CN105097170A - Magnetic nanoparticles, preparation method and application therefor - Google Patents
Magnetic nanoparticles, preparation method and application therefor Download PDFInfo
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- CN105097170A CN105097170A CN201410203774.4A CN201410203774A CN105097170A CN 105097170 A CN105097170 A CN 105097170A CN 201410203774 A CN201410203774 A CN 201410203774A CN 105097170 A CN105097170 A CN 105097170A
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Abstract
The invention provides magnetic nanoparticles. The magnetic nanoparticles contain one or more of group IB metal oxides, group IIB metal oxides, group IIIB metal oxides, group IVB metal oxides, group VB metal oxides, group VI metal oxides, group VII metal oxides and group VIII metal oxides, and the grain diameters are 0.5-15 nm. The invention also provides composite magnetic nanoparticles which are obtained by wrapping the magnetic nanoparticles with hydrophilic polymers, and the grain diameters of the composite magnetic nanoparticles are not greater than 60 nm. Both of the magnetic nanoparticles and the composite magnetic nanoparticles can be used for wave-absorbing materials, manufacturing of electronic devices, information storage materials, magnetic resonance imaging contrast mediums, targeted drugs, cell separation and the like.
Description
Technical field
The application relates to a kind of magnetic nano-particle, preparation method and application thereof.The application also relates to a kind of composite magnetic nano particle, preparation method and application thereof.
Background technology
Along with the development of science and technology, Medical Imaging Technology obtains and develops rapidly, serves vital effect, substantially increase the cure rate of cancer patient, saved more life diagnosis morning and early treatment realizing cancer.
At present, Medical Imaging Technology mainly comprises positron emission tomography imaging (PositronEmissionTomography, PET), computer tomography (ComputedTomography, and magnetic resonance imaging (Magneticresonanceimaging, MRI) etc. CT).Wherein, magnetic resonance imaging is the difference utilizing different tissues proton density in organism, the difference demonstrating signal strength signal intensity is embodied as picture, because it is highly sensitive, selectivity is good, check without wound, multi-parameter imaging, particularly MRI does not comprise ionising radiation (X ray as used in CT has high-energy radiation, may DNA damage be caused), now become clinical in one of the most widely used Medical Imaging Technology.
The power of magnetic resonance signal depends on the relaxation time of proton in the content of water in tissue and hydrone, longitudinal relaxation time (Longitudinalrelaxationtime, T
1) and T2 (Transverserelaxationtime, T
2).Because between tissue, the difference of proton density is only 10%, during clinical MRI checks, often through use image enhancing agents, this image enhancing agents can change the local magnetic field around proton, the relaxation time T of proton
1and T
2also can change, thus change the magnetic resonance signal intensity of tissue, improve image contrast and the definition of normal tissues and disease sites tissue.
There is the metal oxide of multiple unpaired electron, such as Fe
3o
4, γ-Fe
2o
3, Mn
3o
4, GdO etc., because its electron spin magnetic moments is large, relaxivity is high, can be used as good MRI radiography material.Oxide bad dispersibility in aqueous prepared by conventional method is its fatal shortcoming always, by the modifying surface at oxide of the hydrophilic polymer of good biocompatibility or directly carry out coated, the dispersiveness of oxide in water greatly can be improved.
Based on above situation, develop the preparation method of a kind of good water solubility, good biocompatibility, ultra-small grain size magnetic nano-particle that magnetic susceptibility is high, and the nano particle prepared is applied in MRI radiography material, develop contributing to the T that a kind of imaging resolution is high, signal is abundant
1/ T
2the MRI contrast agent of weighted signal, to reduction medical science test-and-treat cost, ensures that people's life and health have great importance.
Summary of the invention
For solving the problem, the ultra-small grain size magnetic nano-particle that the application provides a kind of good water solubility, good biocompatibility, magnetic susceptibility height MRI reduction of contrast signal good, it is characterized in that, described magnetic nano-particle consist of optionally in the oxide of the oxide of the oxide of the oxide of the oxide of IB race metal, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the oxide of VI race metal, the oxide of VII race metal and group VIII metal oxide one or more; The particle diameter of described magnetic nano-particle is 0.5 ~ 15nm.
Preferably, described magnetic nano-particle consist of in the oxide of oxide, the oxide of manganese, the oxide of gadolinium, the oxide of cobalt, the oxide of nickel and the chromium of appointing the oxide of chosen from Fe, zinc one or more.
Preferably, described magnetic nano-particle contains Fe
3o
4, γ-Fe
2o
3, Mn
3o
4, GdO, Gd
2o
3, ZnO, MFe
2o
4or TMn
2o
4; Wherein MFe
2o
4in M be optionally from Zn, Co, Ni, Cr and Mn one or more; TMn
2o
4in T be optionally from one or more of Zn, Fe, Co, Ni and Cr.
Preferably, the particle size range of described magnetic nano-particle is 1 ~ 10nm.
Preferably, the particle size range of described magnetic nano-particle is 3 ~ 5nm.
