CN103065753A - Magnetic nano-particle and preparation method thereof - Google Patents
Magnetic nano-particle and preparation method thereof Download PDFInfo
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- CN103065753A CN103065753A CN2011103185218A CN201110318521A CN103065753A CN 103065753 A CN103065753 A CN 103065753A CN 2011103185218 A CN2011103185218 A CN 2011103185218A CN 201110318521 A CN201110318521 A CN 201110318521A CN 103065753 A CN103065753 A CN 103065753A
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Abstract
The invention provides a magnetic nano-particle comprising a metal cobalt nano-particle core and a silicon gel layer covering outside the metal cobalt nano-particle core, wherein at least one hydroxyl and at least one oxygenous carbon chain are embedded outside the silicon gel layer, the rear end of the oxygenous carbon chain is connected with a function group in a coupling mode, and the function group comprises a sulfoacid group and a quaternary amine group. The magnetic nano-particle core is metal cobalt rather than ferroferric oxide or platinum alloy, so material cost is lower and separation effects are better. Besides, the invention provides a preparation method of the magnetic nano-particle. The preparation method is simple in process. Meanwhile, the metal cobalt is magnetic, so after the separation process of medicine, the magnetic nano-particles can be recycled through the effect of imposed magnetic fields, and therefore energy consumption is lowered and environments are prevented from being polluted.
Description
Technical field
The present invention relates to field of nanometer material technology, more specifically, relate in the Bio-pharmaceutical Industry for separating of a kind of magnetic nanoparticle of using and preparation method thereof.
Background technology
In pharmaceuticals industry, isolation technics is mainly used in recovery, extraction and the purifying of drug target, the steps such as that traditional isolation technics mainly comprises is centrifugal, filtration, chromatography, crystallization, this process often needs to consume a large amount of energy, and in occupation of the production cost more than 60%.Have the medicine that surpasses 1,000 hundred million dollars to obtain by fermentation mode in the pharmaceutical industry of the U.S., and the active drug content in the zymotic fluid is extremely low, high separation costs and huge energy consumption are impelled the new high efficient separation technology of the numerous and confused research and development of scientists.And the magnetic nanoparticle filler has high specific area and unique magnetic characteristic, can significantly reduce separation costs in the separation of reality is used, and effectively reduces energy consumption, also can avoid environmental pollution, therefore has been subject to paying close attention to widely.
The magnetic nanoparticle that is most widely used on the market is mainly metal oxide nanoparticles, such as aluminium oxide, titanium dioxide, tri-iron tetroxide, zinc oxide, zirconia etc.Wherein, only can be with based on the nano particle of tri-iron tetroxide and be magnetic.Disclose in the document " Protein separations using colloidal magnetic nanoparticles " a kind of with tri-iron tetroxide as matrix, the nano-colloid particle of phosphatide coating is adopted on the surface, and this particle can reach 1.2 grams per milliliters to the adsorbance of albumen.But, there is electrostatic interaction between the tri-iron tetroxide matrix of this particle and the phosphatide coating, the phenomenon that coating shedding in the actual separation process, unavoidably occurs, not only can affect the useful life of nano particle, and can cause gathering between the nano particle, the coating that more seriously comes off from nano particle can contaminating protein matter molecule.Therefore, this kind magnetic nanoparticle is difficult to obtain to use in bio-separation.
In addition, the alloy of some transition metal also can be used as matrix, such as ferroplatinum, cobalt-platinum alloy etc.A kind of Armco magnetic iron platinum alloy nano particle is disclosed in the document " Nitrilotriacetic Acid-Modified Magnetic Nanoparticles as a General Agent to Bind Histidine-Tagged Proteins ", at its surface bond complexon I, nickel ion in the complexing again, the recombinant protein that forms histidine mark has affine adsorbing magnetic nanoparticle.The affine adsorption capacity of this particle can reach 2 ~ 3 mg/ml.But need to be with noble metal platinum as raw material in the production process, cost is expensive; And the magnetic of this particle depends on the production process of " ferroplatinum ", and whole complex manufacturing, process are difficult to control.
Because prior art has certain deficiency at aspects such as preparation process, cost control, separating effects.Therefore, be necessary to propose a kind of magnetic nanoparticle and preparation method thereof, with the preparation cost of achieve effective control adsorption stuffing, make preparation process be easy to control, improve filler adsorption effect, reduce separation costs and avoid causing environmental pollution because of the discharging of filler.
