CN114620771B - Nano Fe with amino group on surface 3 O 4 Is prepared by the preparation method of (2) - Google Patents
Nano Fe with amino group on surface 3 O 4 Is prepared by the preparation method of (2) Download PDFInfo
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- 125000003277 amino group Chemical group 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 36
- 108010039918 Polylysine Proteins 0.000 claims abstract description 22
- 229920000656 polylysine Polymers 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 21
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 polyoxymethylene Polymers 0.000 claims description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a nano Fe with amino groups on the surface 3 O 4 The preparation method of (2), the method comprises the following steps: dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N 2 To remove oxygen from the system; heating the reaction system to 30-90 ℃, adding polylysine with a certain mass into the solution, and mechanically stirring to obtain transparent orange solution; transferring the orange solution into a hydrothermal reaction kettle for reaction to obtain bright black nano Fe 3 O 4 A solution; cooling the reaction final liquid, separating by using a magnet, washing with deionized water and acetone for multiple times, and drying to obtain the black superparamagnetic Fe 3 O 4 And (3) nanoparticles. The prepared particle has the outer layer modified by polylysine, has high biosafety and compatibility, has high adsorptivity of metal ions, and can be used in the field of biomedical treatment.
Description
Technical Field
The invention belongs to the technical field of nano materials, and in particular relates to nano Fe with amino groups on the surface 3 O 4 Is prepared by the preparation method of (1).
Background
Nano Fe in recent years 3 O 4 Is becoming a hot spot of research due to nano-Fe 3 O 4 Has unique superparamagnetic performance. The performance can be widely applied to the fields of electronic and biological sensing materials, biological medicines, magnetic fluid, magnetic recording materials, magnetic recording media and the like. Nano Fe 3 O 4 After proper protection and modification, the surface can be applied to the environment in human body, such as nano Fe with the surface modified by functionalization 3 O 4 Can be used for tissue repair, immunoassay, biological fluid detoxification, hyperthermia, drug delivery and cell separation. Nano Fe 3 O 4 Applications in the above-mentioned fields, in particular biomedical applications, require high magnetization values, smaller particle sizes and a narrower particle size distribution. Nano Fe 3 O 4 Chemical preparation methods include coprecipitation, hydrothermal reaction, sol-gel, solvothermal and ultrasonic methods. Nano Fe prepared under general condition 3 O 4 The functionalized magnetic particles are obtained as monocrystalline particles after surface modification treatment with a stabilizer. Commonly used stabilizers include the following classes: monomer stabilizer (such as carboxyl compound and phosphate), inorganic substance (such as silicon and gold), and polymer (such as polyethylene glycol, polyvinyl alcohol and chitosan). In addition, nano Fe prepared by coprecipitation method and gel-sol method 3 O 4 The water solubility of the particles is poor; the particles prepared by the solvothermal method are soluble in organic solvents but insoluble in water and are expensive; the ultrasonic method cannot prepare nanoparticles on a large scale. Among all the preparation methods, the coprecipitation method is to prepare nano Fe 3 O 4 Most importantly, the method is the most commonly used method, and is simple, effective and low in cost. However, fe prepared by this method 3 O 4 Often, the dispersity of the particle size is large, the crystallization has defects, and the corresponding saturation magnetization is low.
Therefore, there is a need to develop a novel nano Fe 3 O 4 。
Disclosure of Invention
The invention aims at: provides nano Fe with amino groups on the surface 3 O 4 The preparation method solves the problems.
The technical scheme of the invention is as follows:
nano Fe with amino group on surface 3 O 4 The preparation method of (2), the method comprises the following steps:
(1) Dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N 2 Removing oxygen in the system to obtain a first solution;
(2) Heating, adding polylysine into the first solution, and mechanically stirring to obtain a transparent orange solution;
(3) Transferring the orange solution into a hydrothermal reaction kettle for reaction to obtain a bright black nano Fe3O4 solution;
(4) Subjecting the nano Fe to 3 O 4 Cooling the solution, separating by using a magnet, washing with deionized water and acetone for multiple times, and drying to obtain black nano Fe with amino groups on the surface 3 O 4 And (3) particles.