Preferably, the particle size range of described magnetic nano-particle is 2 ~ 5nm
Present invention also provides the preparation method of above-mentioned magnetic nano-particle, it is characterized in that, comprise following steps: (a), by the solution containing organic acid and/or acylate, mixes with the solution containing metal ion, obtained presoma;
B the presoma of step (a) gained is placed in Organic Alcohol by (), react under inert gas shielding, obtained described magnetic nano-particle.
Preferably, a kind of organic acid is had in organic acid described in step (a) at least for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl.
Preferably, organic acid described in step (a) is oleic acid and/or linoleic acid.
Preferably, acylate described in step (a) is organic acid slaine and/or ammonium salt, organic acid for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl.
Preferably, acylate described in step (a) is oleate and/or linoleate.
Preferably, one or more optionally in the alkali salt of the alkali metal salt of oleic acid, oleic acid, the ammonium salt of oleic acid, linoleic alkali metal salt, linoleic alkali salt, linoleic ammonium salt of acylate described in step (a).
Preferably, acylate described in step (a) is enuatrol and/or potassium oleate.
Preferably, metal ion described in step (a) is one or more optionally in the ion of the ion of the ion of the ion of IB race metal ion, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the ion of VI race metal, the ion of VII race metal and group VIII metal ion.
Preferably, metal ion described in step (a) be appoint in the ion of the ion of the ion of the ion of the ion of chosen from Fe, zinc, manganese, gadolinium, the ion of cobalt, the ion of nickel and chromium one or more.
Preferably, in described step (a), the temperature preparing presoma is 40 ~ 100 DEG C.
Preferably, in described step (b), under inert gas shielding, reaction temperature is 250 ~ 400 DEG C.
Preferably, in described step (b), under inert gas shielding, the reaction time is 10 ~ 200 minutes.
The application also provides a kind of composite magnetic nano particle, it is characterized in that, outside magnetic nano-particle, is enclosed with hydrophilic polymer; Described magnetic nano-particle consist of optionally in the oxide of the oxide of the oxide of the oxide of the oxide of IB race metal, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the oxide of VI race metal, the oxide of VII race metal and group VIII metal oxide one or more; The particle diameter of described magnetic nano-particle is 0.5 ~ 15nm; The particle diameter of described composite magnetic nano particle is not more than 60nm.
Preferably, described magnetic nano-particle consist of in the oxide of oxide, the oxide of manganese, the oxide of gadolinium, the oxide of cobalt, the oxide of nickel and the chromium of appointing the oxide of chosen from Fe, zinc one or more.
Preferably, described magnetic nano-particle contains Fe
3o
4, γ-Fe
2o
3, Mn
3o
4, GdO, Gd
2o
3, ZnO, MFe
2o
4or TMn
2o
4; Wherein MFe
2o
4in M be optionally from Zn, Co, Ni, Cr and Mn one or more; TMn
2o
4in T be optionally from one or more of Zn, Fe, Co, Ni and Cr.
Preferably, the particle size range of described magnetic nano-particle is 1 ~ 10nm; The particle diameter of described composite magnetic nano particle is 5 ~ 30nm.
Preferably, the particle size range of described magnetic nano-particle is 2 ~ 5nm; The particle diameter of described composite magnetic nano particle is 5 ~ 20nm.
Preferably, described hydrophilic polymer is one or more optionally in tetraethoxysilane, polyethylene glycol, glucan, polyacrylic acid, γ-glycidyl ether oxygen propyl trimethoxy silicane (hereinafter referred to as KH560), gamma-aminopropyl-triethoxy-silane (hereinafter referred to as KH550), polyoxyethylene-poly-oxypropylene polyoxyethylene (hereinafter referred to as F127), polyoxyethylenes (5) nonylplenyl ether (hereinafter referred to as CO-520), albumin.
Preferably, one or more optionally in tetraethoxysilane, polyethylene glycol, glucan and polyacrylic acid of described hydrophilic polymer.
The application also provides the preparation method of above-mentioned composite magnetic nano particle, comprises following steps:
A (), by the solution containing organic acid and/or acylate, mixes with the solution containing metal ion, obtained presoma;
B the presoma of step (a) gained is placed in Organic Alcohol by (), react under inert gas shielding, obtained magnetic nano-particle;
C (), by step (b) gained magnetic nano-particle, is placed in hydrophilic polymer and/or the solution containing hydrophilic polymer, obtained described composite magnetic nano particle.
Preferably, a kind of organic acid is had in organic acid described in step (a) at least for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl.
Preferably, organic acid described in step (a) is oleic acid and/or linoleic acid.
Preferably, acylate described in step (a) is organic acid slaine and/or ammonium salt, organic acid for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl.
Preferably, acylate described in step (a) is oleate and/or linoleate.
Preferably, one or more optionally in the alkali salt of the alkali metal salt of oleic acid, oleic acid, the ammonium salt of oleic acid, linoleic alkali metal salt, linoleic alkali salt, linoleic ammonium salt of acylate described in step (a).
Preferably, metal ion described in step (a) is one or more optionally in the ion of the ion of the ion of the ion of IB race metal ion, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the ion of VI race metal, the ion of VII race metal and group VIII metal ion.
