CN111834074B - For Fe taking oleic acid as ligand3O4Method for purifying nano particles and synthesizing magnetic nano stirrer and application - Google Patents
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Abstract
The invention is to Fe taking oleic acid as ligand3O4A method for purifying nano particles and synthesizing a magnetic nano stirrer and application thereof relate to a technology for synthesizing the magnetic nano stirrer, and belong to the technical field of inorganic nano material synthesis. The technology is to synthesize Fe with oleic acid as ligand3O4Nanoparticles, by effective removal of iron oleate by-product on the surface of the particles, and subsequent Fe3O4The invention provides pretreatment before particle assembly and adjustment of an assembly mode, realizes assembly of small-size nano chains, breaks the world record of the minimum-size nano chains, greatly improves the chain forming probability of nano stirrers, and has strong practicability.
Description
Technical Field
The invention relates to a synthesis technology of a nano stirrer, in particular to a synthesis raw material-Fe for synthesizing the nano stirrer3O4A purification technology of nano particles belongs to the technical field of inorganic nano material synthesis.
Background
Stirring is the best way of mixing the liquids, and macroscopic stirring can be achieved by specially-made tools, such as electric stirrers, mechanical stirrers, and magnetic stirrers. On the other hand, the viscosity of the liquid becomes high on a microscopic scale, the reynolds number decreases, and mixing of the liquid becomes difficult. The conventional approach is to achieve a degree of liquid turbulence by constructing a temperature gradient, sonicating, and modifying the tubing. These methods are either difficult to operate, limited in use, or difficult to modify in a later manner once the pipeline is sized. Stirring is particularly important in this case.
Preparation of nanomagnetic stirrers some developments have been made in recent years, the Song group (Angew. chem.2015,127, 2699-2702) hydrothermally synthesized Fe of 250nm diameter in 20153O4The nanoclusters are self-assembled to form a nano stirrer, and the nano stirrer is supported by the nano stirrerThe palladium-loaded nano particles can realize catalysis while stirring, and are beneficial to the magnetism of the nano stirrer and the recovery of the catalyst after the reaction is finished. 150nm Fe synthesized by Deng group (adv.Mater. 2010,1707515) in 2010 using a hydrothermal method3O4Nanoparticle self-assembly Fe3O4@SiO2The nano stirrer and the zoledronate (medicine for treating bone diseases) are loaded in the mesopores, and the rotation of the nano stirrer enhances the interaction between the medicine and bone cells by applying an external magnetic field in the culture of osteoclasts, so that the effect of inhibiting the differentiation of the bone cells is achieved.
According to the applicant, the existing self-assembly technology for synthesizing the nano stirrer is based on the large-size nano particles and nano clusters synthesized by a hydrothermal method, the nano particles or nano clusters synthesized by the method are often large in size, mostly in submicron size, and easy to aggregate, and the stirring chain assembled by the particles is also large in size, so that the linear arrangement is difficult to realize. In addition, the hydrothermal method needs to be carried out in a high-pressure reaction kettle, the requirement on reaction equipment is high, the safety needs to be ensured, the equipment investment is large, and the expanded production is not facilitated.
The high-temperature cracking method has the advantages that the high temperature can well control the nucleation and growth processes of crystals, so that nanoparticles with smaller particle size and more uniform distribution can be obtained, meanwhile, the reaction is carried out in an organic phase, and the participation of water with strong coordination capacity with iron ions is avoided, so that magnetic nanoparticles with good crystal forms can be obtained. The singapore team in 2013 reported that the magnetic nanoparticles synthesized by the method are assembled into a stirring chain in an aqueous solution, and a world record of the smallest stirring chain is kept, wherein the diameter is 75nm at the minimum and the length is micron-sized. The patent (CN 107138093A) relates to the synthesis of magnetic nano-stirrers, ligand exchange and magnetic field induced assembly. The method is mainly used for assembling the large-size magnetic nanoparticle chain. Firstly, the assembly of the small-size magnetic nanoparticles is influenced by surface oily substances in the small-size magnetic nanoparticle synthesis process; secondly, the magnetic field response is weak relative to large particles; most importantly, the brownian motion of small particles in the solution is obvious, and the directional arrangement and fixation are difficult to realize by a conventional method of assembling and coating at the same time.
The magnetic nano stirrer has been developed in many ways, and the inventor knows that the existing self-assembly technology for synthesizing the nano stirrer is based on the large-size nano particles and nano clusters synthesized by a hydrothermal method, the synthesized nano particles and nano clusters synthesized by a high-temperature cracking method have larger sizes and are easy to aggregate, the formed nano stirrer cannot be linearly arranged, and when the size of the nano particles is reduced, the magnetic property of the nano stirrer is reduced, and the response of an applied magnetic field is weakened. The high temperature cracking method can control the grain size and size distribution of the nanometer grain well, and the seed growing concept can grow small grain into large grain with excellent crystallization degree. Superparamagnetic Fe with good crystallinity can be synthesized by high-temperature cracking method3O4And (3) nanoparticles.
