CN105126716B - A kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle - Google Patents
A kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle, comprise the following steps：1) magnetic ferroferric oxide particle is prepared by solvent-thermal method by raw material of trivalent iron salt；2) using tetraethyl orthosilicate as silicon source, by sol-gal process by the coated with silica of generation on the surface of magnetic ferroferric oxide particle, ferroso-ferric oxide/silica magnetic nano particle is formed；3) ferroso-ferric oxide/silica magnetic nano particle is placed in toluene solution, is uniformly dispersed and obtains solution A；Dimercaptosuccinic acid is added in dimethyl sulphoxide solution, is uniformly dispersed and obtains solution B；Solution A and solution B are mixed into separation of solid and liquid after reaction a period of time, cleaning again, dried, that is, obtains sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle.The magnetic nanoparticle dispersive property of the present invention is good, with good stability and biocompatibility, has potential application value in biomedical sector.
Description
Technical field
Received the invention belongs to medical material field, more particularly to a kind of sulfydryl modification ferroso-ferric oxide/silica magnetic
The preparation method of rice grain.
Background technology
Magnetic nanoparticle is had broad application prospects due to its special magnetic property in bio-medical field, can be summarized
For external application and the class of vivo applications two.Application aspect in vitro, be primarily useful for marking and separate cell, protein, DNA,
Bacterium and virus etc.；And application aspect in vivo, the developer being imaged available for magnetic resonance contrast, pharmaceutical carrier and cross heat cure
Tumour etc..It will make huge in the near future for the health of the mankind using the oxide of iron as the magnetic nanoparticle of representative
Contribution.In order that magnetic nanoparticle can preferably serve the health of the mankind as soon as possible, preparation to nano particle, repair
Decorations, the basic research of functionalization be it is required 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 machine
Tool ball-milling method, obtained particle size distribution is wider, and required time is long, and energy consumption is big, is easily introduced impurity, is unsuitable for preparing biology
Medical magnetic Nano material.Magnetic nano-particle good biocompatibility prepared by bioanalysis, but large-scale culture is difficult, particle
Extraction process is also relatively complicated, and the size tunable scope of gained particle is restricted.Therefore the preparation master of current nano magnetic material
Chemical preparation process is depended on, wherein coprecipitation is simple to operate, and yield is big, but be difficult to obtain homogeneous of size distribution
Grain, such as Chinese invention patent (application publication number：CN 103990423 A).Need addition substantial amounts of in microemulsion method preparation process
Oil-based solvent and surfactant, not easy cleaning.High temperature thermal decomposition method acquisition particle homogeneity is good, particle size is easily controllable,
But need precise control of temperature, largely use surfactant, particle surface easily adsorbs a large amount of organic reagents and is difficult to clean etc. main
Want shortcoming, such as Chinese invention patent (application publication number：CN 102085381 A).
Nano particle is due to small volume, therefore with very high specific surface area, and surface-active is high, it is easy in cell and tissue
Middle accumulation, toxicity is produced with biotic component effect.The bio-toxicity of nano magnetic particle and its chemical constituent, granular size, shape
The factors such as shape, surface-modifying species, structure, aggregation are related.The surface of nano particle can be reduced by the surface modification of particle
Can, reduce and reunite, adjust the biocompatibility and response characteristic of magnetic nanoparticle.
SiO2With good biocompatibility and antidecomposition, oxidation resistance.Fe3O4Nano grain surface coated Si O2
After layer, the mutual attractive force between particle can be suppressed well, Fe is improved3O4Water solubility, stability and the biofacies of nano particle
Capacitive, and SiO2Surface has abundant carboxyl group, makes SiO2/Fe3O4Magnetic coupling particle is easier to be modified or connect function
Macromolecular material, is conducive to it in the application in the fields such as biomedicine.In the ferroso-ferric oxide nucleocapsid knot to coated with silica
Structure surface is carried out in the method operation of sulfydryl modification, Chinese invention patent (application publication number：The A of CN 103599751) use
It is that silane coupler carries out functional modification, Chinese invention patent (application publication number to the surface of carrier：CN 104174039
A) use covalent effect and introduce near-infrared functional group and polyethylene glycol sulfydryl functional group.Both reacts in modifying process
Temperature is more than 60 DEG C, and the former also needs constantly to be passed through nitrogen during the course of the reaction, and solvent methanol highly volatile after the heating
There is toxic action to human body；The latter also needs to carry out amino modified, process step to nano grain surface in sulfydryl modification process
It is excessively cumbersome.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art to aoxidize three there is provided a kind of sulfydryl modification four
The preparation method of iron/silica magnetic nano particle.
