CN100573751C - The preparation method of gelatine cladding water-based magnetofluid - Google Patents
The preparation method of gelatine cladding water-based magnetofluid Download PDFInfo
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- CN100573751C CN100573751C CNB2007100327422A CN200710032742A CN100573751C CN 100573751 C CN100573751 C CN 100573751C CN B2007100327422 A CNB2007100327422 A CN B2007100327422A CN 200710032742 A CN200710032742 A CN 200710032742A CN 100573751 C CN100573751 C CN 100573751C
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Abstract
The present invention relates to a kind of gelatine cladding water-based magnetofluid and preparation method thereof, magnetic fluid comprises water, nanometer Fe
3O
4Particle and dispersant is characterized in that described nanometer Fe
3O
4The dispersant that particle surface coats is a pharmagel, nanometer Fe
3O
4Grain diameter is 1～16nm, nanometer Fe
3O
4The composite particles particle diameter that particle surface coating pharmagel obtains is less than 45nm; The preparation method comprises: chemical coprecipitation prepares nanometer Fe
3O
4Particle and nanometer Fe
3O
4Particle uses the pharmagel finishing.The present invention has good magnetic responsiveness, bioaffinity, biodegradability and suspension stability, the saturation magnetization of magnetic fluid is 1.0～13.0emu/g, the active group that can connect other parts is contained on magnetic gelatine composite nanometer particle of the present invention surface, but the multiple functional polymer of load is used for cell separation, tumor thermotherapy, Magnetic resonance imaging and targeting preparation etc.
Description
Technical field
The invention belongs to nanoscale science and technology and biomedicine field, relate to a kind of gelatine cladding water-based magnetofluid and preparation method thereof.
Background technology
So-called magnetic fluid claims magnetic liquid again; be magnetic nanoparticle high degree of dispersion and colloidal dispersion of forming in carrier fluid that will be adsorbed with surfactant; have the superparamagnetism of nano-solid material and the flowability of liquid concurrently; be a kind of novel liquid functional nano material, be widely used in fields such as sealing, lubricated, damping, grinding, separation, printing and dyeing printing and environmental protection.Magnetic fluid has expanded to cell separation, tumor thermotherapy, magnetic resonance imaging imaging and the targeting preparation etc. of biomedicine field in recent years.
Because non-water-based magnetic fluid has non-biocompatible, so biomedicine field mainly is a water-based magnetic fluid.And the water-based magnetic fluid that coats with surfactant is difficult to carry out surface-functionalized modification, and surface activity is not enough, thereby has limited the application at biomedicine field.The magnetic fluid that biomedicine field uses needs with hydrophilic macromolecule magnetic nanoparticle to be carried out coating decoration, can improve the biocompatibility of magnetic-particle, the active group that can connect other parts on the hydrophilic macromolecule, energy is the multiple functional polymer of load further, for example polypeptide, antibody, enzyme, DNA and RNA etc., thus prepare magnetic-particle carrier material with specific function.
The preparation biomedicine field is the surface modification of the synthetic and magnetic nanoparticle of magnetic nanoparticle with the key technology of magnetic fluid.At present existingly see that with water soluble starch the derivative of CN1822254A, shitosan sees that CN1702782A, glucan see that CN1750183A, polyamide-based dendritic amine polymer see that coating such as CN1913055A has prepared magnetic fluid for biological medicine.Prior art comes with some shortcomings, the one, in the synthetic technology of magnetic nanoparticle, majority is difficult to synthesize the magnetic nanoparticle that meets dimensional requirement fully, unsettled particle is removed with the method for centrifugation as CN1702782A, transmission electron microscope photo from this patent application, particle to cohere phenomenon obvious, illustrate that the controlled condition of synthetic reaction and the effect that coats with macromolecular material are not good enough; The 2nd, magnetic is on the weak side, and for example the saturation magnetization of the magnetic fluid that provides of CN1702782A only is 1.6～2.5emu/g, and the water-based magnetic fluid saturation magnetization of all embodiment preparations is all less than 1.0emu/g.
Summary of the invention
The object of the invention just provides that a kind of particle diameter is littler, gelatine cladding water-based magnetofluid of narrower, the strong magnetic response that distributes, high stability and preparation method thereof.
Magnetic fluid of the present invention adopts chemical coprecipitation synthetic, and the preparation method comprises: chemical coprecipitation prepares nanometer Fe
3O
4Particle and nanometer Fe
3O
4Particle uses the pharmagel finishing.
One of key technology of the present invention is further to have optimized nanometer Fe
3O
4The preparation technology of particle, from reactant concentration, mixing speed, pH value of solution value, reaction temperature to reaction time etc., control the nucleation rate and the nucleus growth speed of nano particle effectively, the particle diameter of nano particle can be removed underproof bulky grain without centrifugation all at the superparamagnetism range scale.
