CN101066988B - Magnetic metal oxide microsphere in core-shell structure and its preparation process - Google Patents
Magnetic metal oxide microsphere in core-shell structure and its preparation process Download PDFInfo
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Abstract
The present invention belongs to the field of inorganic material technology, and is especially one kind of magnetic metal oxide microsphere in core-shell structure and its preparation process. The microsphere has ferroferric oxide microsphere as the core and metal oxide as the shell. It is prepared through the first hydrothermal process to cover one layer of amorphous carbon onto ferroferric oxidemicrosphere to form magnetic carbon microsphere Fe3O4@C, the subsequent dispersing microsphere Fe3O4@C in alcohol water solution of pre-hydrolyzed metal alkoxide for adsorbing inorganic oligomer to the surface of the microsphere, and the final calcining in nitrogen atmosphere to obtain the magnetic metal oxide microsphere in core-shell structure. The process is simple and practical, and has adjustable size of the microsphere. The magnetic metal oxide microsphere has important application in separating protein, separating polypeptide and other fields.
Description
Technical field
The invention belongs to technical field of inorganic material, be specifically related to a kind of magnetic metal oxide microsphere and synthetic method thereof with nucleocapsid structure.
Technical background
Along with developing rapidly of nanosecond science and technology, nano material has shown huge using value in fields such as biomedicine, biotechnology, environmental engineerings.As a kind of novel high efficient separation technology, magnetic separation technique more and more becomes the hot subject of academia and industrial community research.Magnetic separation technique mainly relies on a kind of microballoon or particle with magnetic responsiveness, and these microballoons or particle can combine with target substance and separate from its environment under the effect of externally-applied magnetic field, thereby realizes the effective separation to target substance.The common particle diameter of these microballoons or particle is between tens nanometers are to several microns, its specific surface area is very high, simultaneously, because its surface properties (as surface functional group, surperficial parent/hydrophobicity, surface charge etc.) can regulate and control easily, therefore utilize its can be efficiently, high-throughput, quickly separating target material.
As far back as the seventies in 20th century, Dutch scientist Ugelstad has just prepared the micron order polystyrene magnetic microsphere of monodispersity first, and has successfully developed the magnetic microsphere series product based on polystyrene.Exploitation polystyrene microspheres such as Ugelstad successfully have been applied in fields such as cellular segregation, clinical diagnosis.Many in the world subsequently research groups join in the research of the preparation of magnetic microsphere and application one after another, along with going deep into of research, the many new application of magnetic microsphere or is developed, the Application Areas of magnetic microsphere is extended to other biotechnology, medical science, field of medicaments from original separation, diagnosis, as targeting drug administration preparation, immunoassay, cell culture medium or the like.
With regard to prepared magnetic microsphere, mainly contain two big classes, the one, the magnetic microsphere for preparing with synthetic macromolecule or natural polymer parcel inorganic magnetic particle.This class is studied often at present, and the technology that adopts microcyst is a kind of relatively primary method of preparation magnetic microsphere.This method is simple to operate, but the out-of-shape of microballoon of preparation and size be mostly at micron order even bigger, and another characteristics are that its size distribution is generally all very wide, and these all cause prepared magnetic microsphere to be difficult to play a role in field widely.Dekker is suspended in magnetic-particle in polymine (PEI) solution, by filtering, drying treatment make outsourcing PEI magnetic microsphere (Dekker R F M.Appl.Biotech., 1989,22:289).Cuyper etc. handle magnetic nanoparticle with phosphatide, make the magnetic liposome microballoon (Cuyper M D, JonianM.Langmuir, 1990,7:647).Monomer polymerization method is the preparation