CN101719407A - Preparation method of water-based biological magnetic fluid - Google Patents
Preparation method of water-based biological magnetic fluid Download PDFInfo
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- CN101719407A CN101719407A CN201010300662A CN201010300662A CN101719407A CN 101719407 A CN101719407 A CN 101719407A CN 201010300662 A CN201010300662 A CN 201010300662A CN 201010300662 A CN201010300662 A CN 201010300662A CN 101719407 A CN101719407 A CN 101719407A
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Abstract
The invention relates to a preparation method of a water-based biological magnetic fluid, belonging to the technical field of biological materials. The preparation method comprises the following steps: dissolving ferric iron salt and water-soluble high polymers in diglycol, and heating and stirring the mixture for reaction in a nitrogen protection environment; then, rapidly injecting a diglycol monomethyl ether solution and continuously heating the mixture for reaction; and further adding acetone, adsorbing for separation by a magnet, and washing and dispersing the mixture in de-ionized water to obtain the water-based biological magnetic fluid. The water-soluble Fe3O4 magnetic nanometer particles prepared by the invention have good biological compatibility, narrow particle size distribution of the nanometer particles, good uniformity, high degree of crystallization and good controllability. The prepared water-based biological magnetic fluid has good stability and biological compatibility, and the magnetic response efficiency and the rheological characteristics of the biological magnetic fluid can be adjusted and controlled through the surface characteristics of the magnetic nanometer particles, which comprise the type, the structure and the coating rate of a coating material.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of biological materials, specifically is a kind of preparation method who utilizes the water-based biological magnetic fluid of improved ferroferric oxide nano particle.
Background technology
Magnetic fluid is that a kind of existing solid ferromagnetism has liquid fluidity again, has the special smart material of controllable rheology characteristic with externally-applied magnetic field.Biological magnetic fluid is a kind of bio-medical magnetic fluid, can be applicable to the magnetic target administration, thermotherapy, gene therapy and early diagnosis of tumor in the magnetic fluid cell.Biological magnetic fluid generally is made up of nano magnetic particle, stabilizer and decentralized medium.Usually the nano magnetic particle of using has straight iron powder, ferriferous oxide, ferrocobalt etc., especially with Fe
3O
4In the majority, general diameter is at 10～30nm.Function of stabilizer is by the gathering between the graviational interaction prevention magnetic particle that overcomes interparticle Van der Waals force, perhaps modification is carried out on the magnetic particle surface and strengthened gathering between the affinity prevention magnetic particle of magnetic particle and decentralized medium, the stabilizer of selecting for use usually is organic molecule or high molecular surfactant.Decentralized medium is the carrier fluid of magnetic particle, and generally adopting deionized water at biological field and field of medicaments is decentralized medium.
In recent years, size was less than the Fe of the super paramagnetic of 10nm
3O
4Nano particle is owing to have easily advantage such as modification of high magnetic saturation intensity, nontoxic and particle surface, caused that with biological magnetic fluid bio-medical field such as thermotherapy and magnetic target administration in magnetic resonance imaging, magnetic fluid cell of its preparation people pay close attention to widely.During externally-applied magnetic field, the magnetic fluid that carries these particles of medicine or gene can be by the specific position of target to tumor region.This operation can reduce the harm to healthy organ, and medicine circulation in vivo can be limited, and non-special absorption can be avoided.
Document is found by retrieval, Chinese patent literature CN1822254, and open day 2006-8-23 has put down in writing a kind of " magnetic fluid for biological medicine and preparation method thereof ", and this method is to use classical chemical coprecipitation to prepare Fe
3O
4The magnetic nano particle period of the day from 11 p.m. to 1 a.m is coated on particle surface with water soluble starch, and concentration of reaction solution makes biological magnetic fluid then, and this method unavoidably can be introduced impurity such as inorganic salts.
