CN1217352C - Nano/micron microsphere with superparamagnetism and preparation method - Google Patents
Nano/micron microsphere with superparamagnetism and preparation method Download PDFInfo
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- CN1217352C CN1217352C CN 03100891 CN03100891A CN1217352C CN 1217352 C CN1217352 C CN 1217352C CN 03100891 CN03100891 CN 03100891 CN 03100891 A CN03100891 A CN 03100891A CN 1217352 C CN1217352 C CN 1217352C
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Abstract
The present invention relates to a superparamagnetic nanometer/micron microsphere and a preparation method thereof through silanization, which belongs to the field of microspheres with superparamagnetism function. The surfaces of freshly prepared Fe3O4 nanometer particles are coated by SiO2 with different contents and different layers so as to control the size of the particle diameter of a microsphere and prevent agglomeration. Then, under moderate condition, the processing of silanization is carried out on the surface of a silicon packed magnetic microsphere so as to obtain a class of a superparamagnetic microsphere of which the surface has function groups. The particle diameter of the microsphere is from 30 nm to 1000 nm/from 1 to 20 um; the mass of the magnetic Fe3O4 accounts for 0.5 to 60% of that of the whole microsphere. The magnetic microsphere has the advantages of controllable size of particle diameter, good sphericity, uniform size, uniform magnetic content among different spheres and stable reification performance.
Description
Technical field
The invention belongs to superparamagnetism functional microsphere field, particularly super-paramagnetism nano/micron microballoon and silanization thereof prepare the method for super-paramagnetism nano/micron microballoon.
Background technology
The particularly nano level magnetic function microballoon of magnetic microsphere, but bioactivators such as its surface chemical coupling enzyme, antibody, antigen utilize its superparamagnetism simultaneously, promptly in externally-applied magnetic field, can produce magnetic, after the external magnetic field disappeared, no remanent magnetism was realized fast and convenient isolate reactant.Have tempting application prospect at biomedical sectors such as immobilised enzymes, immune detection, protein purification, target administration, stem cell separation, belong to the field, forward position of current subject.
The method of the synthetic superparamagnetism microballoon of prior art mainly contains investment, monomer copolymerization method, chemical transformation, polymer chemistry reaction method and silanization method.Wherein investment is that magnetic particle is scattered in the biological macromolecule solns, obtains magnetic microsphere by means such as crosslinked, atomizing, flocculation, deposition, evaporations.This method granular biological compatibility simple to operate, preparation is good; But the gained grain shape is irregular, and granular size is wayward, particle size distribution is wide, is mixed with the impurity of emulsifying agent and so in the shell, makes to use to be very restricted.The monomer copolymerization method normally adopts two or more monomer (wherein a kind of is function monomer), polymerization reaction under certain condition, generate the magnetic microsphere of surface band functional group, mainly comprise emulsion (soap-free emulsion) polymerization, suspension polymerisation, dispersin polymerization, seeding polymerization and radiation polymerization.The magnetic microsphere better performances that this method is synthetic, but the content of function monomer is restricted (usually less than 10%), most of functional group is covered by microballoon inside, severe reaction conditions, and synthesis technique is very loaded down with trivial details.Chemical transformation is meant certain density magnetic metal ion infiltration and exchanges in the macroreticular resin and goes, utilize chemical reaction to make metal ion be converted into magnetic metal oxide then, make it to be evenly distributed in the pore structure of polymer, infiltration and step of converting can carry out repeatedly.This method is simple to operate, and magnetic is evenly distributed, and magnetic content is controlled easily, but relatively stricter to the requirement of resin.The polymer chemistry reaction method is the high molecule magnetic microsphere that generates earlier not with functional group, be reflected at the activity functional groups that the magnetic microsphere surface produces high power capacity by surperficial polymer chemistry then, but these reactions are often carried out under the high temperature strong acidic condition, magnetic property to microballoon exerts an influence, cause inner inorganic magnetic particle to decompose, thereby limited the use of this method.The current Silicane Method that adopts is direct magnetic particle (Fe at hydroxyl
3O
4) surface carries out the magnetic microsphere of silanization Processing of Preparation band functional group with the silicone couplet of band functional group, this method preparation process is simple, surperficial functional group content height; But because magnetic particle (Fe
3O
4) particle diameter too little (about 8nm) itself, bunch (cluster) of 200-400nm reunited, usually formed to the magnetic Nano microsphere of preparation easily, and the size of particle is not easy to regulate, and the range of application of particle is restricted.