Further, the trivalent ferric salt in the step (1) is FeCl 3 、Fe 2 (SO 4 ) 3 And Fe (NO) 3 ) 3 Any one of the following.
Further, in the step (1), the polymerization degree n=10 to 30 of the polyoxymethylene, and the concentration of the polyoxymethylene is 0.1 to 3%.
Further, in the step (1), after the trivalent ferric salt is dissolved in the aqueous solution of the polyoxymethylene, the mass percentage of the trivalent ferric salt is 0.01% -10%.
Further, the N in the step (1) 2 The aeration time was 30min.
Further, the temperature rise in the step (2) means that the temperature is raised to 30-90 ℃.
Further, the degree of polymerization of the polylysine in the step (2) is between 5000 and 50000.
Further, the mass of the polylysine in the step (2) is 10-15 times of the mass of the ferric salt.
Further, the time of mechanical stirring in the step (2) is 60-120 min.
Further, the reaction time in the hydrothermal reaction kettle in the step (3) is 3-6h, and the temperature is 100-250 ℃.
The invention has the advantages that:
1. nano Fe prepared by traditional method 3 O 4 The surface can be modified only by subsequent treatment, and the method can prepare polylysine modified nano Fe in situ 3 O 4 ；
2. The organic solvent and polylysine have the function of protective agent, and can control nano Fe 3 O 4 The crystal grows, and the grain size distribution is more uniform;
3. the method utilizes the reducibility of polyformaldehyde and polylysine to prepare Fe by reducing ferric iron 3 O 4 The use of hydrazine hydrate, ammonia water and the like is avoided;
4. polylysine can effectively protect nano Fe 3 O 4 Has higher dispersivity and stability in aqueous solution, and the prepared nano Fe 3 O 4 The outer layer contains rich amino groups with high reactivity, and can be used for carrying medicines or adsorbing heavy metals;
5. the polylysine is a typical polypeptide, is safe to human body and environment, has good biocompatibility and biodegradability, and can ensure the prepared nano Fe 3 O 4 Safety to human body and environment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein, the liquid crystal display device comprises a liquid crystal display device,
FIG. 1 shows a nano Fe with amino groups on the surface 3 O 4 The XRD pattern of the preparation method of (2) in example 1;
FIG. 2 shows a substrate having amino groups on the surface thereof according to the present inventionNano Fe of (2) 3 O 4 SEM images of the preparation process of (a) in example 1.
Detailed Description
The method utilizes a hydrothermal method, and the polyoxymethylene is decomposed into reduced formaldehyde under high-temperature hydrothermal conditions, and is cooperated with polylysine to reduce ferric iron ions, so that nano Fe is formed 3 O 4 . Nano Fe with perfect crystallization is prepared by a one-step reduction method 3 O 4 Functional particles. To improve nano Fe 3 O 4 And impart biosafety of nano Fe 3 O 4 The invention adopts polylysine as a protective agent, a dispersing agent, a reducing agent and a morphology control agent, and prepares the nano Fe with high solution dispersibility, high crystallization and surface amination by using a solvothermal and high-pressure reaction method 3 O 4 And (3) particles.