Further retrieval is found, Chinese patent literature CN101206944, and open day 2008-6-25 has put down in writing a kind of " preparation method of bioavailability water-based magnetofluid ", and this method is to adopt classical chemical coprecipitation to produce Fe earlier
3O
4Magnetic nano-particle adds sodium gluconate aqueous solution then in the dispersion liquid of product, stir ultrasonic preparation water-based magnetic fluid.The Fe that classical coprecipitation prepares
3O
4The nano particle diameter wider distribution, degree of crystallinity is low, contains intermediate impurity effect purity, and chemical stability and dispersion stabilization have much room for improvement.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of preparation method of water-based biological magnetic fluid is provided, utilize the high-temperature liquid-phase Hydrolyze method to use single source of iron can prepare the water-soluble Fe of good biocompatibility through single step reaction
3O
4Magnetic nano-particle, the nano particle diameter narrowly distributing, homogeneity is good, degree of crystallinity is high, controllability is strong, gained water-based biological magnetic fluid stability and good biocompatibility, the magnetic response usefulness of biological magnetic fluid and rheological behavior can comprise that kind, structure and the clad ratio of coating regulate and control by the surface characteristic of magnetic nano-particle.Advantages such as the present invention has that the preparation method is simple, good reproducibility, controllability are strong.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
The first step, trivalent iron salt and the water soluble polymer mol ratio with 300: 1 ~ 1000: 1 is dissolved in the diethylene glycol (DEG) (DEG); stirring reaction heats up under the nitrogen protection environment; be injected into the diethylene glycol monomethyl ether solution of 0.1 ~ 0.3 volume ratio then rapidly and continue to add thermal response, obtain the magnetic fluid base fluid.
Described trivalent iron salt is a kind of in iron chloride or the ferric sulfate, and its concentration in DEG solution is 0.02-0.06g/mL;
Described water soluble polymer is a kind of in Sensor Chip CM 5, polyethylene glycol (PEG), polyvinylpyrrolidone (PVP) or the polyacrylamide;
The reaction of described high-temperature stirring is meant: be 200-600rpm stirring reaction 15-45 minute with the mixing speed under 200-240 ℃ of environment;
The preparation method of described diethylene glycol monomethyl ether solution is: NaOH is added among the DEG, and after the stirring and dissolving reaction, preparing concentration is the diethylene glycol monomethyl ether solution of 0.1-0.5g/mL under the nitrogen protection, and the cooling insulation is at 70-90 ℃ then.
The reaction of described stirring and dissolving is meant: be 200-600rpm stirring reaction 0.5-1.5 hour with the mixing speed under 100-140 ℃ of environment.
Second the step, in the magnetic fluid base fluid, add acetone, through the magnet adsorbing separation, wash and be scattered in deionized water after in prepare water-based biological magnetic fluid.
Described washing is meant: adopt acetone to clean 3-5 time.
The present invention has substantive distinguishing features and marked improvement, and the present invention possesses following advantage and positive role: 1. simple, efficient, the good reproducibility of preparation method.2. the magnetic nano-particle narrow diameter distribution that makes, homogeneity is good, degree of crystallinity is high, controllability is strong.3. the good stability of biological magnetic fluid, good biocompatibility.4. biological magnetic fluid magnetic response usefulness and rheological behavior are controlled.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
NaOH is added among the DEG, and nitrogen protection is warming up to that stirring reaction made NaOH dissolve fully in 0.5 hour under 100 ℃, 200rpm condition in DEG, and preparing concentration is the diethylene glycol monomethyl ether solution of 0.1g/mL, and the cooling insulation is stand-by under 70 ℃ of conditions then.
Take by weighing iron chloride and Sensor Chip CM 5 joins among the DEG according to the ratio of 300: 1 amount of substances; being mixed with concentration is the DEG solution of 0.02g/mL; nitrogen protection was warming up under 200 ℃, 200rpm condition stirring reaction 15 minutes; then diethylene glycol monomethyl ether solution is expelled to rapidly (the diethylene glycol monomethyl ether solution of injection and the volume ratio of reactant mixture are 1: 10) in the said mixture, continued to add thermal response 0.5 hour.