method who studies at most behind Ugelstad, wherein mainly contains suspension polymerization, dispersion copolymerization method, emulsion polymerization (comprising emulsifier-free emulsion polymerization, seeding polymerization) etc.People such as Margel have prepared particle size range in the presence of oil-soluble initiator, suspension stabilizer and inorganic magnetic particle be the magnetic polypropylene aldehydes microballoon (Margel S, Beitler U.USP4,783,336,1988) of 0.03um-80um.It is the hydrophobic magnetic polymer microsphere (Daniel J C, Schuppsier J L.USP4,358,388.1982) of 0.03um-5um that employing microsuspensions such as Daniel have obtained particle size range.The microspherulite diameter of suspension polymerization is also bigger, the size distribution broad.Letex polymerization is to use more a kind of method for preparing the living polymer microballoon of magnetic at present.Furusawa etc. deposit to magnetic-particle on the high molecular emulsion particle that has functional group, adopt seeded emulsion polymerization to make magnetic microsphere (Furusawa K, the Nagashima K of sandwich structure then, Anzai C, Colloid Polym.Sci, 1994,272; 1104).Domestic grandson Zong Hua etc. with magnetic fluid as nuclear, adopt improved emulsion polymerization prepared particle size range be magnetic polystyrene microsphere (Qiu Guangming, Sun Zonghua, chemical reagent, 1993,15 (4): 324) of 0.06um-10um.Ugelstad etc. at first propose in-situ method and prepare the monodisperse magnetic polymer microsphere, its characteristics are to prepare the porous polystyrene microsphere with two step swelling methods earlier, in the duct of polystyrene microsphere, use the alkali precipitation molysite then, thereby monodispersed magnetic polystyrene microsphere (Ugelstad J, Mork P C, Schmid R have been made, et al, Polym.Int, 1993,30:15.).
The 2nd, be prepared into magnetic microsphere with inorganic materials parcel nano magnetic particle, or the inorganic magnetic particle deposited to the magnetic microsphere of inorganic material surface preparation by the method for absorption.Therefore wherein inorganic materials mainly is a silicon-dioxide, because silicon-dioxide is a kind of bio-inert material, and this inorganic composite microsphere is easy to surface-functionalizedly, can be widely used in fields such as biological medicine, clinical diagnosis and immunoassay.Domestic Zhu with China etc. with monodispersed silicon dioxide microsphere as template, utilize the static self-assembly, prepared that nucleocapsid is silicon-dioxide, the centre is the silicone dioxide magnetic microsphere (Zhu Yihua of multi-layered magnetic nano particle, answer letter, Yang Xiaoling, Chinese patent, the number of opening: CN1380133A).Wang Kemin etc. have synthesized the magnetic fluorescence particle (Tan Weihong of coated magnetic particle water soluble fluorescence material respectively by teos hydrolysis in the reverse microemulsion liquid system, Wang Kemin, Xiao Dan, Chinese patent, publication number CN 1342515A), Ramesh etc. are by Fe (CO)
5Sonochemistry deposit prepare the magnetic silica magnetic microsphere (Ramesh S, Prozorov R, and Gedanken A, Chem.Mater., 1997,9:2996).
In the protein research field, investigators find a lot of metal oxides, as ZrO
2, TiO
2Deng the phosphated peptide section in the separation and concentration complex sample optionally (W.Gao, L.Dickinson, C.Grozinger, F.G.Morin, L.Reven, Langmuir 1996,12,6429.; D.Brovelli, G.Hahner, L.Ruiz, R.Hofer, G.Kraus, A.Waldner, JSchlosser, P.Oroszlan, M.Ehrat, N.D.Spencer, Langmuir 1999,15, and 4324.; M.Textor, L.Ruiz, R.Hofer, A.Rossi, K.Feldman, G.Hahner, N.D.Spencer, Langmuir 2000,16, and 3257).Metal oxide with its highly selective and preferably as a result circulation ratio become the another powerful measure of separating and enriching phosphated peptide section.Metal oxide can adopt and load into pillar or the method for directly centrifugation is used for separating and enriching phosphated peptide section.The dress post uses relative complex; Use high speed centrifugation, still have 2 deficiencies: operation is wasted time and energy; High speed centrifugation may cause high-quality non-phosphorylating peptide section and phosphated peptide section co-precipitation to get off.Therefore, the preparation surface coverage has the magnetic microsphere of this quasi-metal oxides can realize selectivity, separation quickly and enrichment function albumen, polypeptide on the one hand simultaneously.
