CN101850227A - Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium - Google Patents

Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium Download PDF

Info

Publication number
CN101850227A
CN101850227A CN 201010175917 CN201010175917A CN101850227A CN 101850227 A CN101850227 A CN 101850227A CN 201010175917 CN201010175917 CN 201010175917 CN 201010175917 A CN201010175917 A CN 201010175917A CN 101850227 A CN101850227 A CN 101850227A
Authority
CN
China
Prior art keywords
preparation
nano
particle
sol
nanoparticle sol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 201010175917
Other languages
Chinese (zh)
Other versions
CN101850227B (en
Inventor
吴爱国
曾乐勇
崔平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN2010101759177A priority Critical patent/CN101850227B/en
Publication of CN101850227A publication Critical patent/CN101850227A/en
Application granted granted Critical
Publication of CN101850227B publication Critical patent/CN101850227B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Abstract

The invention relates to a preparation method for nano particles and nano-particle sol and application of the nano particles and the nano-particle sol in magnetic resonance imaging contrast medium. The preparation method of the nano-particle sol comprises the following steps: dissolving compound of ferric iron and compound containing divalent metal ions into aqueous solution of compound containing hydroxyl or carboxyl to carry out reaction, wherein the divalent metal ions are selected from Fe2+, Zn2+, Ni2+ or Mn2+; and reacting to obtain the sol containing MFe2O4 nano particles, wherein M is Fe, Zn, Ni or Mn. Compared with the prior art, the preparation method for the nano-particle sol has simple preparation method, low preparation cost and no need of nitrogen protection in the reaction process, the nano particle product has the advantages of small particle size, narrow particle size distribution, controllable size, good water solubility, good biocompatibility and the like.

