CN102887546A - Water-soluble ferroferric oxide nano particle, preparation method and application thereof - Google Patents
Water-soluble ferroferric oxide nano particle, preparation method and application thereof Download PDFInfo
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- CN102887546A CN102887546A CN201110205131XA CN201110205131A CN102887546A CN 102887546 A CN102887546 A CN 102887546A CN 201110205131X A CN201110205131X A CN 201110205131XA CN 201110205131 A CN201110205131 A CN 201110205131A CN 102887546 A CN102887546 A CN 102887546A
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Abstract
The invention discloses a water-soluble ferroferric oxide nano particle and a preparation method and application thereof. The preparation method comprises the following steps of: 1, in the presence of phenylcarbinol, carrying out thermal decomposition on an organic precursor of iron, carrying out solid-liquid separation to obtain a ferroferric oxide particle; 2, washing the ferroferric oxide particle obtained in the step 1 by using alcohol with low carbon chain to remove phenylcarbinol; and 3, mixing a water-soluble ligand solution with the ferroferric oxide particle washed in the step 2 to obtain the water-soluble ferroferric oxide particle. By adopting the method provided by the invention, the water-soluble ferroferric oxide particle with uniform particle diameter and good dispersibility can be obtained; and the preparation method has the advantages of convenience, easy operation and mild condition and is suitable for mass production.
Description
Technical field
The present invention relates to a kind of water-soluble ferroferric oxide nanoparticle and its preparation method and application.
Background technology
Magnetic ferroferric oxide nano-particles is a kind of important nano material, it is applied in many fields at present, such as magnetic separation, Magnetic resonance imaging, target drug-carrying, magnetic transportation, magnetic recording material etc., the precondition of these application is to obtain uniform particle diameter, good dispersity, magnetic response is good, surface chemical property is controlled nanoparticle.Usually also require ferriferrous oxide nano-particle to have in the biological medicine application facet good water-soluble.
The current method for preparing ferriferrous oxide nano-particle mainly contains coprecipitation method and high temperature thermal decomposition method.Wherein, coprecipitation method be by under alkaline condition with iron salt hydrolysis, this method can directly obtain water miscible ferriferrous oxide nano-particle, but its crystal formation is relatively poor, Particle dispersity, homogeneity are relatively poor, easily reunite.And the high temperature thermal decomposition method generally refers to be higher than under 250 ℃ in temperature, and under the condition that the tensio-active agents such as oleic acid, oleyl amine exist, the organic precursor that decomposes iron, such as pentacarbonyl-iron, ferric acetyl acetonade, iron oleate etc., the prepared ferriferrous oxide nano-particle crystal formation of this method is better, good dispersity, uniform particle diameter, but it is water-insoluble nanoparticle, therefore, it is carried out phase transition to water difficulty comparatively, need loaded down with trivial details surface ligand displacement link, thereby limited it in the application in the fields such as biological medicine.
Summary of the invention
The objective of the invention is to have good homogeneity, dispersiveness, magnetic responsiveness concurrently in order to overcome the ferriferrous oxide nano-particle that adopts prior art to produce, and water miscible defective, provide a kind of and can have good homogeneity, dispersiveness, magnetic responsiveness concurrently, and the preparation method of water miscible ferriferrous oxide nano-particle and the ferriferrous oxide nano-particle and the application that are obtained by this preparation method.
The invention provides a kind of preparation method of water-soluble ferroferric oxide nanoparticle, wherein, the method may further comprise the steps:
(1) in the presence of phenylcarbinol, the organic precursor of iron is carried out thermolysis, and carry out solid-liquid separation, obtain ferriferrous oxide nano-particle;
(2) alcohol with low carbon chain washs the ferriferrous oxide nano-particle that step (1) obtains, to remove phenylcarbinol wherein;
(3) water soluble ligand solution is mixed with the ferriferrous oxide nano-particle that washs through step (2), obtain the water-soluble ferroferric oxide nanoparticle.
The present invention also provides the water-soluble ferroferric oxide that is prepared by aforesaid method nanoparticle, and wherein, the particle diameter of described water-soluble ferroferric oxide nanoparticle is the 7-12 nanometer.
In addition, the present invention also provides the application of above-mentioned water-soluble ferroferric oxide nanoparticle in Magnetic resonance imaging and target administration.
