CN1480251A - Ferromagnetic multiporous silica gel microsphere and its preparation method - Google Patents
Ferromagnetic multiporous silica gel microsphere and its preparation method Download PDFInfo
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- CN1480251A CN1480251A CNA031304222A CN03130422A CN1480251A CN 1480251 A CN1480251 A CN 1480251A CN A031304222 A CNA031304222 A CN A031304222A CN 03130422 A CN03130422 A CN 03130422A CN 1480251 A CN1480251 A CN 1480251A
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Abstract
A ferromagnetic porous silica gel microsphere with 100-450 sq.m/g is composed of microspheric SiO2 particles as basic material and superparamagnetic Fe2O3 nanoparticles dispersed in said basic material. Its preparing process includes preparing Fe2O3 sol, preparing Fe2O3/SiO2 sol, preparing composite microspheres, and preparing magnetic porous silica gel.
Description
Technical field
The present invention relates to a kind of preparation method of ferromagnetism Bio-sil microballoon, belong to the technology of preparing of magnetic porous silicon dioxide microsphere.
Background technology
The transmission and the piece-rate system of magnetic field control have many application in medical science, biological and chemical field, have therefore obtained development rapidly in recent years.In these systems, usually the orientation that adopts externally-applied magnetic field to control the particulate with magnetic responsiveness moves, therefore can be used for specific medicine orientation be discharged into health certain position, optionally separate cancer cell, from complex biological sample, extract field such as target molecule from bone marrow cell.The fluidization of magnetic field control has become the strong instrument in the biotechnology, and the magnetic supporting dielectric can be immobilized more rapidly in preparation separates, thereby makes things convenient for the recovery of target molecule.The structure of magnetic micro fluidic device has also caused people's attention in recent years, because utilize these devices can realize the transfer of microballoon between micro-ponds such as storage, reaction, detection easily, thereby playing a significant role aspect the microminiaturization of analytical instrument and the automation.
The availability of the magnetic microsphere with special nature is depended in the success or not of top magnetic field control transmission of mentioning and piece-rate system to a great extent.Magnetic microsphere can prepare by several different methods, and these methods roughly can be divided into three classes.In first kind method, the colloid of magnetic oxide directly is deposited in the loose structure of crosslinked polystyrene microsphere or controllable bore diameter glass microsphere, and the outer surface at microballoon is coated with one deck high polymer in case the oxidation Fe nanometer particles in use runs off then.Second class methods are to adhere to one deck magnetic nano-particle on non-porous microballoon, and are wrapped up with high polymer, constitute the magnetic microsphere of hud typed structure.The 3rd class methods are based on magnetic colloid and have the dispersin polymerization of monomer down, and one-step method prepares magnetic microsphere.
Above-mentioned microballoon all has commodity to provide, and also has bibliographical information to utilize trivalent iron salt and tetraethoxysilane (TEOS) to be mixed with nano level microballoon, the iron oxide-SiO 2 composite microsphere that obtains having magnetic after calcining.Its shortcoming is that these magnetic microspheres are non-porous structure, and specific area is little, is unsuitable for using in chemical fields such as chromatographic isolation, catalytic reaction.
Summary of the invention
The object of the invention is to provide a kind of ferromagnetism Bio-sil microballoon and preparation method thereof, and described microballoon specific area is 100-450m
2/ g, the aperture is at 5-15nm, and particle diameter is at 0.5-20 μ m, and preparation method's process of this microballoon is simple, and condition is easily controlled.
The present invention is realized by following proposal, adopts the iron particle of super paramagnetic, is template with the Lauxite, and the ferromagnetic Bio-sil microballoon of preparation is characterized in that, this microballoon is to be 100-450m with the specific area
2/ g, the aperture is at 5-15nm, and particle diameter is at 0.5-20 μ m, and silicon dioxide is the microballoon of base material, and the di-iron trioxide nanoparticle of the tool superparamagnetism that evenly is scattered here and there in this base material constitutes.