Summary of the invention
The object of the invention is to propose a kind of magnetic metal oxide microsphere preparation method with nucleocapsid structure.This method is simple, and microballoon outer shell chemical constitution is adjustable, and microspherulite diameter is easy to control.
The magnetic metal oxide microsphere with nucleocapsid structure that the present invention proposes is a kind ofly to be nuclear, to be the magnetic microsphere of the nucleocapsid structure of shell with the metal oxide that is formed by the metal alkoxide hydrolysis that with the Z 250 microballoon its particle diameter is 210-850nm.Because this microballoon not only has magnetic kernel, also have various metal oxide shells, therefore this microballoon has the kernel of magnetic responsiveness on the one hand, the surface property that has other metal oxides on the other hand, thereby have significant application value at aspects such as protein, polypeptide even some small molecules fractionation by adsorption.
Above-mentioned can being synthesized by following method of magnetic metal oxide microsphere with nucleocapsid structure obtains, and adopts hydrothermal method at Fe
3O
4Surface coverage one deck agraphitic carbon obtains Fe
3O
4The @C microballoon; Then with Fe
3O
4The @C microballoon is dispersed in the alcohol solution of metal alkoxide of prehydrolysis, makes microsphere surface adsorb a large amount of inorganic oligomers, will adsorb the Fe of oligomer at last
3O
4The @C microballoon is calcined in nitrogen atmosphere, and promptly obtaining kernel is that Z 250, shell are the magnetic metal oxide microsphere of metal oxide.Use the Z 250 microballoon of 200-800nm different size, can regulate final magnetic metal oxide microsphere size and be 210-850nm, use the kind that different metal alkoxides can modulation outer layer metal oxide compound.
The preparation method of the magnetic metal oxide microsphere with nucleocapsid structure proposed by the invention is characterized in that concrete steps are as follows:
(1) 0.05-1.0g Z 250 microballoon is dispersed in the 0.1-2M inorganic acid aqueous solution, supersound process 5-10min utilizes the magnet separating, washing, is dispersed in the 10-100mL 20g/L D/W then and in 180-200 ℃ of hydro-thermal reaction 4-12h.Product separates with magnet, and uses deionized water wash, obtains magnetic carbon sphere Fe
3O
4@C uses vacuum drying again, and is standby.
In the above-mentioned synthetic system, Z 250 microballoon content is 0.05-10wt.%, and glucose content is 0.2-2wt%, and all the other are deionized water.
(2) the 0.1-5.0g metal alkoxide being dissolved in the 20mL volume ratio is in alcohol/aqueous solution of 4/1, to stir, and adds the Fe that 0.01-1.0g step (1) obtains
3O
4@C microballoon, and sonic oscillation make microsphere surface adsorb inorganic oligomer; Utilize magnetic field will adsorb the Fe of inorganic oligomer
3O
4The @C microballoon separates, and use washing with alcohol, calcines 50-120 minute in 500-800 ℃ in nitrogen atmosphere at last, promptly obtains the magnetic metal oxide microsphere of nucleocapsid structure.
In the above-mentioned synthetic system, metal alkoxide content is 0.5-25wt.%, and Fe3O4@C microballoon content is 0.05-5.0wt%, and all the other are solvent.
The preparation method of the magnetic metal oxide microsphere with nucleocapsid structure proposed by the invention, wherein used mineral acid is one or more of strong acid such as nitric acid, sulfuric acid or hydrochloric acid.
The preparation method of the magnetic metal oxide microsphere with nucleocapsid structure proposed by the invention, wherein used alcohol be methyl alcohol, ethanol or Virahol etc. one or more.
The preparation method of the magnetic metal oxide microsphere with nucleocapsid structure proposed by the invention, wherein, used metal alkoxide is isopropoxide, propylate, butanolate or the isobutyl alkoxide of titanium, aluminium, zirconium, indium or gallium metal.
