic nano-functional material modified with fluorocarbon bonds. Wherein the mass ratio of the polydopamine-coated magnetic nanoparticle material, the perfluoroalkyl polyether substance and the pyridine in the step 4) is 1:4: 5.
In example 1 (MnFe) 2 O 4 @ PDA/PEG/d-PFPE) nanoparticles are taken as an example, and the specific preparation method is as follows:
(1) superparamagnetic MnFe 2 O 4 Synthesis of nanoparticles
Manganese acetylacetonate (5mmol) and iron acetylacetonate (10mmol) are charged into a 100mL three-neck flask, and octyl ether (30mL) is used as a solvent, and after stirring for 30min at room temperature, oleic acid (30mmol), oleylamine (30mmol) and 1, 2-hexadecyl diol (50mmol) are added, and stirring is carried out for 10min at 50 ℃ under the protection of nitrogen. Then adjusting the temperature to 100 ℃, stirring for 3h, and then stirring for 4 ℃ min -1 The temperature was raised to 200 ℃ and stirring was continued at this temperature for 5 h. Followed by 4 ℃ min -1 The temperature was raised to 300 ℃ and stirring was continued at this temperature for 1 h. Then removing heat source, and adding 50mL of anhydrous ethanol and 5mL of cyclohexane when the temperature is cooled to room temperature at 10000r min -1 Centrifuging for 10min, washing with anhydrous ethanol for 6 times, and mixing the obtained MnFe 2 O 4 The magnetic nanoparticles were added to cyclohexane and stored at 4 ℃.
(2)MnFe 2 O 4 Hydrophilic modification of magnetic nanoparticles
MnFe synthesized in the step (1) 2 O 4 The magnetic nanoparticles were placed in a three-necked flask, 50mL of N, N Dimethylformamide (DMF) was added, followed by 30mmol of dopamine HCl and 30mL of deionized water,the reaction was then carried out for 12h under nitrogen and protected from light. The obtained hydrophilic modified MnFe 2 O 4 The magnetic nanoparticles were separated using a neodymium magnet and washed 6 times with 95% ethanol, followed by drying the black magnetic nanoparticles at 40 ℃ for 8h and storing the product in a drying oven at 4 ℃.
(3) Coating of polydopamine
Taking 1g of the hydrophilic modified MnFe obtained in the step (2) 2 O 4 Adding magnetic nanoparticles into a 100mL three-neck flask, adding 50mL Tris-buffer solution, performing ultrasonic dispersion for 10min, placing the mixture in a constant temperature tank at 25 ℃, stirring for 30min, adding 30mmol dopamine hydrochloric acid, reacting for 3h under the condition of introducing oxygen, washing the obtained product for 6 times by using 95% ethanol, then performing vacuum drying at 40 ℃ for 8h, and placing the product in a drying oven for storage at 4 ℃.
(4) Modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 Putting the @ PDA magnetic nanoparticles into a 100mL three-neck flask, adding 50mL Tris-buffer solution, then adding 0.6g aminopolyethylene glycol (M ═ 2000), reacting at 25 ℃ for 24h to finally obtain MnFe 2 O 4 @ PDA/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then different amounts of d-type perfluoropolyether carboxylic acid (0.1mmol, 0.2mmol, 0.5mmol, 1mmol, 2mmol) and 5mmol pyridine are added, reaction is carried out at 45 ℃ for 12h under the nitrogen protection atmosphere, and then MnFe modified with different fluorine contents is obtained 2 O 4 @ PDA/PEG/d-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 2 preparation of MnFe 2 O 4 @ PDA/PEG/k-PFPE nano-particle
Using superparamagnetic MnFe 2 O 4 And the surface of the nano-particle is coated with polydopamine serving as a substrate material, and then the surface of the nano-particle is modified with k-type perfluoropolyether carboxylic acid chains and polyethylene glycol chains to prepare the magnetic nano-functional material. The steps (1), (2) and (3) are the same as the embodiment 1, and the following specific steps are as follows:
(4) modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 The @ PDA magnetic nanoparticles are placed in a 100mL three-neck flask, 50mL Tris-buffer solution is added, then 0.6g aminopolyethylene glycol (M ═ 2000) is added, and the reaction is carried out for 24h at 25 ℃, so as to finally obtain MnFe 2 O 4 @ PDA/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bond
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 1mmol k type perfluoropolyether carboxylic acid and 5mmol pyridine are added, reaction is carried out at 45 ℃ for 12h under the nitrogen protection atmosphere, and then MnFe is obtained 2 O 4 @ PDA/PEG/k-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 3 preparation of MnFe 2 O 4 @ PDA/PEG/y-PFPE nano-particle
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with polydopamine to serve as a substrate material, and then polyethylene glycol and a y-type perfluoropolyether carboxylic acid chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2) and (3) are the same as the embodiment 1, and the following specific steps are as follows:
(4) modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 The @ PDA magnetic nanoparticles are placed in a 100mL three-necked flask, 50mL Tris-buffer solution is added, and then the sample is added0.6g of aminopolyethylene glycol (M ═ 2000) was added and reacted at 25 ℃ for 24 hours to finally obtain MnFe 2 O 4 @ PDA/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 The @ PDA/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, 1mmol y-type perfluoropolyether carboxylic acid and 5mmol pyridine are added, the reaction is carried out for 12h at 45 ℃ under the nitrogen protection atmosphere, and then MnFe is obtained 2 O 4 @ PDA/PEG/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 4 preparation of MnFe 2 O 4 @ PDA/PEG/z-PFPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with polydopamine serving as a substrate material, and then polyethylene glycol and a z-type perfluoropolyether carboxylic acid chain are modified on the surface of the nano-particle to prepare the magnetic nano-functional material. The steps (1), (2) and (3) are the same as the embodiment 1, and the following specific steps are as follows:
(4) modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 The @ PDA magnetic nanoparticles are placed in a 100mL three-neck flask, 50mL Tris-buffer solution is added, then 0.6g aminopolyethylene glycol (M ═ 2000) is added, and the reaction is carried out for 24h at 25 ℃, so as to finally obtain MnFe 2 O 4 @ PDA/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bond
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ PDA/PEG magnetic nanoparticles were placed in a 100mL flask, 50mL dichloromethane was added, the mixed solution was then ultrasonically dispersed for 10min, followed by the addition of 1mmol of type z perfluoroPolyether carboxylic acid and 0.5mL of pyridine are reacted for 12h at 45 ℃ in the nitrogen protection atmosphere to obtain MnFe 2 O 4 @ PDA/PEG/z-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 5 preparation of MnFe 2 O 4 @ PS/PEG/d-PFPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with Polystyrene (PS) as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and d-type perfluoropolyether acyl chloride to prepare the magnetic nano-functional material. Wherein, the steps (1) and (2) are the same as the embodiment 1, and the following specific steps are as follows:
(3) coating of polystyrene
Taking 1g of the hydrophilic modified MnFe obtained in the step (2) 2 O 4 Adding the magnetic nanoparticles into a 250mL three-neck flask, adding 100mL ethanol, performing ultrasonic dispersion for 10min, sequentially adding 0.5g of styrene and 0.01g of initiator azobisisobutyronitrile, and reacting at 70 ℃ for 5 h. The obtained product was washed 6 times with 95% ethanol and then vacuum-dried at 40 ℃ for 8 hours to obtain MnFe 2 O 4 @PS
Magnetic nanoparticles, and then the product was stored in a drying oven at 4 ℃.
(4) Modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 @ PS magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane was added, followed by 0.6g of chlorinated polyethylene glycol (M ═ 2000) and reacted at 25 ℃ for 24 hours to obtain MnFe 2 O 4 @ PS/PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ PS/PEG magnetic nanoparticles were placed in a 100mL flask, 50mL of dichloromethane were added, the mixed solution was then ultrasonically dispersed for 10min, followed by the addition of 1mmol of d-type perfluoropolyetheracyl chloride and 05mL of pyridine at 45 ℃ for 12h under a nitrogen atmosphere, and then obtaining MnFe 2 O 4 @ PS/PEG/d-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 6 preparation of MnFe 2 O 4 @ PS/PEG/k-PFPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with Polystyrene (PS) as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and k-type perfluoropolyether acyl chloride to prepare the magnetic nano-functional material. Wherein, the steps (1), (2), (3) and (4) are the same as the embodiment 5, and the following specific steps are as follows:
(5) modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ PS/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL of dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 1mmol of k-type perfluoropolyether acyl chloride and 0.5mL of pyridine are added, the mixture reacts at 45 ℃ for 12h under the nitrogen protection atmosphere, and then MnFe is obtained 2 O 4 @ PS/PEG/k-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 7 preparation of MnFe 2 O 4 @ PS/PEG/y-PFPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with Polystyrene (PS) as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and y-type perfluoropolyether acyl chloride to prepare the magnetic nano-functional material. Wherein, the steps (1), (2), (3) and (4) are the same as the embodiment 5, and the following specific steps are as follows:
(5) modification of fluorine carbon bond