Its process of the preparation method of above-mentioned microballoon comprises the preparation of iron oxide colloidal sol, the preparation of iron oxide/silicon dioxide mixed sols, the preparation of organic/inorganic complex microsphere, the preparation of magnetic porous silica gel.
The present invention realizes by following concrete reactions steps:
1. be that 1-3.0 is with FeCl in molar ratio
3.6H
2O and NaHCO
3Mixing and water adding stirs and makes it abundant dissolving.
2. get an amount of silicon dioxide gel, to 2.0-2.5, press Fe with the acid for adjusting pH that comprises red fuming nitric acid (RFNA)
2O
3With SiO
2Mol ratio is that 0.01-1.0 mixes iron oxide colloidal sol with silicon dioxide gel.
3. add urea, formolite reaction monomer in iron oxide/silicon dioxide mixed sols, its mol ratio is 1-1.5, and the percentage of control inorganic constituents is 60%, is 1-4 at pH, at 5-50 ℃ of following reaction 1-24h, filters and collects complex microsphere.
4. the complex microsphere that obtains of method for preparing is after drying respectively at 300-350 ℃, 600-650 ℃ and 900-950 ℃ of each heating and calcining 2-5h.Iron oxide at high temperature undergoes phase transition and obtains ferromagnetism Bio-sil microballoon.
Above-mentioned Fe
2O
3With SiO
2Preferred molar ratio be 0.3-0.5.
Ferromagnetism Bio-sil microballoon by method for preparing adopts and contains chloro octyl group silane reagent and carry out finishing, and the ferromagnetism Bio-sil microballoon that hydrophobic chemical functional group obtains on the bonding can be used as anti-phase magnetic chromatographic stationary phase.
Calcining step is extremely important in above-mentioned preparation method's process.The organic/inorganic complex microsphere that polymerization reaction is prepared carries out the staged high-temperature calcination, can play the effect of three aspects: remove polymer template, induce the mechanical strength of iron oxide phase transformation and enhancing porous microsphere.At first, at 300-350 ℃ of calcination complex microsphere, make the Lauxite charing.Be warmed up to 600-650 ℃ of further calcining then, organic principle is removed in volatilization fully.At last, heat treatment temperature is elevated to 900-950 ℃, not only can strengthens the mechanical strength of porous inorganic oxide microballoon, the phase transformation of all right accelerating oxidation iron transforms from non magnetic, amorphous oxidation iron magnetropism iron oxide.Oxidate microspheres after the high-temperature calcination can be attracted by permanent magnet, therefore shows macroscopical magnetic responsiveness.
Because a large amount of silicon hydroxyls and iron hydroxyl are contained in the surface of magnetic porous silica gel microball of the present invention, not only can be used as anti-phase magnetic chromatographic stationary phase, and can directly separate the carrier of immobile phase or catalytic reaction as normal-phase chromatography; Also can carry out finishing to silica gel microball by silane reagent, alkyl, amino, carboxyl or other selectivity interaction parts in the coupling can be used for the magnetic efficient liquid phase chromatographic stuffing of different clastotypes with preparation.
Advantage of the present invention and effect are:
Provide a kind of specific area big, the porosity height, the magnetic silica gel microball of hydroxyl is rich on the surface, can strengthen adsorptive selectivity by surface chemical modification, is suitable for the carrier as chromatographic stationary phase or catalytic reaction.Its preparation method process is simple, and condition is easily controlled, and is easy to realize industrialization, has potential application prospect in the transmittance process of magnetic field control and separation method.
Description of drawings
Fig. 1 is the prepared porous Fe of the embodiment of the invention 1
2O
3/ SiO
2The stereoscan photograph of microballoon;
Fig. 2 is Fe shown in Figure 1
2O
3/ SiO
2Microballoon magnetic hysteresis loop figure at room temperature;
Fig. 3 is the prepared Fe of the embodiment of the invention 4
2O
3/ SiO
2The C of porous microsphere
8Microballoon behind the bonding is the chromatographic isolation spectrogram of the standard specimen mixture of filler, and peak 1 is a uracil in the spectrogram; Peak 2 is an acetone; Peak 3 is the 4-chloronitrobenzene; Peak 4 is a naphthalene, chromatographic condition: chromatographic column: 150 * 4.6mm; Phase flows: 80% (v/v) methanol-water solution; Flow velocity: 1ml/min; Ultraviolet detection: 254nm.