Therefore, in the work, magnetic nanoparticles with uniform appearance are prepared by a high-temperature cracking method, the particle size is 9-110 nm, and the size is controllable. At the moment, the surface of the nano-particles is often coated with a layer of macromolecular oily by-product consisting of iron ions and organic matters, so that the magnetic interaction among the nano-particles is influenced, and the appearance of a chain is influenced in the process of hydrolyzing and coating the silicon salt. But the by-product is difficult to remove by conventional washing and centrifuging methods. Our work characterized the oily by-product, determined its approximate composition, and then selected the appropriate solvent to swell, through the swelling, the oily by-product, can pass the specific centrifugal speed and particle separation, realized the particle purification, after the purification between the small particles becomes small, the magnetic response is strengthened. The nanoparticles are better aligned when the magnetic field is small, and the silicon dioxide coating is well aligned magnetic chains instead of aggregates mixed with byproducts. Therefore, the magnetic chain with strong magnetism and small size is obtained, and the later test also shows that the magnetic chain has excellent stirring performance.
Disclosure of Invention
The technical problem solved by the invention is as follows: for Fe taking oleic acid as ligand3O4NanoparticlesThe method for purifying and synthesizing the magnetic nano stirring particles and the application thereof, namely Fe synthesized by carrying out pyrolysis on oleic acid3O4The nanoparticles are treated in a specific mode, a corresponding assembly mode is selected, so that the effective assembly of the magnetic nanoparticle chains can be realized, particularly, the minimum nanometer stirring chain is prepared to be less than 200nm, and the magnetic nanometer stirrer is applied to cell reaction or promotes the stirring and mixing of liquid in a narrow space.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: by using oleic acid as ligand Fe3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1) using high temperature cracking method to obtain Fe3O4A nanoparticle;
(2) mixing the Fe obtained in the step (1)3O4Soaking the nano-particles in an organic solvent to swell the ferric oleate by-product;
(3) separating Fe from the product of step (2) by low speed centrifugation3O4Nanoparticles and iron oleate byproduct, Fe centrifugally precipitated3O4Re-dispersing the nanoparticles in an organic solvent;
(4) fe taking oleic acid as ligand in the step (3)3O4Hydrophilic ligand exchange is carried out on the nano particles to obtain water-soluble Fe3O4Nanoparticles, wherein the particle size range of the particles is between 9nm and 110 nm;
(5) for nanosphere Fe with weak magnetism or less than 25nm3O4Carrying out magnetic field induced self-assembly arrangement on the nano particles for a certain time, adding a silicon source for hydrolysis, coating and fixing the arranged nano particles, and carrying out Fe treatment in the step (4)3O4Under the action of an external magnetic field, the nano particles are linearly arranged, tetraethoxysilane is used as a silicon source, and silicon oxide is wrapped and fixed to obtain a magnetic nano stirrer; wherein, the self-assembly and the wrapping of the silicon shell are simultaneously carried out on the particles with the wavelength of 25nm to 110nm and the nano-stereo.
Preferably, there are two types of said oleic acid cleavage process, the first being: mixing and heating ferric chloride serving as an iron source and sodium oleate to obtain an oil-ferrite complex, and then heating and refluxing the oil-ferrite complex in a high-boiling-point solvent to obtain ferroferric oxide nanospheres; wherein the particle size is less than 25 nm; the second method is as follows: and heating and refluxing iron acetylacetonate serving as an iron source in oleic acid and a high-boiling-point solvent to obtain the ferroferric oxide nanocube, wherein the particle size range of the particles is 25-110 nm.
Preferably, the method comprises the following steps:
(1) fe with different sizes and particle diameters less than 25nm is prepared3O4Nanospheres;
(2) mixing the Fe obtained in the step (1)3O4Soaking the nanospheres in an organic solvent to swell the iron oleate byproduct;
(3) separating Fe from the product of step (2) by low speed centrifugation3O4Nanoparticles and iron oleate byproduct, Fe centrifugally precipitated3O4Re-dispersing the nanoparticles in an organic solvent;
(4) fe taking oleic acid as ligand in the step (3)3O4Hydrophilic ligand exchange is carried out on the nano particles to obtain water-soluble Fe3O4Nanoparticles, wherein the particle size range is 9nm to 25 nm;
(5) mixing the Fe obtained in the step (4)3O4Under the action of an external magnetic field, the nano particles are linearly arranged, standing is carried out for 6-24 hours, tetraethoxysilane is used as a silicon source, and silicon oxide is wrapped and fixed to obtain the magnetic nano stirrer.
