CN105126716A - Method for preparing sulfydryl modified ferroferric oxide/silicon dioxide magnetic nanoparticles - Google Patents
Method for preparing sulfydryl modified ferroferric oxide/silicon dioxide magnetic nanoparticles Download PDFInfo
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Abstract
The invention discloses a method for preparing sulfydryl modified ferroferric oxide/silicon dioxide magnetic nanoparticles. The method comprises the following steps that 1, magnetic ferroferric oxide particles are prepared with trivalent ferric salt serving as raw materials through a solvothermal method; 2, tetraethoxysilane is adopted as a silicon source, generated silicon dioxide wraps the surfaces of the magnetic ferroferric oxide particles through a sol-gel method, and ferroferric oxide/silicon dioxide magnetic nanoparticles are formed; 3, the ferroferric oxide/silicon dioxide magnetic nanoparticles are placed in a methylbenzene solution and dispersed evenly to obtain a solution A, dimercaptosuccinate is added to a dimethyl sulfoxide solution and dispersed evenly to obtain a solution B, the solution A and the solution B are mixed and stirred and react for a period of time, then solid-liquid separation, cleaning and drying are carried out, and then the sulfydryl modified ferroferric oxide/silicon dioxide magnetic nanoparticles are obtained. The magnetic nanoparticles are good in dispersing performance, achieve good stability and biocompatibility, and has potential application value in the bio-medical field.
Description
Technical field
The invention belongs to medical material field, particularly relate to the preparation method of a kind of sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Background technology
Magnetic nanoparticle has broad application prospects in bio-medical field due to its special magnetic property, can be summarized as application two classes in external application and body.Application aspect in vitro, mainly can be used for mark and isolated cell, protein, DNA, bacterium and virus etc.; And application aspect in vivo, can be used for the developer of magnetic resonance contrast's imaging, pharmaceutical carrier and cross heat cure tumour etc.The magnetic nanoparticle being representative with the oxide of iron will in the near future for the health of the mankind makes huge contribution.In order to the health enabling magnetic nanoparticle better serve the mankind as soon as possible, be required to the basic research of the preparation of nano particle, modification, functionalization be also one of current study hotspot.
The preparation method of magnetic Nano material can be divided into Physical, bioanalysis and chemical method.Wherein Physical is mainly mechanical attrition method, and obtained particle size distribution is wider, and required time is long, and energy consumption is large, easily introduces impurity, is unsuitable for the magnetic Nano material preparing bio-medical.The magnetic nano-particle good biocompatibility of Biological preparation, but large-scale culture is difficult, and particle leaching process is also comparatively loaded down with trivial details, the range limited system of size tunable of gained particle.Therefore the preparation of nano magnetic material depends on chemical preparation process at present, and wherein coprecipitation is simple to operate, and output is large, but is difficult to obtain the homogeneous particle of size distribution, as Chinese invention patent (application publication number: CN103990423A).Need in microemulsion method preparation process to add a large amount of oil-based solvents and surfactant, not easy cleaning.High temperature thermal decomposition method acquisition particle homogeneity is good, particle size is easy to control, but need precise control of temperature, use surfactant in a large number, particle surface easily adsorbs a large amount of organic reagent and is difficult to the major defects such as cleaning, as Chinese invention patent (application publication number: CN102085381A).
Nano particle due to volume little, therefore have very high specific area, surface-active is high, be easy to cell and tissue in accumulation, produce toxicity with biotic component effect.The bio-toxicity of nano magnetic particle is relevant to factors such as its chemical constituent, granular size, shape, surface-modifying species, structure, gatherings.The surface energy of nano particle can be reduced by the finishing of particle, reduce and reunite, regulate biocompatibility and the response characteristic of magnetic nanoparticle.