Two of key technology of the present invention is to select pharmagel as dispersant, gelatin is a capsule material the most frequently used in the pharmacy, raw material is easy to get, cheap, the average grain diameter of magnetic gelatine composite nanometer particle is less than 45nm in the magnetic fluid of preparation, monodispersity is good, and magnetic fluid of the present invention has good magnetic responsiveness, bioaffinity, biodegradability and suspension stability, can be used for multiple biomedicine fields such as cell separation, tumor thermotherapy, magnetic resonance imaging imaging and targeting preparation.
Gelatine cladding water-based magnetofluid of the present invention comprises water, nanometer Fe
3O
4Particle and dispersant, described nanometer Fe
3O
4The dispersant that particle surface coats is a pharmagel, nanometer Fe
3O
4Grain diameter is 1～16nm, nanometer Fe
3O
4The composite particles particle diameter that particle surface coating pharmagel obtains is less than 45nm.
The preparation method of gelatine cladding water-based magnetofluid may further comprise the steps: (1) compound concentration respectively is the Fe of 0.1～0.8mol/L
3+And Fe
2+The aqueous solution is pressed Fe
3+With Fe
2+The ratio of amount of substance is 1.00～1.75 mixing, obtains mixed liquor; (2) mix liquid, with mass concentration 25%NH
3H
2O pours in the mixed liquor, and mixed liquor and ammoniacal liquor volume ratio are 100: 6-45, NH
3H
2The adding of O can drip or divide several times and pour into, mixing speed 500～3000r/min, and 25～45 ℃ of temperature, the pH value 9～11 of solution, reaction time 30～120min obtains nanometer Fe
3O
4Particle; (3) 0.1～1.0% pharmagel of getting the iron gross mass is put into distilled water, pharmagel and distilled water mass ratio are 1: 100, heat 65～75 ℃ and make it dissolving, pour in the step (2), mixing speed 500～3000r/min, 50～65 ℃ of temperature, the pH value 6～9 of solution obtains the nanometer Fe of modification
3O
4Particle; (4) will contain the nanometer Fe of modification
3O
4The liquid of particle takes out, and with distilled water washing 3～5 times, adjust pH 4～5, ultrasonic wave disperses 10～60min, and washing disperses and can intermittently hocket with ultrasonic wave, obtains gelatine cladding water-based magnetofluid.
The present invention has following advantage and effect:
1, the present invention has good magnetic responsiveness, bioaffinity, biodegradability and suspension stability, and the saturation magnetization of magnetic fluid is 1.0～13.0emu/g.The active group that can connect other parts is contained on magnetic gelatine composite nanometer particle of the present invention surface, but the multiple functional polymer of load, for example polypeptide, antibody, enzyme, DNA and RNA etc. can be widely used in multiple fields such as cell separation, tumor thermotherapy, Magnetic resonance imaging and targeting preparation.
2, magnetic fluid of the present invention adopts chemical coprecipitation synthetic, by further optimization reactant concentration, mixing speed, pH value of solution value, reaction temperature and reaction time etc., the nucleation rate and the nucleus growth speed of nano particle have been controlled effectively, the particle diameter of nano particle can be removed underproof bulky grain without centrifugation all at the superparamagnetism range scale.
3, the pharmagel selected for use of the present invention is as dispersant, and the average grain diameter of magnetic gelatine composite nanometer particle has less than 45nm that monodispersity is good, with low cost, the technology characteristic of simple in the magnetic fluid of preparation.
Description of drawings
Fig. 1 amplifies 200,000 times TEM photo for gelatine cladding water-based magnetofluid of the present invention.
Fig. 2 is the magneto optical effect photo of gelatine cladding water-based magnetofluid of the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further elaborated.
Embodiment one
(1) takes by weighing 27.029g FeCl
36H
2O adds in the redistilled water that boils, and stirring and dissolving is cooled to room temperature, splashes into 3～5mL watery hydrochloric acid, adds 11.361g FeCl then
24H
2O, stirring and dissolving, mixed solution cumulative volume 1000mL, Fe in the mixed liquor
3+And Fe
2+Ratio by amount of substance is 1.75;
(2) mixed liquor is placed reactor preheating and stir and to make it abundant mixing, measure 85.0mL concentration and be 25% NH
3H
2O pours in the reactor, NH
3H
2The adding of O also can drip or divide several times and pour into, and mixing speed is progressively brought up to 2500r/min by 1000r/min, and temperature is controlled at 35 ℃, the pH value 10 of solution, and isothermal reaction 60min obtains nanometer Fe
3O
4Particle;
(3) get the 0.05g pharmagel and put into 5mL distilled water, heat 70 ℃ and make it dissolving, pour in the step (2), mixing speed 2000r/min, 55 ℃ of temperature, the pH value 6～7 of solution, reaction time 70min obtains the nanometer Fe of modification
3O
4Particle;
(4) will contain the nanometer Fe of modification
3O
4The liquid of particle takes out, and with distilled water washing 3～5 times, adjust pH 4～5, ultrasonic wave disperses 15min, and washing disperses and can intermittently hocket with ultrasonic wave, obtains gelatine cladding water-based magnetofluid.