Preferably, in the step (2), an organic solvent comprising toluene, N-dimethylformamide, tetrahydrofuran or o-dichlorobenzene is used for swelling, and the soaking time is 12-48 hours, so that the iron oleate byproduct is swelled; the organic solvent in the step (3) comprises dichloromethane, ethanol, chloroform, toluene, tetrahydrofuran, o-dichlorobenzene or N, N-dimethylformamide.
Preferably, step (3) uses a centrifugation method to separate the particles from the byproducts, and the centrifugation speed is 200-2000 g.
Preferably, in step (4), the hydrophilic ligand is citric acid, polyvinylpyrrolidone or4-mercaptobenzoic acid, Fe for assembly alignment obtained3O4The nano particles are nanospheres or nanocubes, and the size is 9 nm-110 nm.
Preferably, the external magnetic field used in the step (5) is applied by a neodymium iron boron magnet for 6-24 hours.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the magnetic nano stirrer prepared by any method.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: for Fe taking oleic acid as ligand3O4The application of the magnetic nano stirrer is used for stirring in cell reaction or promoting the stirring and mixing of liquid in a narrow space.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the magnetic nano stirrer is applied to the preparation of tumor drugs or the liquid mixing in microchannels, microreactors and micro liquid drops in a biochip.
Has the advantages that:
1. magnetic nanoparticles with uniform appearance, including magnetic nanospheres and nanocubes, are prepared by a high-temperature cracking method, and the size is controllable. At the moment, the surface of the nano-particles is often coated with a layer of macromolecular oily by-product consisting of iron ions and organic matters, so that the magnetic interaction among the nano-particles is influenced, and the appearance of a chain is influenced in the process of hydrolyzing and coating the silicon salt. But the by-product is difficult to remove by conventional washing and centrifuging methods. Our work characterized an oily by-product, determined its approximate composition, and then selected the appropriate solvent and time to swell, the oily by-product, through a specific centrifugal speed and particle separation, achieved particle purification, purification of small particles after the separation of small particles, magnetic response enhancement. The nanoparticles are better arranged under the action of a magnetic field, and the silicon dioxide coats the orderly arranged magnetic chains instead of the aggregates mixed with by-products or the oily hollow spheres. We also propose different coating schemes for different particle sizes. Therefore, the magnetic chain with strong magnetism and small size is obtained, and the later test also shows that the magnetic chain has excellent stirring performance.
2. It is a preparation technology of nano stirrer, in particular to a synthetic raw material-Fe for synthesizing nano stirrer3O4Purification technology of nano particles. The technology synthesizes Fe by cracking oleic acid at high temperature3O4Treating the nanoparticles in a specific manner to obtain iron oleate byproduct and Fe3O4Separating the nanoparticles to obtain purified Fe3O4And (3) carrying out ligand exchange on the nano particles, and then carrying out self-assembly by using an external magnetic field to obtain the nano stirring particles.
3. The technology selects a high-temperature cracking method to prepare the magnetic nanoparticles. The high-temperature cracking method has the advantages that the high temperature can well control the nucleation and growth processes of crystals, so that nanoparticles with smaller particle size and more uniform distribution can be obtained, meanwhile, the reaction is carried out in an organic phase, and the participation of water with strong coordination capacity with iron ions is avoided, so that magnetic nanoparticles with good crystal forms can be obtained.
4. When the metal oxide material is prepared by a high-temperature oleic acid cracking method, oily byproducts are ubiquitous, and the presence of the oily byproducts negatively affects the use of subsequent nano materials. The patented process has general applicability to the purification of oily by-products produced by such preparation processes. The patent verifies that the ferroferric oxide nanospheres and the nanocubes with different sizes are practical and effective by taking the ferroferric oxide nanospheres and the nanocubes as research objects.
5. The purification method is simple to operate, and the separation effect of the nano material and the by-product is good. The oily by-product is first characterized to determine its approximate composition, then the solvent of the synthesis is selected to swell, after more than 12 hours of swelling, and then the by-product is separated from the particles in coordination with a specific centrifugation speed.
6. The method verifies the structure-activity relationship between the nano-particle soaking time and the magnetic chain assembly, and obtains a conclusion that the soaking time influences the swelling degree of the polymer and the separation difficulty degree of the polymer and the particles, and the separation proportion of oily byproducts is increased along with the prolonging of the soaking time, so that the number of silicon dioxide hollow spheres in nano-chains in the arranged and coated product and the aggregation degree among the particles are reduced, the diameter of the nano-magnetic chain is reduced, and the directional arrangement trend is gradually clear.
7. The patent verifies the structure-activity relationship between the centrifugation rate and the flux linkage assembly. Wherein centrifugation plays a key role for the separation of oily by-products. But as the centrifuge rate continued to increase beyond the critical value (2000g), more by-products could not be separated but instead settled with the particles in the bottom layer. The increased aggregation of particles is difficult to chain.