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @ PS/PEG magnetic nanoparticles were placed in a 100mL flask, 50mL of methylene chloride was added, followed by ultrasonic dispersion of the mixed solution for 10min, followed by addition of 1mmol of y-type perfluoropolyether acid chloride and 0.5mL of pyridine is reacted for 12h at 45 ℃ under the protection of nitrogen, and then MnFe is obtained 2 O 4 @ PS/PEG/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 8 preparation of MnFe 2 O 4 @ PS/PEG/z-PFPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with Polystyrene (PS) as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and z-type perfluoropolyether acyl chloride to prepare the magnetic nano-functional material. Wherein, the steps (1), (2), (3) and (4) are the same as the embodiment 5, and the following specific steps are as follows:
(5) modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 The @ PS/PEG magnetic nanoparticles are placed in a 100mL flask, 50mL of dichloromethane is added, then the mixed solution is subjected to ultrasonic dispersion for 10min, 1mmol of z-type perfluoropolyether acyl chloride and 0.5mL of pyridine are added, the reaction is carried out at 45 ℃ for 12h under the nitrogen protection atmosphere, and then MnFe is obtained 2 O 4 @ PS/PEG/z-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 9 preparation of MnFe 2 O 4 @SiO 2 -N-PEG/y-PFPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with silicon dioxide as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and y-type perfluoropolyether acyl fluoride to prepare the magnetic nano-functional material. Wherein the steps (1) and (2) are the same as the embodiment 1, and the following specific steps are as follows:
(3)SiO 2 is coated with
Taking 1g of the hydrophilic modified MnFe obtained in the step (2) 2 O 4 Adding magnetic nanoparticles into a 100mL three-neck flask, adding 60mL ethanol, 5mL ammonia water, stirring at 40 ℃ for 30min, adding 3mL tetraethyl orthosilicate, stirring for 30min, and adding 0.5mL 3-aminopropyl trimethyl ammonium chlorideThe oxysilane is reacted for 1h, the obtained product is washed by 95% ethanol for 6 times, then dried in vacuum for 8h at 40 ℃, and the product is placed in a drying oven for storage at 4 ℃. Obtaining MnFe 2 O 4 @SiO 2 -NH 2 Magnetic nanomaterials.
(4) Modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 @SiO 2 -NH 2 The magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane was added, followed by 0.6g of polyethylene glycol (M ═ 2000), 200mL of thionyl chloride and 0.2mL of pyridine, and reacted at 45 ℃ for 3 hours to obtain MnFe 2 O 4 @SiO 2 -NH-PEG functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @SiO 2 Placing the-NH-PEG magnetic nanoparticles in a 100mL flask, adding 50mL dichloromethane, then ultrasonically dispersing the mixed solution for 10min, then adding 1mmol y-type perfluoropolyether acyl fluoride and 0.5mL pyridine, reacting for 3h at 45 ℃ under the nitrogen protection atmosphere, and then obtaining MnFe 2 O 4 @SiO 2 -N-PEG/y-PFPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 10 preparation of MnFe 2 O 4 @SiO 2 -N-PEG/y-PFPA nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with silicon dioxide as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and a y-type perfluoropolyether alcohol chain to prepare the magnetic nano-functional material. Wherein, the steps (1), (2), (3) and (4) are the same as the embodiment 10, and the following specific steps are as follows:
(5) modification of fluorine carbon bonds
First 1mmol of type y perfluoropolyether alcohol, 0.5mL of thionyl chloride, followed by 0, are added in a 100mL three-necked flask.After 5mL of pyridine was reacted at 45 ℃ for three hours, 0.5g of MnFe synthesized in step (4) was added 2 O 4 @SiO 2 NH-PEG magnetic nano-particles, and then reacting for 3h at 45 ℃ in the nitrogen protection atmosphere to obtain MnFe 2 O 4 @SiO 2 -N-PEG/y-PFPA magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 11 preparation of MnFe 2 O 4 @SiO 2 -N-PEG/PFPPE nanoparticles
Using superparamagnetic MnFe 2 O 4 The surface of the nano-particle is coated with silicon dioxide as a substrate material, and then the surface of the nano-particle is modified with polyethylene glycol and a perfluoropolyether propenyl ether chain to prepare the magnetic nano-functional material. Wherein, the step (1) and the step (2) are the same as the embodiment 10, and the following specific steps are as follows:
(3)SiO 2 is coated with
Taking 1g of the hydrophilic modified MnFe obtained in the step (2) 2 O 4 The magnetic nanoparticles are added into a 100mL three-neck flask, 60mL of ethanol, 5mL of ammonia water and 40 ℃ are added, stirring is carried out for 30min, then 3mL of tetraethyl orthosilicate is added, stirring is carried out for 30min, then 0.3mL of 3-aminopropyl trimethoxysilane and 0.3mL of mercaptopropyl trimethoxysilane are continuously reacted for 1h, the obtained product is washed 6 times by using 95% ethanol, then vacuum drying is carried out at 40 ℃ for 8h, and the product is placed in a drying oven and stored at 4 ℃. Obtaining MnFe 2 O 4 @SiO 2 -NH 2 the/SH magnetic nano material.
