CN100594186C - Chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles - Google Patents
Chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles Download PDFInfo
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- CN100594186C CN100594186C CN200710072462A CN200710072462A CN100594186C CN 100594186 C CN100594186 C CN 100594186C CN 200710072462 A CN200710072462 A CN 200710072462A CN 200710072462 A CN200710072462 A CN 200710072462A CN 100594186 C CN100594186 C CN 100594186C
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Abstract
The invention provides superparamagnetic nano Fe3O4 particles synthesized through in-situ induction of chitosan hydrogels, relating to a method for synthesizing the superparamagnetic nano Fe3O4 particles. The invention solves the problems of serious aggregation of the nano Fe3O4 particles and the complicated method for inducing the chitosan into the surface of the Fe3O4 in the current nano Fe3O4 particles. The method of the invention is that: 1. the chitosan powder is added into dilute acid solution; 2. cross-linking agent is added to make the chitosan hydrogels; 3. the chitosan hydrogels aresequentially dipped in Fe3+ aqueous solution, water, Fe2+ aqueous solution and water, and a plurality of times of circular leaching are made so as to form the chitosan hydrogels that contains iron ions; 4. then basification treatment is carried out; 5. the hydrogels is dissolved or degraded again, and finally the black superparamagnetic Fe3O4 nano particles are obtained upon centrifugalization. The method of the invention requires simple technique and mild conditions and the equipment used in the method is simple and can be obtained easily, thereby mass production can be achieved. The averagediameter of the particles is 15 to 25nm, and the particles distribute evenly with superparamagnetism.
Description
Technical field
The present invention relates to a kind of super-paramagnetism nano ferriferrous oxide particles synthetic method, be specifically related to a kind of under mild conditions the method by the chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles.
Background technology
When ferriferrous oxide particles size particle diameter during less than 30nm, ferroferric oxide nano granules will show superparamagnetism, show stronger magnetic when promptly applying externally-applied magnetic field, show coercive force and residual magnetization when removing externally-applied magnetic field and level off to 0.The superparamagnetism ferroferric oxide nano granules is crossed biomedical sectors such as heat cure and is widely used in magnetic cell separation, targeted drug release system, nuclear magnetic resonance and cancer.
The method of usually synthetic Z 250 is with ammoniacal liquor or hydroxide ion joins the certain mol proportion ferrous iron and ferric ion solution obtains Z 250, but this method exists particle size distribution wide, and particle agglomeration is serious.It is synthetic to contain metal-organic pyrolytic decomposition of iron ion or the enforcement hydro-thermal in autoclave in addition in addition, but these methods need relatively harsher side to answer condition, as high temperature, high pressure and protective atmosphere etc.Implement to coat biocompatibility macromolecule (as polyvinyl alcohol, protein, polyoxyethylene glycol on superparamagnetism ferroferric oxide nano granules surface, chitosan, Lalgine etc.), can effectively improve the biocompatibility of superparamagnetism ferriferrous oxide nano-particle and reduce reunion between the particle.
Chitosan is the rare amino weakly alkaline polysaccharide of occurring in nature, derives from the cell walls of ocean crab shell, mushroom etc.Because chitosan has excellent biocompatibility, biodegradability and biological activity, it is widely used in drug release carrier, tissue engineering bracket, degradable bone implant material field.Amino activity on the chitosan side chain is big, is easy to form chitosan/metallic ion coordination thing, also helps chemical modification or connects the active macromole of other biological.Chitosan is introduced the Z 250 surface more method, as suspension crosslinking technological, surface grafting technology etc.These procedures are more loaded down with trivial details, generally will be divided into multistep implements: at first synthetic ferroferric oxide nano granules, preparing the chitosan solution that contains the Z 250 particle then carries out crosslinked, or behind Z 250 surface and other amino of functionalization or hydroxy functional group with chitosan reaction, form chitin modified ferroferric oxide nano granules.
Summary of the invention
The objective of the invention is chitosan to be introduced Z 250 surface method complicated problems, and a kind of chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles is provided in order to solve serious the reaching of present synthetic nano ferriferrous oxide granule reunion.