8. Aiming at the preparation process of the nano stirrer, the invention explores two assembling modes: firstly, the self-assembly and the wrapping of the silicon shell are carried out simultaneously, and the scheme is suitable for Fe with strong magnetism3O4A nanoparticle; is a mode reported by the prior art, is effective for particles larger than 25nm and nano-sized stereo, and secondly, magnetic field induced self-assembly arrangement is firstly carried out for a certain time, then a silicon source is added for hydrolysis, and the arranged nano-particles are coated and fixed, so that the method is suitable for the Fe nanospheres with weak magnetism or smaller than 25nm3O4And (3) nanoparticles.
9. The technology used in the patent can realize the preparation of magnetic nano stirring chains with different sizes. Stirrers from 160nm in length to micron size can be prepared by this method. Especially small-sized nano stirring chains. The minimum stir chain size is still 75nm 4000nm in journal of the German applied chemistry published by the Hongyu Chen subject group in 2013, and the work of us regulates the minimum diameter to 21nm and the minimum length to 160nm, refreshing the world record. The difficulty of small particle assembly is that the brownian (irregular) motion is obvious, and the magnetic field response is weaker than that of large particles, so that the large particles are difficult to be directionally arranged and assembled into a straight chain. The patent realizes the preparation of the small-size stirring chain by preparing small particles by a high-temperature cracking method, combining with the purification of magnetic nano particles and ligand exchange.
10. The minimum nano stirring chain prepared by the invention is less than 200nm, is the minimum world record at present, can provide a tool for stirring in a small space, and is matched with the size required by cell therapy, so that a new visual angle is hopefully provided for cancer therapy.
Drawings
FIG. 1 shows the physical analysis of oily by-products, where a is FT-IR infrared analysis, b is X-ray crystal diffraction, c and d are X-ray photoelectron spectroscopy, and e and f are thermogravimetric and differential scanning calorimetric analysis.
FIG. 2 is a transmission electron microscope image of a nano-stirrer assembled by 10nm ferroferric oxide nanospheres according to the invention.
FIG. 3 is a transmission electron microscope image of a nano-stirrer synthesized by 25nm ferroferric oxide nanocubes according to the present invention.
FIG. 4 is a transmission electron microscope image of ferroferric oxide nano-stirrers when the magnetic induction arrangement and the coating of 10nm particles are carried out synchronously.
FIG. 5 is a transmission electron microscope image of assembled nano-sized iron oxide spheres without by-product treatment.
FIG. 6 is a transmission electron microscope image of assembled ferroferric oxide nanocubes without by-product treatment.
FIG. 7 is a transmission electron microscope image of assembled ferroferric oxide nanoparticles when the soaking time is less than 12 hours.
FIG. 8 is a transmission electron microscope image of assembled ferroferric oxide nanoparticles extracted at a centrifugation speed of 2500 g.
FIG. 9 stir bar field response performance.
FIG. 10 shows the stirring test for magnetic chains with different diameters.
Fig. 11 is a morphology diagram of the magnetic stirring chain of the present invention, wherein a is a transmission electron microscope diagram of the magnetic stirring chain formed by assembling nanocubes, b is a scanning electron microscope diagram of the magnetic stirring chain formed by assembling nanocubes, and c and d are transmission electron microscope diagrams of the magnetic stirring chain formed by assembling nanospheres.
Detailed Description
Example 1:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1) 3.65g of sodium oleate is weighed and added into 28mL of ethanol, deionized water and normal hexaneThe mixed solution of (1) was stirred to be sufficiently dissolved, and then 1.08g of ferric chloride hexahydrate was added thereto, followed by heating to 70 ℃ for reflux reaction for 4 hours. Cooling to room temperature, extracting with 10mL of water, rotary steaming the extracted solution to obtain reddish brown waxy solid which is ferric oleate mixture, then stirring and mixing the mixture with 20.57g of oleic acid and octadecene, heating to 320 ℃ for 30min, cooling to room temperature, precipitating with 50mL of ethanol to separate out nanospheres, dispersing the precipitate with 50mL of trichloromethane to obtain Fe with particle size of 10nm3O4A nanosphere solution.
(2) And (3) carrying out physical analysis on the by-products generated in the synthesis of the magnetic nanoparticles, thereby establishing a removal method of the by-products. First, the results (FIG. 1a) show that the by-product has the same carbon chain oscillation peak as the product, and the Fe-O peak appears at the same position. By XRD analysis (FIG. 1b), the by-product is not ferroferric oxide crystal and is in an amorphous state. The iron in this by-product was divalent by XPS test analysis (FIG. 1c, d). By TGA thermogravimetric analysis and DSC scanning quantitative analysis (FIG. 1e, f), 99% of the by-products are organic macromolecules, and the decomposition is complete at about 500 ℃. Therefore, the side product can be judged to be a mixture of iron and organic macromolecules, the content of CHO is 96%, the content of Fe is low and 4%, and the iron exists in an ionic state. The macromolecule is formed by polymerization of organic substances added in the pyrolysis process and belongs to the same type as the organic substances added in the reaction, so that the enriched-CH is aimed at2and-C ═ O macromolecules are screened out of corresponding organic solvents and are swelled.