In order to solve the above technical problems, technical scheme proposed by the present invention is：
A kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle, comprises the following steps：
(1) magnetic ferroferric oxide particle is prepared by solvent-thermal method by raw material of trivalent iron salt；
(2) using tetraethyl orthosilicate as silicon source, by sol-gal process by the coated with silica of generation in the magnetic four
The surface of Fe 3 O particle, forms ferroso-ferric oxide/silica magnetic nano particle；
(3) ferroso-ferric oxide/silica magnetic nano particle is placed in toluene solution, being uniformly dispersed, it is molten to obtain
Liquid A；Dimercaptosuccinic acid is added in dimethyl sulphoxide solution, is uniformly dispersed and obtains solution B；Again by the solution A and institute
State solution B and mix separation of solid and liquid after reaction a period of time, by the cleaning of obtained solids, dry, that is, obtain the sulfydryl
Modify ferroso-ferric oxide/silica magnetic nano particle.
Above-mentioned preparation method, it is preferred that in the step (3), ferroso-ferric oxide/silica magnetic nano particle with
The mass ratio of dimercaptosuccinic acid is 1:1~1:5.
Above-mentioned preparation method, it is preferred that in the step (3), ferroso-ferric oxide/silica magnetic nano particle with
The solid-to-liquid ratio of toluene solution is 5:1~10:1, solid-to-liquid ratio unit corresponding relation is g/L；Toluene solution and dimethyl sulphoxide solution
Volume ratio be 1:2~2:1.
Above-mentioned preparation method, it is preferred that in the step (3), the time of reaction is 12~24h.
Above-mentioned preparation method, it is preferred that in the step (1), the specific preparation process of magnetic ferroferric oxide particle
For：Trivalent iron salt is scattered in ethylene glycol solution, dispersant is added, after being uniformly dispersed, anhydrous sodium acetate is added, continues scattered
Finely dispersed mixed liquor is obtained, mixed liquor is transferred in autoclave, when controlling reaction temperature reacts one section for 200 DEG C
Between, obtain the magnetic ferroferric oxide particle that particle diameter distribution is narrow, dispersive property is good.
Above-mentioned preparation method, it is preferred that described dispersant elects polyethylene glycol 2000, the magnetic ferroferric oxide as
Mean particle size is 150nm~300nm, and surface functional group is mainly-OH.
Above-mentioned preparation method, it is preferred that in the step (2), ferroso-ferric oxide/silica magnetic nano particle
Specifically preparation process is：Magnetic ferroferric oxide particle is added in ethanol, is uniformly dispersed；Then ammoniacal liquor and water are added, is continued
Scattered a period of time；Add tetraethyl orthosilicate, 6~12h of gentle agitation, last magnetic separation separation, obtained solids alcohol, water
Alternately cleaning for several times, dry, that is, obtaining ferroso-ferric oxide Surface coating has the core-shell structure magnetic nano particle of silicon dioxide layer.
Above-mentioned preparation method, it is preferred that the liquid-solid ratio of the magnetic ferroferric oxide and solvent is 1:2~1:1, it is described
Solvent refers to ethanol, ammoniacal liquor and water；The solid-to-liquid ratio of magnetic ferroferric oxide and tetraethyl orthosilicate is 62.5:1~165:1, wherein
Solid-to-liquid ratio unit corresponding relation is g/L.
Above-mentioned preparation method, it is preferred that the ethanol, ammoniacal liquor, water volume ratio are 75:23.5:1.5.
Above-mentioned preparation method, it is preferred that the silicon dioxide layer average thickness is 20~90nm.