The present invention states the method for chitose aquagel evoked original position synthesis of super-paramagnetism ferroferric oxide nano granules, may further comprise the steps: one, the chitosan powder is joined in the acetic acid solution, mechanical stirring to chitosan dissolves fully, and being mixed with mass percent concentration is the faint yellow chitosan solution of 2～5% homogeneous; Two, linking agent is slowly joined in the above-mentioned chitosan solution, continue at the uniform velocity to stir 5～20min, leave standstill 8～12h again, obtain chitosan gel rubber; Three, chitosan gel rubber is immersed in 0.05～0.2mol/L Fe successively
3+The aqueous solution, water, 0.02～0.1mol/L Fe
2+The aqueous solution, water in, and, promptly form the aquagel (CS-NH that contains iron ion with infusion three to five times
2----Fe
2+, Fe
3+); Four, the aquagel that will contain iron ion carries out alkalinisation treatment 5～24h, adopts distilled water that the chitosan magnetic hydrogel rinsing of black is extremely neutral then; Five, will add through the chitosan magnetic gel of the black after the step 4 rinsing in the diluted acid, mechanical stirring to gel piece dissolves fully, centrifugation then, can obtain the magnetically responsive substance that has of black, clean to neutral with distilled water again, obtain the superparamagnetism ferroferric oxide nano granules of chitosan in situ coating modification.
Different with aforesaid method is will add H through the chitosan magnetic gel of the black after the step 4 rinsing in step 5 before centrifugation
2O
2Or carry out DeR in the lysozyme soln; H wherein
2O
2The concentration of volume percent 3～8% of solution, the mass percent concentration 0.012～0.018% of lysozyme soln.Other step is identical with aforesaid method.
The present invention has realized under mild conditions by the chitose aquagel evoked original position synthesis of super-paramagnetism ferroferric oxide nano granules.This method technology is simple, mild condition, required equipment be simple and easy to, and can realize producing in batches.The aquagel that contains iron ion by alkalinisation treatment, utilize the sequestering action and the ion exchange of aquagel, the evoked original position synthesis of super-paramagnetism ferroferric oxide nano granules, synthetic ferroferric oxide nano granules median size is 15～25nm, and particle size distribution is even.Magnetic test shows synthetic ferroferric oxide nano granules of the present invention has superparamagnetism, and its residual magnetization and coercive force all level off to 0.Aquagel not only as reaction medium, but also provides the nucleation site of ferroferric oxide nano crystal in reaction.The more important thing is that this method also is implemented in Z 250 surface in situ encasement glycan in synthetic Z 250, this gives this nano particle and has excellent biological compatibility.Amino activity on the chitosan side chain is big, and this will help at magnetic nanoparticle surface bond or coupling other biological functional macromolecule or medicine.This nano magnetic particle is applicable to the biological technical fields such as heat cure, nuclear magnetic resonance contrast medium and nano-probe excessively of target medicine carrier, cancer.
Description of drawings
Fig. 1 is the transmission electron microscope photo of chitose aquagel evoked original position synthetic superparamagnetism ferroferric oxide nano granules, and Fig. 2 is the magnetic hysteresis loop figure of chitose aquagel evoked original position synthetic superparamagnetism ferroferric oxide nano granules.
Embodiment
Embodiment one: present embodiment adopts chitose aquagel evoked in-situ method to synthesize super-paramagnetism nano ferriferrous oxide particles, the step of this method is as follows: one, the chitosan powder is joined in the acetic acid solution, mechanical stirring to chitosan dissolves fully, and being mixed with mass percent concentration is the faint yellow chitosan solution of 2～5% homogeneous; Two, linking agent is slowly joined in the above-mentioned chitosan solution, continue at the uniform velocity to stir 5～20min, leave standstill 8～12h again, obtain chitosan gel rubber; Three, chitosan gel rubber is immersed in 0.06mol/L FeCl successively
3The aqueous solution, water, 0.03mol/L Fe (NO
3)
2The aqueous solution, water in, and, promptly form the aquagel (CS-NH that contains iron ion with infusion three to five times
2---Fe
2+, Fe
3+); Four, the aqueous solution that will contain the aquagel immersion NaOH of iron ion carries out alkalinisation treatment 5～24h, and wherein the NaOH mass percent concentration is 4%, adopts distilled water that the chitosan magnetic hydrogel rinsing of black is extremely neutral then; Five, will add concentration of volume percent through the chitosan magnetic gel of the black after the step 4 rinsing is in 1～5% acetic acid solution, mechanical stirring to gel piece dissolves fully, centrifugation then, can obtain the magnetically responsive substance that has of black, clean to neutral with distilled water again, obtain the ferroferric oxide nano granules of the superparamagnetism of chitosan in situ coating modification.
Present embodiment synthetic ferroferric oxide nano granules median size is 15～25nm, and particle size distribution is even.Present embodiment synthetic ferroferric oxide nano granules has superparamagnetism.