Description

The preparation method of nano particle and nanoparticle sol and both application in magnetic resonance imaging contrast
Technical field
The present invention relates to the preparation method and the application of nano particle and nanoparticle sol, relate in particular to the nano particle and the preparation method of nanoparticle sol and the application in magnetic resonance imaging contrast that comprise bivalent metal ion.
Background technology
Magnetic resonance imaging (MRI) technology is one of most important image technology in the modern medicine clinical diagnosis because safe in utilization, imaging resolution is high, pseudo-shadow is few, the advantages such as abundant information that provide, MRI almost is applied to the inspection at any position of human body at present.Particularly not have characteristics such as X ray (to the human zero damage), the direct imaging of many planes, image big, density resolution directly perceived, repeatable and spatial resolution height be ultrasonic to MRI and CT is incomparable; Add new image forming program and the MRI contrast Material Injection Protocols of continually developing utilization,, good basis and development prospect are provided all for MRI diagnosing tumour and other disease especially based on the exploitation and the development of the MRI contrast preparation of super paramagnetic nano material.
Can super paramagnetic nano material be used as the MRI contrast preparation, need to consider the problems such as water-soluble, grain size, toxicity and biocompatibility of material.Grain size and water-soluble particularly, because in the MRI diagnosing tumor, contrast preparation need to enter cell could make diagnosis effectively delicately, generally needs particle size just can reach good effect below 10nm.Because nontoxic and stronger magnetic property is with nano ferriferrous oxide (Fe 3O 4) for the superparamagnetic MFe of representative 2O 4(wherein M is Fe, Zn, Ni or Mn) nanometer particle material becomes the most widely MRI contrast agent material of research.At present, superparamagnetic preparations of nanomaterials method commonly used comprises coprecipitation and organic salt thermal decomposition method.With Fe 3O 4Nano particle be prepared as example, at first with iron salt dissolved in solvent, and vigorous stirring generates Fe then in alkaline environment 3O 4Nano particle, and the method that makes the product natural sedimentation or adopt magnetic to separate is isolated Fe 3O 4Nano particle; Or take organic molysite such as ferric acetyl acetonades as reactant, in organic phase, prepare Fe 3O 4Nano particle coats or modifies by the surface then and realizes that nano particle is by the transfer of organic phase to water.The superparamagnetic Fe of above method preparation 3O 4Nano particle, general particle diameter is big (more than the 10nm), and poorly water-soluble, must realize that its water disperses by the phase transfer step, and this has just limited the superparamagnetic nanometer particle material in biomedicine, particularly the application in the MRI contrast preparation.Therefore, realize the application of super paramagnetic nano particle in the MRI contrast preparation, must solve a series of problems such as the size Control, toxicity of material, water-soluble, biocompatibility well.
Based on above situation, develop the MFe of a kind of good water solubility, good biocompatibility, nontoxic, even small particle diameter 2O 4The preparation method of nanometer particle material is applied in the nano particle of preparing in the MRI contrast preparation, will help to develop a kind of imaging resolution height, the abundant MRI contrast preparation of signal.Therefore, based on MFe 2O 4The MRI contrast preparation of nano particle ensures that for improving the MRI detection sensitivity, reducing the medical science testing cost people's life and health have great importance.
Summary of the invention
Technical problem to be solved by this invention is: how to prepare highly-water-soluble, even small particle diameter and nontoxic super paramagnetic nano particulate material.
For addressing the above problem, according to an aspect of the present invention, the preparation method of nanoparticle sol is provided, comprises step: ferric compound and the compound that contains bivalent metal ion are dissolved in the aqueous solution of compound of hydroxyl or carboxyl and react, described bivalent metal ion is selected from Fe 2+, Zn 2+, Ni 2+Or Mn 2+Reaction makes and contains MFe 2O 4The colloidal sol of nano particle, wherein M is Fe, Zn, Ni or Mn.
In said method, the aqueous solution of the compound of hydroxyl or carboxyl has stabilization, and stable reaction is carried out, and makes the even and stable dispersion of product particle diameter.The compound of described hydroxyl or carboxyl is preferably sugar, alcohol or organic acid.
Alternatively, also comprise step: in the nanoparticle sol that makes, add surfactant.Preferred surfactant is softex kw or dodecyl sodium sulfate.In order to the particle diameter of control nano particle, prevent that nano particle from reuniting and the overgrown situation of nano particle occurs.
Alternatively, also comprise step: the nanoparticle sol that makes is carried out ageing handle more than 20 hours in 20 ℃ to 99 ℃ water-bath.In order to obtain the uniform nano particle of particle diameter, to meet the needs of preparation MRI contrast preparation.
Alternatively, described ferric compound is 2: 1 to 1: 1 with the mol ratio that contains the compound of bivalent metal ion, and the mol ratio that contains the compound of the compound of bivalent metal ion and hydroxyl or carboxyl is 1: 12 to 1: 1.Creative work through the inventor is found, adopts this ratio can obtain the littler Fe of good water solubility, uniform particles and size 3O 4, ZnFe 2O 4, NiFe 2O 4Or MnFe 2O 4Nano particle.
Alternatively, the reaction temperature of described reaction is preferably 20 ℃ to 30 ℃.The inventor finds, can obtain the controlled Fe of particle diameter in this temperature range 3O 4, ZnFe 2O 4, NiFe 2O 4Or MnFe 2O 4Nano particle.
In addition, another aspect of the present invention also comprises the preparation method of nano particle, comprises step: aforementioned nanoparticle sol is dialysed successively and the freeze drying processing, make pulverous Fe 3O 4, ZnFe 2O 4, NiFe 2O 4Or MnFe 2O 4Nano particle.
According to a further aspect of the invention, aforementioned Fe 3O 4, ZnFe 2O 4, NiFe 2O 4Or MnFe 2O 4Nano particle or nanoparticle sol can be applied in the magnetic resonance imaging contrast.
The preparation method of nanoparticle sol provided by the present invention is simple to operate, preparation cost is low, course of reaction need not nitrogen protection.The nano particle product has advantages such as the little and particle diameter narrow distribution of particle diameter, controllable size, good water solubility, good biocompatibility.
The prepared nano particle of preparation method provided by the present invention is a kind of nano material with superparamagnetism, is with a wide range of applications in magnetic resonance medical science angiographic diagnosis.
Description of drawings
Fig. 1 to 4 is respectively the prepared Fe of various embodiments of the present invention 3O 4, ZnFe 2O 4, NiFe 2O 4And MnFe 2O 4The TEM figure of nano particle;
Fig. 5 is Fe prepared in the embodiment of the invention 3O 4, ZnFe 2O 4, NiFe 2O 4The XRD figure of nano particle;
Fig. 6 is Fe prepared in the embodiment of the invention 3O 4, ZnFe 2O 4, NiFe 2O 4, MnFe 2O 4The magnetization curve figure of nano particle;
Fig. 7 is to Fe prepared in the one embodiment of the invention 3O 4Nano particle carries out T1 and the T2 weighted signal figure of MRI test;
Fig. 8 is to ZnFe prepared in the embodiment of the invention 2O 4, NiFe 2O 4, MnFe 2O 4Nano particle carries out T1 and the T2 weighted signal figure of MRI test.
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.