The present invention is to be based on SiO2, reunion and SiO can be reduced in the surface that nano particle can be reduced2Surface exists abundant
Carboxyl group, enable the dimercaptosuccinic acid with two sulfydryls more easily in SiO2Coat Fe3O4Magnetic coupling particle
Surface carry out functional modification so that greatly improve ferroso-ferric oxide/silica magnetic nano particle dispersiveness,
Stability and biocompatibility etc., make it be more widely used in biomedical sector.
Compared with prior art, the advantage of the invention is that：
1) reaction condition is gentle during preparation method of the invention, and preparation process reagent is nontoxic, and operating procedure is simple, system
The standby magnetic nanoparticle dispersive property obtained is good, with good stability and biocompatibility, in biomedical sector tool
There is potential application value.
2) it is modified during preparation method of the present invention using dimercaptosuccinic acid (DMSA), DMSA is inherently a kind of
Heavy metal antidote, biocompatibility is fabulous, and its molecular formula is HOOC (CHSH)2COOH, DMSA pass through COO functional groups and four oxidations
Three-iron/silica magnetic nano grain surface is combined, and the DMSA sulfydryls that just have two molecular weight of per molecule amount are exposed to
Surface, abundant mercapto functional group has great improvement result, and energy to the dispersive property and bio-compatible performance of particle
Enough for protein binding etc., potentially application provides abundant binding site, improves its potential using value.
Brief description of the drawings
Fig. 1 schemes for the transmission electron microscope detection of ferroso-ferric oxide/silica magnetic nano particle in the embodiment of the present invention 1
Picture.
Fig. 2 be the embodiment of the present invention 1 in ferroso-ferric oxide/silica magnetic nano particle coated with silica layer
Thickness Relative distribution figure.
Fig. 3 schemes for the transmission electron microscope detection of ferroso-ferric oxide/silica magnetic nano particle in the embodiment of the present invention 2
Picture.
Fig. 4 be the embodiment of the present invention 2 in ferroso-ferric oxide/silica magnetic nano particle coated with silica layer
Thickness Relative distribution figure.
Fig. 5 be the embodiment of the present invention 3 in preparation magnetic ferroferric oxide grain size distribution.
Fig. 6 schemes for the transmission electron microscope detection of ferroso-ferric oxide/silica magnetic nano particle in the embodiment of the present invention 3
Picture.
Fig. 7 be the embodiment of the present invention 3 in ferroso-ferric oxide/silica magnetic nano particle coated with silica layer
Thickness Relative distribution figure.
Fig. 8 is the magnetic particles of ferroferric oxide (a) and sulfydryl modification ferroso-ferric oxide/dioxy in the embodiment of the present invention 3
Fourier's infrared detection spectrogram of SiClx (b) magnetic nanoparticle.
Fig. 9 is the magnetic particles of ferroferric oxide (a) and sulfydryl modification ferroso-ferric oxide/dioxy in the embodiment of the present invention 3
The VSM detection figures of SiClx (b) magnetic nanoparticle.
Figure 10 is the magnetic particles of ferroferric oxide and sulfydryl modification ferroso-ferric oxide/titanium dioxide in the embodiment of the present invention 3
The hemolytic experiment of silicon magnetic nanoparticle-hemolysis rate figure.
Figure 11 is the magnetic particles of ferroferric oxide and sulfydryl modification ferroso-ferric oxide/titanium dioxide in the embodiment of the present invention 3
Cell is with respect to proliferation rate figure obtained by the cytotoxicity experiment MTT of silicon magnetic nanoparticle various concentrations.
Figure 12 is the magnetic particles of ferroferric oxide and sulfydryl modification ferroso-ferric oxide/titanium dioxide in the embodiment of the present invention 3
Cell obtained by cytotoxicity experiment MTT is with respect to proliferation rate figure under the different incubation times of silicon magnetic nanoparticle.
Embodiment
For the ease of understanding the present invention, more complete is made to the present invention below in conjunction with Figure of description and preferred embodiment
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can pass through product made from known method.