(4) Modification of polyethylene glycol
Taking 0.3g of MnFe synthesized in the step (3) 2 O 4 @SiO 2 -NH 2 the/SH magnetic nanoparticles were placed in a 100mL three-necked flask, 50mL of dichloromethane was added, followed by 0.6g of polyethylene glycol (M2000), 200mL of thionyl chloride and 0.2mL of pyridine were added, and reacted at 45 ℃ for 3 hours to obtain MnFe 2 O 4 @SiO 2 -NH-PEG/SH functional magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
(5) Modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @SiO 2 the-NH-PEG/SH magnetic nanoparticles were placed in a 100mL flask, 50mL of dichloromethane was added, then the mixed solution was ultrasonically dispersed for 10min, then 1mmol of perfluoropolyether allyl ether and 0.3g of photoinitiator (2-hydroxy-2-methyl-1-phenyl acetone) were added, and irradiated under an ultraviolet lamp for 12 h. Subsequently obtaining MnFe 2 O 4 @SiO 2 -N-PEG/S-PFPPE magnetic nanoparticles. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Example 12
Using superparamagnetic MnFe 2 O 4 The surface of the nano particle is coated with silicon dioxide as a substrate material, and then the surface of the nano particle is modified with a polyethylene glycol chain, and then the nano particle is reacted with triethoxy perfluoropolyether silane to prepare the magnetic nano functional material. Wherein, the steps (1), (2), (3) and (4) are the same as the embodiment 10, and the following specific steps are as follows:
(5) modification of fluorine carbon bonds
Taking 0.5g of MnFe synthesized in the step (4) 2 O 4 @SiO 2 the-NH-PEG magnetic nanoparticles are placed in a 100mL flask, 50mL of ethanol, 0.5mL of ammonia water and 0.2mL of deionized water are added, then the mixed solution is subjected to ultrasonic dispersion for 10min, then 1mmol of triethoxy perfluoropolyether silane is added, and stirring is carried out at 45 ℃ for 6 h. And then obtaining the magnetic nano-particles modified with fluorine-carbon bonds. The material was then washed 6 times with 95% ethanol, then dried under vacuum at 40 ℃ for 8h, and the product was stored in a drying cabinet at 4 ℃.
Second, a new magnetic nanometer functional material
The magnetic nano functional material can be used for removing fluorocarbon surfactant in human blood. Wherein the MnFe 2 O 4 The magnetic nanoparticles have a particle size of 5-100 nm and a magnetic property of 70-150 emu g -1 The substrate material is a superparamagnetic material, has good coercive force, can be quickly magnetized to display magnetism under the action of an external magnetic field, and can be magnetized after the external magnetic field is removedThe magnetic nano functional material prepared by the method can be quickly separated from blood under the action of a magnetic field, so that the blood is prevented from being polluted due to the residual substances in the blood.
The inert protective layer comprises polydopamine, polystyrene and SiO 2 One or more of them, and also can use phenolic resin. The inert protective layers are coated on the surface of the substrate material, so that toxicity and irritation to blood cells can not be generated in the process of contacting the substrate material with blood, the treated blood still has physiological activity, and the health of a living organism can not be influenced.
The hydrophilic group comprises polyethylene glycol, and the perfluoroalkyl polyether material comprises one or more of perfluoropolyether carboxylic acid (d, k, y, z type), perfluoropolyether acyl chloride (d, k, y, z type), perfluoropolyether acyl fluoride (d, k, y, z type), perfluoropolyether amide (d, k, y, z type), perfluoropolyether alcohol (d, k, y, z type), perfluoropolyether allyl ether, perfluoropolyether acrylate, trimethoxy perfluoropolyether silane, triethoxy perfluoropolyether silane.
In addition, the magnetic nanoparticles synthesized in example 1 were subjected to TEM test, IR spectrum and XPS analysis, as shown in FIGS. 1,2 and 3, and the results of the analysis showed that the present invention was successfully applied to MnFe 2 O 4 The surface of the nano-particles is coated with polydopamine shell, the magnetic nano-particles can better modify fluorocarbon bonds and hydrophilic groups, and infrared data show that the material is 1077cm when PEG chains are modified -1 And a stretching peak with ether bond is formed, so that the PEG bond can be proved to be successfully modified, and XPS data contrast analysis obtains successful modification of fluorine-carbon bond, so that the magnetic nano-particle with specific recognition on the fluorocarbon surfactant can be successfully prepared.