Reaction adds acetone after finishing in product, the magnet adsorbing separation, and acetone cleans 3 times, is scattered in to prepare water-based biological magnetic fluid in the deionized water.
The water-soluble Fe for preparing
3O
4Magnetic nano-particle does not have obvious aggregate and exists, and particle size distribution is narrower, and average grain diameter is about 3nm, and clad ratio is 7%, can be scattered in the stable magnetic fluid of formation in the deionized water, does not have obvious sedimentation.
Embodiment 2
NaOH is added among the DEG, and nitrogen protection is warming up to that stirring reaction made NaOH dissolve fully in 1 hour under 120 ℃, 400rpm condition in DEG, and preparing concentration is the diethylene glycol monomethyl ether solution of 0.3g/mL, and the cooling insulation is stand-by under 80 ℃ of conditions then.
Take by weighing ferric sulfate and polyethylene glycol (PEG) joins among the DEG according to the ratio of 500: 1 amount of substances; being mixed with concentration is the DEG solution of 0.04g/mL; nitrogen protection was warming up under 220 ℃, 400rpm condition stirring reaction 30 minutes; then diethylene glycol monomethyl ether solution is expelled to rapidly (the diethylene glycol monomethyl ether solution of injection and the volume ratio of reactant mixture are 2: 10) in the said mixture, continued to add thermal response 1 hour.
Reaction adds acetone after finishing in product, the magnet adsorbing separation, and acetone cleans 4 times, is scattered in to prepare water-based biological magnetic fluid in the deionized water.
The water-soluble Fe for preparing
3O
4Magnetic nano-particle does not have obvious aggregate and exists, and particle size distribution is narrower, and average grain diameter is about 4nm, and clad ratio is 5%, can be scattered in the stable magnetic fluid of formation in the deionized water, does not have obvious sedimentation.
Embodiment 3
NaOH is added among the DEG, and nitrogen protection is warming up to that stirring reaction made NaOH dissolve fully in 1.5 hours under 140 ℃, 600rpm condition in DEG, and preparing concentration is the diethylene glycol monomethyl ether solution of 0.5g/mL, and the cooling insulation is stand-by under 90 ℃ of conditions then.
Take by weighing iron chloride and polyvinylpyrrolidone (PVP) joins among the DEG according to the ratio of 1000: 1 amount of substances; being mixed with concentration is the DEG solution of 0.06g/mL; nitrogen protection was warming up under 240 ℃, 600rpm condition stirring reaction 45 minutes; then diethylene glycol monomethyl ether solution is expelled to rapidly (the diethylene glycol monomethyl ether solution of injection and the volume ratio of reactant mixture are 3: 10) in the said mixture, continued to add thermal response 1.5 hours.
Reaction adds acetone after finishing in product, the magnet adsorbing separation, and acetone cleans 5 times, is scattered in to prepare water-based biological magnetic fluid in the deionized water.
The water-soluble Fe for preparing
3O
4Magnetic nano-particle does not have obvious aggregate and exists, and particle size distribution is narrower, and average grain diameter is about 5nm, and clad ratio is 4%, can be scattered in the stable magnetic fluid of formation in the deionized water, does not have obvious sedimentation.
Embodiment 4
NaOH is added among the DEG, and nitrogen protection is warming up to that stirring reaction made NaOH dissolve fully in 1 hour under 120 ℃, 400rpm condition in DEG, and preparing concentration is the diethylene glycol monomethyl ether solution of 0.3g/mL, and the cooling insulation is stand-by under 80 ℃ of conditions then.
Take by weighing ferric sulfate and polyacrylamide joins among the DEG according to the ratio of 500: 1 amount of substances; being mixed with concentration is the DEG solution of 0.04g/mL; nitrogen protection was warming up under 220 ℃, 400rpm condition stirring reaction 30 minutes; then diethylene glycol monomethyl ether solution is expelled to rapidly (the diethylene glycol monomethyl ether solution of injection and the volume ratio of reactant mixture are 2: 10) in the said mixture, continued to add thermal response 1 hour.