Claims (10)

1. the preparation method of nanoparticle sol is characterized in that, comprises step:
Ferric compound and the compound that contains bivalent metal ion are dissolved in the aqueous solution of compound of hydroxyl or carboxyl and react, described bivalent metal ion is selected from Fe 2+, Zn 2+, Ni 2+Or Mn 2+
Reaction makes and contains MFe 2O 4The colloidal sol of nano particle, wherein M is Fe, Zn, Ni or Mn.
2. the preparation method of nanoparticle sol as claimed in claim 1 is characterized in that, also comprises step: add surfactant in the nanoparticle sol that makes.
3. the preparation method of nanoparticle sol as claimed in claim 2, it is characterized in that: described surfactant is softex kw or dodecyl sodium sulfate.
4. the preparation method of nanoparticle sol as claimed in claim 1 is characterized in that: described hydroxyl or carboxylic compound are sugar, alcohol or organic acid.
5. the preparation method of nanoparticle sol as claimed in claim 1 is characterized in that, also comprises step: the nanoparticle sol that makes is carried out ageing handle more than 20 hours in 20 ℃ to 99 ℃ water-bath.
6. the preparation method of nanoparticle sol as claimed in claim 1, it is characterized in that: the mol ratio of the compound of described ferric compound and bivalent metal ion is 2: 1 to 1: 1, and the mol ratio of the compound of the compound of bivalent metal ion and hydroxyl or carboxyl is 1: 12 to 1: 1.
7. the preparation method of nanoparticle sol as claimed in claim 1, it is characterized in that: the reaction temperature for preparing described nanoparticle sol is 20 ℃ to 30 ℃.
8. each described nanoparticle sol application in magnetic resonance imaging contrast in the claim 1 to 7.
9. nanometer particle process method is characterized in that, comprises step: each described nanoparticle sol in the claim 1 to 6 is dialysed successively and the freeze drying processing, make pulverous nano particle.
10. the application of the described nano particle of claim 9 in magnetic resonance imaging contrast.
CN2010101759177A 2010-05-18 2010-05-18 Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium Active CN101850227B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101759177A CN101850227B (en) 2010-05-18 2010-05-18 Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010101759177A CN101850227B (en) 2010-05-18 2010-05-18 Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium

Publications (2)

Publication Number Publication Date
CN101850227A true CN101850227A (en) 2010-10-06
CN101850227B CN101850227B (en) 2012-05-09

Family

ID=42802009

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101759177A Active CN101850227B (en) 2010-05-18 2010-05-18 Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium

Country Status (1)

Country Link
CN (1) CN101850227B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102908992A (en) * 2012-10-18 2013-02-06 中国科学院宁波材料技术与工程研究所 Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same
CN106729709A (en) * 2016-12-13 2017-05-31 东南大学 Injecting temperature sensitive magnetic Nano curdling glue, its preparation method and its application

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101318135A (en) * 2008-07-03 2008-12-10 浙江大学 Method for preparation of visible light responding zinc ferrous acid nanocrystalline colloidal sol
CN101547706A (en) * 2007-04-12 2009-09-30 延世大学校产学协力团 Magnetic resonance imaging contrast agents comprising zinc-containing magnetic metal oxide nanoparticles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101547706A (en) * 2007-04-12 2009-09-30 延世大学校产学协力团 Magnetic resonance imaging contrast agents comprising zinc-containing magnetic metal oxide nanoparticles
CN101318135A (en) * 2008-07-03 2008-12-10 浙江大学 Method for preparation of visible light responding zinc ferrous acid nanocrystalline colloidal sol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《Journal of Non-Crystalline Solids》 20081024 M.R. Barati et al. The role of surfactant in synthesis of magnetic nanocrystalline powder of NiFe2O4 by sol-gel auto-combustion method 5184-5185 2-4 第354卷, 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102908992A (en) * 2012-10-18 2013-02-06 中国科学院宁波材料技术与工程研究所 Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same
CN102908992B (en) * 2012-10-18 2014-07-02 中国科学院宁波材料技术与工程研究所 Bifunctional material for detecting and adsorbing mercury ions as well as synthesizing method and application of same
CN106729709A (en) * 2016-12-13 2017-05-31 东南大学 Injecting temperature sensitive magnetic Nano curdling glue, its preparation method and its application
CN106729709B (en) * 2016-12-13 2020-05-05 东南大学 Injectable temperature-sensitive magnetic nano-emulsion gel, preparation method and application thereof