TABLE 1 Components of magnetic Nano-functional materials prepared in examples 1-12
Examples Base material Coated inert protective layer Hydrophilic chain organic matter Organic matter containing fluorine-carbon bond
Example 1 MnFe 2 O 4 Polydopamine (PDA) Polyethylene glycol (PEG) Type d perfluoropolyether carboxylic acids (d-PFPE)
Example 2 MnFe 2 O 4 Polydopamine (PDA) Polyethylene glycol (PEG) K-type perfluoropolyether carboxylic acids (k-PFPE)
Example 3 MnFe 2 O 4 Polydopamine (PDA) Polyethylene glycol (PEG) y type perfluoropolyether carboxylic acid (y-PFPE)
Example 4 MnFe 2 O 4 Polydopamine (PDA) Polyethylene glycol (PEG) z type perfluoropolyether carboxylic acids (z-PFPE)
Example 5 MnFe 2 O 4 Polystyrene (PS) Polyethylene glycol (PEG) Type d perfluoropolyetheracyl chloride (d-PFPE)
Example 6 MnFe 2 O 4 Polystyrene (PS) Polyethylene glycol (PEG) K-type perfluoropolyetheracyl chloride (k-PFPE)
Example 7 MnFe 2 O 4 Polystyrene (PS) Polyethylene glycol (PEG) y type perfluoropolyetheracyl chloride (y-PFPE)
Example 8 MnFe 2 O 4 Polystyrene (PS) Polyethylene glycol (PEG) Z-type perfluoropolyetheracyl chloride (z-PFPE)
Example 9 MnFe 2 O 4 Silicon dioxide (SiO) 2 ) Polyethylene glycol (PEG) y type perfluoropolyether acyl fluoride (y-PFPE)
Example 10 MnFe 2 O 4 Silicon dioxide (SiO) 2 ) Polyethylene glycol (PEG) y type perfluoropolyether alcohols (y-PFPA)
Example 11 MnFe 2 O 4 Silicon dioxide (SiO) 2 ) Polyethylene glycol (PEG) y type perfluoropolyether olefins (y-PFPPE)
Example 12 MnFe 2 O 4 Silicon dioxide (SiO) 2 ) Polyethylene glycol (PEG) Triethoxy perfluoropolyether silane
Application of magnetic nano functional material
Adding bovine serum albumin solution containing fluorocarbon surfactant into a sample bottle, then adding the novel magnetic nano functional material, sealing, placing in a constant temperature oscillator, and performing constant temperature oscillation at 0-20 ℃ for 200r min -1 After 30min of speed oscillation capture, placing the neodymium magnet and standing for 10-120 s, taking supernatant and placing the supernatant in a dialysis bag for dialysis, then filtering the supernatant by using a 0.22 mu m filter membrane, measuring the residual concentration of the fluorocarbon surfactant, and calculating the removal rate by the formula (1). At the same time, to the magnetic nanoparticlesThe fluorine content of the particles, the amount of the added magnetic nanoparticles, and the capturing time were investigated.
Figure BDA0002780146850000121
Wherein Re is the removal rate, C o Is the initial solubility of the fluorocarbon surfactant of 1ppm, C r Is the residual concentration of the fluorocarbon surfactant.
(1) Fluorine content of magnetic nanoparticles
(ii) configuration of simulated blood
35g of bovine serum albumin, 1mg of PFOA and tris (hydroxymethyl) aminomethane are prepared into 1L solution with the pH value of 7.4, wherein the tris (hydroxymethyl) aminomethane can adjust the pH value of a solvent system and prevent protein molecules from being denatured.
② Capture experiment
10mL of PFOA-like blood (1ppm) obtained in step I were placed in 5 20mL sample bottles, and 0.01g of MnFe (0.1mmol, 0.2mmol, 0.5mmol, 1mmol, 2mmol) having different fluorine contents prepared in example 1 was added in this order 2 O 4 @ PDA/PEG/y-PFPE magnetic nanoparticles, ultrasonic dispersing for 2min, capturing at 25 deg.C for 10min, and separating with neodymium magnet. 1mL of the supernatant was dialyzed for 24h, filtered through a 0.22 μm filter, and then tested by LC-MS/MS, and PFOA removal rates were calculated as 96%, 96.6%, 96.8%, 97%, and 97.5% in this order, as shown in FIG. 4.
(2) Dosage of magnetic nanoparticles
(ii) configuration of simulated blood
35g of bovine serum albumin, 1mg of PFOA and tris (hydroxymethyl) aminomethane are prepared into 1L solution with the pH value of 7.4, wherein the tris (hydroxymethyl) aminomethane can adjust the pH value of a solvent system and can protect protein molecules.