SiO
2there is good biocompatibility and anti-decomposition, oxidation resistance.Fe
3o
4nano grain surface coated Si O
2after layer, the mutual attractive force between particle can be suppressed well, improve Fe
3o
4water-soluble, the stability of nano particle and biocompatibility, and SiO
2surface also exists abundant carboxyl group, makes SiO
2/ Fe
3o
4the easier modification of magnetic coupling particle or connect functional high molecule material, is conducive to its application in fields such as biomedicines.Carrying out in the method operation of sulfydryl modification to the tri-iron tetroxide nucleocapsid structure surface of coated with silica, what Chinese invention patent (application publication number: CN103599751A) adopted is that silane coupler carries out functional modification to the surface of carrier, and what Chinese invention patent (application publication number: CN104174039A) adopted is that covalent effect introduces near-infrared functional group and polyethylene glycol sulfydryl functional group.Both reaction temperatures in modifying process are all more than 60 DEG C, and the former also needs constantly to pass into nitrogen in course of reaction, and solvent methanol after the heating highly volatile to human body, there is toxic action; The latter also needs to carry out amino modified to nano grain surface in sulfydryl modification process, and process step is too loaded down with trivial details.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides the preparation method of a kind of sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A preparation method for sulfydryl modification tri-iron tetroxide/silica magnetic nano particle, comprises the following steps:
(1) be that raw material prepares magnetic ferroferric oxide particle by solvent-thermal method with trivalent iron salt;
(2) take ethyl orthosilicate as silicon source, by sol-gal process by generate coated with silica on the surface of described magnetic ferroferric oxide particle, formed tri-iron tetroxide/silica magnetic nano particle;
(3) described tri-iron tetroxide/silica magnetic nano particle is placed in toluene solution, is uniformly dispersed and obtains solution A; Dimercaptosuccinic acid is joined in dimethyl sulphoxide solution, be uniformly dispersed and obtain solution B; Again described solution A and described solution B mix and blend are reacted Separation of Solid and Liquid after a period of time, by the solids cleaning, dry obtained, namely obtain described sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Above-mentioned preparation method, preferably, in described step (3), the mass ratio of tri-iron tetroxide/silica magnetic nano particle and dimercaptosuccinic acid is 1:1 ~ 1:5.
Above-mentioned preparation method, preferably, in described step (3), the solid-to-liquid ratio of tri-iron tetroxide/silica magnetic nano particle and toluene solution is 5:1 ~ 10:1, and solid-to-liquid ratio unit corresponding relation is g/L; The volume ratio of toluene solution and dimethyl sulphoxide solution is 1:2 ~ 2:1.
Above-mentioned preparation method, preferably, in described step (3), the time of reaction is 12 ~ 24h.
Above-mentioned preparation method, preferably, in described step (1), the concrete preparation process of magnetic ferroferric oxide particle is: be scattered in by trivalent iron salt in ethylene glycol solution, add dispersant, after being uniformly dispersed, add anhydrous sodium acetate, continue dispersion and obtain finely dispersed mixed liquor, mixed liquor is transferred in autoclave, controlling reaction temperature is 200 DEG C of reaction a period of times, obtains narrow diameter distribution, magnetic ferroferric oxide particle that dispersive property is good.
Above-mentioned preparation method, preferably, described dispersant elects Macrogol 2000 as, and described magnetic ferroferric oxide mean particle size is 150nm ~ 300nm, and surface functional group is mainly-OH.
Above-mentioned preparation method, preferably, in described step (2), the concrete preparation process of tri-iron tetroxide/silica magnetic nano particle is: add in ethanol by magnetic ferroferric oxide particle, be uniformly dispersed; Then add ammoniacal liquor and water, continue dispersion a period of time; Add ethyl orthosilicate again, gentle agitation 6 ~ 12h, last magnetic separation is separated, and the solids alcohol obtained, water alternately clean for several times, drying, namely obtain the core-shell structure magnetic nano particle that tri-iron tetroxide Surface coating has silicon dioxide layer.
Above-mentioned preparation method, preferably, the liquid-solid ratio of described magnetic ferroferric oxide and solvent is 1:2 ~ 1:1, and described solvent refers to ethanol, ammoniacal liquor and water; The solid-to-liquid ratio of magnetic ferroferric oxide and ethyl orthosilicate is 62.5:1 ~ 165:1, and wherein solid-to-liquid ratio unit corresponding relation is g/L.
