CN103219118A - High-stability magnetic functional particles and preparation method thereof - Google Patents

High-stability magnetic functional particles and preparation method thereof Download PDF

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Publication number
CN103219118A
CN103219118A CN2013100223113A CN201310022311A CN103219118A CN 103219118 A CN103219118 A CN 103219118A CN 2013100223113 A CN2013100223113 A CN 2013100223113A CN 201310022311 A CN201310022311 A CN 201310022311A CN 103219118 A CN103219118 A CN 103219118A
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magnetic
particle
preparation
stability
functional particles
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CN2013100223113A
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薛晨阳
马修春
丑修建
张强
李俊漾
张文栋
刘俊
熊继军
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North University of China
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North University of China
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Abstract

The invention discloses high-stability magnetic functional particles and a preparation method thereof. The preparation method of the high-stability controllable recovery magnetic functional particles comprises the following steps of: 1, preparing C/Fe3O4 magnetic particles through a high-temperature carbon reduction process; and 2, covering the C/Fe3O4 magnetic particles with SiO2 through a sol-gel method to prepare the high-stability controllable recovery magnetic functional particles. The cores of the high-stability magnetic functional particles are Fe3O4 magnetic cores, the outer layers of the Fe3O4 magnetic cores are wrapped by carbon fiber layers, and the outermost layers are wrapped by SiO2 layers. The high-stability magnetic functional particles have the main advantages of simple raw material, simple preparation process, easiness in operation, no need of adding a protectant and the like, capability of effectively preventing introduction of other substances, good dispersibility, high stability, good biocompatibility, hydrophilicity and excellent stability and can be used for industrial large-scale production.