Reaction adds acetone after finishing in product, the magnet adsorbing separation, and acetone cleans 4 times, is scattered in to prepare water-based biological magnetic fluid in the deionized water.
The water-soluble Fe for preparing
3O
4Magnetic nano-particle does not have obvious aggregate and exists, and particle size distribution is narrower, and average grain diameter is about 4nm, and clad ratio is 5%, can be scattered in the stable magnetic fluid of formation in the deionized water, does not have obvious sedimentation.
Embodiment 1-4 effect is as follows:
The water-soluble Fe that embodiment 1-4 prepares
3O
4Magnetic nano-particle, narrow diameter distribution, homogeneity is good, degree of crystallinity is high, controllability is strong, be scattered in the stability and the good biocompatibility of gained water-based biological magnetic fluid in the deionized water, kind, structure and the clad ratio of the coating that magnetic response usefulness and rheological behavior can be by magnetic nano-particles are regulated and control.
Claims (7)
1. the preparation method of a water-based biological magnetic fluid is characterized in that, may further comprise the steps:
The first step, trivalent iron salt and the water soluble polymer mol ratio with 300: 1 ~ 1000: 1 is dissolved in the diethylene glycol (DEG), stirring reaction heats up under the nitrogen protection environment;
Be injected into the diethylene glycol monomethyl ether solution of 0.1 ~ 0.3 volume ratio then rapidly and continue to add thermal response, obtain the magnetic fluid base fluid;
Second the step, in the magnetic fluid base fluid, add acetone, through the magnet adsorbing separation, wash and be scattered in deionized water after in prepare water-based biological magnetic fluid.
2. the preparation method of water-based biological magnetic fluid according to claim 1 is characterized in that, described trivalent iron salt is a kind of in iron chloride or the ferric sulfate, its concentration in diethylene glycol solution: 0.02-0.06g/mL.
3. the preparation method of water-based biological magnetic fluid according to claim 1 is characterized in that, described water soluble polymer is a kind of in Sensor Chip CM 5, polyethylene glycol, polyvinylpyrrolidone or the polyacrylamide.
4. the preparation method of water-based biological magnetic fluid according to claim 1 is characterized in that, the reaction of described high-temperature stirring is meant: be 200-600rpm stirring reaction 15-45 minute with the mixing speed under 200-240 ℃ of environment.
5. the preparation method of water-based biological magnetic fluid according to claim 1; it is characterized in that; the preparation method of described diethylene glycol monomethyl ether solution is: NaOH is added in the diethylene glycol (DEG); after stirring and dissolving is reacted under the nitrogen protection; preparing concentration is the diethylene glycol monomethyl ether solution of 0.1-0.5g/mL, and the cooling insulation is at 70-90 ℃ then.
6. the preparation method of water-based biological magnetic fluid according to claim 1 is characterized in that, the reaction of described stirring and dissolving is meant: be 200-600rpm stirring reaction 0.5-1.5 hour with the mixing speed under 100-140 ℃ of environment.
7. the preparation method of water-based biological magnetic fluid according to claim 1 is characterized in that, described washing is meant: adopt acetone to clean 3-5 time.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100161A (en) * | 2019-12-24 | 2020-05-05 | 中国安全生产科学研究院 | Magnetic nano composite material for ATRP reaction and preparation method thereof |
| CN113299475A (en) * | 2021-05-31 | 2021-08-24 | 华中科技大学 | Water-based magnetofluid and in-situ growth preparation method and application thereof |
-
2010
- 2010-01-25 CN CN201010300662A patent/CN101719407A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100161A (en) * | 2019-12-24 | 2020-05-05 | 中国安全生产科学研究院 | Magnetic nano composite material for ATRP reaction and preparation method thereof |
| CN113299475A (en) * | 2021-05-31 | 2021-08-24 | 华中科技大学 | Water-based magnetofluid and in-situ growth preparation method and application thereof |
| CN113299475B (en) * | 2021-05-31 | 2022-05-31 | 华中科技大学 | Water-based magnetofluid and in-situ growth preparation method and application thereof |
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Open date: 20100602 |