(3) Soaking Fe in the step (1) in 3mL of toluene3O4Soaking the nanospheres in the solution for 12 h.
(4) The Fe treated in the step (2) is3O4The nanosphere solution was centrifuged at 500g of centrifugal force and the resulting precipitate was dispersed in 1mL of chloroform to give Fe3O4A solution of nanospheres.
(5) Mixing the Fe obtained in step (3)3O4Adding 1000 mu L of the nanosphere solution into a mixed solution of 0.3g of citric acid, 12mL of 1, 2-dichlorobenzene and N, N-dimethylformamide, uniformly mixing, and heating to 100 ℃ for reaction overnight. Cooling the reaction solution toCentrifuging at room temperature, removing supernatant to obtain precipitate, washing the precipitate with ethanol, centrifuging again to obtain precipitate, and dispersing in water to obtain water soluble 10nm Fe3O4A nanosphere solution.
(6) Mixing the Fe obtained in the step (4)3O4The nanosphere solution is mixed with 12mL of isopropanol and deionized water and placed in a 4mL glass sample bottle, after being uniformly mixed by vortex, the nanosphere solution is immediately placed beside a neodymium iron boron magnet and is kept stand overnight, so that stirrers are arranged in advance. Then 60. mu.L of ammonia water and 10. mu.L of ethyl orthosilicate were added for coating fixation. Centrifuging, taking the precipitate, removing supernatant, cleaning the precipitate with ethanol, and dispersing in ethanol to obtain the nano stirrer with the width of 43nm and the length of 160 nm. The morphology under transmission electron microscope is shown in detail in FIG. 2.
Example 2:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1) adding 0.706g of ferric acetylacetonate into a mixed solution of 10.4g of oleic acid, 4-phenylbenzoic acid and dibenzyl ether, placing the mixture into a three-neck round-bottom flask, keeping the mixture for 1h, heating the mixture to 290 ℃, reacting the mixture for 30min, cooling the mixture to room temperature, washing the mixture with a mixed solution of 40mL of toluene and 10mL of n-hexane, centrifuging and dispersing the mixture to obtain 25nm Fe3O4A nanocube.
(2) Measuring 1mL of Fe in the step (1)3O4The nanocube solution was dispersed in 3mL of toluene and soaked for 36 h.
(3) The Fe treated in the step (2) is3O4The nanocubes were centrifuged at 500g and the resulting precipitate was dispersed in 1mL chloroform to give Fe3O4A solution of nanocubes.
(4) 500. mu.L of Fe from step (3)3O4The method comprises the following steps of uniformly mixing a nanocube solution, 0.3g of citric acid, 12mL of a mixed solution of 1, 2-dichlorobenzene and N, N-dimethylformamide (the volume ratio is 1:1), and heating for reacting overnight. Cooling the reaction solution to room temperature, centrifuging, collecting supernatant, collecting precipitate, washing the precipitate with ethanol, and centrifuging again to obtain the final productThe available precipitate was redispersed with 1mL of deionized water to give 25nm Fe which was water soluble3O4A nanocube solution.
(5) Mixing the Fe obtained in the step (4)3O4Mixing the nano cubic solution with isopropanol and ionized water, adding 60 mu L of ammonia water and 10 mu L of ethyl orthosilicate, placing the mixture in a 4mL glass sample bottle, uniformly mixing the mixture in a vortex manner, immediately placing the mixture beside a neodymium iron boron magnet, standing the mixture overnight, washing the mixture with ethanol after centrifugation, and dispersing the mixture in the ethanol to obtain a nano stirrer with the width of 40nm and the length of 5-15 mu m. The morphology under transmission electron microscope is shown in detail in FIG. 3.
Example 3:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) The nanosphere soaking method was the same as example 1.
(3) The Fe treated in the step (2) is3O4The nanosphere solution was centrifuged at 500g of centrifugal force and the resulting precipitate was dispersed in 1mL of chloroform to give Fe3O4A solution of nanospheres.
(4) The nanosphere solution ligand exchange method was the same as example 1.
(5) The assembly procedure was the same as in example 1. To obtain the nano stirrer with the width of 50nmm and the length of 280 nm.
Example 4:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) The nanosphere soaking method was the same as example 1.
(3) The Fe treated in the step (2) is3O4The nanosphere solution was centrifuged at 1500g and the resulting precipitate was dispersed in 1mL chloroform to give Fe3O4A solution of nanospheres.