Summary of the invention
One object of the present invention is to provide a kind of stable performance, bio-separation function admirable, gets final product the magnetic nanoparticle that the realize target material separates with impurity by simple externally-applied magnetic field.Another purpose of the present invention is to provide the preparation method of a kind of magnetic nanoparticle that a kind of technique is simple, preparation process is easy to control.
For realizing first purpose of the present invention, the invention provides a kind of magnetic nanoparticle, comprise metallic cobalt nano particle kernel and the layer of silica gel that is coated on described metallic cobalt nano particle kernel outside, described layer of silica gel surface inserting has at least one hydroxyl and at least one to contain the oxygen carbochain, and the described end that contains the oxygen carbochain contains a functional group at least.
As a further improvement on the present invention, described functional group comprises sulfonic acid group, quaternary amines.
As a further improvement on the present invention, the described oxygen carbochain that contains comprises at least 2 oxygen atoms.
For realizing another object of the present invention, the invention provides this preparation method of a kind of magnetic nanoparticle and mainly may further comprise the steps:
(1) take fatty alcohol as solvent, take cobalt salt and boron hydride as raw material, forms the metallic cobalt nano particle that the surface is provided with several hydroxyls;
(2) the metallic cobalt nano particle is joined in the tetraethoxysilane solution and with the 3-glycidoxy-propyltrimethoxy silane and react, make the outside of metallic cobalt nano particle coat one deck layer of silica gel, and inlay the carbochain that at least one end contains active epoxy group on the layer of silica gel;
(3) on active epoxy group, can be used for the functional group of bio-separation by the coupling agent coupling.
As a further improvement on the present invention, the fatty alcohol in the described step (1) is ethanol, propyl alcohol, ethylene glycol, glycerine or any two or more mixture.
As a further improvement on the present invention, described cobalt salt is cobalt chloride, and described boron hydride is sodium borohydride.
As a further improvement on the present invention, described preparation method also comprises: described step (1) is carried out in the reactor of magnetic devices in the bottom.
As a further improvement on the present invention, the average particle size range of described metallic cobalt nano particle is 500 ~ 900nm.
As a further improvement on the present invention, in the described step (3), comprise sodium sulfite, trimethylamine with the coupling agent of active epoxy group generation coupling reaction.
As a further improvement on the present invention, contain endways on the carbochain of active epoxy group by described coupling reaction and derive sulfonic acid group, quaternary amines.
Compared with prior art, the invention has the beneficial effects as follows: because metallic cobalt has magnetic, therefore after the medicine separation process, be convenient to the recovery of this particle, thereby can reduce energy consumption, avoid environmental pollution, this preparation method's preparation process is easy to control simultaneously, and technique is simple and manufacturing cost is relatively cheap.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, is used from explanation the present invention with various embodiments of the present invention one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the cutaway view of the middle metallic cobalt nano particle reaction unit of preparation method's step (1) of a kind of magnetic nanoparticle of the present invention.
Among the figure:
Sprayer 11, sprayer 12, reactor 2, reaction solution layer 21, reaction terminating liquid layer 22, metallic cobalt nano-particle layer 23, magnetic devices 3.
Fig. 2 is the present invention forms the metallic cobalt nano particle of great amount of hydroxy group on the surface cutaway view.
Fig. 3 is that preparation method's step (2) of a kind of magnetic nanoparticle of the present invention is middle through the cutaway view of finishing rear surface formation with the metallic cobalt nano particle of active epoxy group.
Fig. 4 is the cutaway view of a kind of magnetic nanoparticle in the first execution mode of the present invention.
Fig. 5 is the cutaway view of another kind of magnetic nanoparticle in the second execution mode of the present invention.
Embodiment
Accompanying drawing is used to provide a further understanding of the present invention, is used from explanation the present invention with various embodiments of the present invention one, but is not construed as limiting the invention.The invention paper term definition and explanation, then introduced the related embodiment of a kind of magnetic metal cobalt nano-particle that separates for biological medicine and preparation method thereof.
1. definition and the explanation of used term in specification and the claim
Before introducing in detail following embodiment details, define first or set forth some terms.
Term " sol-gel process " refers to raw material is dispersed in the solvent, then generate activated monomer through hydrolysis, activated monomer carries out polymerization, begins to become colloidal sol, and then generate the gel with certain space structure, prepare nano particle and required material through super-dry and heat treatment.
Term " group " refers to the stationary atom group as the molecular composition part of some compound, as: hydrogen base, amino, azo group, free radical etc.