② Capture experiment
10mL of PFOA-like blood (1ppm) obtained in step I were placed in 5 20mL sample bottles, and MnFe prepared in example 1 was added in different amounts (0.001g, 0.005g, 0.01g, 0.05g, 0.1g) 2 O 4 @PDA/PEG/PTFE (PFPE ═ 0.1mmol) magnetic nanoparticles, ultrasonically dispersed for 2min, captured at 25 ℃ for 10min, and then placed on a neodymium magnet for separation. 1mL of the supernatant was dialyzed for 24h, filtered through a 0.22 μm filter, and then tested using LC-MS/MS, and PFOA removal rates were calculated as 86.6%, 92.3%, 96.8%, 99.49%, and 99.51% in this order, as shown in FIG. 5.
(3) Time of acquisition
(ii) configuration of simulated blood
Preparing 35g of bovine serum albumin, 1mg of PFOA and tris (hydroxymethyl) aminomethane into 1L solution with the pH value of 7.4, wherein the tris (hydroxymethyl) aminomethane can adjust the pH value of a solvent system and protect protein molecules.
② Capture experiment
10mL of PFOA-simulated blood (1ppm) obtained in step (i) was taken and placed in 5 20mL sample bottles, and 0.5g of MnFe prepared in example 1 was added 2 O 4 @ PDA/PEG/PFPE (PFPE ═ 0.1mmol) magnetic nanoparticles, ultrasonically dispersed for 2min, captured at 25 ℃ and then placed on a neodymium magnet for separation. 1mL of each supernatant was dialyzed for 24 hours at different capture times (2min, 5min, 10min, 30min, 60min), filtered with a 0.22 μm filter, and then tested using LC-MS/MS, and PFOA removal rates were calculated to be 87.9%, 96.5%, 99.61%, 99.79%, 99.93% in this order, as shown in FIG. 6.
In the research, albumin in blood is found to be a main carrier of the fluorocarbon surfactant, and due to a large number of disulfide bonds in the molecular structure of the albumin, the albumin can be well combined with the fluorocarbon surfactant, which is also a reason that the fluorocarbon surfactant in the blood is difficult to remove. The invention selects the nontoxic and degradable perfluoropolyether chain as the identification group of the fluorocarbon surfactant, can quickly identify the fluorocarbon surfactant in blood, can be quickly and efficiently combined with the fluorocarbon surfactant, and can be quickly removed by an external magnetic field.
It can be seen from the above study that the higher the fluorine content on the surface of the magnetic particles, the better the PFOA removal rate in the blood system, and the grafting amount of the fluorocarbon chains on the surface is limited, and after reaching a certain amount, the PFOA removal rate is not improved more significantly. The same applies to the amount of magnetic particles added and the time of standing on a neodymium magnet, and even when PFPE is 0.1mmol, that is, the fluorine content on the surface of the magnetic particles is low, the PFOA removal rate can reach 99% or more when the amount of magnetic particles added is 0.05 g; similarly, when the capture time is 10min, the removal rate of PFOA reaches 99%.
(4) Performance verification of examples 2-12
The performance of the magnetic particles prepared in examples 2 to 12 was verified, and the magnetic particles were used to treat simulated blood containing PFHxA, GenX, PFOA, PFOS as follows:
firstly, referring to the preparation method of the simulated blood, PFHxA, GenX, PFOA and PFOS simulated blood with the concentration of 1ppm are respectively prepared;
and placing 10mL of simulated blood (1ppm) containing fluorocarbon surfactant in the step I into 20mL sample bottles respectively, adding 0.5g of the magnetic nanoparticles prepared in the examples 2-12, performing ultrasonic dispersion for 2min, capturing for 30min at 25 ℃, and then placing on a neodymium magnet for separation. 1mL of the supernatant was dialyzed for 24 hours, filtered through a 0.22 μm filter, and then tested by LC-MS/MS to calculate the removal rates of PFHxA, GenX, PFOA, PFOS. The results of the measurements are shown in the following table.