Description

A kind of high stability magnetic function particle and preparation method thereof
Technical field
The invention belongs to micro-nano science and technology field, more specifically, disclose a kind of high stability magnetic function particle and preparation method thereof.
Background technology
The magnetic function particle not only has the superior surface nature of nano material, also there is induction in magnetic field, and this makes them more and more be subjected to people's attention in the application of all many-sides such as chemistry, physics, biomedicine, electronic material and transducer.The magnetic function particle of high stability can be used as the magnetic control carrier and is applied to all many-sides, is used for bio-sensing etc. as Magnetic Isolation, catalysis, medicament slow release, target control and as a kind of characteristic manner.
The magnetic function particle is made carrier, utilization biomolecule specificity affinity interaction principle, affinity ligand is coupled at the Magnetic Isolation carrier surface, under the orientation control of externally-applied magnetic field, by operations such as affine absorption, cleaning and desorbs, can a step from the primitive organism system of complexity, directly isolate target biological molecules, have the simple and convenient and affine high selectivity double dominant of separating of Magnetic Isolation.Be applied in all many-sides such as cell separation, immune detection, immobilised enzymes and affine separation at present.
The purpose of targeted therapy is to improve the drug concentration of therapentic part, reduces bad reaction, reduces drug dose, improves the fail safe of medicine, validity and patient's biddability.It is that medicine and suitable magnetic active component are configured in the drug delivery system that the control of the magnetic target medicine of malignant tumour discharges treatment, and medicine carrying particle localization is concentrated the position in being released to tumour under the outside magnetic field effect, thereby reaches the purpose of raising medication effect.Each particle of magnetic function particle can be counted as a single magnetic domain, has magnetic responsiveness, particle can move quickly into target site in directed location under the stationary magnetic field, thereby can further shorten the time of medicine orienting enriching, this is the basis that the magnetic function particle is applied to Magnetic Isolation, organizational project and neoplasm targeted therapy.Under action of alternating magnetic field, can produce thermal effect, can control the release of targeted drug better, be considered to a kind of more satisfactory pharmaceutical carrier, also be the basis of tumor thermotherapy simultaneously.
In recent years, have the people that chemiluminescence is combined with nanometer technology, proposed the chemiluminescence magnetic enzyme immunoassay (EIA), this way combines magnetic separation technique, immunology way with the chemiluminescence detection technology.But the magnetic function particle surface is connected with the function of conjugated protein and rolls into a ball repeatly, reactive protein (as antibody) is coated on the magnetic function particle,, forms magnetic bead-antibody-antigenic compound with the own antigenic material effect of tool, under the effect of magnetic field force, compound and other separating substances.Utilize the ALP labelled antibody that can catalysis AMPPD decomposes then, consider the back and add AMPPD in that immunity is counter, produce light signal, thereby detection signal reaches the purpose that detects determined antigen content.
Can see by above-mentioned application, the stable performance of high stability magnetic function particle, toxic and side effect is little, has excellent biological compatibility, and dispersed high in blood, is one of biomaterial of tool application prospect.It is significant to prepare high stability magnetic function particle.
Preparation method to the magnetic function particle in the prior art mainly comprises following several:
1. microemulsion method
Microemulsion method is a kind of effective ways of the preparation ultramicron that grew up in recent years.So-called microemulsion is meant 2 kinds of immiscible liquid of stable dispersion are formed on the thermodynamics macroscopical homogeneous and uneven mixture on the microcosmic, usually need to add surfactant, cosurfactant etc., to impel the formation of oil-in-water or water in oil microemulsion.The product of this method gained remove particle diameter little, be evenly distributed.
2. coprecipitation
After coprecipitation is meant and adds precipitation reagent in containing two or more cationic solution, the method that all ions precipitate fully.Mol ratio is that dripping alkali liquid can make Fe in 1: 2 divalence and the ferric salt solution 3O 4, control pH value scope 9-14 carries out under the oxygen free condition, otherwise Fe 3O 4The mixed valence molysite is oxidized to Fe entirely 3+Oxidized easily.
But more than existing preparation method's defective comprises: microemulsion method surfactant difficulty is removed, output is little, and the cost height, complex process.The complex process of coprecipitation, each stage of the rinsing from co-precipitation, grain growth to precipitation in the process of preparation powder, drying, calcining all may cause particle to be grown up and the formation of aggregate.