The Fe of acidization preparation surface bag silicon related to the present invention
3O
4Magnetic-particle is (referring to TheChinese Journal of Process Engineering, Vol.2. (4): 319-320).This method at first adopts coprecipitation to obtain the Fe of fresh deposition
3O
4Nano particle utilizes magnet to wash separation, is dispersed in through pretreated Na sedimentation products is ultrasonic
2SiO
3In the solution, drip HCl solution then in solution, the pH value that changes solution is isolated product to faintly acid, obtains the surface and is coated with SiO
2Magnetic microsphere, A of the present invention, the B step has been used for reference this method, and innovates on this basis, prepares the microballoon of different-grain diameter.
The direct silanization method close with the present invention prepare the superparamagnetism microballoon (referring to Journal ofColloid and Interface Science, Vol.141 (2): be to utilize end to contain functional group 505-511) (as-NH
2) silicone couplet and the magnetic particle of surperficial hydroxyl (as Fe
3O
4) carry out thermal dehydration, obtain the magnetic microsphere of silanization.Because the particle diameter of magnetic particle is too little, agglomeration is unavoidable in the course of reaction, and the grain shape that obtains is irregular, and there are some defectives in synthetic microballoon on performance, as part Fe
3O
4Particle is exposed, and the magnetic content of variable grain is big outside, and homogeneity is poor, reunites easily in actual applications, influences result of use.
Summary of the invention
One of purpose of the present invention is the deficiency that exists on the preparation magnetic microsphere at existing direct silanization method, it is controlled to propose a kind of microspherulite diameter, narrow diameter distribution, the superparamagnetism microballoon of preparing does not have agglomeration, and the stable silanization of chemical property prepares the method for super-paramagnetism nano/micron microballoon.
Another object of the present invention provides a kind of microspherulite diameter scalable, the super-paramagnetism nano of narrow diameter distribution/micron microballoon.
The present invention is (as Fe at inorganic particles with superparamagnetism
3O
4) outside wraps one or more layers silicon dioxide, thereby can change and control the size of magnetic-particle, form uniform magnetic microsphere, carry out back silanization processing again on bag silicon magnetic microsphere surface then.Can prepare different-grain diameter, adapt to multi-purpose superparamagnetism microballoon, and the generation of agglomeration in can avoiding using.
Main technical schemes of the present invention is: adopt acidization to prepare surperficial coated Si O earlier
2The superparamagnetism microballoon, by changing SiO
2And Fe
3O
4Ratio, repeat the microballoon that encapsulation steps can prepare different magnetic content and different-grain diameter, adopt improved Silicane Method then, utilize to have certain functional group (as-NH
2) silicone couplet and the hydroxyl of above-mentioned microsphere surface by dehydration, form the Si-O-Si key, thereby obtain the superparamagnetism microballoon that the surface has functional group.This microspherulite diameter between 30-1000nm or 1 μ m-20 μ m, the Fe in the superparamagnetism microballoon
3O
4Nano particle diameter is about 8-15nm, magnetic Fe
3O
4Accounting for whole microballoon percentage by weight is between the 0.5-60%.Magnetic microsphere particle diameter controlled amount, balling-up are good, magnetic uniform content between the particle size distribution homogeneous, different ball, reaction condition gentleness, physical and chemical performance are stable.
The method that silanization prepares the superparamagnetism microballoon comprises that coprecipitation prepares the nano-scale magnetic particle, and acidization is at magnetic-particle surface coated Si O
2With with various silicone couplets the magnetic microsphere of bag behind the silicon carried out silanization and handles.The particle size that it is characterized in that magnetic microsphere is adjustable, and particle balling preparation and good dispersion, no serious agglomeration, preparation technology are simple.
The method that silanization of the present invention prepares super-paramagnetism nano/micron microballoon mainly may further comprise the steps:
A. coprecipitation prepares superparamagnetism Fe
3O
4Nano particle
At 80-90 ℃, under the nitrogen protection, to containing Fe
2+And Fe
3+Molysite aqueous solution in impouring alkali lye, high-speed stirred is isolated sedimentation products with magnet, obtains fresh Fe
3O
4Nano particle.
