CN101256870A - Double cladding water-based magnetofluid and method for producing the same - Google Patents

Double cladding water-based magnetofluid and method for producing the same Download PDF

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CN101256870A
CN101256870A CNA2007100327418A CN200710032741A CN101256870A CN 101256870 A CN101256870 A CN 101256870A CN A2007100327418 A CNA2007100327418 A CN A2007100327418A CN 200710032741 A CN200710032741 A CN 200710032741A CN 101256870 A CN101256870 A CN 101256870A
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CN100573750C (en
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苑星海
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Jiaying University
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Abstract

The present invention relates to a double covered water-based magnetic fluid and manufacture method thereof, the magnetic fluid includes water, nano Fe<SUB>3</SUB>O<SUB>4</SUB> granule and dispersing agent, which is characterized in that grain diameter of nano Fe<SUB>3</SUB>O<SUB>4</SUB> granule is 1-16 nm, dispersing agent is medicinal agaragar and polyethylene glycol at the covered surface of nano Fe<SUB>3</SUB>O<SUB>4</SUB> granule, compound granule particle diameter obtained by medicinal agaragar and polyethylene glycol at the covered surface of nano Fe<SUB>3</SUB>O<SUB>4</SUB> granule is smaller than 45nm; medicinal agaragar and polyethylene glycol is taken as dispersing agent, a double covered water-based magnetic fluid is produced by synthesizing of nano Fe<SUB>3</SUB>O<SUB>4</SUB> granule and modus of surface step-by-step modification, which surface has function group; activity group of carboxy group and hydroxyl group, etc make the double covered water-based magnetic fluid with good magnetic responsiveness, biological affinity, biodegradability and suspension stability, saturation magnetization of magnetic fluid is 1.0-10.0emu/g used in biomedicine field for special therapy and diagnose of medicine carrier etc.