Embodiment 1：
A kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle of the invention, including with
Lower step：
(1) 1mmol FeCl is taken3·6H2Then O adds 30ml ethylene glycol, 2g polyethylene glycol 2000s, magnetic force in beaker
Stirring is further continued for adding 3g anhydrous sodium acetates, stirring obtains finely dispersed mixed solution to being uniformly dispersed.Again by mixed solution
Add in autoclave, be warming up to 200 DEG C and react 6h, reaction terminates water-cooled to room temperature, Magneto separate, by what is obtained after separation
Decorating film is washed several times with alcohol, is placed into 60 DEG C of drying boxes and is dried in vacuo, obtains magnetic ferroferric oxide particle.
(2) the magnetic ferroferric oxide particle for taking 50mg steps (1) to prepare is scattered in 75mL ethanol solution, ultrasound
40min, continuously adds 23.5mL deionized water, 1.5mL ammoniacal liquor (25wt%), ultrasonic 40min.Then mixed solution is entered
Row electric stirring, while being slowly added to 0.4mL tetraethyl orthosilicates, (magnetic ferroferric oxide granular mass and tetraethyl orthosilicate are consolidated
Liquor ratio is 125g:1L), gentle agitation 8h is continued.After reaction terminates, Magneto separate, alcohol, water are alternately cleaned for several times, vacuum at 60 DEG C
Dry, obtain the magnetic nanoparticle of coated with silica ferroso-ferric oxide structure (ferroso-ferric oxide/silica).
(3) ferroso-ferric oxide/silica magnetic nano particle for taking 100mg steps (2) to prepare is scattered in 20mL toluene
In solution, ultrasonic 30min obtains solution A.Take 250mg dimercaptosuccinic acid be scattered in 10mL dimethyl sulphoxide solution it is molten
In liquid, ultrasonic 30min obtains solution B；Solution A, solution B are mixed into 24h, reaction terminates, and alcohol is washed several times, it is true at 60 DEG C
Sky is dried, and obtains sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle.
Ferroso-ferric oxide obtained by the present embodiment step (2)/silica magnetic nano particle is dispersed in ethanol
In, transmission electron microscope detection, TEM results are carried out as shown in figure 1, wherein, a represents that multiplication factor scale is 500nm；B represents amplification
Multiple scale is 200nm；C represents that multiplication factor scale is 100nm.Using nano measurer (grain size analysis) software to not
Less than 200 particles carry out statistical analysis, SiO2Coating thickness is distributed as shown in Fig. 2 average thickness is about 32.5nm.
Embodiment 2：
A kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle of the invention, including with
Lower step：
(1) 1mmol FeCl is taken3·6H2Then O adds 30ml ethylene glycol, 2g polyethylene glycol 2000s, magnetic force in beaker
Stirring is further continued for adding 3g anhydrous sodium acetates, stirring obtains finely dispersed mixed solution to being uniformly dispersed.Again by mixed solution
Add in autoclave, be warming up to 200 DEG C and react 6h, reaction terminates water-cooled to room temperature, Magneto separate, by what is obtained after separation
Decorating film is washed several times with alcohol, is placed into 60 DEG C of drying boxes and is dried in vacuo, obtains magnetic ferroferric oxide particle.
(2) the magnetic ferroferric oxide particle for taking 50mg steps (1) to prepare is scattered in 150mL ethanol solution, ultrasound
40min, continuously adds 47mL deionized water, 3mL ammoniacal liquor (25wt%), ultrasonic 40min.Then electricity is carried out to mixed solution
Dynamic stirring, while being slowly added to the 0.8mL tetraethyl orthosilicates (solid-to-liquid ratio of magnetic ferroferric oxide granular mass and tetraethyl orthosilicate
For 62.5g:1L), gentle agitation 12h is continued.After reaction terminates, Magneto separate, alcohol, water are alternately cleaned for several times, and vacuum is done at 60 DEG C
It is dry, obtain the magnetic nanoparticle of coated with silica ferroso-ferric oxide structure (ferroso-ferric oxide/silica).