B. acidization prepares surperficial coated Si O
2Magnetic Fe
3O
4The Nano/micron microballoon
(1). the fresh Fe that step (A) is prepared
3O
4Nano particle, the ultrasonic Na that is dispersed in through preliminary treatment (the pH value being transferred to about 12-13 in advance) with hydrochloric acid
2SiO
3In the solution;
(2). the solution of step (1) is warming up to 80-90 ℃; under nitrogen protection and stirring condition, in solution, add hydrochloric acid or the sulfuric acid of the about 2mol/l of concentration, the pH value of solution is transferred to about 5-7 by alkalescence; isolate product and fully wash with magnet, obtain surperficial coated Si O with deionized water
2Magnetic Fe
3O
4Nano microsphere;
(3). repeating step (2) can obtain different SiO
2The magnetic Fe of the different-grain diameter of the covering amount and the coating number of plies
3O
4The Nano/micron microballoon;
C. super-paramagnetism nano/micron the microballoon of functional group is with on silanization preparation surface
(1). will join with the silicone couplet of functional group in methyl alcohol or the ethanol, wherein, the percent by volume of silicone couplet and methyl alcohol or ethanol is 10-20%, fully mixes;
(2). in the solution of step (1), add surperficial coated Si O
2Magnetic Fe
3O
4The Nano/micron microballoon, wherein, surperficial coated Si O
2Magnetic Fe
3O
4The mass percent of Nano/micron microballoon and solution is 0.5-5%, adds a spot of organic acid and water simultaneously, and wherein, the percent by volume of organic acid and solution is 1-10%, and the percent by volume of water and solution is 0.5-2%, ultrasonic 30-60min;
(3). the solution impouring of step (2) is filled in the container of glycerine, and wherein, the solution of step (2) and the volume ratio of glycerine are 1: 1-2, fully stir, be warmed up to 70-95 ℃ of reaction; After water in the question response thing and methyl alcohol or ethanol evaporate fully, stop reaction, fully wash with the product Magnetic Isolation and with deionized water.
Above-mentioned magnetic Fe
3O
4The preparation condition of nano particle is Fe in the molysite aqueous solution
2+And Fe
3+Mol ratio be 1: 2 to 1: 0, add the OH of alkali
-With 2Fe in the molysite aqueous solution
2++ 3Fe
3+The mol ratio of sum is 1: 0.1 to 1: 1.5; Described alkali is NH
4OH, KOH, NaOH, Na
2CO
3Or NaHCO
3
Above-mentioned silicone couplet is γ-An Jibingjisanyiyangjiguiwan (WD-50, KM-50, KH-550, A-1100), [γ (β-aminoethyl) aminopropyl] trimethoxy silane (WD-52, KM-52, A-1120), (γ-glycidyl ether) methoxy silane (WD-60, KM-60, KH-560, A-187), dodecyl triethoxysilane or n-hexane base trimethoxy silane (A-0800, A-0700, D-6224, H-7334).
Described organic acid is glacial acetic acid, phosphoric acid or other organic acid.
The method that silanization of the present invention prepares super-paramagnetism nano/micron microballoon compared with prior art, method of the present invention on preparation technology at first to magnetic Fe
3O
4Nano grain surface has carried out bag silicon to be handled, and makes original particle diameter less (about 10nm), the Fe that is easy to reunite
3O
4It is bigger that nano particle becomes particle diameter, and (30nm-1000nm/1-20 μ m) can regulate as required within the specific limits, promptly changes the coated Si O of institute by the simple encapsulation steps that repeats
2Amount and coat the number of plies, thereby reach the purpose of control microspherulite diameter, the particle balling preparation of generation is good, the size homogeneous can effectively be avoided the generation of agglomeration.Existing Silicane Method is to adopt directly at Fe
3O
4Nano grain surface carries out silanization to be handled, and handles by the thermal dehydration of glycerine, and reaction temperature is utilized Fe at 170-180 ℃
3O
4The Fe-OH group of nano grain surface generates the effect that the Fe-O-Si key plays the coupling function group.The present invention carries out the thermal dehydration reaction on the bag silicon magnetic microsphere surface that has the Si-OH group, form so-called Si-O-Si key at microsphere surface, and this reaction is easier to be carried out, and reaction condition is gentleer than original, and operation is more easy.Because at Fe
3O
4The surface has coated dense SiO
2, the bead chemical property of generation is stable, and microballoon can be stablized and preserve more than several weeks in the hydrochloric acid or sulfuric acid of 3mol/L, not then dissolving fully in 30min of the naked powder of Bao Fuing.