Summary of the invention
The present invention is directed to present magnetic function particle and only limit to prepared in laboratory, and characteristics such as complicated process of preparation, cost height, easy oxidation and bad dispersibility, controlled recovery magnetic function particle of a kind of high stable and preparation method thereof invented.This method technological process is simple, cost is low, good stability, crystal grain are not easy to reunite and can further improve the ability of industrial mass production, reduces production costs greatly.The present invention provides crucial material support towards its extensive use demand at aspects such as industry, medical treatment.
The preparation method of the controlled recovery magnetic function of high stable of the present invention particle is characterized in that, may further comprise the steps:
Step 1 is processed into C/Fe by the pyrocarbon reducing process 3O 4Magnetic-particle;
Step 2 is by the described C/Fe of sol-gel normal direction 3O 4Magnetic-particle coated Si O 2, make the controlled recovery magnetic function of described high stable particle.
Preferably, the described pyrocarbon reducing process of described step 1 is to use the carbon reduction in the absorbent cotton to contain Fe ion in the Fe solion, under oxygen atmosphere it is oxidized to Fe again 3O 4, generate C/Fe 3O 4Magnetic-particle.Further preferably, described step 1 specifically comprises: at first, and FeCl 36H 2O adds the water stirring and dissolving and makes certain density FeCl 3Solution; Secondly, absorbent cotton is immersed in FeCl 3In the solution, take out the back then and in high temperature furnace, carry out reduction reaction with uniform temperature and vacuum condition; Once more, the material after the reduction reaction with alcohol envelope and grinding, is removed namagnetic substance with magnetic force repeatedly, obtain described C/Fe 3O 4Magnetic-particle.
Preferably, the described sol-gel process of described step 2 comprises described C/Fe 3O 4Magnetic-particle with react by the ethanol of a certain amount of ratio hydrolysis and tetraethoxysilane (TEOS), make described C/Fe 3O 4Magnetic-particle surface coated Si O 2Further preferably, described step 2 specifically comprises: at first, and with the Fe of described wrap carbon fiber layer 3O 4The magnetic nuclear particle places beaker, adds a certain amount of ethanol in beaker, adds and a certain proportion of tetraethoxysilane (TEOS) stirring fast again, adds a little hydrochloric acid and deionized water reaction certain hour and guarantees the tetraethoxysilane complete hydrolysis; Secondly, after applying ultrasonic concussion and removing namagnetic substance with magnetic force for several times repeatedly, high temperature is qualitative under uniform temperature and vacuum condition; Once more, take out material and grind, obtain the controlled recovery magnetic function of described high stable particle.Wherein, described C/Fe 3O 4Magnetic-particle is the Fe of coated outside carbon fiber layer 3O 4The magnetic nuclear particle.
Utilize said method, can obtain high stability magnetic function particle of the present invention, its center is Fe 3O 4Magnetic nuclear, Fe 3O 4The outer parcel of magnetic nuclear one deck carbon fiber layer, outermost layer parcel SiO 2Layer.
The problem of the invention solves existing preparation magnetic-particle complicated process of preparation, cost height, oxidation easily, easily reuniting has invented that a kind of technology is simple, cost is low, the new technology approach of the preparation magnetic functional particulate of good dispersion, high stability.Its advantage mainly contains: (1) raw material is simple.(2) preparation technology is simple to operate.(3) need not to add protective agent etc., effectively prevent to introduce other materials.(4) good dispersion, SiO 2As the dipolar interaction of coating layer between can the shielding magnetic particle, stop particle aggregation.(5) stability is high, SiO 2Make coating layer and can prevent effectively that particulate oxidation from losing magnetism.(6) SiO 2As coating layer, have excellent biological compatibility, hydrophily and extraordinary stability, for being used in biomedical aspect, it accomplishes fluently solid foundation, can be used as the carrier of cell separation, targeted drug, immune detection.(7) can be used for industrial mass production, efficiently solving current magnetic functional particles carrier can only prepared in laboratory, is difficult to satisfy application demand.
Description of drawings
Fig. 1 is the C/Fe of the embodiment of the invention 3O 4The transmission electron microscope picture of particle;
Fig. 2 is the SiO of the embodiment of the invention 2/ C/Fe 3O 4The transmission electron microscope picture of particle;
Fig. 3 is the C/Fe of the embodiment of the invention 3O 4Particle and SiO 2/ C/Fe 3O 4The XRD figure of particle;
Fig. 4 is the C/Fe of the embodiment of the invention 3O 4Particle and SiO 2/ C/Fe 3O 4The magnetic hysteresis loop figure of particle;
Fig. 5 is the SiO of the embodiment of the invention 2/ C/Fe 3O 4The grain structure schematic diagram.
Embodiment
Provide preferred embodiment of the present invention below in conjunction with accompanying drawing, to describe technical scheme of the present invention in detail.