Preferably, the described hydrophilic polymer of step (c) is one or more optionally in tetraethoxysilane, polyethylene glycol, glucan, polyacrylic acid, KH560, KH550, F127, CO-520, albumin.
Preferably, metal ion described in step (a) be appoint in the ion of the ion of the ion of the ion of the ion of chosen from Fe, zinc, manganese, gadolinium, the ion of cobalt, the ion of nickel and chromium one or more.
Preferably, in described step (a), the temperature preparing presoma is 40 ~ 100 DEG C.
Preferably, under inert gas shielding, reaction temperature is 250 ~ 400 DEG C.
Preferably, under inert gas shielding, the reaction time is 10 ~ 200 minutes.
Preferably, in step (c), the weight ratio of described magnetic nano-particle and hydrophilic polymer is 1:5 ~ 25; Preferable range is 1:12 ~ 18, and preferred scope is 1:14 ~ 16 further.
As one preferred embodiment, the preparation of composite magnetic nano particle comprises the steps:
A oleate is dissolved in organic solvent mixed liquor by (), add in metal salt solution, reacts at 40 ~ 100 DEG C, obtained oleic acid metal precursor;
B presoma is dissolved in oleyl alcohol by (), react under high temperature, obtained oxide nano-particles;
C () carries out surface modification or parcel to obtained nano-oxide, the hydrophilic polymer for wrapping up comprises tetraethoxysilane, polyethylene glycol, glucan, KH560, KH550, F127, polyacrylic acid, albumin.
Arbitrary magnetic nano-particle that the application provides and arbitrary composite magnetic nano particle, all can be used as absorbing material.
Arbitrary magnetic nano-particle that the application provides and arbitrary composite magnetic nano particle, all can be used for manufacturing electronic device.
Arbitrary magnetic nano-particle that the application provides and arbitrary composite magnetic nano particle, all can be used as information storage material aspect, particularly there is magnetic nano-particle and the composite magnetic nano particle of giant magnetoresistance effect, as information storage material, significantly can provide storage density.
Arbitrary magnetic nano-particle that the application provides and arbitrary composite magnetic nano particle, all can be used for magnetic resonance imaging contrast, for the preparation of MRI imaging with having T
1during the radiography material of the magnetic resonance imaging signal of weighting, infantile tumour can be diagnosed.
Arbitrary magnetic nano-particle that the application provides and arbitrary composite magnetic nano particle, all can be used for targeted drug.
Arbitrary magnetic nano-particle that the application provides and arbitrary composite magnetic nano particle, all can be used for cell separation technology.
The beneficial effect of technical scheme described in the application is:
(1) magnetic nano-particle provided and composite magnetic nano particle, have that even particle size distribution, size are controlled, the advantage such as good water solubility, good biocompatibility;
(2) magnetic nano-particle provided and composite magnetic nano particle, all can be used for the aspects such as absorbing material, electronic device manufacture, information storage material, magnetic resonance imaging contrast, targeted drug and cell separation;
(3) magnetic nano-particle provided and composite magnetic nano particle, have medical MRI radiography function, and compared with the gadolinium complex contrast agent of medically clinical practice, radiography performance is significantly improved, and can be used for early detection and the diagnosis of tumour.
(4) preparation method provided is simple, is easy to large-scale production.
Should be understood that within the scope of the technical scheme that discloses in the application, above-mentioned each technical characteristic of the application and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the application's method.The use that better implementation method described in literary composition and material only present a demonstration.
Accompanying drawing explanation
The Fe of Fig. 1 prepared by embodiment 2
3o
4the phenogram of magnetic nano particle subsample, wherein (a) is transmission electron microscope photo; B () is high-resolution-ration transmission electric-lens photo; C () is electronic energy spectrum; D () is M-H magnetization curve.
The Fe of Fig. 2 prepared by embodiment 2
3o
4the magnetic resonance imaging test T of magnetic nano-particle
1/ T
2weighted imaging figure.
The Mn of Fig. 3 prepared by embodiment 3
3o
4the phenogram of magnetic nano particle subsample, wherein (a) is transmission electron microscope photo; B () is high-resolution-ration transmission electric-lens photo; C () is electronic energy spectrum; D () is M-H magnetization curve.
The Mn of Fig. 4 prepared by embodiment 3
3o
4the magnetic resonance imaging test T of magnetic nano-particle
1/ T
2weighted imaging figure.
The phenogram of the GdO magnetic nano particle subsample of Fig. 5 prepared by embodiment 4, wherein (a) is transmission electron microscope photo; B () is high-resolution-ration transmission electric-lens photo; C () is electronic energy spectrum.
The magnetic resonance imaging test T of the GdO magnetic nano-particle of Fig. 6 prepared by embodiment 4
1/ T
2weighted imaging figure.
The phenogram of the ZnO magnetic nano particle subsample of Fig. 7 prepared by embodiment 5, wherein (a) is transmission electron microscope photo; B () is high-resolution-ration transmission electric-lens photo; C () is electronic energy spectrum.