Description

Double cladding water-based magnetofluid and preparation method thereof
Technical field
The invention belongs to nanoscale science and technology and biomedicine field, relate to a kind of double cladding water-based magnetofluid and preparation method thereof.
Technical background
So-called magnetic fluid claims magnetic liquid again; be magnetic nanoparticle high degree of dispersion and colloidal dispersion of forming in carrier fluid that will be adsorbed with surfactant; have the superparamagnetism of nano-solid material and the flowability of liquid concurrently; be a kind of novel liquid functional nano material, be widely used in fields such as sealing, lubricated, damping, grinding, separation, printing and dyeing printing and environmental protection.Magnetic fluid has expanded to cell separation, tumor thermotherapy, magnetic resonance imaging imaging and the targeting preparation etc. of biomedicine field in recent years.
Because non-water-based magnetic fluid has non-biocompatible, so biomedicine field mainly is a water-based magnetic fluid.And the water-based magnetic fluid that coats with surfactant is difficult to carry out surface-functionalized modification, and surface activity is not enough, thereby has limited the application at biomedicine field.The magnetic fluid that biomedicine field uses needs with hydrophilic macromolecule magnetic nanoparticle to be carried out coating decoration, can improve the biocompatibility of magnetic-particle, the active group that can connect other parts on the hydrophilic macromolecule, energy is the multiple functional polymer of load further, for example polypeptide, antibody, enzyme, DNA and RNA etc., thus prepare magnetic-particle carrier material with specific function.
The preparation biomedicine field is the surface modification of the synthetic and magnetic nanoparticle of magnetic nanoparticle with the key technology of magnetic fluid.At present existingly see that with water soluble starch the derivative of CN1822254A, shitosan sees that CN1702782A, glucan see that CN1750183A, polyamide-based dendritic amine polymer see that coating such as CN1913055A has prepared magnetic fluid for biological medicine.Prior art comes with some shortcomings, the one, in the synthetic technology of magnetic nanoparticle, majority is difficult to synthesize the magnetic nanoparticle that meets dimensional requirement fully, unsettled particle is removed with the method for centrifugation as CN1702782A, transmission electron microscope photo from this patent application, particle to cohere phenomenon obvious, illustrate that the controlled condition of synthetic reaction and the effect that coats with macromolecular material are not good enough; The 2nd, magnetic is on the weak side, and for example the saturation magnetization of the water-based magnetic fluid that provides of CN1702782A only is 1.6～2.5emu/g, and the water-based magnetic fluid saturation magnetization of all embodiment preparations is all less than 1.0emu/g.
Summary of the invention
The object of the invention just provides that a kind of particle diameter is littler, double cladding water-based magnetofluid of narrower, the strong magnetic response that distributes, high stability and preparation method thereof.
One of key technology of the present invention is further to have optimized nanometer Fe 3O 4The preparation technology of particle, from reactant concentration, mixing speed, pH value of solution value, reaction temperature to reaction time etc., control the nucleation rate and the nucleus growth speed of nano particle effectively, the particle diameter of nano particle can be removed underproof bulky grain without centrifugation all at the superparamagnetism range scale.
Two of key technology of the present invention is to select medicinal agar and polyethylene glycol as dispersant, nanometer Fe 3O 4The mode that synthetic and the surface modification of particle are carried out step by step prepares double cladding water-based magnetofluid, has the advantages that technology is simple, modifying process is easily controlled.
The present invention can realize by the following method: double cladding water-based magnetofluid comprises water, nanometer Fe 3O 4Particle and dispersant is characterized in that described nanometer Fe 3O 4Grain diameter is 1～16nm, nanometer Fe 3O 4The dispersant that particle surface coats is medicinal agar and Macrogol 4000～6000, nanometer Fe 3O 4The composite particles particle diameter that medicinal agar that particle surface coats and Macrogol 4000～6000 obtain is less than 45nm.The nanometer Fe of covering with medicinal agar and polyethylene glycol double-contracting 3O 4Uniform particles is scattered in aqueous phase, forms the water-based magnetic fluid that exists steady in a long-term.The nanometer Fe that medicinal agar and polyethylene glycol double-contracting are covered 3O 4Particle surface has a large amount of function group: carboxyl and hydroxyl isoreactivity group, make double cladding water-based magnetofluid have good magnetic responsiveness, bioaffinity, biodegradability and suspension stability, can be used for pharmaceutical carrier, further widen the range of application of magnetic fluid at modern biomedicine field as special treatment and diagnosis.
Preparation method's chemical precipitation method of double cladding water-based magnetofluid adopts chemical coprecipitation synthesis of nano Fe 3O 4Particle, nanometer Fe 3O 4Synthetic and the surface modification of particle are carried out step by step, and may further comprise the steps: (1) compound concentration respectively is the Fe of 0.1～0.8mol/L 3+And Fe 2+The aqueous solution is pressed Fe 3+With Fe 2+The ratio of amount of substance is 1.00～1.75 mixing, obtains mixed liquor; (2) mix liquid, with mass concentration 25%NH 3H 2O pours in the mixed liquor, and the volume ratio of mixed liquor and ammoniacal liquor is 100: 6-45, NH 3H 2The adding of O can drip or divide several times and pour into, mixing speed 500～3000r/min, and 25～45 ℃ of temperature, the pH value 9～11 of solution, reaction time 30～120min obtains nanometer Fe 3O 4Particle; (3) 0.1～1.0% medicinal agar of getting the iron gross mass is put into distilled water, medicinal agar and distilled water mass ratio are 1: 100, heat 80～95 ℃ and make it dissolving, pour in the step (2), mixing speed 500～3000r/min, 50～65 ℃ of temperature, the pH value 6～9 of solution, reaction 60～120min obtains the nanometer Fe that medicinal agar coats 3O 4Particle; (4) will contain the nanometer Fe that agar coats 3O 4The liquid of particle takes out, and with distilled water washing 3～5 times, adjust pH 4～5 disperses 10～60min with ultrasonic wave, and washing disperses and can intermittently hocket with ultrasonic wave; (5) 0.1～1.0% polyethylene glycol of getting the iron gross mass is put into distilled water and is made it dissolving, polyethylene glycol and distilled water mass ratio are 1: 100, pour into and carry out in the reactant liquor coating the second time, mixing speed 500～3000r/min, 50～65 ℃ of temperature, reaction 60～120min gets double cladding water-based magnetofluid.