Embodiment
Embodiment 1: magnetic porous microballoon synthetic
In the beaker that contains 150ml distilled water, add 21.5g FeCl
3.6H
2O and 15g NaHCO
3, stirring the red ferrum collosol that obtains clarifying, its pH is 2-2.5.In another beaker, add 225ml Ludox (30%) and 16g urea respectively, after the stirring and dissolving, enriching HNO
3Transfer pH to 1.5.While stirring ferrum collosol and Ludox are mixed, readjustment pH to 1.5 under agitation adds 22ml formaldehyde (37%) solution rapidly, stops after mixing stirring, and room temperature leaves standstill reaction and spends the night.The complex microsphere that centrifugal collection reaction generates, water, water-methanol (1: 1), methyl alcohol and acetone washing successively.60 ℃ of vacuumizes are spent the night, and obtaining 31g can free-pouring yellow microballoon.Complex microsphere is heat-treated, respectively at 300-350 ℃, 600-650 ℃ and 900-950 ℃ of calcining 2h.By magnetic separate remove non magnetic aerosil particles after, obtaining 15g can free-pouring brownish red magnetic microsphere.Weight percent with oxide content in the mixed sols is recently calculated, and the yield of magnetic microsphere is 21%.
Sign to magnetic porous microballoon shows that the average grain diameter of microballoon is 4 μ m, and specific area is 150m
2/ g, average pore size is 10nm, and the percentage by weight of iron oxide is 19%, and the saturation magnetization rate that normalization calculates based on iron oxide is 31.6emu/g.
Embodiment 2: magnetic porous microballoon synthetic
In the beaker that contains 110ml distilled water, add 5.7g FeCl respectively
3.6H
2O and 4.0g NaHCO
3, stirring the red ferrum collosol that obtains clarifying, its pH is 2-2.5.In another beaker, add 90ml Ludox (30%) and 6.4g urea respectively, after the stirring and dissolving, enriching HNO
3Transfer pH to 1.5.While stirring ferrum collosol and Ludox are mixed, readjustment pH to 1.5 under agitation adds 8.8ml formaldehyde (37%) solution rapidly, stops after mixing stirring, and room temperature leaves standstill reaction and spends the night.The complex microsphere that centrifugal collection reaction generates, water, water-methanol (1: 1), methyl alcohol and acetone washing successively.60 ℃ of following vacuumizes are spent the night, and obtain the yellow microballoon of 11.6g.Complex microsphere is heat-treated, respectively at 250-300 ℃, 500-550 ℃ and 850-900 ℃ of calcining 1-2h.By magnetic separate remove non magnetic aerosil particles after, obtaining average grain diameter is the brownish red magnetic microsphere of 5 μ m.
Embodiment 3: magnetic porous microballoon synthetic
In the beaker that contains 110ml distilled water, add 8.6g FeCl
3.6H
2O and 6.0g NaHCO
3, stirring the red ferrum collosol that obtains clarifying, its pH is 2-2.5.In another beaker, add 90ml Ludox (30%) and 6.4g urea respectively, after the stirring and dissolving, enriching HNO
3Transfer pH to 1.5.While stirring ferrum collosol and Ludox are mixed, readjustment pH to 1.5 under agitation adds 8.8ml formaldehyde (37%) solution rapidly, stops after mixing stirring, and room temperature leaves standstill reaction and spends the night.The complex microsphere that centrifugal collection reaction generates, water, water-methanol (1: 1), methyl alcohol and acetone washing successively.60 ℃ of following vacuumizes are spent the night, and obtain the yellow microballoon of 11.6g.Complex microsphere is heat-treated, respectively at 250-300 ℃, 500-550 ℃ and 850-900 ℃ of calcining 1-2h.By magnetic separate remove non magnetic aerosil particles after, obtaining 5.7g can free-pouring brownish red magnetic microsphere.Weight percent with oxide content in the mixed sols is recently calculated, and the yield of magnetic microsphere reaches 20%.