Description of drawings
Fig. 1: the Fe of Bao Fuing not
3O
4Nano particle TEM figure.
Fig. 2: the surperficial coated Si O of the embodiment of the invention 5
2Silanization magnetic microsphere SEM figure.
Embodiment
Below by embodiment technical scheme of the present invention is described further:
Embodiment 1
Coprecipitation prepares magnetic Fe
3O
4Nano particle
In the 1 liter of stirring reactor that fills the 500ml deionized water, add 0.043 mole of FeCl
24H
2O and 0.086 mole of FeCl
36H
2O is warming up to 85-90 ℃ under nitrogen protection, impouring contains 0.478 mole of NH in the high-speed stirred process
3H
2The O aqueous solution, solution colour blackening at once utilizes magnetic field the product that deposits to be isolated and used respectively the NaCl of deionized water and 0.02M to wash once then.
The about 30g of above-mentioned magnetic agglomerate gross weight, wherein Fe
3O
4About 10g, transmission electron microscope observing Fe
3O
4Particle is bordering on sphere, has superparamagnetism, and average grain diameter is 8nm.
Embodiment 2
In filling 1 liter of stirring reactor of 700ml deionized water, add 0.21 mole of FeCl
24H
2O and 0.31 mole of FeCl
36H
2O is warming up to 70 ℃, and impouring 100ml contains 1 mole NaHCO
3The aqueous solution, Magnetic Isolation incline supernatant get final product the Fe of prepared fresh
3O
4Nano particle.
The about 60g of above-mentioned magnetic agglomerate gross weight, wherein Fe
3O
4About 35g, transmission electron microscope observing Fe
3O
4Particle is bordering on sphere, has superparamagnetism, and average grain diameter is 15nm.
Embodiment 3
Acidization prepares SiO
2The magnetic microsphere that coats
Calculate 10g Fe
3O
4Coat 20g SiO
2Need corresponding N a
2SiO
39H
2The about 95g of O, preset Na
2SiO
3The pH value of solution is to 12-13
(1). the fresh Fe that embodiment 1 is prepared
3O
4Nano particle, ultrasonic being dispersed in through pretreated Na
2SiO
3In the solution.
(2). solution is warming up to 85 ℃, under the high-speed stirred condition, in solution, adds the hydrochloric acid of the about 2mol/l of concentration; The pH value of solution is transferred to about 5-7 by alkalescence, isolate product and use deionized water wash 3-4 time, drying with magnet.Obtain surperficial coated Si O
2Magnetic microsphere, SiO
2And Fe
3O
4Weight ratio be 2: 1.
Embodiment 4
Calculating coats 20g SiO again at the microsphere surface of embodiment 3
2Need Na
2SiO
39H
2The about 95g of O.
(1). with the fresh bag silicon grain that embodiment 3 prepares, the ultrasonic Na that is dispersed in
2SiO
3In the solution.
(2). solution is warming up to 85 ℃, under high-speed stirred (400-600rpm) condition, in solution, adds the hydrochloric acid of the about 2mol/l of concentration; The pH value of solution is transferred to about 5-7 by alkalescence, with magnet isolate product and with deionized water fully wash, drying, obtain the surface and coat two-layer SiO
2Magnetic microsphere, SiO
2And Fe
3O
4Weight ratio be 4: 1.
Fresh bag silicon grain repeating step (2) with preparing can obtain different SiO
2The magnetic microsphere of the different-grain diameter of the covering amount and the coating number of plies.
Embodiment 5
Silanization method prepares the magnetic function microballoon
(1). get 10ml silicone couplet KH-550 and add in the 250ml absolute methanol, fully mix.
(2). in the solution of step (1), add the bag silicon magnetic microsphere of 2g embodiment 4,5ml glacial acetic acid or phosphoric acid and 2.5g water, ultrasonic 30-60min.
(3). the solution impouring of step (2) is filled in the 500ml there-necked flask of 200ml glycerine, fully stir, be warmed up to 75-80 ℃ of reaction 3-4 hour.
(4). fully wash 4-5 time with the product Magnetic Isolation and with deionized water, obtain surface band-NH
2The silanization magnetic microsphere of group.Particle diameter is about 100nm.
Embodiment 6
(1). get 20g silicone couplet WD-52, add absolute ethyl alcohol, the solution 100ml of preparation 20wt%.
(2). in the solution of step (1), add the Fe of 1g embodiment 4 bag silicon
3O
4Magnetic microsphere, ultrasonic 20 minutes.