Also Published As

Publication number Publication date
CN101850227B (en) 2012-05-09

Similar Documents

Publication Publication Date Title
Sandler et al. Best practices for characterization of magnetic nanoparticles for biomedical applications
Islam et al. Manganese ferrite nanoparticles (MnFe2O4): size dependence for hyperthermia and negative/positive contrast enhancement in MRI
Jesus et al. Synthesis and magnetic interaction on concentrated Fe3O4 nanoparticles obtained by the co-precipitation and hydrothermal chemical methods
CN102125699B (en) Fe3O4/TiO2 composite nano-particles as well as preparation method and application thereof in magnetic resonance imaging contrast medium
Caruntu et al. Reactivity of 3d transition metal cations in diethylene glycol solutions. Synthesis of transition metal ferrites with the structure of discrete nanoparticles complexed with long-chain carboxylate anions
Tegafaw et al. Dual-mode T1 and T2 magnetic resonance imaging contrast agent based on ultrasmall mixed gadolinium-dysprosium oxide nanoparticles: Synthesis, characterization, and in vivo application
Modaresi et al. Magnetic properties of ZnxFe3− xO4 nanoparticles: A competition between the effects of size and Zn doping level
Zhang et al. Synthesis and characterization of Gd-doped magnetite nanoparticles
Rezaei et al. Magnetic nanoparticles: a review on synthesis, characterization, functionalization, and biomedical applications
Banerjee et al. Synthesis, characterization, and evaluation of PEGylated first-row transition metal ferrite nanoparticles as T 2 contrast agents for high-field MRI
Bala et al. Cobalt and magnesium ferrite nanoparticles: preparation using liquid foams as templates and their magnetic characteristics
Ma et al. Precisely Tuning the Contrast Properties of Zn x Fe3–x O4 Nanoparticles in Magnetic Resonance Imaging by Controlling Their Doping Content and Size
Mohammadi et al. Superparamagnetic cobalt ferrite nanoparticles as T 2 contrast agent in MRI: in vitro study
Jalili et al. Bimagnetic hard/soft and soft/hard ferrite nanocomposites: Structural, magnetic and hyperthermia properties
Cardona et al. Enhanced magnetic properties and MRI performance of bi-magnetic core–shell nanoparticles
Kaman et al. Preparation of Mn-Zn ferrite nanoparticles and their silica-coated clusters: Magnetic properties and transverse relaxivity
CN103204546A (en) Method for preparing nano cobalt ferrite
Yin et al. Dysprosium-doped iron oxide nanoparticles boosting spin–spin relaxation: A computational and experimental study
Zhou et al. Solvothermal synthesis of CoFe2O4 submicron compact spheres and tunable coercivity induced via low-temperature thermal treatment
Dogan et al. Manganese doped-iron oxide nanoparticles and their potential as tracer agents for magnetic particle imaging (MPI)
Akhtar et al. Functionalized cobalt ferrite cubes: toxicity, interactions and mineralization into ferritin proteins
Antarnusa et al. Synthesis of Fe3O4 at different reaction temperatures and investigation of its magnetic properties on giant magnetoresistance (GMR) sensors for bio-detection applications
CN110384805A (en) A kind of Superparamagnetic Iron Oxide nanocluster body and its preparation method and application
CN101850227B (en) Preparation method for nano particle and nano-particle sol and application of nano particle and nano-particle sol in magnetic resonance imaging contrast medium
Limaye et al. Magnetic studies of SiO2 coated CoFe2O4 nanoparticles

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CI01 Correction of invention patent gazette

Correction item: Claims1

Correct: Correct (Zn)

False: Error (Xn)

Number: 19

Volume: 28

CI02 Correction of invention patent application

Correction item: Claims1

Correct: Correct (Zn)

False: Error (Xn)

Number: 19

Page: Description

Volume: 28

ERR Gazette correction

Free format text: CORRECT: CLAIM OF RIGHT 1; FROM: ERROR (XN) TO: CORRECT (ZN)