Above-mentioned preparation method, preferably, described ethanol, ammoniacal liquor, water volume ratio are 75:23.5:1.5.
Above-mentioned preparation method, preferably, described silicon dioxide layer average thickness is 20 ~ 90nm.
The present invention is based on SiO
2the surface energy of nano particle can be reduced, reduce and reunite and SiO
2surface also exists abundant carboxyl group, enables dimercaptosuccinic acid with two sulfydryls more easily at SiO
2coated Fe
3o
4functional modification is carried out on the surface of magnetic coupling particle, thus improves dispersiveness, the stability and biocompatibility etc. of tri-iron tetroxide/silica magnetic nano particle greatly, makes it be more widely used at biomedical sector.
Compared with prior art, the invention has the advantages that:
1) in preparation method's process of the present invention, reaction condition is gentle, preparation process reagent is nontoxic, and operating procedure is simple, and the magnetic nanoparticle dispersive property prepared is good, there is good stability and biocompatibility, at biomedical sector, there is potential using value.
2) adopt dimercaptosuccinic acid (DMSA) to carry out modification in preparation method's process of the present invention, DMSA is a heavy metal species antidote inherently, and biocompatibility is fabulous, and its molecular formula is HOOC (CHSH)
2cOOH, DMSA is combined with tri-iron tetroxide/silica magnetic nano grain surface by COO functional group, and the DMSA of per molecule amount is exposed to surface with regard to there being the sulfydryl of two molecular weight, abundant mercapto functional group has great improvement result to the dispersive property of particle and bio-compatible performance, and abundant binding site can be provided for potential application such as protein combination, improve its potential using value.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope detected image of the tri-iron tetroxide/silica magnetic nano particle in the embodiment of the present invention 1.
Fig. 2 is the coated with silica layer thickness Relative distribution figure of the tri-iron tetroxide/silica magnetic nano particle in the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope detected image of the tri-iron tetroxide/silica magnetic nano particle in the embodiment of the present invention 2.
Fig. 4 is the coated with silica layer thickness Relative distribution figure of the tri-iron tetroxide/silica magnetic nano particle in the embodiment of the present invention 2.
Fig. 5 is the grain size distribution of the magnetic ferroferric oxide of preparation in the embodiment of the present invention 3.
Fig. 6 is the transmission electron microscope detected image of the tri-iron tetroxide/silica magnetic nano particle in the embodiment of the present invention 3.
Fig. 7 is the coated with silica layer thickness Relative distribution figure of the tri-iron tetroxide/silica magnetic nano particle in the embodiment of the present invention 3.
Fig. 8 is Fourier's infrared detection spectrogram of magnetic particles of ferroferric oxide (a) in the embodiment of the present invention 3 and sulfydryl modification tri-iron tetroxide/silica (b) magnetic nanoparticle.
Fig. 9 is that the magnetic particles of ferroferric oxide (a) in the embodiment of the present invention 3 detects figure with the VSM of sulfydryl modification tri-iron tetroxide/silica (b) magnetic nanoparticle.
Figure 10 is the hemolytic experiment-hemolysis rate figure of magnetic particles of ferroferric oxide in the embodiment of the present invention 3 and sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Figure 11 is the magnetic particles of ferroferric oxide in the embodiment of the present invention 3 and the relative rate of increase figure of cytotoxicity experiment MTT gained cell of sulfydryl modification tri-iron tetroxide/silica magnetic nano particle variable concentrations.