Embodiment two: what present embodiment and embodiment one were different is will add H through the chitosan magnetic gel of the black after the step 4 rinsing in step 5 before centrifugation
2O
2Or carry out DeR in the lysozyme soln; H wherein
2O
2The concentration of volume percent 4% of solution, the mass percent concentration 0.015% of lysozyme soln.Other step is identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one and two is that linking agent is the physical crosslinking agent in step 2, and described physical crosslinking agent is tri-polyphosphate, glycerophosphate or glycerine.Other step is identical with embodiment one and two.
Embodiment four: what present embodiment was different with embodiment one and two is that linking agent is a chemical cross-linking agent in step 2, and described chemical cross-linking agent is epoxy chloropropane, water-soluble carbodiimide or glutaraldehyde.Other step is identical with embodiment one and two.
Embodiment five: that present embodiment is different with embodiment one and two is ferrous ion (Fe in step 3
2+) by FeCl
2, FeSO
4Or the above-mentioned molysite that contains crystal water provides.Other step is identical with embodiment one and two.
Embodiment six: that present embodiment is different with embodiment one and two is iron ion (Fe in step 3
3+) by Fe
2(SO
4)
3, Fe (NO
3)
3Or the above-mentioned molysite that contains crystal water provides.Other step is identical with embodiment one and two.
Embodiment seven: present embodiment is different with embodiment one and two be in step 3 soak solution concentration, soak time and cycle index by the size decision of gel piece; For the gel piece of 2cm * 2cm * 2cm, be soaked in the Fe of 0.2mol/L respectively
3+The Fe of the aqueous solution and 0.1mol/L
2+Each 30min in the aqueous solution, 3 bouts of circulation immersion get final product.Other step is identical with embodiment one and two.
Embodiment eight: what present embodiment was different with embodiment one and two is as follows at the method for alkalization processing described in the step 4: the aquagel that will contain iron ion is immersed in the aqueous solution or alcohol solution of ammoniacal liquor, KOH, wherein the ammoniacal liquor mass percent concentration is 5～10%, the aqueous solution mass percent concentration of KOH is 3～10%, ethanol in the alcohol solution: the volume ratio of water is 2: 8.Other step is identical with embodiment one and two.
Embodiment ten: present embodiment super-paramagnetism nano ferriferrous oxide particles synthetic method step is as follows: one, 2g chitosan powder is joined in 2% (volume ratio) acetic acid solution of 100ml, at the uniform velocity stir 2h, be mixed with the chitosan solution of 2% (mass/volume); Two, add 10% (mass ratio) glutaraldehyde solution that slowly adds 5ml then, at the uniform velocity stir 10min, leave standstill 10h, thereby obtain the chitosan gel rubber of 2cm * 2cm * 2cm; Three, (2cm * 2cm * 2cm) is immersed in the FeSO of 0.075mol/L with the chitosan gel rubber of preparation
445min in the aqueous solution behind the iron ion that does not adsorb with deionized water flush away surface, is immersed in it Fe of 0.15mol/L again
2(SO
4)
345min in the aqueous solution, this immersion process circulation is carried out 3 times, forms the aquagel that contains iron ion; Four, the aquagel that will contain iron ion then immerses in 7% (mass ratio) ammonia soln of 50 ℃ and soaks 12h, and the chitosan magnetic hydrogel rinsing that will obtain black again is to neutrality; Five, the black magnetic chitosan gel rubber after the rinsing is joined in 3% (volume ratio) acetic acid solution, at the uniform velocity stir 12h, centrifugation obtains the superparamagnetism ferroferric oxide nano granules of black chitosan in situ coating modification then.
Adopt this method synthetic ferroferric oxide nano granules median size 20nm (see figure 1), and particle size distribution is even, does not reunite between the particle.Magnetic test shows present embodiment synthetic ferroferric oxide nano granules has the superparamagnetism (see figure 2), can learn that residual magnetization and coercive force all level off to 0 from magnetic hysteresis loop figure.