(4) The nanosphere solution ligand exchange method was the same as example 1.
(5) The assembly procedure was the same as in example 1. To obtain a nano stirrer with the width of 36nm and the length of 400 nm.
Example 5:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)25nm of Fe3O4The nanocube solution was prepared as in example 1.
(2) The nanocube soaking method was the same as in example 1.
(3) The Fe treated in the step (2) is3O4Centrifuging the nanocube solution under 500g of centrifugal force, dispersing the obtained precipitate in 1mL of ethanol to obtain Fe3O4A solution of nanocubes.
(4) The nanocube solution ligand exchange method was the same as in example 1.
(5) The assembly procedure was the same as in example 1. To obtain the nano stirrer with the width of 56nm and the length of 1-2 mu m.
Example 6:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)25nm of Fe3O4The nanocube solution was prepared as in example 2.
(2) The nanocube soaking method was the same as in example 2.
(3) The Fe treated in the step (2) is3O4Centrifuging the nanocube solution under 1500g of centrifugal force, dispersing the obtained precipitate in 1mL of dichloromethane to obtain Fe3O4A solution of nanocubes.
(4) The nanocube solution ligand exchange method was the same as in example 2.
(5) The assembly procedure was the same as in example 2. To obtain the nano stirrer with the width of 94nm and the length of 0.6 to 2 mu m.
Example 7:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)25nm of Fe3O4The nanocube solution was prepared as in example 2.
(2) The nanocube soaking method was the same as in example 2.
(3) The Fe treated in the step (2) is3O4Centrifuging the nanocube solution at 2000g centrifugal force, dispersing the obtained precipitate in 1mL chloroform to obtain Fe3O4A solution of nanocubes.
(4) The nanocube solution ligand exchange method was the same as in example 2.
(5) The assembly procedure was the same as in example 2. To obtain the nano stirrer with the width of 70nm and the length of 0.6 to 2 mu m.
The invention can be realized at different centrifugal speeds of 500 g-2000 g, and the higher the speed is, the smaller the diameter of the obtained stirrer is.
Example 8:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) 1mL of Fe in step (1)3O4The nanosphere solution was dispersed in 3mL o-dichlorobenzene and soaked for 24 h.
(3) Nanosphere centrifugation was performed as in example 1.
(4) The nanosphere solution ligand exchange method was the same as example 1.
(5) The assembly procedure was the same as in example 1. Obtaining the nano stirrer with the width of-36 nm and the length of 5-700 nm.
Example 9:
for Fe taking oleic acid as ligand3O4A method for purifying nanoparticles and synthesizing magnetic nano-stirrers, comprisingThe method comprises the following steps:
(1)25nm of Fe3O4The nanocube solution was prepared as in example 2.
(2) Measuring 1mL of Fe in the step (1)3O4The nanocube solution was dispersed in 3mL of tetrahydrofuran and soaked for 36 h.
(3) The nanocube centrifugation method was the same as in example 2.
(4) The nanocube solution ligand exchange method was the same as in example 2.
(5) The assembly procedure was the same as in example 2. To obtain the nano stirrer with the width of 200nm and the length of 1.5-4 mu m.
Example 10:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)25nm of Fe3O4The nanocube solution was prepared as in example 2.
(2) Measuring 1mL of Fe in the step (1)3O4The nanocube solution was dispersed in 3mL of N, N dimethylformamide and soaked for 48 h.
(3) The nanocube centrifugation method was the same as in example 2.
(4) The nanocube solution ligand exchange method was the same as in example 2.
(5) The assembly procedure was the same as in example 2. To obtain the nano stirrer with the width of 160nm and the length of 1-2 mu m.
The method can be used for soaking for 12-48 hours, wherein the soaking time is long, and the size of the stirrer is small.
Example 11:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1) iron (III) acetylacetonate (0.706g) was added to a mixture of 5g oleic acid and benzyl ether. The mixture solution was degassed at room temperature for 1 hour. The solution was then heated to 290 ℃ at a rate of 15 ℃/min with vigorous magnetic stirring. Will reactThe mixture was held at this temperature for 60 minutes. Cooled to room temperature, centrifuged and dispersed in 10mL chloroform to give 110nm Fe3O4A solution of nanocubes.
(2) The organic solvent soaking treatment method of the nanocubes is the same as that of example 2.
(3) The nanocube centrifugation method was the same as in example 2.
(4) The nanocube solution ligand exchange method was the same as in example 2.
(5) Mixing the Fe obtained in the step (4)3O4The nanocube solution is uniformly mixed with 12mL of isopropanol and deionized water, then 60 mu L of ammonia water and 10 mu L of ethyl orthosilicate are added for vortex mixing, and the mixture is immediately placed beside a neodymium iron boron magnet and stands for 6 hours, so that stirrers are arranged and coated and fixed at the same time. Centrifuging, taking the precipitate, removing supernatant, cleaning the precipitate with ethanol, and dispersing in ethanol to obtain the nano stirrer with the width of 140nm and the length of 1.5 mu nm.