Unlike traditional hydrothermal process, the principle is that polyformaldehyde is used as reductant and can be decomposed into formaldehyde small molecules with stronger reducibility at high temperature, so that ferric ions are reduced, ferric ions can be slowly reduced into ferrous ions in a controlled manner due to slow decomposition process and moderate reducibility of formaldehyde, nanometer ferroferric oxide is formed, excessive reduction is prevented from forming elementary iron, the yield is improved, and the reaction process is slow and the protection effect of polylysine is provided, so that the particle size of the formed nanometer particles is smaller, and the generation of micron-sized particles is avoided. Nano Fe prepared 3 O 4 Has good dispersibility and heavy metal adsorption capacity in aqueous solution. The preparation method comprises the following steps:
(1) Dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N 2 For 30min to remove oxygen in the system, wherein the polyformaldehyde has a polymerization degree of n=10-30 and a polyformaldehyde concentration of 0.1% -3%, and the ferric salt is FeCl 3 、Fe 2 (SO 4 ) 3 Or Fe (NO) 3 ) 3 The mass percentage of the ferric salt in the polyoxymethylene aqueous solution is 0.01% -10%;
(2) Heating the reaction system to 30-90 ℃, adding polylysine with a certain mass into the solution, and mechanically stirring for 60-120 min to obtain transparent orange solution, wherein the polymerization degree of the polylysine is 5000-50000; the mass of the added polylysine is 10-15 times of the mass of the ferric salt;
(3) Transferring the orange solution into a hydrothermal reaction kettle to react for 3-6 hours at the temperature of 100-250 ℃ to obtain bright black nano Fe 3 O 4 A solution;
(4) Cooling the reaction final liquid, separating by using a magnet, washing with deionized water and acetone for multiple times, and drying to obtain the black superparamagnetic Fe 3 O 4 And (3) nanoparticles.
In order to make the above objects, features and advantages of the present invention more comprehensible, the following technical solutions of the present invention are further described with reference to the accompanying drawings and examples. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
In the following detailed description of the embodiments of the present invention, the schematic drawings are not to be taken in a local scale for the convenience of description, and are merely examples, which should not limit the scope of the present invention. In addition, the three-dimensional space of length, width and depth should be included in actual fabrication.
Example 1
The nano Fe with amino groups on the surface is prepared according to the following steps 3 O 4 ：
1. 0.5g FeCl was taken 3 Adding into 50g of aqueous solution of polyformaldehyde, and stirring thoroughly for 10min to obtain FeCl with mass percentage of 1% 3 Aqueous polyoxymethylene solution, said solution is introduced with N 2 Removing the solution for 30minOxygen for decomposition;
2. the reaction system was warmed to 70℃and 2g of polylysine was added to FeCl 3 Mechanically stirring for 1h to obtain an orange transparent solution;
3. transferring the reaction system into a hydrothermal reaction kettle, and reacting for 3 hours at 150 ℃ to obtain bright and black nano Fe 3 O 4 A solution;
4. cooling the reaction final liquid, separating by using a magnet, circulating deionized water and acetone for three times, washing and drying to finally obtain the polylysine-protected brownish-black nano Fe 3 O 4 And (3) particles.
Referring to fig. 1 and 2, fig. 1 shows a nano Fe with amino groups on the surface according to the present invention 3 O 4 The XRD pattern of the preparation method of (2) in example 1; FIG. 2 shows a nano Fe with amino groups on the surface 3 O 4 SEM images of the preparation process of (a) in example 1. As shown in FIG. 1, nano Fe 3 O 4 XRD diffraction peaks of (2) with Fe 3 O 4 The XRD standard spectrum of (2) corresponds to that of Fe, and 7 diffraction peaks correspond to that of Fe 3 O 4 Diffraction peaks of (220), (311), (400), (422), (511), (440) and (622) crystal planes (see standard card JCPLDS No. 21-1272), proving nano Fe 3 O 4 Is generated. As shown in FIG. 2, fe 3 O 4 The particles are more uniform and have the particle size smaller than 30nm. Therefore, the prepared particles are nano-scale, and micron-scale agglomerated particles do not appear, which indicates that the nano-particles have good dispersibility.