Embodiment 11: present embodiment super-paramagnetism nano ferriferrous oxide particles synthetic method step is as follows: one joins 5g chitosan powder in 2.5% (volume ratio) acetic acid solution of 100ml, at the uniform velocity stir 5h, be mixed with the chitosan solution of 5% (mass/volume); Two, add 15% of 20ml then
(mass ratio) thus sodium tripolyphosphate solution obtains the chitosan gel rubber of 1.5cm * 1.5cm * 1.5cm; Three, the certain size chitosan gel rubber with preparation is immersed in Fe (NO
3)
330min in the solution behind the iron ion that does not adsorb with deionized water flush away surface, is immersed in FeCl with it again
230min in the solution, this immersion process circulation is carried out 4 times, can obtain to contain the aquagel of iron ion; Four, the aquagel that will contain iron ion then immerses in 4% (mass ratio) NaOH solution of 50 ℃ and soaks 10h, obtains the black magnetic aquagel, and adopt distilled water with the hydrogel rinsing to neutral; Five, the black magnetic aquagel after the rinsing is joined in 5% (volume ratio) acetic acid solution, at the uniform velocity stir 8h, centrifugation obtains the superparamagnetism ferroferric oxide nano granules of black chitosan in situ coating modification then.
Present embodiment synthetic ferroferric oxide nano granules median size: 15nm, and particle size distribution is even, does not reunite between the particle.Present embodiment synthetic ferroferric oxide nano granules has superparamagnetism.
Claims (7)
1, chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles, the step that it is characterized in that this method is as follows: one, the chitosan powder is joined in the acetic acid solution, mechanical stirring to chitosan dissolves fully, and being mixed with mass percent concentration is the faint yellow chitosan solution of 2～5% homogeneous; Two, linking agent is slowly joined in the above-mentioned chitosan solution, continue at the uniform velocity to stir 5～20min, leave standstill 8～12h again, obtain chitosan gel rubber, described linking agent is physical crosslinking agent or chemical cross-linking agent, wherein the physical crosslinking agent is tri-polyphosphate, glycerophosphate or glycerine, and chemical cross-linking agent is epoxy chloropropane, water-soluble carbodiimide or glutaraldehyde; Three, chitosan gel rubber is immersed in 0.05～0.2mol/L Fe successively
3+The aqueous solution, water, 0.02～0.1mol/L Fe
2+The aqueous solution, water in, and, promptly form the aquagel that contains iron ion with infusion three to five times; Four, the aquagel that will contain iron ion carries out alkalinisation treatment 5～24h, adopts distilled water that the chitosan magnetic hydrogel rinsing of black is extremely neutral then; Five, will add through the chitosan magnetic gel of the black after the step 4 rinsing in the dilute acid soln, mechanical stirring to gel piece dissolves fully, and centrifugation then can obtain the magnetically responsive substance that has of black, clean to neutral with distilled water again, obtain the ferroferric oxide nano granules of superparamagnetism.
2, chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles according to claim 1 is characterized in that diluted acid is that concentration of volume percent is 1～5% acetic acid solution.
3, chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles according to claim 1 is characterized in that will adding H through the chitosan magnetic gel of the black after the step 4 rinsing before centrifugation in step 5
2O
2Or carry out DeR in the lysozyme soln; H wherein
2O
2The concentration of volume percent 3～8% of solution, the mass percent concentration 0.012～0.018% of lysozyme soln.
4, according to claim 1 or 3 described chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles, it is characterized in that ferrous ion is by Fe (NO in step 3
3)
2, FeCl
2, FeSO
4Or the above-mentioned molysite that contains crystal water provides.
5, according to claim 1 or 3 described chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles, it is characterized in that iron ion is by Fe in step 3
2(SO
4)
3, FeCl
3, Fe (NO
3)
3Or the above-mentioned molysite that contains crystal water provides.
6,, it is characterized in that in step 3 being soaked in the Fe of 0.2mol/L respectively for the gel piece of 2cm * 2cm * 2cm according to claim 1 or 3 described chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles
3+The Fe of the aqueous solution and 0.1mol/L
2+Each 30min in the aqueous solution, 3 bouts of circulation immersion get final product.
7, according to claim 1 or 3 described chitose aquagel evoked original position synthesis of super-paramagnetism nano ferriferrous oxide particles, it is characterized in that at the method for alkalization processing described in the step 4 as follows: the aquagel that will contain iron ion is immersed in the aqueous solution or alcohol solution of the aqueous solution of ammoniacal liquor, NaOH, KOH, wherein the ammoniacal liquor mass percent concentration is 5～10%, the aqueous solution mass percent concentration of the aqueous solution of NaOH or KOH is 3～10%, ethanol in the alcohol solution: the volume ratio of water is 2: 8.
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| CN102850599A (en) * | 2012-09-18 | 2013-01-02 | 厦门大学 | Magnetic chitosan/nano Fe3O4 composite and preparation method and application thereof |
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