(3) ferroso-ferric oxide/silica magnetic nano particle for taking 100mg steps (2) to prepare is scattered in 10mL toluene
In solution, ultrasonic 30min obtains solution A.Take 250mg dimercaptosuccinic acid be scattered in 20mL dimethyl sulphoxide solution it is molten
In liquid, ultrasonic 30min obtains solution B；Solution A, solution B are mixed into 18h, reaction terminates, and alcohol is washed several times, it is true at 60 DEG C
Sky is dried, and obtains sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle.
Ferroso-ferric oxide obtained by the present embodiment step (2)/silica magnetic nano particle is dispersed in ethanol
In, transmission electron microscope detection, TEM results are carried out as shown in figure 3, wherein, a represents that multiplication factor scale is 500nm；B represents amplification
Multiple scale is 200nm.Statistical analysis is carried out to no less than 200 particles using nano measurer (grain size analysis) softwares,
SiO2Coating thickness is distributed as shown in figure 4, average thickness is about 87nm.
Embodiment 3：
A kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle of the invention, including with
Lower step：
(1) 1mmol FeCl is taken3·6H2Then O adds 30ml ethylene glycol, 2g polyethylene glycol 2000s, magnetic force in beaker
Stirring is further continued for adding 3g anhydrous sodium acetates, stirring obtains finely dispersed mixed solution to being uniformly dispersed.Again by mixed solution
Add in autoclave, be warming up to 200 DEG C and react 6h, reaction terminates water-cooled to room temperature, Magneto separate, by what is obtained after separation
Decorating film is washed several times with alcohol, is placed into 60 DEG C of drying boxes and is dried in vacuo, obtains magnetic ferroferric oxide particle.Grain size distribution
As shown in figure 5, Average Particle Diameters are 157nm.
(2) the magnetic ferroferric oxide particle for taking 50mg steps (1) to prepare is scattered in 150mL ethanol solution, ultrasound
40min, continuously adds 47mL deionized water, 3mL ammoniacal liquor (25wt%), ultrasonic 40min.Then electricity is carried out to mixed solution
Dynamic stirring, while being slowly added to the 0.3mL tetraethyl orthosilicates (solid-to-liquid ratio of magnetic ferroferric oxide granular mass and tetraethyl orthosilicate
For 165g:1L), gentle agitation 6h is continued.After reaction terminates, Magneto separate, alternately cleaning for several times, is dried in vacuo at 60 DEG C for alcohol, water,
Obtain the magnetic nanoparticle of coated with silica ferroso-ferric oxide structure (ferroso-ferric oxide/silica).
(3) ferroso-ferric oxide/silica magnetic nano particle for taking 100mg steps (2) to prepare is scattered in 10mL toluene
In solution, ultrasonic 30min obtains solution A.Take 250mg dimercaptosuccinic acid be scattered in 10mL dimethyl sulphoxide solution it is molten
In liquid, ultrasonic 30min obtains solution B；Solution A, B are mixed into 12h, reaction terminates, and alcohol is washed several times, vacuum is done at 60 DEG C
It is dry, obtain sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle.
Ferroso-ferric oxide obtained by the present embodiment step (2)/silica magnetic nano particle is dispersed in ethanol
In, transmission electron microscope detection, TEM results are carried out as shown in fig. 6, wherein, a represents that multiplication factor scale is 1000nm；B represents amplification
Multiple scale is 100nm.Statistical analysis is carried out to no less than 200 particles using nano measurer (grain size analysis) softwares,
SiO2 coating thicknesses are distributed as shown in fig. 7, average thickness is about 17nm.
Sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle obtained by being prepared during this is implemented carries out Fourier
As a result infrared spectrum analysis, its result as shown in figure 8, show that silica is successfully coated on ferroso-ferric oxide surface, and two mercaptos
Base succinic acid is modified successfully ferroso-ferric oxide/nano SiO 2 particle.575.62cm in curve-1Left and right is Fe3O4Middle Fe-
The characteristic absorption peak of O vibrations, 460cm-1Place is the vibration peak of O-Si-O groups, in 1091.11cm-1The absworption peak at place corresponds to
Si-O-Si antisymmetric stretching vibration, 929cm-1The absworption peak at place is caused by Si-O-H stretching vibrations, shows silicon dioxide layer
In the presence of.- SH vibration absorption peak is very weak, and with the CO in background gas2Overlap of peaks is vibrated, therefore in the absence of bright in curve
Aobvious characteristic peak.