Adopt method provided by the invention to prepare ferriferrous oxide nano-particle, carry out thermolysis by the organic precursor with iron, can obtain the ferriferrous oxide nano-particle of uniform particle diameter, good dispersity; And by the ferriferrous oxide nano-particle of gained being carried out the modification of water soluble ligand, can obtain water miscible ferriferrous oxide nano-particle.The result shows by Zeta electric potential, the ferriferrous oxide nano-particle that adopts method of the present invention to prepare has higher stability, this will be conducive to the water-soluble ferroferric oxide nanoparticle and have more wide application prospect at biomedicine field, such as Magnetic resonance imaging, target administration etc.In addition, method of the present invention is easy, easy handling, mild condition, and can realize batch production.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the water-soluble ferroferric oxide nanoparticle that makes of embodiment 1;
Fig. 2 is the Zeta electric potential distribution plan of the water-soluble ferroferric oxide nanoparticle that makes of embodiment 1;
Fig. 3 is the particle size distribution figure of the water-soluble ferroferric oxide nanoparticle that makes of embodiment 1;
Fig. 4 is the magnetic hysteresis loop figure of the water-soluble ferroferric oxide nanoparticle of embodiment 1 preparation.
Embodiment
According to the preparation method of water-soluble ferroferric oxide nanoparticle provided by the invention, wherein, the method may further comprise the steps:
(1) in the presence of phenylcarbinol, the organic precursor of iron is carried out thermolysis, and carry out solid-liquid separation, obtain ferriferrous oxide nano-particle;
(2) alcohol with low carbon chain washs the ferriferrous oxide nano-particle that step (1) obtains, to remove phenylcarbinol wherein;
(3) water soluble ligand solution is mixed with the ferriferrous oxide nano-particle that washs through step (2), obtain the water-soluble ferroferric oxide nanoparticle.
According to the present invention, in the step (1), described phenylcarbinol master joins in the reaction system as reaction medium, and described phenylcarbinol is easy to remove by washing, can not be wrapped in the surface of ferriferrous oxide nano-particle.The present invention is not particularly limited the quality of the organic precursor of the described iron ratio with the volume of phenylcarbinol, and under the preferable case, in the quality of the organic precursor of 1mg iron, the volume of described phenylcarbinol is 10-40mL, more preferably 25-40mL.
According to the present invention, in the step (1), organic precursor of described iron can be existing various organic precursors that can decompose the iron that generates ferriferrous oxide nano-particles, for example, can be selected from ferric acetyl acetonade, pentacarbonyl-iron and the iron oleate one or more.
According to the present invention, in the step (1), the condition of described thermolysis is not particularly limited, as long as being decomposed, organic precursor of iron generates ferriferrous oxide nano-particle, for example, the condition of described thermolysis generally includes heat decomposition temperature and thermal decomposition time, preferably, described heat decomposition temperature is 150-200 ℃, and thermal decomposition time is 1-4 hour.
According to the present invention, the ferriferrous oxide nano-particle that generates is easily oxidized, therefore, preferably, described pyrolysis carries out in inert atmosphere, described inert atmosphere refers to not any one gas or the gaseous mixture with reactant and product generation chemical reaction, such as in nitrogen, helium and the periodic table of elements zero group gas one or more.Keep inert atmosphere method can in reaction system, pass into above-mentioned not with any one gas or the gaseous mixture of reactant and product generation chemical reaction.
According to the present invention, in step (1), after the organic precursor of iron carried out thermolysis, the thermal decomposition product that obtains is carried out the method that solid-liquid separation obtains ferriferrous oxide nano-particle can be the conventional various solid-liquid separating methods in this area, obtain ferriferrous oxide nano-particle as long as can separate, for example, the methods such as gravity settling, centrifugation, filtration.Because ferriferrous oxide nano-particle has magnetic, therefore, the method that can preferably adopt magnetic to separate is carried out solid-liquid separation and is obtained ferriferrous oxide nano-particle, for example, magnet is being attached on the container outer wall, attracting ferriferrous oxide nano-particle, and solvent is being discharged from container.
According to the present invention, in step (2), purpose with the washing of the alcohol of low carbon chain is in order to remove the phenylcarbinol on the ferriferrous oxide nano-particle surface that thermolysis obtains in the step (1), to make the over-all properties of the ferriferrous oxide nano-particle that obtains more excellent.The alcohol of described low carbon chain can be selected from the alcohol of the various low carbon chain of this area routine, as, carbonatoms is the alcohol of C1-C4, specifically can be selected from methyl alcohol, ethanol, propyl alcohol and the butanols one or more, but consider from composite factors such as price and environmental protection, the alcohol of described low carbon chain is preferably ethanol.
The present invention is not particularly limited the concentration of the water soluble ligand solution described in the step (3), the present inventor finds through further investigation, when the concentration of described water soluble ligand solution more than or equal to 0.01mol/L, when being preferably 0.01-0.05mol/L, the water-soluble ferroferric oxide nanoparticle of gained water-soluble fabulous.