Figure 12 is the magnetic particles of ferroferric oxide in the embodiment of the present invention 3 and the relative rate of increase figure of cytotoxicity experiment MTT gained cell under the different incubation times of sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Detailed description of the invention
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, the various reagent used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
Embodiment 1:
A preparation method for sulfydryl modification tri-iron tetroxide/silica magnetic nano particle of the present invention, comprises the following steps:
(1) FeCl of 1mmol is got
36H
2o, in beaker, then adds 30ml ethylene glycol, 2g Macrogol 2000, and magnetic agitation to being uniformly dispersed, then continues to add 3g anhydrous sodium acetate, stirs and obtains finely dispersed mixed solution.Add in autoclave by mixed solution again, be warming up to 200 DEG C and react 6h, reaction terminates water-cooled to room temperature, and Magneto separate by the decorating film alcohol wash number time obtained after separation, then is put into 60 DEG C of drying box vacuum drying, obtained magnetic ferroferric oxide particle.
(2) get magnetic ferroferric oxide Granular composite prepared by 50mg step (1) in the ethanolic solution of 75mL, ultrasonic 40min, continues to add the deionized water of 23.5mL, the ammoniacal liquor (25wt%) of 1.5mL, ultrasonic 40min.Then electric stirring is carried out to mixed solution, slowly add 0.4mL ethyl orthosilicate (solid-to-liquid ratio of magnetic ferroferric oxide granular mass and ethyl orthosilicate is 125g:1L) simultaneously, continue gentle agitation 8h.After reaction terminates, Magneto separate, alcohol, water alternately clean for several times, and vacuum drying at 60 DEG C, obtains the magnetic nanoparticle of coated with silica tri-iron tetroxide structure (tri-iron tetroxide/silica).
(3) get tri-iron tetroxide/silica magnetic nanoparticulate dispersed prepared by 100mg step (2) in 20mL toluene solution, ultrasonic 30min, obtains solution A.The dimercaptosuccinic acid getting 250mg is scattered in the dimethyl sulphoxide solution solution of 10mL, ultrasonic 30min, obtains solution B; By solution A, solution B mix and blend 24h, reaction terminates, and alcohol wash number time, vacuum drying at 60 DEG C, obtains sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Be dispersed in ethanol by the tri-iron tetroxide of the present embodiment step (2) gained/silica magnetic nano particle, carry out transmission electron microscope detection, as shown in Figure 1, wherein, a represents that multiplication factor scale is 500nm to TEM result; B represents that multiplication factor scale is 200nm; C represents that multiplication factor scale is 100nm.Nanomeasurer (grain size analysis) software is adopted to carry out statistical analysis, SiO to being no less than 200 particles
2as shown in Figure 2, average thickness is about 32.5nm in coating thickness distribution.
Embodiment 2:
A preparation method for sulfydryl modification tri-iron tetroxide/silica magnetic nano particle of the present invention, comprises the following steps:
(1) FeCl of 1mmol is got
36H
2o, in beaker, then adds 30ml ethylene glycol, 2g Macrogol 2000, and magnetic agitation to being uniformly dispersed, then continues to add 3g anhydrous sodium acetate, stirs and obtains finely dispersed mixed solution.Add in autoclave by mixed solution again, be warming up to 200 DEG C and react 6h, reaction terminates water-cooled to room temperature, and Magneto separate by the decorating film alcohol wash number time obtained after separation, then is put into 60 DEG C of drying box vacuum drying, obtained magnetic ferroferric oxide particle.
(2) get magnetic ferroferric oxide Granular composite prepared by 50mg step (1) in the ethanolic solution of 150mL, ultrasonic 40min, continues to add the deionized water of 47mL, the ammoniacal liquor (25wt%) of 3mL, ultrasonic 40min.Then electric stirring is carried out to mixed solution, slowly add 0.8mL ethyl orthosilicate (solid-to-liquid ratio of magnetic ferroferric oxide granular mass and ethyl orthosilicate is 62.5g:1L) simultaneously, continue gentle agitation 12h.After reaction terminates, Magneto separate, alcohol, water alternately clean for several times, and vacuum drying at 60 DEG C, obtains the magnetic nanoparticle of coated with silica tri-iron tetroxide structure (tri-iron tetroxide/silica).
