The specific embodiment
MFe of the present invention
2O
4(wherein M is Fe, Zn, Ni or Mn) nano particle specifically prepares by following steps:
1, take by weighing or measure have the containing of stabilization in right amount-OH or-compound or its solution of COOH, it is dissolved in the suitable quantity of water, stir and fully obtain after the dissolving concentration be 0.01mol/L to 0.9mol/L have the containing of stabilization-OH or-the COOH compound water solution;
2, take by weighing mol ratio comprising ferric compound and comprising Fe between 2: 1 to 1: 1 respectively
2+, Zn
2+, Ni
2+Or Mn
2+The compound of bivalent metal ion, with the compound that contains bivalent metal ion and have the containing of stabilization-OH or-ratio of mol ratio between 1: 12 to 1: 1 of COOH compound join in the above-mentioned aqueous solution, under 0 ℃ to 99 ℃ temperature, being preferably under the temperature between 20 ℃ to 30 ℃ fully, stirring reaction obtained MFe more than 1 hour
2O
4(wherein M is Fe, Zn, Ni or Mn) nanoparticle sol;
3, after reaction is finished, the water-bath that product is put between 20 ℃ to 99 ℃ was carried out the ageing processing more than 20 hours;
4, after ageing is finished, in product, add an amount of surfactant, continue to stir more than the 30min;
5, with prepared MFe
2O
4Nanoparticle sol is packed in the reagent bottle, puts into about 4 ℃ refrigerator and treats the contrast preparation as preparation MRI; Perhaps product is dialysed, and carry out obtaining powdery product work for subsequent use after freeze drying is processed and prepare the MRI contrast preparation.
Above-mentioned surfactant is preferably softex kw (CTAB) or dodecyl sodium sulfate (SDS), can effectively improve the agglomeration of nano particle.
By the prepared MFe of said method
2O
4(wherein M is Fe, Zn, Ni or Mn) nano particle can be dispersed in water and the aqueous solution, forms the colloidal sol of clear, proves that colloidal sol has good dispersiveness.And in 4 ℃ of environment, can long-term stability deposit more than 1 year, show MFe
2O
4Nanoparticle sol has good water-soluble and stable.
Below in conjunction with embodiment above-mentioned embodiment is elaborated.
Embodiment 1
Fe
3O
4The preparation of nano particle (1):
(1) take by weighing citric acid 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee citric acid, and it is stand-by to obtain citric acid solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 3mmol FeCl
24H
2O joins in the citric acid solution of above-mentioned preparation, and fully stirs under 20 ℃ temperature;
(3) react after 3 hours, the water-bath of product being put into 65 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains Fe
3O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous Fe
3O
4Nanometer particle material is for subsequent use.
Embodiment 2
Fe
3O
4The preparation of nano particle (2):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol FeCl
24H
2O is dissolved into it in 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure lactic acid 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 90 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains Fe
3O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous Fe
3O
4Nanometer particle material is for subsequent use.
Embodiment 3
Fe
3O
4The preparation of nano particle (3):
(1) take by weighing glucose 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee glucose, and it is stand-by to obtain glucose solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 3mmol FeCl
24H
2O joins in the glucose solution of above-mentioned preparation, and fully stirs under 25 ℃ temperature;
(3) react after 3 hours, the water-bath of product being put into 65 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains Fe
3O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous Fe
3O
4Nanometer particle material is for subsequent use.
Embodiment 4
Fe
3O
4The preparation of nano particle (4):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol FeCl
24H
2O is dissolved into it in 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure glycerine 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 90 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains Fe
3O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous Fe
3O
4Nanometer particle material is for subsequent use.
Embodiment 5
ZnFe
2O
4The preparation of nano particle (1):
(1) take by weighing citric acid 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee citric acid, and it is stand-by to obtain citric acid solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 2mmol ZnCl
2Join in the citric acid solution of above-mentioned preparation, and under 20 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 45 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains ZnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous ZnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 6
ZnFe
2O
4The preparation of nano particle (2):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol ZnCl
2It is dissolved in the 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure lactic acid 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 90 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains ZnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous ZnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 7
ZnFe
2O
4The preparation of nano particle (3):
(1) take by weighing glucose 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee glucose, and it is stand-by to obtain glucose solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 2mmol ZnCl
2Join in the glucose solution of above-mentioned preparation, and under 25 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 45 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains ZnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous ZnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 8
ZnFe
2O
4The preparation of nano particle (4):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol ZnCl
2It is dissolved in the 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure glycerine 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 90 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains ZnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous ZnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 9
NiFe
2O
4The preparation of nano particle (1):
(1) take by weighing citric acid 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee citric acid, and it is stand-by to obtain citric acid solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 2mmol NiCl
26H
2O joins in the citric acid solution of above-mentioned preparation, and fully stirs under 20 ℃ temperature;
(3) react after 3 hours, the water-bath of product being put into 70 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains NiFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous NiFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 10
NiFe
2O
4The preparation of nano particle (2):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol NiCl
26H
2O is dissolved into it in 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure lactic acid 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 55 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains NiFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous NiFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 11
NiFe
2O
4The preparation of nano particle (3):
(1) take by weighing glucose 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee glucose, and it is stand-by to obtain glucose solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 2mmol NiCl
26H
2O joins in the glucose solution of above-mentioned preparation, and fully stirs under 25 ℃ temperature;
(3) react after 3 hours, the water-bath of product being put into 70 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains NiFe
2O
4Nanoparticle sol.