According to the present invention, described water soluble ligand can be existing various water soluble ligands, can combine with the ferriferrous oxide nano-particle that generates as long as satisfy, thereby generating the water-soluble ferroferric oxide nanoparticle gets final product, preferably, described water soluble ligand is Tetramethylammonium hydroxide part (being called for short TMAH).
Under the preferable case, it is more even for described water soluble ligand is mixed with ferriferrous oxide nano-particle, thereby obtain the water-soluble ferroferric oxide nanoparticle of uniform particle diameter, under the preferable case, the mixture of described water soluble ligand and ferriferrous oxide nano-particle can also be vibrated or ultrasonic.
The present invention also provides the water-soluble ferroferric oxide that obtains by aforesaid method nanoparticle, and wherein, the particle diameter of described water soluble nanometer particles is the 7-12 nanometer.
The water-soluble ferroferric oxide nanoparticle that the method according to this invention obtains can be widely used at biomedicine field, for example, and Magnetic resonance imaging and target administration.
The present invention is further illustrated below with reference to embodiment, but therefore do not limit the present invention.
Embodiment 1
The present embodiment is used for illustrating the preparation of water-soluble ferroferric oxide nanoparticle provided by the invention.
(1) in the 50mL there-necked flask, adds 0.5g ferric acetyl acetonade and 25mL phenylcarbinol, magnetic agitation makes the methyl ethyl diketone dissolved ferric iron, under the protection of nitrogen, at the uniform velocity be warming up to 195 ℃, and at 195 ℃ of lower reaction 2h, after magnetic resolution, obtain the black ferroferric oxide nanoparticle, Fig. 1 is the transmission electron microscope photo of this ferriferrous oxide nano-particle;
(2) get 200 microlitres by the ferriferrous oxide nano-particle of step (1) gained, wash with the 10mL ethanolic soln, utilize the ferriferrous oxide nano-particle after magnet separates the acquisition washing, wash as stated above three times;
(3) be that the tetramethylammonium hydroxide aqueous solution of 0.05mol/L mixes with the ferriferrous oxide nano-particle after the washing of step (2) gained and 5mL concentration, 30 ℃ of lower ultra-sonic dispersion 30 minutes, can obtain the water-soluble ferroferric oxide nanoparticle of transparent and homogeneous.
Fig. 2 is the zeta potential profile of water-soluble ferroferric oxide nanoparticle, and its value is-55.1mV; Fig. 3 is that (X-coordinate represents electromotive force to the size distribution figure that obtains by dynamic light scattering of water-soluble ferroferric oxide nanoparticle, ordinate zou represents total quantity), can find out, the particle diameter of the nanoparticle after modifying with Tetramethylammonium hydroxide mainly is distributed in 8-10nm; Fig. 4 is the magnetic hysteresis loop figure (X-coordinate represents magnetic field, and ordinate zou represents saturation magnetic field intensity) of water-soluble ferroferric oxide nanoparticle, and its saturation magnetization is about 64.8emu/g.
Embodiment 2
The present embodiment is used for illustrating the preparation of water-soluble ferroferric oxide nanoparticle provided by the invention.
(1) add 0.5g ferric acetyl acetonade and 15mL phenylcarbinol in the 50mL there-necked flask, magnetic agitation makes the methyl ethyl diketone dissolved ferric iron, under the protection of nitrogen, at the uniform velocity be warming up to 150 ℃, and at 150 ℃ of lower reaction 4h, after magnetic resolution, obtain the black ferroferric oxide nanoparticle;
(2) get 200 microlitres by the ferriferrous oxide nano-particle of step (1) gained, wash with the 10mL ethanolic soln, utilize the ferriferrous oxide nano-particle after magnet separates the acquisition washing, wash as stated above three times;
(3) be that the tetramethylammonium hydroxide aqueous solution 5mL of 0.01mol/L mixes with the ferriferrous oxide nano-particle after the washing of step (2) gained and 5mL concentration, 30 ℃ of lower ultra-sonic dispersion 30 minutes, can obtain the water-soluble ferroferric oxide nanoparticle of transparent and homogeneous.
Embodiment 3
The present embodiment is used for illustrating the preparation of water-soluble ferroferric oxide nanoparticle provided by the invention.
(1) add 0.5g ferric acetyl acetonade and 12.5mL phenylcarbinol in the 50mL there-necked flask, magnetic agitation makes the methyl ethyl diketone dissolved ferric iron, under the protection of nitrogen, at the uniform velocity be warming up to 175 ℃, and at 175 ℃ of lower reaction 2h, after magnetic resolution, obtain the black ferroferric oxide nanoparticle;
(2) get 200 microlitres by the ferriferrous oxide nano-particle of step (1) gained, wash with the 10mL ethanolic soln, utilize the ferriferrous oxide nano-particle after magnet separates the acquisition washing, wash as stated above three times;
(3) falling ferriferrous oxide nano-particle and 5mL concentration after the washing of step (2) gained is that the tetramethylammonium hydroxide aqueous solution of 0.03mol/L mixes, 30 ℃ of lower ultra-sonic dispersion 30 minutes, can obtain the water-soluble ferroferric oxide nanoparticle of transparent and homogeneous.