The preparation method of the magnetic metal oxide microsphere with nucleocapsid structure proposed by the invention, its particle diameter can be controlled at nano-scale to be changed to micron, send out the consumption that alcohol, water, alkali ratio and the tetraalkyl orthosilicate of answering in the system are made presoma by control, can make the silica magnetic fluorescent microsphere of different-grain diameter.This microballoon has magnetic responsiveness and can send fluorescence under ultraviolet, excited by visible light.The inventive method is simple, and raw material is easy to get.Prepared complex microsphere particle diameter be narrow distribution and size controlled.
The research of magnetic microsphere mainly biases toward its magnetic property both at home and abroad at present, and target of the present invention is to propose a kind of magnetic metal oxide microsphere with function surface.The present invention covers the very thin carbon of one deck at the Z 250 microsphere surface earlier and is designated as Fe3O4@C, and further adsorb inorganic oligomer, method by calcined dehydration has obtained the outer various metal oxides that are at last, and kernel is the functional magnetic metal oxide microballoon of magnetic particle.Have following characteristics by the microballoon of crossing this method preparation: (1) has magnetic kernel, magnetic responsiveness (2) microspherulite diameter adjustable size joint, and (3) microballoon has nucleocapsid structure.(4) method for preparing microsphere is simple, and stability is high.
Description of drawings
Among Fig. 1 (a), (b), (c) be Fe respectively
3O
4, Fe
3O
4@C and Fe
3O
4@TiO
2The transmission electron microscope picture of microballoon.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1
The Z 250 microballoon that takes by weighing the 0.1g median size and be 300nm is dispersed in the 1M aqueous hydrochloric acid, supersound process 5min, utilize the magnet separating, washing then 3 times, be dispersed in the 40mL 20g/L D/W microballoon after the washing and in 180 ℃ of hydro-thermal reaction 6h.Product separates with magnet, and with deionized water wash 4 times, with the magnetic carbon sphere Fe that obtains
3O
4@C is standby behind vacuum drying.
Take by weighing the 0.5g aluminum isopropylate and be dissolved in 20mL alcohol/water (volume ratio 4/1) solution and stir 10min, add the above-mentioned Fe that obtains of 0.2g
3O
4@C microballoon and sonic oscillation 2min utilize magnetic field will adsorb the Fe of aluminium hydroxide oligomer then
3O
4The @C microballoon separates, and with washing with alcohol 3 times, calcines 1 hour in 600 ℃ in nitrogen at last, and the kernel that promptly obtains about 320nm is that Z 250 microballoon shell is the microballoon of aluminum oxide.
Embodiment 2
The Z 250 microballoon that takes by weighing the 0.2g median size and be 200nm is dispersed in the 0.5M aqueous hydrochloric acid, supersound process 8min, utilize the magnet separating, washing then 5 times, be dispersed in the 20mL 20g/L D/W microballoon after the washing and in 180 ℃ of hydro-thermal reaction 10h.Product separates with magnet, and with deionized water wash 3 times, with the magnetic carbon sphere Fe that obtains
3O
4@C is standby behind vacuum drying.
Take by weighing the 0.7g zirconium iso-propoxide and be dissolved in 20mL alcohol/water (volume ratio 4/1) solution and stir 10min, add the above-mentioned Fe that obtains of 0.1g
3O
4@C microballoon and sonic oscillation 3min utilize magnetic field will adsorb the Fe of zirconium hydroxide oligomer then
3O
4The @C microballoon separates, and with washing with alcohol 3 times, calcines 2 hours in 500 ℃ in nitrogen at last, and the kernel that promptly obtains about 220nm is that Z 250 microballoon shell is a zirconium oxide microballoons.
Embodiment 3
The Z 250 microballoon that takes by weighing the 0.3g median size and be 600nm is dispersed in the 2M aqueous hydrochloric acid, supersound process 10min, utilize the magnet separating, washing then 4 times, be dispersed in the 80mL 20g/L D/W microballoon after the washing and in 190 ℃ of hydro-thermal reaction 5h.Product separates with magnet, and with deionized water wash 3 times, with the magnetic carbon sphere Fe that obtains
3O
4@C is standby behind vacuum drying.