(3) get tri-iron tetroxide/silica magnetic nanoparticulate dispersed prepared by 100mg step (2) in 10mL toluene solution, ultrasonic 30min, obtains solution A.The dimercaptosuccinic acid getting 250mg is scattered in the dimethyl sulphoxide solution solution of 20mL, ultrasonic 30min, obtains solution B; By solution A, solution B mix and blend 18h, reaction terminates, and alcohol wash number time, vacuum drying at 60 DEG C, obtains sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Be dispersed in ethanol by the tri-iron tetroxide of the present embodiment step (2) gained/silica magnetic nano particle, carry out transmission electron microscope detection, as shown in Figure 3, wherein, a represents that multiplication factor scale is 500nm to TEM result; B represents that multiplication factor scale is 200nm.Nanomeasurer (grain size analysis) software is adopted to carry out statistical analysis, SiO to being no less than 200 particles
2as shown in Figure 4, average thickness is about 87nm in coating thickness distribution.
Embodiment 3:
A preparation method for sulfydryl modification tri-iron tetroxide/silica magnetic nano particle of the present invention, comprises the following steps:
(1) FeCl of 1mmol is got
36H
2o, in beaker, then adds 30ml ethylene glycol, 2g Macrogol 2000, and magnetic agitation to being uniformly dispersed, then continues to add 3g anhydrous sodium acetate, stirs and obtains finely dispersed mixed solution.Add in autoclave by mixed solution again, be warming up to 200 DEG C and react 6h, reaction terminates water-cooled to room temperature, and Magneto separate by the decorating film alcohol wash number time obtained after separation, then is put into 60 DEG C of drying box vacuum drying, obtained magnetic ferroferric oxide particle.As shown in Figure 5, Average Particle Diameters is 157nm to grain size distribution.
(2) get magnetic ferroferric oxide Granular composite prepared by 50mg step (1) in the ethanolic solution of 150mL, ultrasonic 40min, continues to add the deionized water of 47mL, the ammoniacal liquor (25wt%) of 3mL, ultrasonic 40min.Then electric stirring is carried out to mixed solution, slowly add 0.3mL ethyl orthosilicate (solid-to-liquid ratio of magnetic ferroferric oxide granular mass and ethyl orthosilicate is 165g:1L) simultaneously, continue gentle agitation 6h.After reaction terminates, Magneto separate, alcohol, water alternately clean for several times, and vacuum drying at 60 DEG C, obtains the magnetic nanoparticle of coated with silica tri-iron tetroxide structure (tri-iron tetroxide/silica).
(3) get tri-iron tetroxide/silica magnetic nanoparticulate dispersed prepared by 100mg step (2) in 10mL toluene solution, ultrasonic 30min, obtains solution A.The dimercaptosuccinic acid getting 250mg is scattered in the dimethyl sulphoxide solution solution of 10mL, ultrasonic 30min, obtains solution B; By solution A, B mix and blend 12h, reaction terminates, and alcohol wash number time, vacuum drying at 60 DEG C, obtains sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
Be dispersed in ethanol by the tri-iron tetroxide of the present embodiment step (2) gained/silica magnetic nano particle, carry out transmission electron microscope detection, as shown in Figure 6, wherein, a represents that multiplication factor scale is 1000nm to TEM result; B represents that multiplication factor scale is 100nm.Adopt nanomeasurer (grain size analysis) software to carry out statistical analysis to being no less than 200 particles, as shown in Figure 7, average thickness is about 17nm to the distribution of SiO2 coating thickness.
Sulfydryl modification tri-iron tetroxide/silica magnetic the nano particle preparing gained in this enforcement is carried out FTIR spectrum analysis, its result as shown in Figure 8, result shows that silica is successfully coated on tri-iron tetroxide surface, and dimercaptosuccinic acid is modified successfully tri-iron tetroxide/nano SiO 2 particle.575.62cm in curve
-1left and right is Fe
3o
4the characteristic absorption peak of middle Fe-O vibration, 460cm
-1place is the vibration peak of O-Si-O group, at 1091.11cm
-1the absworption peak at place corresponds to the antisymmetric stretching vibration of Si-O-Si, 929cm
-1the absworption peak at place is caused by Si-O-H stretching vibration, shows the existence of silicon dioxide layer.The vibration absorption peak of-SH is very weak, and with the CO in background gas
2vibration peak is overlapping, therefore in curve, there is not obvious characteristic peak.