Table 2 examples 2-12 removal effects of magnetic nano-functional materials on different fluorocarbon surfactants in simulated blood
Using magnetic nano-functional materials The removal rates of PFHxA, GenX, PFOA and PFOS are sequentially
Example 2 97％，99.5％，98％，98.2％
Practice ofExample 3 98.5％，99.7％，98.6％，98.8％
Example 4 98.9％，99.6％，98.4％，98.6％
Example 5 98.8％，99.9％，98.5％，98.7％
Example 6 98.4％，99.3％，99.2％，99.4％
Example 7 98.9％，99.99％，99.5％，99.7％
Example 8 97.3％，99.2％，98.5％，98.7％
Example 9 97.8％、98％、97％，97.2％
Example 10 97.9％，98.9％，97.8％，98％
Example 11 98.8％，99.3％，98.7％，98.9％
Example 12 99.2％，99.9％，99.3％，99.5％
As can be seen from fig. 7, the magnetic nano-functional material prepared in example 1 has a high removal rate for the fluorocarbon surfactants PFHxA, PFOA, PFOS, and GenX, and similarly, the data in the above example also shows that the magnetic nano-functional material prepared by modifying different types of fluorocarbon bonds has a high removal rate for the fluorocarbon surfactants PFHxA, GenX, PFOS, and PFOA in the simulated blood. Therefore, the magnetic nano functional material for removing the fluorocarbon surfactant in the blood has a good removing effect on the fluorocarbon surfactant, and the effect of quickly separating the magnetic nano functional material from the blood can be achieved by selecting the strong-magnetic nano particles.
Fourth, animal simulation experiment
The magnetic nanometer functional material is subjected to cytotoxicity test, the toxicity influence test of the magnetic material on HeLa cells is analyzed by adopting an MTT method, the specific condition of cell activity is obtained under the conditions of different concentrations of the magnetic nanometer functional material, as shown in figure 8, when the concentration of the material is increased to 200 mu g L -1 The cell activity is still more than 90%, which shows that the magnetic material synthesized by the invention has no toxicity. Therefore, the magnetic nanoparticles prepared by the method do not have great influence on the activity of cells in blood in the process of removing the fluorocarbon surfactant in the blood.
The magnetic nano functional material is applied to animal simulation experiments, the experiments are operated in a sterile environment, and corresponding experimental devices are designed according to the experimental operations, as shown in fig. 9, the magnetic nano functional material comprises a blood constant temperature device, an electromagnetic capture device and a peristaltic pump, wherein the blood constant temperature device is communicated with the electromagnetic capture device and the peristaltic pump through hoses, so that the blood of an animal can be driven by the peristaltic pump to sequentially pass through the blood constant temperature device, the electromagnetic capture device and the blood constant temperature device and finally return to the inside of the animal.
The specific operation is as follows: the anti-blood coagulation agent is firstly injected into the vein of the mouse, and then the venous blood of the mouse is driven by the peristaltic pump to flow into the electromagnetic capture device, wherein the magnetic nano particles are distributed on the reticular magnetic medium under the action of the strong magnetic field, so that the design not only increases the contact area with the blood, but also prevents the harm caused by the magnetic material entering the mouse body. After the fluorocarbon surfactant in the blood is captured by the magnetic material, the fluorocarbon surfactant returns to the body of the mouse again through the constant temperature device. Considering that the half-life of the fluorocarbon surfactant in mice is about 5h, the treatment time of blood is set to be within 1h in order to reduce the error of data.
Simulation experiment 1
Feeding food (2ppm) containing PFOA to a mouse for 3 days, taking 50 mu L venous blood for LC-MS/MS test, wherein the concentration of the PFOA in the blood is the initial concentration, adding 2g of the magnetic nanoparticles synthesized in the example 1 into a magnetic capture device, then using an experimental device to treat the blood of the mouse, taking 50 mu L of the blood which passes through the electromagnetic capture device every 10min for LC-MS/MS test, setting the treatment time to be 1h, and keeping the treated mouse healthy and alive without rejection. Sampling at 0min, 10min, 20min, 30min, 40min, 50min, and 60min respectively to test the residual concentration of PFOA to be 1.2ppm, 380ppb, 76ppb, 16ppb, 1.92ppb, 0.92ppb, and 0.055ppb in this order.
Simulation experiment 2
Feeding PFOS-containing food (2ppm) to a mouse for 3 days, taking 50 mu L of venous blood for LC-MS/MS test, wherein the concentration of PFOS in the blood is the initial concentration, adding 2g of the magnetic nanoparticles synthesized in example 1 into a magnetic capture device, then using an experimental device to treat the blood of the mouse, taking 50 mu L of the blood after passing through an electromagnetic capture device every 10min for LC-MS/MS test, lasting for 1h, and keeping the treated mouse healthy and alive without rejection. PFOS residual concentrations of 1.3ppm, 410ppb, 86ppb, 15ppb, 1.5ppb, 0.85ppb and 0.045ppb by sampling at times of 0min, 10min, 20min, 30min, 40min, 50min and 60min, respectively.