The Silica-coated Fe of Fig. 8 prepared by embodiment 9
3o
4the phenogram of composite magnetic nano particle sample, wherein (a) is transmission electron microscope photo; B () is high-resolution-ration transmission electric-lens photo.
Embodiment
Present application discloses a kind of preparation method preparing magnetic nano-particle of simple universal, then use stabilizer (such as hydrophilic polymer) to its modifying surface or parcel, thus obtain stable magnetic nano particle compound.Reaching by controlling stabilizing agent dosage etc. the particle diameter controlling compound, making it have good permeability and retention effect (EPR effect, i.e. passive target function of tumor) to tumor tissues.Add and by MRI weighted imaging figure, its radiography function to be evaluated.Complete technical scheme described in the application on this basis.
Described magnetic nano-particle is prepared especially by following steps:
A oleate is dissolved in organic solvent mixed liquor by (), add in metal salt solution, reacts at 40-100 DEG C, obtained oleic acid metal precursor;
B presoma is dissolved in oleyl alcohol by (), react under high temperature, obtained magnetic oxide nano particle;
C () is to the modifying surface of obtained magnetic nano-particle or parcel, thus obtained stable magnetic nano particle compound.
Loaded in reagent bottle by prepared magnetic nano-particle, the refrigerator putting into about 4 DEG C is waited to be used as MRI radiography material; Or dialysed by product, and after carrying out freeze drying process, obtain powdery product do preparation for subsequent use MRI radiography material.
The magnetic nano particle compound prepared by said method can be uniformly dispersed in the aqueous solution, can preserve for a long time in the environment of 4 DEG C, occurs without deposited phenomenon, proves that magnetic nano particle compound has well dispersed and aqueous stability.
The above-mentioned feature that the application mentions, or the feature that embodiment is mentioned can combination in any.All features that this case specification discloses can with any composition forms and use, each feature disclosed in specification, anyly can be provided identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage and number calculate by weight.
When not doing specified otherwise, the test condition that the application is general is as follows:
(1) transmission electron microscope characterizes (being called for short TEM to characterize)
JEOL-2100 type transmission electron microscope carries out, test condition: 200Kv, 101 μ A.
(2) high resolution TEM characterizes (being called for short HRTEM to characterize)
JEOL-2100 type transmission electron microscope carries out, test condition: 200Kv, 101 μ A.
(3) electron spectrum characterizes (being called for short EDS to characterize)
JEOL-2100 transmission electron microscope carries out, test condition: 200Kv, 101 μ A.
(4) particle size determination
Domain size distribution (irregularly shaped just by the ultimate range measured value in shape) is characterized according to ImageJ statistics.
(5) M-H curve characterizes
Model-9PPMS type physical testing system is carried out, test condition: 300k ,-30-30kOe.
(6) MRI characterizes
Test condition is T
1: TR=8000ms, TE=200ms, T
2: TR=4000ms, TE=200ms.
Embodiment 1 prepares oleic acid metal precursor
(1) take 3 ~ 3.5g slaine, under room temperature magnetic agitation, be dissolved in the 15mL aqueous solution, obtain solution A stand-by;
(2) take 7 ~ 11g enuatrol, under room temperature magnetic agitation, be dissolved in 5mL water, 25mL ethanol and 45mL cyclohexane mixed solution, to guarantee that enuatrol fully dissolves, obtain B solution stand-by;
(3) B solution is added in solution A, at 80 DEG C, magnetic agitation 4 hours;
(4) treat that above-mentioned reactant liquor is cooled to room temperature, be poured into separatory funnel and leave standstill, collect organic solvent layer;
(5) wash organic layer solution with warm water, wash 3 times;
(6) by the reactant of previous step at 40 DEG C dry 24 hours, by clean for cyclohexane evaporation, obtained oleic acid metal precursor.
Embodiment 2
(1) take 2g iron oleate presoma, room temperature mechanical is dissolved in 18mL oleyl alcohol under stirring;
(2) 320 DEG C are heated to, at N
2the lower mechanical agitation of protection 1 hour, obtains magnetic Fe
3o
4nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with acetone, reactant liquor is washed three times, obtain pure magnetic Fe
3o
4nano-particle solution.
Adopt TEM, HRTEM, EDS and M-H to obtained magnetic Fe
3o
4nano particle is analyzed, and result is as shown in Fig. 1 (a-d), and result shows the good dispersion of nano particle, uniform particle sizes, and has certain patterned features, and according to ImageJ statistics, particle diameter is 4nm.
To obtained magnetic Fe
3o
4nano particle carries out the T of MRI
1weighted imaging.MRI test condition is T
1: TR=8000ms, TE=200ms, T2:TR=4000ms, TE=200ms.As can be seen from Figure 2, with the T of the aqueous solution
1weighted imaging picture contrasts, magnetic Fe
3o
4nano particle T
1weighted imaging picture obviously brightens, the magnetic Fe obtained by proving
3o
4nano particle can as good T
1radiography material.
Embodiment 3
(1) take 3g manganese oleate, room temperature mechanical is dissolved in 30mL oleyl alcohol under stirring;
(2) 380 DEG C are heated to, at N
2the lower mechanical agitation of protection 10 minutes, obtains magnetic Mn
3o
4nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with acetone, reactant liquor is washed three times, obtain pure magnetic Mn
3o
4nano-particle solution.