The preparation method of the controlled recovery magnetic function of high stable of the present invention particle adopts the pyrocarbon reducing process to be processed into C/Fe 3O 4Particle is again by sol-gel process coated Si O 2, make SiO 2/ C/Fe 3O 4Particle, this SiO 2/ C/Fe 3O 4Particle is the controlled recovery magnetic function of a high stable of the present invention particle.
Preparation method of the present invention specifically comprises:
1, C/Fe 3O 4The preparation of magnetic-particle
(1) FeCl 36H 2O adds the water stirring and dissolving and makes certain density FeCl 3Solution.
(2) absorbent cotton is immersed in the FeCl that step (1) obtains 3In the solution, take out the reduction reaction of afterwards in high temperature furnace, carrying out certain hour under uniform temperature and the vacuum condition.Material alcohol envelope after the taking-up is ground, and repeatedly magnetic force is removed namagnetic substance.Obtain C/Fe 3O 4Nanometer magnetic nuclear.
Iron ion with in the main component carbon reduction solution of absorbent cotton is oxidized to Fe with it again under certain oxygen atmosphere 3O 4Method, make particle as shown in Figure 1, particle surface has one deck carbon fiber as thin as a wafer, this layer carbon fiber can play the protection Fe 3O 4Be oxidized to the effect of iron oxide, simultaneously, the particle that obtains is solid-state, can carry out real-time optimization to experiment by observing intuitively.
Fig. 1 is experiment gained C/Fe 3O 4The transmission electron microscope picture of particle, the particle of as can be seen from the figure preparing are square, and one deck carbon fiber parcel is arranged on every side.
2. high stability SiO 2/ C/Fe 3O 4The preparation of magnetic functional particles
Get above-mentioned C/Fe 3O 4Particle places beaker, adds a certain amount of ethanol in beaker, adds and a certain proportion of tetraethoxysilane (TEOS) stirring fast again, adds a little hydrochloric acid and deionized water reaction certain hour and guarantees the tetraethoxysilane complete hydrolysis.Ultrasonic concussion, after magnetic force was removed namagnetic substance for several times, high temperature was qualitative under uniform temperature and vacuum condition.Take out the back material and grind, obtain high stability SiO 2/ C/Fe 3O 4The magnetic functional particles.SiO 2Coating layer effectively plays the qualitative C/Fe of preventing as shown in Figure 2 3O 4Oxidation, the effect that improves granule stability.
Fig. 2 is experiment gained SiO 2/ C/Fe 3O 4The transmission electron microscope picture of particle, as can be seen from the figure the outermost light SiO that made reprisals 2Layer.
From Fig. 3 (a) is C/Fe 3O 4The XRD curve of particle, Fe as can be seen 3O 4Particle is owing to ingress of air in solid phase, and part is oxidized.Fig. 3 (b) as can be seen in as can be seen 2 θ located a ripple bag at 20-30 °, this ripple bag has proved amorphous Si O 2With Vitrea existence, and do not had the peak of iron oxide, particle does not have oxidized, proves SiO 2Surface modification has improved the stability of particle, has prevented that effectively particle is oxidized.
Fig. 4 is the magnetic hysteresis loop of two kinds of particles, the saturation magnetization height, and remanent magnetism is little, satisfies the magnetic recovery condition fully.Coat saturated this words intensity in back as can be seen and obviously reduce, remanent magnetism is little, satisfies the magnetic control recovering condition equally, and proof list bread covers evenly simultaneously, coats successfully.
Fig. 5 shows the prepared SiO of the embodiment of the invention 2/ C/Fe 3O 4The grain structure schematic diagram.Its center is Fe 3O 4Magnetic nuclear 1, Fe 3O 4The outer parcel of magnetic nuclear one deck carbon fiber layer 2, outermost layer parcel SiO 2Layer 3.
The problem of the invention solves existing preparation magnetic-particle complicated process of preparation, cost height, oxidation easily, easily reuniting has invented that a kind of technology is simple, cost is low, the new technology approach of the preparation magnetic functional particulate of good dispersion, high stability.Its advantage mainly contains: (1) raw material is simple.(2) preparation technology is simple to operate.(3) need not to add protective agent etc., effectively prevent to introduce other materials.(4) good dispersion, SiO 2As the dipolar interaction of coating layer between can the shielding magnetic particle, stop particle aggregation.(5) stability is high, SiO 2Make coating layer and can prevent effectively that particulate oxidation from losing magnetism.(6) SiO 2As coating layer, have excellent biological compatibility, hydrophily and extraordinary stability in the moment, for being used in biomedical aspect, it accomplishes fluently solid foundation, can be used as the carrier of cell separation, targeted drug, immune detection.(7) can be used for industrial mass production, efficiently solving current magnetic functional particles carrier can only prepared in laboratory, is difficult to satisfy application demand.
Those skilled in the art can carry out various remodeling and change to the present invention.Therefore, the present invention has covered various remodeling and the change in the scope that falls into appending claims and equivalent thereof.