Term " bonding " refers to adjacent two or more interatomic strong interaction.
Term " chemical bond " refer in the molecule or crystal in the general designation of strong interaction force between adjacent two or more atoms (or ion), it mainly comprises " covalent bond ", " ionic bond ", " metallic bond ".
Term " polar solvent " refers to contain the solvent of the molecule of permanent electric dipole, and its polarity is strong, and dielectric constant is large, and it mainly comprises: hydroxyl or carbonyl isopolarity group.
Term " terminator " refers to that terminator also claims " chain terminating agent ", is to react rapidly with initator (or catalyst) or growing chain, thereby effectively destroys its activity, the material that polymerization reaction is stopped.Stop polymerization reaction in good time, can obtain molecular weight evenly, the high-quality polymeric articles of molecular structure stabilized.Terminator also has the effect of wearing out of preventing concurrently except playing a part elimination system activated centre.
Term " chromatographic isolation " refers to the effective ways of each component in a kind of separate complex mixture.It is to utilize different material having different distribution coefficients mutually with in the system that mobile phase consists of by fixing, when two-phase is done relative motion, these materials move with mobile phase, and alternately carry out repeated multiple times distribution two, thereby make each material reach separation.
Term " ion-exchange " refers to exchange by means of the ion in the Solid-state Ion-exchange agent and the ion in the weak solution, to reach the purpose of extracting or removing some ion in the solution, is a kind of unit operations that belongs to the mass transfer separation process.
The invention provides a kind of magnetic nanoparticle, the layer of silica gel that it comprises metallic cobalt nano particle kernel and is coated on described metallic cobalt nano particle kernel outside.Wherein, described layer of silica gel surface inserting has at least one hydroxyl and at least one to contain the oxygen carbochain, and the described end that contains the oxygen carbochain contains a functional group at least.
Further, described functional group comprises sulfonic acid group, quaternary amines, and the described oxygen carbochain that contains comprises at least 2 oxygen atoms.
The present invention also provides a kind of magnetic nanoparticle and preparation method thereof, and this preparation method mainly may further comprise the steps: (1) take fatty alcohol as solvent, take cobalt salt and boron hydride as raw material, forms the metallic cobalt nano particle that the surface is provided with several hydroxyls; (2) the metallic cobalt nano particle is joined in the tetraethoxysilane solution and with the 3-glycidoxy-propyltrimethoxy silane and react, make the outside of metallic cobalt nano particle coat one deck layer of silica gel, and inlay the carbochain that at least one end contains active epoxy group on the layer of silica gel; (3) pass through the functional group that the coupling agent coupling is used for bio-separation at active epoxy group.
Wherein, the fatty alcohol in the described step (1) is ethanol, propyl alcohol, ethylene glycol, glycerine or any two or more mixture.
Wherein, described cobalt salt is cobalt chloride, and described boron hydride is sodium borohydride.
Wherein, described preparation method also comprises: described step (1) is carried out in the reactor of magnetic devices in the bottom.
Wherein, in the described step (3), comprise with the coupling agent of active epoxy group generation coupling reaction: sodium sulfite, trimethylamine, contain endways on the carbochain of active epoxy group and derive sulfonic acid group, quaternary amines.
Below with a plurality of embodiment a kind of magnetic nanoparticle of the present invention and preparation method thereof is described.
Embodiment 1
Fig. 1 is the cutaway view of the middle metallic cobalt nano particle reaction unit of preparation method's step (1) of a kind of magnetic nanoparticle of the present invention.
Specification be the 500ml volume and with the reactor 2 of magnetic devices 3 in add 120ml atoleine and 30ml 6-sulfydryl-1-hexanol to consist of reaction terminating liquid layer 22.The magnetic devices of these reactor 2 bottoms is electromagnet 3.And then in reactor 2, add the 100ml absolute ethyl alcohol as reaction solution.Reaction solution is by 5g CoCl
2With 3g NaBH
4Ethanolic solution (each 100ml) form.Two kinds of solution spray in the reactor 2 by sprayer 11 and sprayer 12 respectively, to consist of reaction solution layer 21.The jet velocity of this sprayer is 2ml/min.Along with CoCl in the reaction solution layer 21
2And NaBH
4It is large that the carrying out of reaction, metallic cobalt nano particle constantly become, and gravity constantly increases.When gravity during greater than the magnetic field repulsive force that makes progress that produced by electromagnet 3, the metallic cobalt nano particle enters in the reaction terminating liquid layer 22, and with the reaction of reaction terminating agent 6-sulfydryl-1-hexanol, form the metallic cobalt nano particle that contains great amount of hydroxy group on its surface, join shown in Figure 2.The average diameter of this metallic cobalt nano particle is 900 nanometers, and is deposited in metallic cobalt nano-particle layer 23 zones of reactor 2 bottoms.Generate the chemical reaction process of metallic cobalt nano particle in the reactor 2 shown in chemical equation (1) and (2).