By the present embodiment prepare obtained by magnetic ferroferric oxide particle, sulfydryl modification ferroso-ferric oxide/silica magnetic
Property nano particle carry out VSM detections, testing result is as shown in figure 9, the saturation magnetization of magnetic ferroferric oxide particle is
After 156.04emu/g, coated silica layer and DMSA modifications, saturation magnetization has weakened, and is 125.98emu/g.
With physiological saline will the present embodiment step (1), prepare in (3) obtained by magnetic ferroferric oxide particle, sulfydryl repaiies
Decorations ferroso-ferric oxide/silica magnetic nano particle be configured to various concentrations solution (0.0625mg/ml, 0.25mg/ml,
1mg/ml, 3mg/ml, 5mg/ml, 7mg/ml), whole samples test tube is with 37 DEG C of temperature water bath 72h；It is right using distilled water as the positive
According to physiological saline is negative control；The solution of the above-mentioned various concentrations of 1ml is taken respectively, is added at 25uL dilution anticoagulated whole bloods, 37 DEG C
Gas bath shakes 150min, 10g/min centrifugation 5min, takes supernatant mensuration absorbance at 540 wavelength, every group of parallel 3 sample, weight
Multiple experiment.As a result as shown in Figure 10, sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle blood compatibility is good, i.e.,
Make under high concentration 7mg/ml, hemolysis rate is less than 5%, about 3%.And the hemolysis rate of ferroferric oxide magnetic nanoparticle is big
In sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle, when concentration is 7mg/ml, its hemolysis rate is more than 20%,
Far beyond 5%.
Individual cells suspension is made into the nutrient solution containing 10% hyclone, with every hole 5 × 103Individual cell is inoculated into 96
Orifice plate, per pore volume 100uL.Cultivate after 24h, inhale and abandon 50uL stostes, the present embodiment step (1) of addition 50uL various concentrations,
(3) magnetic ferroferric oxide particle, sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle obtained by being prepared in, make
Final concentration of 1mg/ml, 0.25mg/ml, 0.0625mg/ml, 0.0156mg/ml.Feminine gender group is nutrient solution, and positive group is diformazan
Base sulfoxide.37 DEG C, 5% (V/V) CO2Air jet flow case in cultivate, respectively cultivate 24,36,48,60,72h.After the completion of culture,
Add tetrazolium bromide (MTT) solution (5mg/ml phosphate buffers (PBS) are matched somebody with somebody) 20uL per hole.Continue to be incubated 4 hours, terminate training
Support, culture supernatant in turnover panel reject hole.Add 150uL dimethyl sulfoxide (DMSO)s per hole, vibrate 10 minutes, crystal is fully melted.
490nm wavelength is selected, each hole absorbance value is determined on enzyme linked immunological monitor, repeats to test, records result.Cytotoxicity is real
Test cell obtained by MTT with respect to proliferation rate figure as is illustrated by figs. 11 and 12.As can be known from Fig. 11, with the increasing of concentrations of nanoparticles
Plus, l cell L-929 cells decline with respect to appreciation rate, and sulfydryl modification ferroso-ferric oxide/silica magnetic is received
Rice grain is small compared with ferroferric oxide magnetic nanoparticle cytotoxicity, when concentrations of nanoparticles is less than 1mg/ml, and cell is relative to be increased
Value rate is all higher than 75%, and cytotoxicity is classified as 1 grade, is considered as no cytotoxicity.As can be known from Fig. 12, with the increasing of incubation time
Plus, cell has declined with respect to appreciation rate, and sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle is compared with four oxidations three
Ferromagnetic nanoparticle cytotoxicity is small, and when incubation time is less than 60h, cell is all higher than 75%, cytotoxicity with respect to appreciation rate
1 grade is classified as, is considered as no cytotoxicity.