The magnetic ferroferric oxide particle of gained prepared by the present embodiment, sulfydryl modification tri-iron tetroxide/silica magnetic nano particle carries out VSM detection, testing result as shown in Figure 9, the saturation magnetization of magnetic ferroferric oxide particle is 156.04emu/g, after coated silica layer and DMSA modify, saturation magnetization weakens to some extent, is 125.98emu/g.
With physiological saline by preparing the magnetic ferroferric oxide particle of gained in the present embodiment step (1), (3), sulfydryl modification tri-iron tetroxide/silica magnetic nano particle is mixed with variable concentrations solution (0.0625mg/ml, 0.25mg/ml, 1mg/ml, 3mg/ml, 5mg/ml, 7mg/ml), whole sample tube is with the temperature water bath 72h of 37 DEG C; Take distilled water as positive control, physiological saline is negative control; Get the solution of the above-mentioned variable concentrations of 1ml respectively, add 25uL and dilute anticoagulated whole blood, at 37 DEG C, the centrifugal 5min of gas bath concussion 150min, 10g/min, gets supernatant and measures absorbance in 540 wavelength places, often organize parallel 3 samples, repeat experiment.As shown in Figure 10, sulfydryl modification tri-iron tetroxide/silica magnetic nano particle blood compatibility is good, even if under high concentration 7mg/ml, hemolysis rate is less than 5%, is about 3% for result.And the hemolysis rate of ferroferric oxide magnetic nanoparticle is all greater than sulfydryl modification tri-iron tetroxide/silica magnetic nano particle, when concentration is 7mg/ml, its hemolysis rate is greater than 20%, far exceeds 5%.
Individual cells suspension is made into, with every hole 5 × 10 with the nutrient solution of the hyclone containing 10%
3individual cell is inoculated into 96 orifice plates, every pore volume 100uL.After cultivating 24h, 50uL stoste is abandoned in suction, add magnetic ferroferric oxide particle, the sulfydryl modification tri-iron tetroxide/silica magnetic nano particle of preparing gained in the present embodiment step (1) of 50uL variable concentrations, (3), make final concentration be 1mg/ml, 0.25mg/ml, 0.0625mg/ml, 0.0156mg/ml.Negative group is nutrient solution, and positive group is dimethyl sulfoxide (DMSO).37 DEG C, 5% (V/V) CO
2air jet flow case in cultivate, cultivate 24 respectively, 36,48,60,72h.After cultivation completes, every hole adds tetrazolium bromide (MTT) solution (5mg/ml phosphate buffer (PBS) is joined) 20uL.Continue to hatch 4 hours, stop cultivating, culture supernatant in turnover panel reject hole.Every hole adds 150uL dimethyl sulfoxide (DMSO), vibrates 10 minutes, crystal is fully melted.Select 490nm wavelength, enzyme linked immunological monitor measures each hole absorbance value, repeat experiment, record result.The relative rate of increase figure of cytotoxicity experiment MTT gained cell as is illustrated by figs. 11 and 12.As can be known from Fig. 11, along with the increase of concentrations of nanoparticles, the relative appreciation rate of l cell L-929 cell declines, and sulfydryl modification tri-iron tetroxide/silica magnetic nano particle is little compared with ferroferric oxide magnetic nanoparticle cytotoxicity, when concentrations of nanoparticles is less than 1mg/ml, the relative appreciation rate of cell is all greater than 75%, and cytotoxicity is classified as 1 grade, is considered as no cytotoxicity.As can be known from Fig. 12, along with the increase of incubation time, the relative appreciation rate of cell declines to some extent, and sulfydryl modification tri-iron tetroxide/silica magnetic nano particle is little compared with ferroferric oxide magnetic nanoparticle cytotoxicity, when incubation time is less than 60h, the relative appreciation rate of cell is all greater than 75%, and cytotoxicity is classified as 1 grade, is considered as no cytotoxicity.