Embodiment 4
The present embodiment is used for illustrating the preparation of water-soluble ferroferric oxide nanoparticle provided by the invention.
(1) add 0.5g ferric acetyl acetonade and 8mL phenylcarbinol in the 50mL there-necked flask, magnetic agitation makes the methyl ethyl diketone dissolved ferric iron, under the protection of nitrogen, at the uniform velocity be warming up to 195 ℃, and at 195 ℃ of lower reaction 2h, after magnetic resolution, obtain the black ferroferric oxide nanoparticle;
(2) get 200 microlitres by the ferriferrous oxide nano-particle of step (1) gained, wash with the 10mL methanol solution, utilize the ferriferrous oxide nano-particle after magnet separates the acquisition washing, wash as stated above three times;
(3) be that the tetramethylammonium hydroxide aqueous solution of 0.05mol/L mixes with the ferriferrous oxide nano-particle after the washing of step (2) gained and 5mL concentration, 30 ℃ of lower ultra-sonic dispersion 10 minutes, can obtain the water-soluble ferroferric oxide nanoparticle of transparent and homogeneous.
Embodiment 5
The present embodiment is used for illustrating the preparation of water-soluble ferroferric oxide nanoparticle provided by the invention.
(1) add 0.5g iron oleate and 20mL benzyl alcohol solution in the 50mL there-necked flask, magnetic agitation makes the methyl ethyl diketone dissolved ferric iron, under the protection of nitrogen, at the uniform velocity be warming up to 195 ℃, and at 195 ℃ of lower reaction 3h, after magnetic resolution, obtain the black ferroferric oxide nanoparticle;
(2) get 200 microlitres by the ferriferrous oxide nano-particle of step (1) gained, wash with the 10mL ethanolic soln, utilize the ferriferrous oxide nano-particle after magnet separates the acquisition washing, wash as stated above three times;
(3) be that the tetramethylammonium hydroxide aqueous solution of 0.02mol/L mixes with the ferriferrous oxide nano-particle after the washing of step (2) gained and 5mL concentration, 30 ℃ of lower ultra-sonic dispersion 30 minutes, can obtain the water-soluble ferroferric oxide nanoparticle of transparent and homogeneous.
Claims (10)
1. the preparation method of a water-soluble ferroferric oxide nanoparticle is characterized in that, the method may further comprise the steps:
(1) in the presence of phenylcarbinol, the organic precursor of iron is carried out thermolysis, and carry out solid-liquid separation, obtain ferriferrous oxide nano-particle;
(2) alcohol with low carbon chain washs the ferriferrous oxide nano-particle that step (1) obtains, to remove phenylcarbinol wherein;
(3) water soluble ligand solution is mixed with the ferriferrous oxide nano-particle that washs through step (2), obtain the water-soluble ferroferric oxide nanoparticle.
2. preparation method according to claim 1, wherein, in the step (1), in the quality of the organic precursor of 1mg iron, the volume of described phenylcarbinol is 10-40mL, is preferably 25-40mL.
3. preparation method according to claim 1 and 2, wherein, in the step (1), organic precursor of described iron is selected from one or more in ferric acetyl acetonade, pentacarbonyl-iron and the iron oleate.
4. preparation method according to claim 1, wherein, in the step (1), the condition of described thermolysis comprises: the temperature of thermolysis is 150-200 ℃, the time of thermolysis is 1-4 hour.
5. according to claim 1 or 4 described preparation methods, wherein, described thermolysis is carried out under protection of inert gas.
6. preparation method according to claim 1, wherein, in the step (2), the alcohol of described low carbon chain is selected from one or more in methyl alcohol, ethanol, propyl alcohol and the butanols.
7. preparation method according to claim 1, wherein, in the step (3), the concentration of described water soluble ligand solution is more than or equal to 0.01mol/L, is preferably 0.01-0.05mol/L.
8. according to claim 1 or 7 described preparation methods, wherein, described water soluble ligand is the Tetramethylammonium hydroxide part.
9. the water-soluble ferroferric oxide nanoparticle that obtains of the described preparation method of any one claim according to claim 1-8, wherein, the particle diameter of described water-soluble ferroferric oxide nanoparticle is the 7-12 nanometer.
10. the application of the described water-soluble ferroferric oxide nanoparticle of claim 9 in Magnetic resonance imaging and target administration.
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