Claims (4)
1. a kind of preparation method of sulfydryl modification ferroso-ferric oxide/silica magnetic nano particle, it is characterised in that including with
Lower step：
(1) magnetic ferroferric oxide particle is prepared by solvent-thermal method by raw material of trivalent iron salt；Magnetic ferroferric oxide particle
Specific preparation process be：Trivalent iron salt is scattered in ethylene glycol solution, after addition dispersant is uniform, anhydrous second is added
Sour sodium, continues to disperse to obtain finely dispersed mixed liquor, mixed liquor is transferred in autoclave, controlling reaction temperature is
200 DEG C of reaction a period of times, obtain the magnetic ferroferric oxide particle that particle diameter distribution is narrow, dispersive property is good；Described dispersant
Elect polyethylene glycol 2000 as；The magnetic ferroferric oxide mean particle size is 150nm~300nm, and surface functional group is main
For-OH；
(2) using tetraethyl orthosilicate as silicon source, the coated with silica of generation is aoxidized in the magnetic four by sol-gal process
The surface of three iron particles, forms ferroso-ferric oxide/silica magnetic nano particle；Ferroso-ferric oxide/silica magnetic is received
The specific preparation process of rice grain is：Magnetic ferroferric oxide particle is added in ethanol, is uniformly dispersed；Then add ammoniacal liquor with
Water, continues scattered a period of time；Add tetraethyl orthosilicate, 6~12h of gentle agitation, last magnetic separation separation, obtained solids
With alcohol, water alternately cleaning for several times, dry, that is, the core-shell structure magnetic that obtaining ferroso-ferric oxide Surface coating has silicon dioxide layer receives
Rice grain；
(3) ferroso-ferric oxide/silica magnetic nano particle is placed in toluene solution, is uniformly dispersed and obtains solution A；
Dimercaptosuccinic acid is added in dimethyl sulphoxide solution, is uniformly dispersed and obtains solution B；Again by the solution A and described molten
Liquid B mixes separation of solid and liquid after reaction a period of time, by the cleaning of obtained solids, dries, that is, obtains the sulfydryl modification
Ferroso-ferric oxide/silica magnetic nano particle；Ferroso-ferric oxide/silica magnetic nano particle and dimercaptosuccinic acid
Mass ratio be 1:1~1:5；The solid-to-liquid ratio of ferroso-ferric oxide/silica magnetic nano particle and toluene solution is 5:1~
10:1, 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；Reaction
Time be 12~24h.
2. preparation method as claimed in claim 1, it is characterised in that the liquid-solid ratio of the magnetic ferroferric oxide and solvent is
1:2~1:1, the solvent refers to ethanol, ammoniacal liquor and water；The solid-to-liquid ratio of magnetic ferroferric oxide and tetraethyl orthosilicate is 62.5:1
~165:1, wherein solid-to-liquid ratio unit corresponding relation is g/L.
3. preparation method as claimed in claim 1, it is characterised in that the ethanol, ammoniacal liquor, water volume ratio are 75:23.5:
1.5。
4. preparation method as claimed in claim 1, it is characterised in that the silicon dioxide layer average thickness is 20~90nm.
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| CN107469797B (en) * | 2017-09-11 | 2019-02-22 | 济南大学 | A kind of preparation method of the modified porous magnetic composite microsphere of dimercaptosuccinic acid |
| CN109103221B (en) | 2018-08-17 | 2020-08-28 | 京东方科技集团股份有限公司 | Pixel defining layer, preparation raw material and preparation method thereof, and display substrate |
| CN111575267B (en) * | 2020-05-06 | 2024-05-14 | 吕梁学院 | Artificial micro-nano robot and preparation method thereof |
| CN114192119A (en) * | 2021-11-30 | 2022-03-18 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Sulfydryl modified magnetic particle dispersion liquid and preparation method and application thereof |
| CN114716778B (en) * | 2022-03-25 | 2023-04-07 | 江苏新日电动车股份有限公司 | Spraying-free composite material for preventing heavy metal pollution and preparation method thereof |
| CN114620779A (en) * | 2022-03-29 | 2022-06-14 | 江苏月旭新材料科技有限公司 | Silicon dioxide nano magnetic bead and preparation method and application thereof |
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