Adopt TEM, HRTEM, EDS and M-H to obtained magnetic Mn
3o
4nano particle is analyzed, and result is as shown in Fig. 3 (a ~ d), and result shows the good dispersion of nano particle, uniform particle sizes, and has certain patterned features, and according to ImageJ statistics, particle diameter is 3.5nm.
To obtained magnetic Mn
3o
4nano particle carries out the T of MRI
1weighted imaging.MRI test condition is T
1: TR=8000ms, TE=200ms, T2:TR=4000ms, TE=200ms.As can be seen from Figure 4, with the T of the aqueous solution
1weighted imaging picture contrasts, magnetic Mn
3o
4nano particle T
1weighted imaging picture obviously brightens, the magnetic Mn obtained by proving
3o
4nano particle can as good T
1radiography material.
Embodiment 4
(1) take 2g oleic acid gadolinium, room temperature mechanical is dissolved in 18mL oleyl alcohol under stirring;
(2) 280 DEG C are heated to, at N
2the lower mechanical agitation of protection 90 minutes, obtains magnetic GdO nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with acetone, reactant liquor is washed three times, obtain pure magnetic GdO nano-particle solution.
Adopt TEM, HRTEM, EDS and M-H to analyze obtained magnetic GdO nano particle, result is as shown in Fig. 5 (a ~ c), and result shows the good dispersion of nano particle, uniform particle sizes, and there is certain patterned features, according to ImageJ statistics, particle diameter is 1.5nm.
Obtained magnetic GdO nano particle is carried out to the T of MRI
1weighted imaging.MRI test condition is T
1: TR=8000ms, TE=200ms.As can be seen from Figure 6, with the T of the aqueous solution
1weighted imaging picture contrasts, magnetic GdO nano particle T
1weighted imaging picture obviously brightens, and the magnetic GdO nano particle obtained by proving can as good T
1radiography material.
Embodiment 5
(1) take 2g zinc oleate, room temperature mechanical is dissolved in 18mL oleyl alcohol under stirring;
(2) 380 DEG C are heated to, at N
2the lower mechanical agitation of protection 50 minutes, obtains magnetic ZnO nanoparticle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with cyclohexane, reactant liquor is washed three times, obtain pure magnetic ZnO nanoparticle solution.
Adopt TEM, HRTEM, EDS and M-H to analyze obtained magnetic ZnO nanoparticle, result is as shown in Fig. 7 (a ~ c), and result shows the good dispersion of nano particle, uniform particle sizes, and there is certain patterned features, according to ImageJ statistics, particle diameter is 10nm.
Embodiment 6
(1) take 2g iron oleate, room temperature mechanical is dissolved in 18mL oleyl alcohol under stirring;
(2) 300 DEG C are heated to, at N
2the lower mechanical agitation of protection 40 minutes hours, obtains magnetic Fe
3o
4nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with cyclohexane acetone mixture, reactant liquor is washed three times, obtain pure magnetic Fe
3o
4nano-particle solution.
Adopt TEM to obtained extra small Fe
3o
4nano particle is analyzed, and according to ImageJ statistics, domain size distribution is at 2.5nm.
Embodiment 7
(1) take 2g iron oleate+2g manganese oleate, room temperature mechanical is dissolved in 25mL oleyl alcohol under stirring;
(2) be heated to 250 DEG C, under He protection, mechanical agitation 80 minutes, obtains magnetic Fe
xmn
1-xo
4nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with the mixed liquor of cyclohexane acetone water, reactant liquor is washed three times, obtain pure magnetic ZnO nanoparticle solution.
Adopt TEM to obtained magnetic Fe
xmn
1-xo
4nano particle is analyzed, and according to ImageJ statistics, particle diameter is 2nm.
Embodiment 8
(1) take 3.5g manganese oleate, room temperature mechanical is dissolved in 18mL oleyl alcohol under stirring;
(2) be heated to 290 DEG C, under Ar protection, mechanical agitation 3 hours, obtains extra small Mn
3o
4nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with the mixed liquor of cyclohexane acetone water, reactant liquor is washed three times, obtain pure magnetic Mn
3o
4nano-particle solution.
Adopt TEM to obtained extra small Mn
3o
4nano particle is analyzed, and according to ImageJ statistics, particle diameter is 14nm.
Embodiment 9
(1) take 3g oleic acid gadolinium, room temperature mechanical is dissolved in 24mL oleyl alcohol under stirring;
(2) 320 DEG C are heated to, at N
2the lower mechanical agitation of protection 1 hour, obtains magnetic Fe
3o
4nano particle;
(3) treat that above-mentioned reactant liquor is cooled to room temperature, with acetone, reactant liquor is washed three times, obtain pure magnetic Fe
3o
4nano-particle solution.
(4) pure particle diameter is surpassed Fe
3o
4nano-particle solution at 40 DEG C dry 24 hours, obtains Powdered Fe
3o
4nano particle.