The magnetic nanoparticle that gelatin of the present invention coats be shaped as almost spherical, iron-holder 8.792mg/mL, saturation magnetization is 3.0emu/g.Magnetic fluid of the present invention is through granularmetric analysis report test, 2～15nm, about 82.9%; 5.1～10nm, about 16.2%; 10.1～15nm is about 0.9%, particle diameter is at 2～15nm.
Embodiment two
(1) takes by weighing 54.058g FeCl
36H
2O is added in the redistilled water that boils, and stirring and dissolving is cooled to room temperature, splashes into 3～5mL HCl, adds 22.722g FeCl then
24H
2O, stirring and dissolving, mixed solution cumulative volume 1000mL, Fe in the mixed liquor
3+And Fe
2+Ratio by amount of substance is 1.75;
(2) mixed liquor is placed reactor preheating and stir and to make it abundant mixing, measure 168.0mL concentration and be 25% NH
3H
2O pours in the reactor, and mixing speed is progressively brought up to 3000r/min by 1000r/min, and temperature is controlled at 35 ℃, the pH value 10 of solution, and isothermal reaction 60min obtains nanometer Fe
3O
4Particle;
(3) get the 0.1g pharmagel and put into 10mL distilled water, heat 70 ℃ and make it dissolving, pour in the step (2), mixing speed 2000r/min, 55 ℃ of temperature, the pH value 6～7 of solution, reaction time 60min obtains the nanometer Fe of modification
3O
4Particle;
(4) will contain the nanometer Fe of modification
3O
4The liquid of particle takes out, and with distilled water washing 3～5 times, adjust pH 4～5, ultrasonic wave disperses 20min, obtains gelatine cladding water-based magnetofluid.
The magnetic nanoparticle that gelatin of the present invention coats be shaped as almost spherical, particle diameter is at 2～15nm, iron-holder 17.584mg/mL, saturation magnetization is 3.6emu/g.
Claims (3)
1, a kind of preparation method of gelatine cladding water-based magnetofluid is characterized in that may further comprise the steps:
(1) compound concentration is the Fe of 0.1～0.8mol/L respectively
3+And Fe
2+The aqueous solution is pressed Fe
3+With Fe
2+The ratio of amount of substance is 1.00～1.75 mixing, obtains mixed liquor;
(2) mix liquid, with mass concentration 25%NH
3H
2O pours in the mixed liquor, and mixed liquor and ammoniacal liquor volume ratio are 100: 6-45, and mixing speed 500～3000r/min, 25～45 ℃ of temperature, the pH value 9～11 of solution, reaction time 30～120min obtains nanometer Fe
3O
4Particle;
(3) 0.1～1.0% pharmagel of getting the iron gross mass is put into distilled water, pharmagel and distilled water mass ratio are 1: 100, heat 65～75 ℃ and make it dissolving, pour in the step (2), mixing speed 500～3000r/min, 50～65 ℃ of temperature, the pH value 6～9 of solution, reaction time 60～120min obtains the nanometer Fe of modification
3O
4Particle;
(4) will contain the nanometer Fe of modification
3O
4The liquid of particle takes out, and with distilled water washing 3～5 times, adjust pH 4～5, ultrasonic wave disperses 10～60min, obtains gelatine cladding water-based magnetofluid.
2, the preparation method of gelatine cladding water-based magnetofluid according to claim 1 is characterized in that NH in the step (2)
3H
2The adding of O is adopted dropping or is divided and pour into several times.
3, the preparation method of gelatine cladding water-based magnetofluid according to claim 1 is characterized in that washing disperses intermittently to hocket with ultrasonic wave in the step (4).
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| US20150204857A1 (en) * | 2012-08-23 | 2015-07-23 | Stemcell Technologies Inc. | Compositions and Methods for Rapid and Reversible Biomolecular Labeling |
| CN103273081B (en) * | 2013-05-31 | 2015-04-08 | 上海师范大学 | Process for preparing ferriferrous oxide magnetic fluid |
| CN104538165B (en) * | 2014-12-17 | 2017-03-29 | 河南工程学院 | A kind of method for preparing stable waterborne fluid |
| CN106504844B (en) * | 2016-10-06 | 2018-11-30 | 东阳市特意新材料科技有限公司 | A kind of preparation method of biological magnetic fluid |
| CN107595775A (en) * | 2017-09-25 | 2018-01-19 | 江苏长龙国际贸易有限公司 | A kind of preparation method of shelf stable form magnetic liposome material |
| CN115463252A (en) * | 2022-08-31 | 2022-12-13 | 武汉理工大学 | Magnetic bone cement for infectious bone defect treatment and preparation method and application thereof |
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