Simulation experiment 3
After feeding a food (2ppm) containing GenX to mice for 3 days, 50. mu.L of venous blood, at which the concentration of GenX in blood is the initial concentration, was subjected to LC-MS/MS test, 2g of the magnetic nanoparticles synthesized in example 1 were added to a magnetic capture device, and then the mice were treated with blood using an experimental device, 50. mu.L of blood passed through an electromagnetic capture device was taken every 10min for LC-MS/MS test for 1 hour, and the treated mice were still alive and free from rejection. The residual concentrations of GenX were measured to be 1.1ppm, 350ppb, 73ppb, 12ppb, 1.15ppb, 0.73ppb, 0.043ppb by sampling at times of 0min, 10min, 20min, 30min, 40min, 50min, and 60min, respectively.
The data of animal experiments show that the magnetic nanoparticles prepared by the method have a good effect of removing the fluorocarbon surfactant in blood, and the initial concentration of the fluorocarbon surfactant of 1ppm in the blood can be reduced to about 50ppt within 1h of treatment time, so that the material and the device designed by the method have great application prospects in treatment of the fluorocarbon surfactant in human blood.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.

Claims (3)

1. A novel magnetic nano-functional material for removing fluorocarbon surfactant from blood is characterized in that the novel magnetic nano-functional material is prepared by the following method:
1) modification: selecting strong magnetic spherical MnFe 2 O 4 The preparation method comprises the following steps of (1) taking nano particles as a substrate material, putting the magnetic nano particles into an organic solvent, then adding dopamine hydrochloric acid, reacting under a dark condition to obtain magnetic nano particles, separating the obtained magnetic nano particles by using a neodymium magnet, and removing particles suspended in a solution to obtain modified magnetic nano particles;
2) coating: adding the modified magnetic nanoparticles and dopamine hydrochloric acid into a reactor filled with a Tris-buffer solution, and stirring for a period of time at room temperature to obtain a polydopamine-coated magnetic nanoparticle material;
3) hydrophilic modification: adding the polydopamine-coated magnetic nanoparticle material obtained in the step 2) into a reactor filled with Tris-buffer solution, adding hydrophilic groups, and then starting reaction at 20-30 ℃ to obtain a hydrophilic group-modified magnetic nanoparticle material;
4) and (3) fluorocarbon modification: adding the magnetic nano-particle material modified with hydrophilic groups obtained in the step 3) into an organic solvent for ultrasonic dispersion, then adding a perfluoroalkyl polyether substance and pyridine, stirring, heating and reacting for a period of time, washing with an ethanol solution for multiple times, and drying to obtain the novel magnetic nano-functional material modified with fluorocarbon bonds;
the hydrophilic group comprises polyethylene glycol, the perfluoroalkyl polyether alkyl substance comprises one or more of d, k, y or z type perfluoropolyether carboxylic acid, d, k, y or z type perfluoropolyether acyl chloride, d, k, y or z type perfluoropolyether acyl fluoride, d, k, y or z type perfluoropolyether amide, d, k, y or z type perfluoropolyether alcohol, perfluoropolyether allyl ether, perfluoropolyether acrylate, trimethoxy perfluoropolyether silane and triethoxy perfluoropolyether silane;
the mass ratio of the dopamine hydrochloride to the magnetic nanoparticles in the step 1) is 1-10: 1;
the mass ratio of the dopamine hydrochloric acid to the magnetic nanoparticles in the step 2) is 1-10: 1;
the mass ratio of the magnetic nanoparticles to the hydrophilic groups in the step 3) is 1: 2;
the mass ratio of the polydopamine-coated magnetic nanoparticle material, the perfluoroalkyl polyether substance and the pyridine in the step 4) is 1:4: 5.
2. The novel magnetic nano-functional material for removing fluorocarbon surfactant in blood as claimed in claim 1, wherein said MnFe is selected from the group consisting of 2 O 4 The magnetic nanoparticles have a particle size of 5-100 nm and a magnetic property of 70-150 emu g -1 。
3. The use of the novel magnetic nano-functional material for removing fluorocarbon surfactant from blood as claimed in claim 1 or 2, wherein the novel magnetic nano-functional material is used for removing fluorocarbon surfactant from simulated blood, comprising the following steps:
adding bovine serum albumin solution containing fluorocarbon surfactant into a sample bottle, then putting the novel magnetic nano functional material, sealing and then placing the novel magnetic nano functional material into a constant temperature oscillator, oscillating and capturing for a period of time at 0-20 ℃, then placing the novel magnetic nano functional material on a neodymium magnet for standing, taking supernatant, placing the supernatant into a dialysis bag for dialysis, then filtering the supernatant by using a filter membrane, and determining the removal rate of the fluorocarbon surfactant.
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