FIG. 9 the stirrer was dry with stirring on, and the SEM frozen its stirred state, i.e. the stirrer was messy with spin centers; when the magnetic field is off, the magnetic field is directionally arranged along the direction of the magnetic field. Showing the magnetic field response performance.
FIG. 10 shows the stirring test for magnetic chains with different diameters. Fe3O4The magnetic chains assembled by the nanospheres and the cubes have a flickering phenomenon, and the stirring performance is proved.
Comparative example 1:
for Fe taking oleic acid as ligand3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer comprises the following steps:
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) The nanosphere soaking method was the same as example 1.
(3) The nanosphere solution centrifugation method was the same as example 1.
(4) The nanosphere solution ligand exchange method was the same as example 1.
(5) Mixing the Fe obtained in the step (4)3O4Mixing the nanosphere solution with 12ml isopropanol and deionized water, and mixingAdding 60 mu L of ammonia water and 10 mu L of ethyl orthosilicate, placing the mixture into a 4mL glass sample bottle, mixing the mixture evenly by vortex, immediately placing the mixture beside a neodymium iron boron magnet, and standing the mixture overnight. And (3) washing with ethanol after centrifugation, and dispersing in ethanol to obtain the nano stirrer, wherein the nano particles in the stirrer are distributed along the axial direction, the width of the nano stirrer is 80nm, and the length of the nano stirrer is 5-15 microns. The morphology under transmission electron microscope is shown in detail in FIG. 4.
Comparative example 2:
the magnetic nanospheres with the size of 10nm are directly subjected to magnetic assembly arrangement without organic solvent soaking pretreatment.
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) The nanosphere solution ligand exchange method was the same as example 1.
(3) The assembly procedure was the same as in example 1. The obtained nano stirrers are connected together in a net structure, and the chain forming effect is poor. The morphology under transmission electron microscope is shown in detail in FIG. 5.
Comparative example 3:
the nanocubes are directly subjected to magnetic assembly arrangement without organic solvent soaking pretreatment.
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 2.
(2) The nanosphere solution ligand exchange method was the same as example 2.
(3) The assembly procedure was the same as in example 2. The obtained nano stirrers are connected together in a net structure, the chain forming effect is poor, and the result shows that the magnetic nanoparticles are difficult to assemble into chains without organic solvent pretreatment. The product is shown in FIG. 6.
Comparative example 4:
in magnetic assembly arrangements with magnetic nanospheres, lower soaking times are used.
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) 1mL of Fe in step (1)3O4The nanosphere solution was dispersed in 3mL tetrahydrofuran and soaked for 10 h.
(3) Nanosphere centrifugation was performed as in example 1.
(4) The nanosphere solution ligand exchange method was the same as example 1.
(5) The assembly procedure was the same as in example 1. The obtained product contains spherical substances wrapped by silicon dioxide, and the aggregation degree of the nano particles is severe, so that a small amount of chain can be formed, but the chain forming size and the shape are irregular. The morphology under transmission electron microscope is shown in detail in FIG. 7.
Comparative example 5:
in the magnetic assembly arrangement with 10nm magnetic nanospheres, critical value centrifugation speed is used for purification.
(1)10nm of Fe3O4The nanosphere solution was prepared as in example 1.
(2) The nanosphere soaking method was the same as example 1.
(3) The Fe treated in the step (2) is3O4The nanosphere solution was centrifuged at 2500g of centrifugal force and the resulting precipitate was dispersed in 1mL of chloroform to give Fe3O4A solution of nanospheres.
(4) The nanosphere solution ligand exchange method was the same as example 1.
(5) The assembly procedure was the same as in example 1. At this time, no nanobelt was obtained, and mostly dispersed large aggregates. The morphology under transmission electron microscope is shown in detail in FIG. 8.
Finally, it should be emphasized that the ranges of the technical parameters mentioned in the technical solutions of the present invention, such as concentration, volume, solvent ratio, etc., can be adjusted without being limited by the actual parameters mentioned herein. In addition, the above detailed description of the present invention is only for illustrating the technical solutions of the present invention and not limited to the specific examples described in the present invention, and it should be understood by those skilled in the art that any modifications or equivalent substitutions for achieving the same technical effects are within the scope of the present invention.