Take by weighing 1.0g Virahol indium and be dissolved in 20mL alcohol/water (volume ratio 4/1) solution and stir 10min, add the above-mentioned Fe that obtains of 0.2g
3O
4@C microballoon and sonic oscillation 2min utilize magnetic field will adsorb the Fe of indium hydroxide oligomer then
3O
4The @C microballoon separates and with washing with alcohol 3 times, calcines 50-80 minute in 700 ℃ in nitrogen at last, and the kernel that promptly obtains about 650nm is that Z 250 microballoon shell is the Indium sesquioxide microballoon.
Embodiment 4
The Z 250 microballoon that takes by weighing the 1.0g median size and be 800nm is dispersed in the 1.5M aqueous hydrochloric acid, supersound process 8min, utilize the magnet separating, washing then 5 times, be dispersed in the 100mL 20g/L D/W microballoon after the washing and in 180 ℃ of hydro-thermal reaction 12h.Product separates with magnet, and with deionized water wash 3 times, with the magnetic carbon sphere Fe that obtains
3O
4@C is standby behind vacuum drying.
Take by weighing 1.0g propyl carbinol titanium be dissolved in 20mL alcohol/water (volume ratio 4/1) solution stir 10min after, add the above-mentioned Fe that obtains of 0.3g
3O
4@C microballoon and sonic oscillation 2min utilize magnetic field will adsorb the Fe of metatitanic acid oligomer then
3O
4The @C microballoon separates and with washing with alcohol 3 times, calcines 60 minutes in 800 ℃ in nitrogen at last, and the kernel that promptly obtains about 820nm is that Z 250 microballoon shell is a titanium dioxide microballoon sphere.
Fe
3O
4, Fe
3O
4@C and Fe
3O
4@TiO
2Transmission electron microscope see shown in Fig. 1 (a)-(c).
Claims (3)
1. preparation method with magnetic metal oxide microsphere of nucleocapsid structure, the kernel of this magnetic metal oxide microsphere is the Z 250 microballoon, size of cores is 200-800nm, and shell is the metal oxide that is formed by the metal alkoxide hydrolysis, is of a size of 210-850nm; It is characterized in that the concrete steps that prepare are as follows:
(1) 0.05-1.0g Z 250 microballoon is dispersed in the 0.1-2M inorganic acid aqueous solution, supersound process 5-10min utilizes the magnet separating, washing, is dispersed in the 10-100mL 20g/L D/W then and in 180-200 ℃ of hydro-thermal reaction 4-12h; Product separates with magnet, and uses deionized water wash, obtains magnetic carbon sphere Fe
3O
4@C, through vacuum drying, standby;
In the above-mentioned synthetic system, Z 250 microballoon content is 0.05-10wt.%, and glucose content is 0.2-2wt%, and all the other are deionized water;
(2) the 0.1-5.0g metal alkoxide is dissolved in volume ratio 4/1 and is 20mL alcohol/aqueous solution, stir, add the Fe that 0.01-1.0g step (1) obtains
3O
4@C microballoon, and sonic oscillation make microsphere surface adsorb inorganic oligomer, utilize magnetic field will adsorb the Fe of inorganic oligomer
3O
4The @C microballoon separates, and use washing with alcohol, calcines 50-120 minute in 500-800 ℃ in nitrogen atmosphere at last, promptly obtains the magnetic metal oxide microsphere of nucleocapsid structure; Wherein, described metal alkoxide is the propyl carbinol salt or the isobutyl alkoxide of titanium, aluminium, zirconium, indium or gallium metal;
In the above-mentioned synthetic system, metal alkoxide content is 0.5-25wt.%, Fe
3O
4@C microballoon content is 0.05-5.0wt%, and all the other are solvent.
2. the preparation method with magnetic metal oxide microsphere of nucleocapsid structure according to claim 1 is characterized in that used mineral acid is one or more of nitric acid, sulfuric acid or hydrochloric acid.
3. the preparation method with magnetic metal oxide microsphere of nucleocapsid structure according to claim 1, the used alcohol of its feature be methyl alcohol, ethanol or Virahol one or more.
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