The present invention has following advantage and effect:
1, the particle diameter of nano particle of the present invention is all at the superparamagnetism range scale, remove underproof bulky grain without centrifugation, have good magnetic responsiveness, bioaffinity, biodegradability and suspension stability, the saturation magnetization of magnetic fluid is 1.0～10.0emu/g.
2, medicinal agar and Macrogol 4000～6000th selected for use of the present invention, the most frequently used capsule material in the pharmacy, raw material is easy to get, and is cheap, can reduce the cost of magnetic fluid; Adopt the water-based magnetic fluid that double-contracting is covered to contain the multiple active group that can connect other parts simultaneously, be convenient to be connected with multiple medicine, protein, gene or cell etc., medicinal agar and polyethylene glycol also have certain stabilization to the medicine of some facile hydrolysis, thereby be more suitable for, and can be used as the magnetic target medicine carrier as the magnetic carrier material; The polyethylene glycol physicochemical property is stable, not only with water and with multiple organic solvent compatibility is arranged, and has enlarged the range of application of magnetic fluid, and broader applications are in biomedical sector.
3, the present invention has controlled the nucleation rate and the nucleus growth speed of nano particle effectively by further optimizing the chemical coprecipitation synthesis technique, makes Fe 3O 4Grain diameter is tiny and even; By optimizing modified technique and covering with agar, polyethylene glycol double-contracting, coat closelyr, have the advantages that covered effect is better, the nano particle monodispersity is good, suspending stabilized and life period is long.
Description of drawings
Fig. 1 amplifies 200,000 times TEM photo for double cladding water-based magnetofluid of the present invention.
Fig. 2 is the magneto optical effect photo of double cladding water-based magnetofluid of the present invention.
Embodiment
Below in conjunction with embodiment, the invention will be further elaborated.
Embodiment one
(1) takes by weighing 27.029g FeCl 36H 2O adds in the redistilled water boil, stirring and dissolving, be cooled to room temperature after, splash into 3～5mL watery hydrochloric acid, add 11.361g FeCl then 24H 2O, stirring and dissolving, mixed solution cumulative volume 1000mL, Fe in the mixed liquor 3+And Fe 2+Ratio by amount of substance is 1.75;
(2) mixed liquor is placed reactor preheating and stir and to make it abundant mixing, measure 85.0mL concentration and be 25% NH 3H 2O pours in the reactor, NH 3H 2The adding of O also can drip or divide several times and pour into, and mixing speed is progressively brought up to 2500r/min by 1000r/min, and temperature is controlled at 35 ℃, the pH value 10 of solution, and isothermal reaction 60min obtains nanometer Fe 3O 4Particle;
(3) take by weighing the medicinal agar of 0.06g and put into 6mL distilled water, heat 90 ℃ and make it dissolving, pour in the step (2), mixing speed is progressively brought up to 2500r/min by 1000r/min, 55 ℃ of temperature, and pH value of solution value 7～8, reaction 60min obtains the nanometer Fe that agar coats 3O 4Particle;
(4) will contain the nanometer Fe that agar coats 3O 4The liquid of particle takes out with second distillation water washing 3～5 times, adjusts its pH value to 5 with watery hydrochloric acid again, disperses 20min with ultrasonic wave;
(5) Macrogol 4000 that takes by weighing 0.05g is thrown and make it dissolving in the 5mL redistilled water, pours into and carries out in the reactant liquor coating second time, and mixing speed is progressively brought up to 2500r/min by 1000r/min, 55 ℃ of temperature, and reaction 60min must double cladding water-based magnetofluid.
The magnetic nanoparticle that double-contracting of the present invention is covered be shaped as almost spherical, iron-holder 8.792mg/mL, saturation magnetization is 2.0emu/g.Magnetic fluid of the present invention is through granularmetric analysis report test, 2～15nm, about 87.0%; 5.1～10nm is about 13.0%, particle diameter is at 2～10nm.
Embodiment two
(1) takes by weighing 108.116g FeCl 36H 2O is added in the redistilled water that boils, stirring and dissolving, be cooled to room temperature after, splash into 3～5mL HCl, add 45.444g FeCl then 24H 2O, stirring and dissolving, mixed solution cumulative volume 1000mL, Fe in the mixed liquor 3+And Fe 2+Ratio by amount of substance is 1.75;
(2) mixed liquor is placed reactor preheating and stir and to make it abundant mixing, get 325mL concentration and be 25% NH 3H 2O pours in the reactor, and mixing speed is progressively brought up to 3000r/min by 1000r/min, 35 ℃ of temperature, pH value of solution value 10, isothermal reaction 60min.Obtain nanometer Fe 3O 4Particle;
(3) take by weighing the medicinal agar of 0.24g and put into 24mL distilled water, heat 90 ℃ and make it dissolving, pour in the step (2), mixing speed is progressively brought up to 2500r/min by 1000r/min, 55 ℃ of temperature, pH value of solution value 7～8, reaction 60min obtains the nanometer Fe that agar coats 3O 4Particle;
(4) will contain the nanometer Fe that agar coats 3O 4The liquid of particle takes out with second distillation water washing 3～5 times, adjusts its pH value to 5 with watery hydrochloric acid again, disperses 25min with ultrasonic wave;
(5) Macrogol 6000 that takes by weighing 0.20g is thrown and make it dissolving in the 20mL redistilled water, pour into and carry out in the reactant liquor coating the second time, mixing speed is progressively brought up to 2500r/min by 1000r/min, 55 ℃ of temperature, reaction 60min gets double cladding water-based magnetofluid.
In this magnetic fluid, the magnetic nanoparticle that double-contracting is covered be shaped as almost spherical, particle diameter is at 2～15nm, iron-holder 35.168mg/mL, saturation magnetization is 3.7emu/g.