CoCl
2 + 2NaBH
4 
Co + H
2 + B
2H
6 + 2NaCl （1）
B
2H
6 + 6CH
3CH
2OH
2B(OCH
2CH
3)
3 + 6H
2 （2）
Stop buffer in reaction terminating liquid layer 22 is 6-sulfydryl-1-hexanol, and it contains the terminal sulfydryl that is, can form weak force with a metallic cobalt nanometer surface, thereby stops the growth of metallic cobalt nanometer, also forms great amount of hydroxy group on a metallic cobalt nanometer surface simultaneously.Fig. 3 is the schematic diagram of the metallic cobalt nano particle behind the surface modification active epoxy group in the embodiment of the invention 1.
There is the metallic cobalt nano particle of hydroxyl to take out and washing surface bond, again be dispersed in the 200ml tetraethoxysilane solution, and the 3-glycidoxy-propyltrimethoxy silane of adding 20ml, reaction is 16 hours under room temperature (20 ℃) condition, make active epoxy group on the metallic cobalt nanometer surface bond, epoxy density is 0.3-0.4mmol/g, shown in the following chemical equation of its chemical reaction process (3).
Wherein,
Be tetraethoxysilane;
Be 3-epoxy the third oxygen trimethoxy silane.
The metallic cobalt nano particle of surface modified active epoxide group is dispersed in the deionized water of 200ml again, adds the sodium sulfite (Na of 20g
2SO
3) solid, reaction is 6 hours under 45 ℃ of conditions, contains endways on the carbochain of active epoxy group to derive the sulfonic acid group with cation exchange effect, and groups density is 0.2-0.3mmol/g.This sulfonic acid group has the cation-exchange chromatography medium of bio-separation function, and the structure of the final magnetic nanoparticle that generates as shown in Figure 4.
Embodiment 2
Consult equally Fig. 1, specification be the 500ml volume and with the reactor 2 of magnetic devices 3 in add 120ml atoleine and 30ml 6-sulfydryl-1-hexanol to consist of reaction terminating liquid layer 22.The magnetic devices of these reactor 2 bottoms is electromagnet 3.And then in reactor 2, add the 100ml absolute ethyl alcohol as reaction solution.Reaction solution is by 3g CoCl
2With 6g NaBH
4Ethanolic solution (each 100ml) form.Two kinds of solution spray in the reactor 2 by sprayer 11 and sprayer 12 respectively, to consist of reaction solution layer 21.The jet velocity of this sprayer is 1ml/min.Along with CoCl in the reaction solution layer 21
2And NaBH
4It is large that the carrying out of reaction, metallic cobalt nano particle constantly become, and gravity constantly increases.When gravity during greater than the magnetic field repulsive force that makes progress that produced by electromagnet 3, the metallic cobalt nano particle enters in the reaction terminating liquid layer 22, and with the reaction of reaction terminating agent 6-sulfydryl-1-hexanol, form the metallic cobalt nano particle that contains great amount of hydroxy group on its surface, join shown in Figure 2.The average diameter of this metallic cobalt nano particle is 500 nanometers, and is deposited in metallic cobalt nano-particle layer 23 zones of reactor 2 bottoms.The chemical equation of the chemical reaction process of generation metallic cobalt nano particle is identical with embodiment 1 in the reactor 2.
Stop buffer in reaction terminating liquid layer 22 is 6-sulfydryl-1-hexanol, and it contains the terminal sulfydryl that is, can form weak force with a metallic cobalt nanometer surface, thereby stops the growth of metallic cobalt nanometer, also forms great amount of hydroxy group on a metallic cobalt nanometer surface simultaneously.Fig. 3 is the schematic diagram of the metallic cobalt nano particle behind the surface modification active epoxy group in the embodiment of the invention 2.