Claims (7)

1. the preparation method of the controlled recovery magnetic function of a high stable particle is characterized in that, may further comprise the steps:
Step 1 is processed into C/Fe by the pyrocarbon reducing process 3O 4Magnetic-particle;
Step 2 is by the described C/Fe of sol-gel normal direction 3O 4Magnetic-particle coated Si O 2, make the controlled recovery magnetic function of described high stable particle.
2. preparation method as claimed in claim 1 is characterized in that, the described pyrocarbon reducing process of described step 1 is to use the carbon reduction in the absorbent cotton to contain Fe ion in the Fe solion, under oxygen atmosphere it is oxidized to Fe again 3O 4, generate C/Fe 3O 4Magnetic-particle.
3. preparation method as claimed in claim 2 is characterized in that, described step 1 specifically comprises: at first, and FeCl 36H 2O adds the water stirring and dissolving and makes certain density FeCl 3Solution; Secondly, absorbent cotton is immersed in FeCl 3In the solution, take out the back then and in high temperature furnace, carry out reduction reaction with uniform temperature and vacuum condition; Once more, the material after the reduction reaction with alcohol envelope and grinding, is removed namagnetic substance with magnetic force repeatedly, obtain described C/Fe 3O 4Magnetic-particle.
4. preparation method as claimed in claim 1 is characterized in that, the described sol-gel process of described step 2 comprises described C/Fe 3O 4Magnetic-particle with react by the ethanol of a certain amount of ratio hydrolysis and tetraethoxysilane (TEOS), make described C/Fe 3O 4Magnetic-particle surface coated Si O 2
5. preparation method as claimed in claim 4 is characterized in that, described step 2 specifically comprises: at first, and with the Fe of described wrap carbon fiber layer 3O 4The magnetic nuclear particle places beaker, adds a certain amount of ethanol in beaker, adds and a certain proportion of tetraethoxysilane (TEOS) stirring fast again, adds a little hydrochloric acid and deionized water reaction certain hour and guarantees the tetraethoxysilane complete hydrolysis; Secondly, after applying ultrasonic concussion and removing namagnetic substance with magnetic force for several times repeatedly, high temperature is qualitative under uniform temperature and vacuum condition; Once more, take out material and grind, obtain the controlled recovery magnetic function of described high stable particle.
6. according to any described preparation method among the claim 1-5, it is characterized in that described C/Fe 3O 4Magnetic-particle is the Fe of coated outside carbon fiber layer 3O 4The magnetic nuclear particle.
7. a high stability magnetic function particle is characterized in that its center is Fe 3O 4Magnetic nuclear, Fe 3O 4The outer parcel of magnetic nuclear one deck carbon fiber layer, outermost layer parcel SiO 2Layer.
CN2013100223113A 2012-06-11 2013-01-07 High-stability magnetic functional particles and preparation method thereof Pending CN103219118A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104084140A (en) * 2014-07-04 2014-10-08 淮海工学院 Adsorbent for heavy metal copper ions in high-salinity wastewater and preparation method of adsorbent
CN109370396A (en) * 2018-08-31 2019-02-22 王雪峰 A kind of preparation method of high intensity radiation shielding coating
CN114384239A (en) * 2021-12-09 2022-04-22 深圳君和生物科技有限公司 Immunomagnetic bead storage system and immunomagnetic bead system

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104084140A (en) * 2014-07-04 2014-10-08 淮海工学院 Adsorbent for heavy metal copper ions in high-salinity wastewater and preparation method of adsorbent
CN104084140B (en) * 2014-07-04 2016-08-24 淮海工学院 Heavy metal copper ion adsorbent and preparation method thereof in a kind of high-salt wastewater
CN109370396A (en) * 2018-08-31 2019-02-22 王雪峰 A kind of preparation method of high intensity radiation shielding coating
CN114384239A (en) * 2021-12-09 2022-04-22 深圳君和生物科技有限公司 Immunomagnetic bead storage system and immunomagnetic bead system
CN114384239B (en) * 2021-12-09 2022-10-18 深圳君和生物科技有限公司 Immunomagnetic bead storage system and immunomagnetic bead system

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Application publication date: 20130724