Example two
The nano Fe with amino groups on the surface is prepared according to the following steps 3 O 4 ：
1. 0.5g of Fe (NO) 3 ) 3 Adding into 50g of polyoxymethylene water, stirring thoroughly for 30min to obtain 1% Fe (NO) 3 ) 3 Aqueous polyoxymethylene solution, said solution is introduced with N 2 Fully removing dissolved oxygen in the solution for 30 min;
2. the temperature of the reaction system was raised to 70℃and2g of polylysine was added to Fe (NO) 3 ) 3 Mechanically stirring for 1h to obtain an orange transparent solution;
3. transferring the reaction system into a hydrothermal reaction kettle, and reacting for 3 hours at 220 ℃ to obtain bright and black nano Fe 3 O 4 A solution;
4. cooling the reaction final liquid, separating by using a magnet, circulating deionized water and acetone for three times, washing and drying to finally obtain the polylysine-protected brownish-black nano Fe 3 O 4 And (3) particles.
In conclusion, the nano Fe with the amino group on the surface 3 O 4 The preparation method of (2) utilizes polyoxymethylene to slowly decompose into formaldehyde at high temperature so as to reduce Fe 3+ The formaldehyde has moderate reducibility, prevents excessive reduction from generating simple substance iron, improves the yield, and prevents the reduction speed from being too high, thereby leading to the increase of the grain diameter. In addition, the prepared particle has the outer layer modified by polylysine, has high biosafety and compatibility, has high adsorptivity of metal ions, and can be used in the field of biomedical treatment. In particular, the other methods are compared to table 1 below.
TABLE 1
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. Nano Fe with amino group on surface 3 O 4 Is characterized in that the method comprises the following steps:
(1) Dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N 2 Removing oxygen in the system to obtain a first solution;
(2) Heating, adding polylysine into the first solution, and mechanically stirring to obtain a transparent orange solution;
(3) Transferring the orange solution into a hydrothermal reaction kettle for reaction to obtain bright black nano Fe 3 O 4 A solution;
(4) Subjecting the nano Fe to 3 O 4 Cooling the solution, separating by using a magnet, washing with deionized water and acetone for multiple times, and drying to obtain black nano Fe with amino groups on the surface 3 O 4 And (3) particles.
2. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the ferric salt in the step (1) is FeCl 3 、Fe 2 (SO 4 ) 3 And Fe (NO) 3 ) 3 Any one of the following.
3. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the polymerization degree n=10-30 of the polyformaldehyde in the step (1), and the concentration of the polyformaldehyde is 0.1% -3%.
4. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: in the step (1), after the ferric salt is dissolved in the aqueous solution of the polyoxymethylene, the mass percentage of the ferric salt is 0.01-10%.
5. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the N in the step (1) 2 The aeration time was 30min.
6. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the temperature rise in the step (2) means that the temperature is raised to 30-90 ℃.
7. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the degree of polymerization of the polylysine in the step (2) is 5000-50000.
8. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the mass of the polylysine in the step (2) is 10-15 times of the mass of the ferric salt.
9. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the time of mechanical stirring in the step (2) is 60-120 min.
10. A nano-Fe with amino groups on its surface as set forth in claim 1 3 O 4 The preparation method of (2) is characterized in that: the reaction time in the hydrothermal reaction kettle in the step (3) is 3-6h, and the temperature is 100-250 ℃.
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| KR20160145991A (en) * | 2015-06-11 | 2016-12-21 | 전북대학교산학협력단 | Magnetic nano composite and preparation method thereof |
| CN106395914A (en) * | 2016-08-31 | 2017-02-15 | 上海美吉生物医药科技有限公司 | Superparamagnetic Fe3O4 coated by oleic acid and preparation method thereof |
| CN114028423A (en) * | 2021-12-13 | 2022-02-11 | 广东粤港澳大湾区国家纳米科技创新研究院 | Application of modified nano iron oxide in preparation of medicine for preventing and/or treating inflammatory bowel diseases |
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| CZ301067B6 (en) * | 2006-02-24 | 2009-10-29 | Ústav makromolekulární chemie AV CR | Iron oxide-based superparamagnetic nanoparticles with modified surface, process of their preparation and use |
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| CN114028423A (en) * | 2021-12-13 | 2022-02-11 | 广东粤港澳大湾区国家纳米科技创新研究院 | Application of modified nano iron oxide in preparation of medicine for preventing and/or treating inflammatory bowel diseases |
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