Embodiment 4: the preparation of magnetic chromatograph packing material
In the toluene of 100ml drying, add the magnetic porous silica gel of 5g, obtain homogenate after the ultrasonic dispersion.Homogenate is heated to makes refluxing toluene about 100 ℃.40ml left and right sides toluene is removed in distillation, adds 6 triethylamines and 4ml octyl group trichlorosilane, reflux 18h in nitrogen atmosphere.After the cooling, filtered and recycled silanization magnetic microsphere is successively with 50ml toluene, carrene, ethanol and acetone washing.60 ℃ of following vacuumize 9h.
Take by weighing 3g silanization magnetic microsphere, be dispersed in the 40ml isopropyl alcohol, make homogenate, in the stainless steel empty tube column of the 150 * 4.6mm that under the high pressure of 8000psi, packs into.With 80% (v/v) methanol-water solution is the phase that flows, and has obtained the baseline separation to the correct mixture that contains uracil, acetone, 4-chloronitrobenzene and naphthalene.
Claims (4)
1. ferromagnetism Bio-sil microballoon, this microballoon adopts the iron particle of super paramagnetic, is that template is prepared from the Lauxite, and it is characterized in that: this microballoon is to be 100-450m with the specific area
2/ g, the aperture is at 5-15nm, and particle diameter is at 0.5-20 μ m, and silicon dioxide is the microballoon of base material, and the di-iron trioxide particulate of the nano level superparamagnetism that evenly is scattered here and there in this base material constitutes.
2. method for preparing by the described ferromagnetism Bio-sil of claim 1 microballoon, its process comprises the preparation of iron oxide colloidal sol, the preparation of iron oxide/silicon dioxide mixed sols, the preparation of organic/inorganic complex microsphere, the preparation of magnetic porous silica gel, it is characterized in that comprising following concrete steps:
1). be that 1-3.0 is with FeCl in molar ratio
3.6H
2O and NaHCO
3Mixing and water adding stirs and makes it abundant dissolving;
2). get an amount of silicon dioxide gel, to 2.0-2.5, press Fe with the acid for adjusting pH that comprises red fuming nitric acid (RFNA)
2O
3With SiO
2Mol ratio is that 0.01-1.0 mixes iron oxide colloidal sol with silicon dioxide gel;
3). add urea, formolite reaction monomer in iron oxide/silicon dioxide mixed sols, its mol ratio is 1-1.5, and the percentage of control inorganic constituents is 60%, is 1-4 at pH, at 5-50 ℃ of following reaction 1-24h, filters and collects complex microsphere;
4). respectively at 300-350 ℃, 600-650 ℃ and 900-950 ℃ of each heating and calcining 2-5h, iron oxide at high temperature undergoes phase transition and obtains ferromagnetism Bio-sil microballoon the complex microsphere that method for preparing obtains after drying.
3. by the preparation method of the described ferromagnetism Bio-sil of claim 2 microballoon, it is characterized in that: Fe
2O
3With SiO
2Preferred molar ratio be 0.3-0.5.
4. press the purposes of claim 1 or the described ferromagnetism Bio-sil of claim 2 microballoon, it is characterized in that containing chloro octyl group silane reagent by the surface employing to microballoon carries out finishing, the ferromagnetism Bio-sil microballoon that hydrophobic chemical functional group obtains on the bonding can be used as anti-phase magnetic chromatographic stationary phase.