Claims (10)
1. a preparation method for sulfydryl modification tri-iron tetroxide/silica magnetic nano particle, is characterized in that, comprise the following steps:
(1) be that raw material prepares magnetic ferroferric oxide particle by solvent-thermal method with trivalent iron salt;
(2) take ethyl orthosilicate as silicon source, by sol-gal process by generate coated with silica on the surface of described magnetic ferroferric oxide particle, formed tri-iron tetroxide/silica magnetic nano particle;
(3) described tri-iron tetroxide/silica magnetic nano particle is placed in toluene solution, is uniformly dispersed and obtains solution A; Dimercaptosuccinic acid is joined in dimethyl sulphoxide solution, be uniformly dispersed and obtain solution B; Again described solution A and described solution B mix and blend are reacted Separation of Solid and Liquid after a period of time, by the solids cleaning, dry obtained, namely obtain described sulfydryl modification tri-iron tetroxide/silica magnetic nano particle.
2. preparation method as claimed in claim 1, it is characterized in that, in described step (3), the mass ratio of tri-iron tetroxide/silica magnetic nano particle and dimercaptosuccinic acid is 1:1 ~ 1:5.
3. preparation method as claimed in claim 1, it is characterized in that, in described step (3), the solid-to-liquid ratio of tri-iron tetroxide/silica magnetic nano particle and toluene solution is 5:1 ~ 10:1, and solid-to-liquid ratio unit corresponding relation is g/L; The volume ratio of toluene solution and dimethyl sulphoxide solution is: 1:2 ~ 2:1.
4. preparation method as claimed in claim 1, it is characterized in that, in described step (3), the time of reaction is 12 ~ 24h.
5. the preparation method as described in any one of Claims 1 to 4, it is characterized in that, in described step (1), the concrete preparation process of magnetic ferroferric oxide particle is: be scattered in by trivalent iron salt in ethylene glycol solution, add dispersant evenly after, add anhydrous sodium acetate, continue dispersion and obtain finely dispersed mixed liquor, mixed liquor is transferred in autoclave, controlling reaction temperature is 200 DEG C of reaction a period of times, obtains narrow diameter distribution, magnetic ferroferric oxide particle that dispersive property is good.
6. preparation method as claimed in claim 5, it is characterized in that, described dispersant elects Macrogol 2000 as, and described magnetic ferroferric oxide mean particle size is 150nm ~ 300nm.
7. the preparation method as described in any one of Claims 1 to 4, it is characterized in that, in described step (2), the concrete preparation process of tri-iron tetroxide/silica magnetic nano particle is: add in ethanol by magnetic ferroferric oxide particle, be uniformly dispersed; Then add ammoniacal liquor and water, continue dispersion a period of time; Add ethyl orthosilicate again, gentle agitation 6 ~ 12h, last magnetic separation is separated, and the solids alcohol obtained, water alternately clean for several times, drying, namely obtain the core-shell structure magnetic nano particle that tri-iron tetroxide Surface coating has silicon dioxide layer.
8. preparation method as claimed in claim 7, it is characterized in that, the liquid-solid ratio of described magnetic ferroferric oxide and solvent is 1:2 ~ 1:1, and described solvent refers to ethanol, ammoniacal liquor and water; The solid-to-liquid ratio of magnetic ferroferric oxide and ethyl orthosilicate is 62.5:1 ~ 165:1, and wherein solid-to-liquid ratio unit corresponding relation is g/L.
9. preparation method as claimed in claim 7, it is characterized in that, described ethanol, ammoniacal liquor, water volume ratio are 75:23.5:1.5.
10. preparation method as claimed in claim 7, it is characterized in that, described silicon dioxide layer average thickness is 20 ~ 90nm.
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