Embodiment 12
NiFe
2O
4The preparation of nano particle (4):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol NiCl
26H
2O is dissolved into it in 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure glycerine 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 55 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains NiFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous NiFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 13
MnFe
2O
4The preparation of nano particle (1):
(1) take by weighing citric acid 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee citric acid, and it is stand-by to obtain citric acid solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 2mmol MnCl
24H
2O joins in the citric acid solution of above-mentioned preparation, and fully stirs under 20 ℃ temperature;
(3) react after 3 hours, the water-bath of product being put into 65 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains MnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous MnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 14
MnFe
2O
4The preparation of nano particle (2):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol MnCl
24H
2O is dissolved into it in 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure lactic acid 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 65 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains MnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous MnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 15
MnFe
2O
4The preparation of nano particle (3):
(1) take by weighing glucose 6mmol, it is dissolved in the 100mL deionized water, vigorous stirring is fully dissolved to guarantee glucose, and it is stand-by to obtain glucose solution;
(2) take by weighing 4mmol FeCl respectively
36H
2O and 2mmol MnCl
24H
2O joins in the glucose solution of above-mentioned preparation, and fully stirs under 25 ℃ temperature;
(3) react after 3 hours, the water-bath of product being put into 65 ℃ carries out the ageing processing, and digestion time is 24 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains MnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous MnFe
2O
4Nanometer particle material is for subsequent use.
Embodiment 16
MnFe
2O
4The preparation of nano particle (4):
(1) takes by weighing 4mmol FeCl respectively
36H
2O and 2mmol MnCl
24H
2O is dissolved into it in 100mL deionized water, and vigorous stirring is to guarantee abundant dissolving;
(2) measure glycerine 2mL, join in the above-mentioned solution, and under 30 ℃ temperature, fully stir;
(3) react after 3 hours, the water-bath of product being put into 65 ℃ carries out the ageing processing, and digestion time is 20 hours;
(4) adding 5mL concentration in the product is the CTAB of 0.5mmol/L, continues to stir 30 minutes, obtains MnFe
2O
4Nanoparticle sol;
(5) product is dialysed and after freeze drying processes, obtain pulverous MnFe
2O
4Nanometer particle material is for subsequent use.
Fig. 1-the 4th, embodiment 1,5,9,13 prepared Fe
3O
4, ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4The TEM figure of nano particle.As can be seen from the figure, Fe
3O
4, ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4The dispersiveness of nano particle is better, and particle diameter is even, and the average-size of single particle is about 3-5nm.
Fig. 5 is embodiment 1,5,9 prepared Fe
3O
4, ZnFe
2O
4, NiFe
2O
4The XRD figure of nano particle (Cu K α target, λ=0.15418nm).The Fe of cubic structure as can see from Figure 5
3O
4, ZnFe
2O
4, NiFe
2O
4(220) of nano particle, (311), (400), (511) and (440) diffraction maximum, according to 2 θ of (311) diffraction maximum=35.444 °, 35.264 ° and 35.699 °, can judgment curves (a), (b) and (c) corresponding Fe respectively
3O
4, ZnFe
2O
4And NiFe
2O
4Nano particle.
Fig. 6 is embodiment 1,5,9,13 prepared Fe
3O
4, ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4The magnetization curve of nano particle.Adopt the synthesis property testing system of U.S. Quantum Design, model Model-9; Test condition: VSM (vibrating specimen magnetometer) test, temperature 300K.As can be seen from Figure 6, Fe
3O
4, ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4The saturation magnetization of nano particle is respectively 40.0,33.8,27.6,23.1emu/g, and its coercivity and remanent magnetism are 0, show Fe
3O
4, ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4Nano particle all has superparamagnetism.Therefore the Fe for preparing
3O
4, ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4Nano particle can be advantageously applied in the magnetic resonance imaging contrast.
Fig. 7 is to the prepared Fe of embodiment 1
3O
4Nano particle carries out T1 and the T2 weighted signal figure of MRI test.The MRI test condition is T1:TR=800ms, TE=6ms; T2:TR=4000ms, TE=120ms.Wherein, the aqueous solution that the left side first is classified as in contrast is followed successively by the Fe that concentration reduces gradually from right to left
3O
4Nanoparticle sol; Upper figure is that T1, figure below are T2 weighted signal figure.
As can be seen from Figure 7 Fe
3O
4Nanoparticle sol has T1 and T2 weighted signal simultaneously, and the T2 weighted signal weakens along with the reduction of concentration, and the T1 weighted signal weakens along with the reduction of concentration strengthens afterwards earlier.
Fig. 8 is to embodiment 5,9,13 prepared ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4Nano particle carries out T1 and the T2 weighted signal figure of MRI test.The MRI test condition is T1:TR=800ms, TE=6ms; TR=4000ms, TE=120ms.Wherein, the aqueous solution that the left side first is classified as in contrast is followed successively by ZnFe from top to bottom
2O
4, NiFe
2O
4, MnFe
2O
4Nanoparticle sol, from right to left ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4The concentration of nano particle reduces gradually; Upper figure is that T1, figure below are T2 weighted signal figure.
As can be seen from Figure 8 ZnFe
2O
4, NiFe
2O
4, MnFe
2O
4Nanoparticle sol has T1 and T2 weighted signal simultaneously, and the T2 weighted signal weakens along with the reduction of concentration, and the T1 weighted signal weakens along with the reduction of concentration strengthens afterwards earlier.
Though the present invention with preferred embodiment openly as above; but it is not to be used for limiting claim; any those skilled in the art without departing from the spirit and scope of the present invention; can make possible change and modification, so protection scope of the present invention should be as the criterion with the scope that claim of the present invention was defined.