(3). the mixture adding of step (2) is filled in the 250ml there-necked flask of 200ml glycerine, stir, normal temperature reacts more than 12 hours down.
(4). product is fully washed 4-5 time with deionized water, and Magnetic Isolation is removed unreacted silicone couplet, obtains surface band-NH
2The silanization magnetic microsphere of group.Particle diameter is about 100nm.
Embodiment 7
Acidization prepares SiO
2The magnetic microsphere that coats
Calculate 10g Fe
3O
4Coat 40g SiO
2Need corresponding N a
2SiO
39H
2The about 190g of O, preset Na
2SiO
3The pH value of solution is to 12-13
(1). the fresh Fe that embodiment 2 is prepared
3O
4Nano particle, ultrasonic being dispersed in through pretreated Na
2SiO
3In the solution.
(2). solution is warming up to 85 ℃, under the high-speed stirred condition, in solution, adds the sulfuric acid of the about 1mol/l of concentration; The pH value of solution is transferred to about 5-7 by alkalescence, isolate product and use deionized water wash 3-4 time with magnet, in dry.Obtain surperficial coated Si O
2Magnetic microsphere, SiO
2And Fe
3O
4Weight ratio be 4: 1.
Embodiment 8
Calculating coats 20g SiO again at the microsphere surface of embodiment 7
2Need Na
2SiO
39H
2The about 95g of O.
(1). with the fresh bag silicon grain that embodiment 7 prepares, the ultrasonic Na that is dispersed in
2SiO
3In the solution.
(2). solution is warming up to 85 ℃, under high-speed stirred (400-600rpm) condition, in solution, adds the sulfuric acid of the about 1mol/l of concentration; The pH value of solution is transferred to about 5-7 by alkalescence, with magnet isolate product and with deionized water fully wash, drying, obtain the surface and coat two-layer SiO
2Magnetic microsphere, SiO
2And Fe
3O
4Weight ratio be 6: 1.
Fresh bag silicon grain repeating step (2) with preparing can obtain different SiO
2The magnetic microsphere of the different-grain diameter of the covering amount and the coating number of plies.
Embodiment 9
Silanization method prepares the magnetic function microballoon
(1). get 10ml silicone couplet KM-50 and add in the 250ml absolute ethyl alcohol, fully mix.
(2). in the solution of step (1), add the bag silicon magnetic microsphere of 2g embodiment 8,5ml phosphoric acid and 3.0g water, ultrasonic 45-60min.
(3). the solution impouring of step (2) is filled in the 500ml there-necked flask of 200ml glycerine, fully stir, be warmed up to 70-75 ℃ of reaction 4-5 hour.
(4). fully wash 4-5 time with the product Magnetic Isolation and with deionized water, obtain surface band-NH
2The silanization magnetic microsphere of group.Particle diameter is about 200nm.
Embodiment 10
(1). get 20g silicone couplet KM-52, add absolute methanol, the solution 100ml of preparation 20wt%.
(2). in the solution of step (1), add the Fe of 1g embodiment 8 bag silicon
3O
4Magnetic microsphere, ultrasonic 45-60 minute.
(3). the mixture adding of step (2) is filled in the 250ml there-necked flask of 200ml glycerine, stir, normal temperature reacts more than 14 hours down.
(4). product is fully washed 4-5 time with deionized water, and Magnetic Isolation is removed unreacted silicone couplet, obtains surface band-NH
2The silanization magnetic microsphere of group.Particle diameter is about 200nm.