Claims (4)

1, water base magnetic sulphur body is covered in a kind of double-contracting, comprises water, nanometer Fe 3O 4Particle and dispersant is characterized in that described nanometer Fe 3O 4Grain diameter is 1～16nm, nanometer Fe 3O 4The dispersant that particle surface coats is medicinal agar and Macrogol 4000～6000, nanometer Fe 3O 4The composite particles particle diameter that medicinal agar that particle surface coats and polyethylene glycol obtain is less than 45nm.
2, a kind of preparation method of double cladding water-based magnetofluid is characterized in that may further comprise the steps:
(1) compound concentration is the Fe of 0.1～0.8mol/L respectively 3+And Fe 2+The aqueous solution is pressed Fe 3+With Fe 2+The ratio of amount of substance is 1.00～1.75 mixing, obtains mixed liquor;
(2) mix liquid, with mass concentration 25%NH 3H 2O pours in the mixed liquor, and the volume ratio of mixed liquor and ammoniacal liquor is 100: 6-45, and mixing speed 500～3000r/min, 25～45 ℃ of temperature, the pH value 9～11 of solution, reaction time 30～120min obtains nanometer Fe 3O 4Particle;
(3) 0.1～1.0% medicinal agar of getting the iron gross mass is put into distilled water, medicinal agar and distilled water mass ratio are 1: 100, heat 80～95 ℃ and make it dissolving, pour in the step (2), mixing speed 500～3000r/min, 50～65 ℃ of temperature, the pH value 6～9 of solution, reaction 60～120min obtains the nanometer Fe that medicinal agar coats 3O 4Particle;
(4) will contain the nanometer Fe that medicinal agar coats 3O 4The liquid of particle takes out, and with distilled water washing 3～5 times, adjust pH 4～5 disperses 10～60min with ultrasonic wave;
(5) 0.1～1.0% Macrogol 4000～6000 of getting the iron gross mass are put into distilled water and are made it dissolving, polyethylene glycol and distilled water mass ratio are 1: 100, pour into and carry out in the reactant liquor coating the second time, mixing speed 500～3000r/min, 50～65 ℃ of temperature, reaction 60～120min obtains double cladding water-based magnetofluid.
3,, it is characterized in that NH in the step (2) according to the described method for preparing double cladding water-based magnetofluid of claim 2 3H 2The adding of O can drip or divide several times and pour into.
4,, it is characterized in that washing disperses and can intermittently hocket with ultrasonic wave in the step (4) according to the described method for preparing double cladding water-based magnetofluid of claim 2.
CNB2007100327418A 2007-12-26 2007-12-26 Double cladding water-based magnetofluid and preparation method thereof Expired - Fee Related CN100573750C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102488636A (en) * 2011-12-22 2012-06-13 吴江市德佐日用化学品有限公司 Hand sanitizer
CN104538165A (en) * 2014-12-17 2015-04-22 河南工程学院 Method for preparing stable water base fluid
CN104637644A (en) * 2015-03-06 2015-05-20 山东大学 Particle coating method for preparing magnetic liquid
CN107595775A (en) * 2017-09-25 2018-01-19 江苏长龙国际贸易有限公司 A kind of preparation method of shelf stable form magnetic liposome material
JP2018133488A (en) * 2017-02-16 2018-08-23 学校法人同志社 Liquid magnet and liquid magnet manufacturing method
CN110828094A (en) * 2019-11-13 2020-02-21 黑龙江省科学院高技术研究院 Preparation method of magnetic fluid for high-magnetic-sedimentation-resistance sealing under strong magnetic field condition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102488636A (en) * 2011-12-22 2012-06-13 吴江市德佐日用化学品有限公司 Hand sanitizer
CN104538165A (en) * 2014-12-17 2015-04-22 河南工程学院 Method for preparing stable water base fluid
CN104637644A (en) * 2015-03-06 2015-05-20 山东大学 Particle coating method for preparing magnetic liquid
JP2018133488A (en) * 2017-02-16 2018-08-23 学校法人同志社 Liquid magnet and liquid magnet manufacturing method
CN107595775A (en) * 2017-09-25 2018-01-19 江苏长龙国际贸易有限公司 A kind of preparation method of shelf stable form magnetic liposome material
CN110828094A (en) * 2019-11-13 2020-02-21 黑龙江省科学院高技术研究院 Preparation method of magnetic fluid for high-magnetic-sedimentation-resistance sealing under strong magnetic field condition
CN110828094B (en) * 2019-11-13 2021-05-14 黑龙江省科学院高技术研究院 Preparation method of magnetic fluid for high-magnetic-sedimentation-resistance sealing under strong magnetic field condition

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