(5) under ultrasound condition, by 10mgFe
3o
4be dissolved in 10mL cyclohexane, F120 is dissolved in 20mL cyclohexane, and two solution movement stir lower mixing, then add 400mL ammoniacal liquor, stirring reaction 1 hour.
(6) add 150mL tetraethoxysilane, mechanic whirl-nett reaction 24 hours, obtain and be enclosed with SiO
2the extra small Fe of shell
3o
4nano-particle compound.
Adopt TEM to obtained magnetic Fe
3o
4nano-particle compound is analyzed, and result as shown in Figure 8, shows the good dispersion of nano particle, uniform particle sizes, and according to ImageJ statistics, domain size distribution is at 25 ~ 30nm.
Although the present invention with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are not departing from spirit and scope of the invention; can make possible variation and amendment, the scope that therefore protection scope of the present invention should define with the claims in the present invention is as the criterion.
Claims (10)
1. a magnetic nano-particle, it is characterized in that, described magnetic nano-particle contain optionally in the oxide of the oxide of the oxide of the oxide of the oxide of IB race metal, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the oxide of VI race metal, the oxide of VII race metal and group VIII metal oxide one or more; Preferably containing appoint in the oxide of the oxide of the oxide of the oxide of the oxide of chosen from Fe, zinc, manganese, gadolinium, the oxide of cobalt, the oxide of nickel and chromium one or more; Further preferably containing Fe
3o
4, γ-Fe
2o
3, Mn
3o
4, GdO, Gd
2o
3, ZnO, MFe
2o
4or TMn
2o
4; Wherein MFe
2o
4in M be optionally from Zn, Co, Ni, Cr and Mn one or more; TMn
2o
4in T be optionally from one or more of Zn, Fe, Co, Ni and Cr;
The particle diameter of described magnetic nano-particle is 0.5 ~ 15nm; Preferred particle size range is 1 ~ 10nm; Preferred particle size range is 2 ~ 5nm further.
2. the preparation method of magnetic nano-particle described in claim 1, is characterized in that, comprises following steps:
A (), by the solution containing organic acid and/or acylate, mixes with the solution containing metal ion, obtained presoma;
B the presoma of step (a) gained is placed in Organic Alcohol by (), react under inert gas shielding, obtained described magnetic nano-particle.
3. method according to claim 2, is characterized in that, organic acid described in step (a) for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl; Preferred organic acid is oleic acid and/or linoleic acid.
4. method according to claim 2, is characterized in that, acylate described in step (a) is organic acid slaine and/or ammonium salt, organic acid for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl; Preferred acylate is oleate and/or linoleate; Further preferred acylate is one or more optionally in the alkali salt of the alkali metal salt of oleic acid, oleic acid, the ammonium salt of oleic acid, linoleic alkali metal salt, linoleic alkali salt and linoleic ammonium salt; Preferred acylate is enuatrol and/or potassium oleate further;
Metal ion described in step (a) is one or more optionally in the ion of the ion of the ion of the ion of IB race metal ion, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the ion of VI race metal, the ion of VII race metal and group VIII metal ion; Preferred metal ion be appoint in the ion of the ion of the ion of the ion of the ion of chosen from Fe, zinc, manganese, gadolinium, the ion of cobalt, the ion of nickel and chromium one or more.
5. method according to claim 2, is characterized in that, in described step (a), the temperature preparing presoma is 40 ~ 100 DEG C; In described step (b), under inert gas shielding, reaction temperature is 250 ~ 400 DEG C; In described step (b), under inert gas shielding, the reaction time is 10 ~ 200 minutes.
6. a composite magnetic nano particle, is characterized in that, outside magnetic nano-particle, be enclosed with hydrophilic polymer; Described magnetic nano-particle contain optionally in the oxide of the oxide of the oxide of the oxide of the oxide of IB race metal, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the oxide of VI race metal, the oxide of VII race metal and group VIII metal oxide one or more; Described magnetic nano-particle preferably consist of in the oxide of oxide containing the oxide of appointing the oxide of chosen from Fe, zinc, manganese, the oxide of gadolinium, the oxide of cobalt, the oxide of nickel and chromium one or more; Described magnetic nano-particle preferably consists of further containing Fe
3o
4, γ-Fe
2o
3, Mn
3o
4, GdO, Gd
2o
3, ZnO, MFe
2o
4or TMn
2o
4; Wherein MFe
2o
4in M be optionally from Zn, Co, Ni, Cr and Mn one or more; TMn
2o
4in T be optionally from one or more of Zn, Fe, Co, Ni and Cr;
The particle diameter of described magnetic nano-particle is 0.5 ~ 15nm, and the particle diameter of described composite magnetic nano particle is not more than 60nm; Preferred scope is, the particle size range of described magnetic nano-particle is 1 ~ 10nm, and the particle diameter of described composite magnetic nano particle is 5 ~ 30nm; Preferred scope is that the particle size range of described magnetic nano-particle is 2 ~ 5nm further, and the particle diameter of described composite magnetic nano particle is 5 ~ 20nm;
Described hydrophilic polymer is optional one or more in tetraethoxysilane, polyethylene glycol, glucan, polyacrylic acid, γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, polyoxyethylene-poly-oxypropylene polyoxyethylene, polyoxyethylenes (5) nonylplenyl ether, albumin.