Claims (10)
1. By using oleic acid as ligand Fe3O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer is characterized by comprising the following steps: the method comprises the following steps:
(1) make itPreparing Fe by high-temperature cracking method3O4A nanoparticle;
(2) mixing the Fe obtained in the step (1)3O4Soaking the nano-particles in an organic solvent to swell the ferric oleate by-product;
(3) separating Fe from the product of step (2) by low speed centrifugation3O4Nanoparticles and iron oleate byproduct, Fe centrifugally precipitated3O4Re-dispersing the nanoparticles in an organic solvent;
(4) fe taking oleic acid as ligand in the step (3)3O4Hydrophilic ligand exchange is carried out on the nano particles to obtain water-soluble Fe3O4A nanoparticle;
(5) for nanosphere Fe of 9 nm-25 nm3O4Nano particles are firstly arranged in a certain time of magnetic field induction self-assembly, then a silicon source is added for hydrolysis, the arranged nano particles are coated and fixed, and Fe is added3O4Under the action of an external magnetic field, the nanospheres are linearly arranged, tetraethoxysilane is used as a silicon source, and silicon oxide is wrapped and fixed to obtain a magnetic nano stirrer; wherein for nano cubic Fe of 25 nm-110 nm3O4And (3) nano particles are coated by self-assembly and silicon shells at the same time.
2. Fe with oleic acid as ligand in claim 13O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer is characterized by comprising the following steps: the high-temperature cracking method has two types, wherein the first type is as follows: mixing and heating ferric chloride serving as an iron source and sodium oleate to obtain an oil-ferrite complex, and then heating and refluxing the oil-ferrite complex in a high-boiling-point solvent to obtain ferroferric oxide nanospheres; wherein the particle size is less than 25 nm; the second method is as follows: and heating and refluxing iron acetylacetonate serving as an iron source in oleic acid and a high-boiling-point solvent to obtain the ferroferric oxide nanocube, wherein the particle size range of the particles is 25-110 nm.
3. Fe with oleic acid as ligand in claim 23O4Purification of nanoparticlesThe method for synthesizing the magnetic nano stirrer is characterized by comprising the following steps: the method comprises the following steps:
(1) fe with different sizes and particle diameters less than 25nm is prepared3O4Nanospheres;
(2) mixing the Fe obtained in the step (1)3O4Soaking the nanospheres in an organic solvent to swell the iron oleate byproduct;
(3) separating Fe from the product of step (2) by low speed centrifugation3O4Nanoparticles and iron oleate byproduct, Fe centrifugally precipitated3O4Re-dispersing the nanoparticles in an organic solvent;
(4) fe taking oleic acid as ligand in the step (3)3O4Hydrophilic ligand exchange is carried out on the nano particles to obtain water-soluble Fe3O4Nanoparticles, wherein the particle size range is 9nm to 25 nm;
(5) mixing the Fe obtained in the step (4)3O4Under the action of an external magnetic field, the nano particles are linearly arranged, standing is carried out for 6-24 hours, tetraethoxysilane is used as a silicon source, and silicon oxide is wrapped and fixed to obtain the magnetic nano stirrer.
4. Fe with oleic acid as ligand in claim 13O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer is characterized by comprising the following steps: swelling by using an organic solvent comprising toluene, tetrahydrofuran, o-dichlorobenzene or N, N-dimethylformamide in the step (2), wherein the soaking time is 12-48 hours, so that the iron oleate byproduct is swelled; the organic solvent in the step (3) comprises dichloromethane, ethanol, chloroform, toluene, tetrahydrofuran, N-dimethylformamide or o-dichlorobenzene.
5. Fe with oleic acid as ligand in claim 13O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer is characterized by comprising the following steps: in the step (3), the particles are separated from the by-products by using a centrifugal method, wherein the centrifugal rotating speed is 200-2000 g.
6. Fe with oleic acid as ligand in claim 13O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer is characterized by comprising the following steps: in the step (4), the hydrophilic ligand is citric acid, polyvinylpyrrolidone or 4-mercaptobenzoic acid, and the obtained Fe for assembly arrangement3O4The nano particles are nanospheres with the size of 9nm to 25nm or nanocubes with the size of 25nm to 110 nm.
7. Fe with oleic acid as ligand in claim 13O4The method for purifying the nano particles and synthesizing the magnetic nano stirrer is characterized by comprising the following steps: and (3) applying an external magnetic field used in the step (5) through a magnet, wherein the magnet is a neodymium iron boron magnet, and the application time of the magnetic field is 6-24 hours.
8. A magnetic nanoscrer prepared according to any of the methods of claims 1-7.
9. The method of claim 8 on Fe with oleic acid as the ligand3O4The application of purifying nano particles and synthesizing magnetic nano stirrers is characterized in that: the magnetic nano stirrer is applied to stirring in cell reaction or promoting the stirring and mixing of liquid in a narrow space.
10. The method of claim 8 on Fe with oleic acid as the ligand3O4The application of purifying nano particles and synthesizing magnetic nano stirrers is characterized in that: the magnetic nano stirrer is applied to the preparation of tumor drugs or the liquid mixing in microchannels, microreactors and micro liquid drops in a biochip.
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