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|---|---|---|---|
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| CN1203916C CN1203916C (en) | 2005-06-01 |
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| WO2006125452A1 (en) * | 2005-05-23 | 2006-11-30 | Universite De Geneve | Injectable superparamagnetic nanoparticles for treatment by hyperthermia and use for forming an hyperthermic implant |
| CN101817091A (en) * | 2010-04-28 | 2010-09-01 | 燕山大学 | Method for preparing iron nano-magnetic particles by taking T4 phage as template |
| CN102145896A (en) * | 2010-02-08 | 2011-08-10 | 中国科学院过程工程研究所 | Superparamagnetism silicon dioxide mesoporous nanoparticle with three-dimensional mesoporous channel and preparation method thereof |
| CN101692363B (en) * | 2009-09-24 | 2012-10-17 | 安徽大学 | Magnetic porous composite material and preparing method thereof |
| CN101678316B (en) * | 2007-03-13 | 2012-10-24 | 安捷伦科技有限公司 | Methods and devices using a shrinkable support for porous monolithic materials |
| CN107175064A (en) * | 2017-05-26 | 2017-09-19 | 安徽旭辰生物科技有限公司 | A kind of magnetic microsphere silica gel and preparation method thereof |
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| WO2006125452A1 (en) * | 2005-05-23 | 2006-11-30 | Universite De Geneve | Injectable superparamagnetic nanoparticles for treatment by hyperthermia and use for forming an hyperthermic implant |
| CN101678316B (en) * | 2007-03-13 | 2012-10-24 | 安捷伦科技有限公司 | Methods and devices using a shrinkable support for porous monolithic materials |
| CN101692363B (en) * | 2009-09-24 | 2012-10-17 | 安徽大学 | Magnetic porous composite material and preparing method thereof |
| CN102145896A (en) * | 2010-02-08 | 2011-08-10 | 中国科学院过程工程研究所 | Superparamagnetism silicon dioxide mesoporous nanoparticle with three-dimensional mesoporous channel and preparation method thereof |
| CN101817091A (en) * | 2010-04-28 | 2010-09-01 | 燕山大学 | Method for preparing iron nano-magnetic particles by taking T4 phage as template |
| CN107175064A (en) * | 2017-05-26 | 2017-09-19 | 安徽旭辰生物科技有限公司 | A kind of magnetic microsphere silica gel and preparation method thereof |
| CN107175064B (en) * | 2017-05-26 | 2020-07-24 | 安徽旭辰生物科技有限公司 | Magnetic microsphere silica gel and preparation method thereof |
| CN108124413B (en) * | 2017-12-26 | 2019-08-06 | 山东大学 | Porous hollow iron nanometer spherical electromagnetic wave absorbent material and preparation method and application |
| CN108124413A (en) * | 2017-12-26 | 2018-06-05 | 山东大学 | A kind of porous hollow iron nanometer spherical electromagnetic wave absorbent material and preparation method and application |
| CN109813812A (en) * | 2019-01-04 | 2019-05-28 | 通标标准技术服务（天津）有限公司 | Determination of organochlorine pesticides in soil detection method |
| CN109813812B (en) * | 2019-01-04 | 2021-12-07 | 通标标准技术服务（天津）有限公司 | Method for detecting organochlorine pesticide residue in soil |
| CN110215896A (en) * | 2019-06-05 | 2019-09-10 | 南京亘闪生物科技有限公司 | A kind of lithium absorption resin of porous silicon ball support and preparation method thereof |
| CN113249374A (en) * | 2020-02-12 | 2021-08-13 | 苏州百源基因技术有限公司 | RNA stabilizing solution and preparation and application thereof |
| CN112871098A (en) * | 2021-01-19 | 2021-06-01 | 苏州为度生物技术有限公司 | Super-hydrophilic magnetic microsphere prepared based on spray drying method |
| CN113083217A (en) * | 2021-03-25 | 2021-07-09 | 苏州环亚欣智能科技有限公司 | Preparation method of magnetic silica gel microspheres with controllable high pore diameters |
| CN113559830A (en) * | 2021-08-11 | 2021-10-29 | 天津博蕴纯化装备材料科技有限公司 | Magnetic porous spherical silica gel microspheres and preparation method thereof |
| CN113559830B (en) * | 2021-08-11 | 2023-08-18 | 天津博蕴纯化装备材料科技有限公司 | Magnetic porous spherical silica gel microsphere and preparation method thereof |
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