7. the preparation method of composite magnetic nano particle described in claim 6, is characterized in that, comprise following steps:
A (), by the solution containing organic acid and/or acylate, mixes with the solution containing metal ion, obtained presoma;
B the presoma of step (a) gained is placed in Organic Alcohol by (), react under inert gas shielding, obtained magnetic nano-particle;
C (), by step (b) gained magnetic nano-particle, is placed in hydrophilic polymer and/or the solution containing hydrophilic polymer, obtained described composite magnetic nano particle.
8. method according to claim 7, is characterized in that, organic acid described in step (a) for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl; Preferred organic acid is oleic acid and/or linoleic acid;
Described acylate is organic acid slaine and/or ammonium salt, organic acid for having 16 ~ 24 carbon numbers, the straight chain unsaturated organic acid containing a carboxyl; Preferred acylate is oleate and/or linoleate; Further preferred acylate is one or more optionally in the alkali salt of the alkali metal salt of oleic acid, oleic acid, the ammonium salt of oleic acid, linoleic alkali metal salt, linoleic alkali salt, linoleic ammonium salt;
Metal ion described in step (a) is one or more optionally in the ion of the ion of the ion of the ion of IB race metal ion, IIB race metal, IIIB race metal, IVB race metal, VB race metal, the ion of VI race metal, the ion of VII race metal and group VIII metal ion; Preferred metal ion be appoint in the ion of the ion of the ion of the ion of the ion of chosen from Fe, zinc, manganese, gadolinium, the ion of cobalt, the ion of nickel and chromium one or more;
The described hydrophilic polymer of step (c) is optional one or more in tetraethoxysilane, polyethylene glycol, glucan, polyacrylic acid, γ-glycidyl ether oxygen propyl trimethoxy silicane, gamma-aminopropyl-triethoxy-silane, polyoxyethylene-poly-oxypropylene polyoxyethylene, polyoxyethylenes (5) nonylplenyl ether, albumin.
9. method according to claim 7, is characterized in that, in described step (a), the temperature preparing presoma is 40 ~ 100 DEG C;
In described step (b), under inert gas shielding, reaction temperature is 250 ~ 400 DEG C;
In described step (b), under inert gas shielding, the reaction time is 10 ~ 200 minutes;
In described step (c), the weight ratio of magnetic nano-particle and hydrophilic polymer is 1:5 ~ 25; The weight ratio of preferred magnetic nano-particle and hydrophilic polymer is 1:12 ~ 18; The weight ratio of preferred magnetic nano-particle and hydrophilic polymer is 1:14 ~ 16 further.
10. composite magnetic nano particle described in magnetic nano-particle described in claim 1 and claim 6 is in the application of absorbing material, in the application of electronic device manufacture view, the application in information storage material, the application in magnetic resonance imaging contrast, the application in targeted drug, the application in cell separation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151205A (en) * | 2016-11-07 | 2017-09-12 | 西北大学 | Erucic acid metal complex and preparation method thereof |
| CN107213474A (en) * | 2016-11-07 | 2017-09-29 | 西北大学 | A kind of iron-based magnetic nanocrystals magnetic resonance T1The preparation method and applications of contrast agent |
| CN109529060A (en) * | 2019-01-23 | 2019-03-29 | 中国科学院宁波材料技术与工程研究所 | Magnetic composite nano material and its preparation method and application |
| CN109626439A (en) * | 2018-12-11 | 2019-04-16 | 中国科学院宁波材料技术与工程研究所 | A kind of metal-doped ferrite nano material, comprising its magnetic nano-particle preparation method and applications |
| CN110744887A (en) * | 2019-10-15 | 2020-02-04 | 哈尔滨工程大学 | Magnesium-lithium-based composite material with high electromagnetic shielding performance and preparation method thereof |
| CN115520907A (en) * | 2022-04-14 | 2022-12-27 | 西安超磁纳米生物科技有限公司 | Ultra-small ferrite nano-particles with active groups, and preparation and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882364A (en) * | 2003-11-17 | 2006-12-20 | 皇家飞利浦电子股份有限公司 | Contrast agent for medical imaging techniques and usage thereof |
| CN1969190A (en) * | 2004-04-20 | 2007-05-23 | 爱默蕾大学 | Multimodality nanostructures, methods of fabrication thereof, and methods of use thereof |
| CN101090785A (en) * | 2004-11-26 | 2007-12-19 | 首尔国立大学工业基金会 | Novel methods of large scale production monodisperse nano grain |
| CN101241788A (en) * | 2007-01-15 | 2008-08-13 | 中国科学院化学研究所 | Biological compatibility magnetic nano crystal for high dissolving and stable distribution in physiologicalbuffer liquid and its making method |