There is the metallic cobalt nano particle of hydroxyl to take out and washing surface bond, again be dispersed in the 200ml tetraethoxysilane solution, and the 3-glycidoxy-propyltrimethoxy silane of adding 40ml, reaction is 8 hours under room temperature (50 ℃) condition, make active epoxy group on the metallic cobalt nanometer surface bond, epoxy density is 0.8-1.0mmol/g.The chemical reaction process of this technological process is identical with embodiment 1.
The metallic cobalt nano particle of surface modified active epoxide group is dispersed in the deionized water of 200ml again, add the 50ml trimethylamine aqueous solution, reaction is 6 hours under 45 ℃ of conditions, contain endways to derive on the carbochain of active epoxy group and form the quaternary amines with anion exchange effect, groups density is 0.5-0.6mmol/g.This quaternary amines has the anion-exchange chromatography medium of bio-separation function, and the structure of the final magnetic nanoparticle that generates as shown in Figure 5.
Compared with prior art, because the kernel of magnetic nanoparticle is lower-cost metallic cobalt, but not the higher noble metal platinum of cost, so the material cost of this magnetic nanoparticle is relatively low; Secondly, being different from prior art uses tri-iron tetroxide as the kernel of magnetic nanoparticle, therefore the cobalt atom of magnetic nanoparticle of the present invention and layer of silica gel adhesion are good, can not produce that layer of silica gel comes off and the phenomenon of polluting detected sample, so separating effect is better; Again, because this nano particle has magnetic as the metallic cobalt of kernel, therefore after detached job is finished, be convenient to the recovery of nano particle, thereby avoided the pollution of environment; At last, preparation method's technique of this magnetic nanoparticle is simple, step is less, low-carbon environment-friendly.
Be to be understood that, although this specification is described according to execution mode, but be not that each execution mode only comprises an independently technical scheme, this narrating mode of specification only is for clarity sake, those skilled in the art should make specification as a whole, technical scheme among each embodiment also can through appropriate combination, form other execution modes that it will be appreciated by those skilled in the art that.
Above listed a series of detailed description only is specifying for feasibility execution mode of the present invention; they are not to limit protection scope of the present invention, allly do not break away from equivalent execution mode or the change that skill spirit of the present invention does and all should be included within protection scope of the present invention.
Claims (10)
1. magnetic nanoparticle, comprise metallic cobalt nano particle kernel and the layer of silica gel that is coated on described metallic cobalt nano particle kernel outside, it is characterized in that: described layer of silica gel surface inserting has at least one hydroxyl and at least one to contain the oxygen carbochain, and the described end that contains the oxygen carbochain contains a functional group at least.
2. magnetic nanoparticle according to claim 1, it is characterized in that: described functional group comprises sulfonic acid group, quaternary amines.
3. magnetic nanoparticle according to claim 1, it is characterized in that: the described oxygen carbochain that contains comprises at least 2 oxygen atoms.
4. the preparation method of a magnetic nanoparticle is characterized in that, this preparation method mainly may further comprise the steps:
(1) take fatty alcohol as solvent, take cobalt salt and boron hydride as raw material, forms the metallic cobalt nano particle that the surface is provided with several hydroxyls;
(2) the metallic cobalt nano particle is joined in the tetraethoxysilane solution and with the 3-glycidoxy-propyltrimethoxy silane and react, make the outside of metallic cobalt nano particle coat one deck layer of silica gel, and inlay the carbochain that at least one end contains active epoxy group on the layer of silica gel;
(3) pass through the functional group that the coupling agent coupling is used for bio-separation at active epoxy group.
5. preparation method according to claim 4 is characterized in that: the fatty alcohol in the described step (1) is ethanol, propyl alcohol, ethylene glycol, glycerine or any two or more mixture.
6. preparation method according to claim 4, it is characterized in that: described cobalt salt is cobalt chloride, described boron hydride is sodium borohydride.
7. preparation method according to claim 4 is characterized in that, described preparation method also comprises: described step (1) is carried out in the reactor of magnetic devices in the bottom.
8. according to claim 4 or 7 each described preparation methods, it is characterized in that: the average particle size range of described metallic cobalt nano particle is 500 ~ 900nm.
9. preparation method according to claim 4 is characterized in that: in the described step (3), comprise sodium sulfite, trimethylamine with the coupling agent of active epoxy group generation coupling reaction.
10. preparation method according to claim 9 is characterized in that: contain endways by described coupling reaction on the carbochain of active epoxy group and derive sulfonic acid group, quaternary amines.
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Application publication date: 20130424 |