Claims (6)
1. a silanization prepares the method for super-paramagnetism nano/micron microballoon, and it is characterized in that: the method that described silanization prepares super-paramagnetism nano/micron microballoon may further comprise the steps:
A. acidization prepares surperficial coated Si O
2Magnetic Fe
3O
4The Nano/micron microballoon
(1). the fresh Fe that will prepare
3O
4Nano particle, ultrasonic being dispersed in hydrochloric acid is transferred to Na between the 12-13 in advance with the pH value
2SiO
3In the solution;
(2). the solution of step (1) is warming up to 80-90 ℃, under nitrogen protection and stirring condition, in solution, adds hydrochloric acid or sulfuric acid, the pH value of solution is transferred to 5-7 by alkalescence, isolate product and fully wash, obtain surperficial coated Si O with deionized water
2Magnetic Fe
3O
4Nano microsphere;
Repeating step (2) is with the magnetic Nano/micron microballoon that obtains different-grain diameter;
B. super-paramagnetism nano/micron the microballoon of functional group is with on silanization preparation surface
(1). will join with the silicone couplet of functional group in methyl alcohol or the ethanol, wherein, the percent by volume of silicone couplet and methyl alcohol or ethanol is 10-20%, fully mixes;
(2). in the solution of step (1), add surperficial coated Si O
2Magnetic Fe
3O
4The Nano/micron microballoon, wherein, surperficial coated Si O
2Magnetic Fe
3O
4The mass percent of Nano/micron microballoon and solution is 0.5-5%, adds a spot of organic acid and water simultaneously, and wherein, the percent by volume of organic acid and solution is 1-10%, and the percent by volume of water and solution is 0.5-2%, and is ultrasonic;
(3). the solution impouring of step (2) is filled in the container of glycerine, and wherein, the solution of step (2) and the volume ratio of glycerine are 1: 1-2, fully stir, be warmed up to 70-95 ℃ of reaction; After water in the question response thing and methyl alcohol or ethanol evaporate fully, stop reaction, fully wash with the product Magnetic Isolation and with deionized water.
2. the method for claim 1, it is characterized in that: described silicone couplet is γ-An Jibingjisanyiyangjiguiwan, [γ (β-aminoethyl) aminopropyl] trimethoxy silane, (γ-glycidyl ether) methoxy silane, dodecyl triethoxysilane or n-hexane base trimethoxy silane.
3. the method for claim 1, it is characterized in that: described organic acid is glacial acetic acid or phosphoric acid.
4. the method for claim 1, it is characterized in that: the ultrasonic time of described step B is 30-60min.
5. super-paramagnetism nano/micron microballoon of preparing as any described method of claim 1~4, it is characterized in that: described microspherulite diameter is between 30-1000nm or 1 μ m-20 μ m.
6. microballoon as claimed in claim 5 is characterized in that: the Fe in described super-paramagnetism nano/micron microballoon
3O
4Nano particle diameter is 8-15nm, magnetic Fe
3O
4Accounting for whole microballoon percentage by weight is between the 0.5-60%.
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CN1990528B (en) * | 2005-12-26 | 2010-06-16 | 中国科学院成都有机化学有限公司 | Method for functionalization on magnetic nano particle surface |
CN1805086B (en) * | 2006-01-23 | 2010-07-28 | 浙江大学宁波理工学院 | Preparation method of silane coupled nanometer magnetic composite ferroferric oxide material |
CN100457641C (en) * | 2006-03-13 | 2009-02-04 | 同济大学 | Suspending type magnetic particle for adsorbing oil dirt on water and its preparing method |
CN100389092C (en) * | 2006-09-14 | 2008-05-21 | 上海交通大学 | Method for preparing nano magnetic silicon ball |
CN100425627C (en) * | 2007-01-04 | 2008-10-15 | 吉林大学 | Preparation process of magnetic partical/polymer/silicon dioxide structure magnetic microball |
CN100511499C (en) * | 2007-06-15 | 2009-07-08 | 华南师范大学 | Superparamagnetism material carrying CuO and preparation method thereof |
CN101789299B (en) * | 2010-01-13 | 2012-05-23 | 西安恒旭科技发展有限公司 | Method for preparing nanometer SiO2-coated micrometer Fe3O4 compound particles |
CN102211930A (en) * | 2011-05-12 | 2011-10-12 | 上海电力学院 | Preparation method of nano crystal MnZn ferrite with high saturation magnetization intensity |
DE102012211947A1 (en) * | 2012-07-09 | 2014-01-09 | Evonik Industries Ag | Magnetic core-shell particles with high separation efficiency |
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CN103134926B (en) * | 2013-02-27 | 2015-05-27 | 上海交通大学 | Magnetic microsphere carrier and its making method |
CN105016418B (en) * | 2015-06-24 | 2017-03-08 | 昆明理工大学 | A kind of processing method of zinc-plated spent acid |
CN112604645A (en) * | 2020-12-10 | 2021-04-06 | 广东省测试分析研究所(中国广州分析测试中心) | Nano magnetic particle and preparation method and application thereof |
CN113522229B (en) * | 2021-07-21 | 2022-10-28 | 南京工业大学 | Magnetic bead for efficiently adsorbing extracellular DNA in environment and preparation method thereof |
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