| CN102105175A (en) * | 2008-05-27 | 2011-06-22 | 香港中文大学 | Nanoparticles, methods of making same and cell labelling using same |
| CN102451476A (en) * | 2010-10-29 | 2012-05-16 | 中国科学院化学研究所 | Radionuclide-doped magnetic nano crystal with biocompatibility, and preparation method of radionuclide-doped magnetic nano crystal |
| CN102614533A (en) * | 2012-03-28 | 2012-08-01 | 上海师范大学 | Method for preparing water-soluble manganese oxide magnetic resonance contrast agent and application thereof |
| CN102786810A (en) * | 2011-05-18 | 2012-11-21 | 中国石油化工股份有限公司 | Magnetic polymer particle, its preparation method and its application |
| CN103153348A (en) * | 2010-08-05 | 2013-06-12 | 韩华石油化学株式会社 | Preparation of extremely small and uniform sized, iron oxide-based paramagnetic or pseudo-paramagnetic nanoparticles and mri t1 contrast agents using the same |
| CN103400677A (en) * | 2013-06-24 | 2013-11-20 | 中国水产科学研究院黄海水产研究所 | Preparation method of magnetic Fe3O4@SiO2-NH2 nanoparticles |
| CN103531324A (en) * | 2013-11-05 | 2014-01-22 | 黑龙江大学 | Method for preparing Fe3O4 magnetic fluid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103203031A (en) * | 2013-03-29 | 2013-07-17 | 上海师范大学 | Fe3O4/DOPA/(Gd/DTPA) nano material, and preparation method and application of material |
-
2014
- 2014-05-14 CN CN201410203774.4A patent/CN105097170A/en active Pending
- 2014-05-14 CN CN202010276104.0A patent/CN111477420A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1882364A (en) * | 2003-11-17 | 2006-12-20 | 皇家飞利浦电子股份有限公司 | Contrast agent for medical imaging techniques and usage thereof |
| CN1969190A (en) * | 2004-04-20 | 2007-05-23 | 爱默蕾大学 | Multimodality nanostructures, methods of fabrication thereof, and methods of use thereof |
| CN101090785A (en) * | 2004-11-26 | 2007-12-19 | 首尔国立大学工业基金会 | Novel methods of large scale production monodisperse nano grain |
| CN101241788A (en) * | 2007-01-15 | 2008-08-13 | 中国科学院化学研究所 | Biological compatibility magnetic nano crystal for high dissolving and stable distribution in physiologicalbuffer liquid and its making method |
| CN102105175A (en) * | 2008-05-27 | 2011-06-22 | 香港中文大学 | Nanoparticles, methods of making same and cell labelling using same |
| CN103153348A (en) * | 2010-08-05 | 2013-06-12 | 韩华石油化学株式会社 | Preparation of extremely small and uniform sized, iron oxide-based paramagnetic or pseudo-paramagnetic nanoparticles and mri t1 contrast agents using the same |
| CN102451476A (en) * | 2010-10-29 | 2012-05-16 | 中国科学院化学研究所 | Radionuclide-doped magnetic nano crystal with biocompatibility, and preparation method of radionuclide-doped magnetic nano crystal |
| CN102786810A (en) * | 2011-05-18 | 2012-11-21 | 中国石油化工股份有限公司 | Magnetic polymer particle, its preparation method and its application |
| CN102614533A (en) * | 2012-03-28 | 2012-08-01 | 上海师范大学 | Method for preparing water-soluble manganese oxide magnetic resonance contrast agent and application thereof |
| CN103400677A (en) * | 2013-06-24 | 2013-11-20 | 中国水产科学研究院黄海水产研究所 | Preparation method of magnetic Fe3O4@SiO2-NH2 nanoparticles |
| CN103531324A (en) * | 2013-11-05 | 2014-01-22 | 黑龙江大学 | Method for preparing Fe3O4 magnetic fluid |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107151205A (en) * | 2016-11-07 | 2017-09-12 | 西北大学 | Erucic acid metal complex and preparation method thereof |
| CN107213474A (en) * | 2016-11-07 | 2017-09-29 | 西北大学 | A kind of iron-based magnetic nanocrystals magnetic resonance T1The preparation method and applications of contrast agent |
| CN107151205B (en) * | 2016-11-07 | 2021-03-09 | 西北大学 | Erucic acid metal complex and preparation method thereof |
| CN109626439A (en) * | 2018-12-11 | 2019-04-16 | 中国科学院宁波材料技术与工程研究所 | A kind of metal-doped ferrite nano material, comprising its magnetic nano-particle preparation method and applications |
| CN109529060A (en) * | 2019-01-23 | 2019-03-29 | 中国科学院宁波材料技术与工程研究所 | Magnetic composite nano material and its preparation method and application |
| CN110744887A (en) * | 2019-10-15 | 2020-02-04 | 哈尔滨工程大学 | Magnesium-lithium-based composite material with high electromagnetic shielding performance and preparation method thereof |
| CN110744887B (en) * | 2019-10-15 | 2021-10-01 | 哈尔滨工程大学 | Magnesium-lithium-based composite material with high electromagnetic shielding performance and preparation method thereof |
| CN115520907A (en) * | 2022-04-14 | 2022-12-27 | 西安超磁纳米生物科技有限公司 | Ultra-small ferrite nano-particles with active groups, and preparation and application thereof |
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