CN101647780B - Core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and preparation method thereof - Google Patents

Core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and preparation method thereof Download PDF

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CN101647780B
CN101647780B CN2009100932240A CN200910093224A CN101647780B CN 101647780 B CN101647780 B CN 101647780B CN 2009100932240 A CN2009100932240 A CN 2009100932240A CN 200910093224 A CN200910093224 A CN 200910093224A CN 101647780 B CN101647780 B CN 101647780B
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CN101647780A (en
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张慧
盘登科
范婷
陈建刚
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The present invention relates to a core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and a preparation method thereof, belonging to the technical field of magnetic nano material technology and drug slow/control release technology. The magnetic nano-composite particle has a typical core-shell structure. The preparation method comprises the following steps: preparing a nano ferroferric oxide particle with a controllable particle diameter and even distribution in advance by adopting a solvent thermal method, and then coating a layer of organic carbon being rich in hydroxy on the surface of the particle; further coating inorganic anion intercalation houghite with different thickness on the surface of the particle through coprecipitation self assembly, obtaining a magnetic control targeting drug carrier with the core-shell structure through baking, and then obtaining a magnetic drug-loaded nano-particle having the core-shell structure and the slow/control release performance by means of a structure memory effect load antiinflammatory agent or anticarcinogen with a houghite structure. The invention has the advantages that the prepared novel magnetic nanocomposite particle has even particle diameter distribution and integrated core-shell structure.

Description

Based on Fe 3O 4With core-shell type magnetic nano-composite particle of hydrotalcite and preparation method thereof
Technical field
The invention belongs to magnetic Nano material technology and medicine sustained and controlled release technical field, particularly relate to a kind of Fe 3O 4With core-shell type magnetic nano-composite particle of magnalium hydrotalcite and preparation method thereof.
Background technology
In recent years, the magnetic Nano complex of functionalization particularly magnetic Nano medicine carrying particle on biological medicine, caused widely and to have paid close attention to (M.De, people such as P.S., Adv.Mater., 2008,20,1-17).After magnetic Nano medicine carrying particle enters in the human body by injection or oral mode, apply the magnetic field of certain intensity in the outside of diseased region, utilize the performance of inducing in magnetic field, the engulfing of macrophage that can avoid reticuloendothelial system makes the magnetic medicine carrier gathering navigate to diseased region.Subsequently, medicine is located release in every way, concentrates on diseased region and plays a role, thereby reduced dispenser dosage, (Lubbe, A.S. wait the people, Journal of Surgical Research to reach the effect of efficient, quick-acting and low toxicity, 2001,95,200-206).In recent years, researcher has been developed many magnetic medicine carriers, comprises active carbon/Fe, starch/Fe 3O 4, shitosan/Fe 3O 4, mesoporous silicon/Fe 2O 3Or Fe 3O 4, high molecular polymer/Fe 3O 4, medicament intercalated houghite/MgFe 2O 4Deng, in the hope of behind carrying medicament by the guiding of externally-applied magnetic field reach magnetic control target to the purpose of locating therapy disease (Zhang, the people such as H., J.Mater.Chem., 2009,19,3069-3077).But, shortcoming such as still there are many problems in transmission of this magnetic target medicine and Controlled Release System, and inhomogeneous as the particle size distribution of magnetic Nano medicine carrying particle, drug loading is lower, and magnetic is more weak relatively.Therefore, further seek suitable pharmaceutical carrier and magnetisable material and prepare key subject and the research emphasis that the uniform magnetic Nano medicine carrying of particle diameter particle is the transmission of current magnetic target medicine and control release field.
Brucite (LDH) is the host-guest lamellar structure compound of a class function admirable, receives much attention at catalysis, photochemistry and biomedicine field in recent years.Because brucite has the recoverability (structure memory effect) of structure after unique interlayer anion interchangeability and the appropriate roasting, many medicines comprise that anti-inflammatory agent and anticarcinogen etc. are arrived hydrotalcite layers by intercalation, prepare the good sustained-release preparation of the better sustained release performance of a class biocompatibility.The segregative advantage of synthetic hydrotalcite sustained release performance and magnetic nano-particle, the people such as Zhang have prepared a class based on medicament intercalated houghite and magnesium ferrite (MgFe 2O 4) magnetic Nano medicine carrying particle, find that it has typical nucleocapsid structure and significant magnetic control drug sustained release performance (a.Zhang, the people such as H., J.Mater.Chem., 2009,19,3069-3077; B. Chinese invention patent 2006101133260).And people such as Gabriela have prepared magnetic aspirin intercalated houghite and carried out serial sign, find that it has stronger magnetic, the surface that aspirin and magnetic particle coexist as the aspirin intercalated houghite forms a kind of random complex (Gabriela, C. wait the people, Journal of Magnetismand Magnetic Materials, 2007,311,26-30).Recently, the method that people such as Li adopt layer assembly roasting after the surface of ferroso-ferric oxide particle coats brucite obtain a kind of multifunction magnetic composite oxides (Li, people such as L., Angew.Chem.Int.Ed., 2009,48,1-6).Yet, the existing more or less of the magnetic Nano medicine carrying particle in these researchs such as morphology control and immature, magnetic relatively a little less than, shortcomings such as complicated process of preparation, limited they at magnetic control target to the application aspect locating therapy and the medicine sustained release.
Therefore, this patent adopts solvent-thermal method to prepare in advance the tri-iron tetroxide (Fe that particle diameter is controlled and be evenly distributed 3O 4) nano particle, then it is carried out finishing, make its surface coat the organic carbon that one deck is rich in hydroxyl.Further coat the inorganic anion intercalated houghite of different-thickness on its surface by the co-precipitation self assembly, obtain having the magnetic control target medicine carrier of nucleocapsid structure through roasting, then by the structure memory effect carrying medicament (ibuprofen of brucite, or diclofenac, or doxifluridine) obtains a kind of novel magnetic nano-composite particle with nucleocapsid structure and magnetic targeting sustained and controlled release performance.It is simple relatively that this magnetic nano-composite particle has preparation technology, and particle size distribution is even, and nucleocapsid structure is complete, and magnetic is stronger, and advantages such as good biocompatibility are the magnetic control target medicine sustained and controlled release preparations of a class function admirable.
Summary of the invention
The object of the present invention is to provide a kind of Fe 3O 4With core-shell type magnetic nano-composite particle of magnalium hydrotalcite and preparation method thereof, it is inhomogeneous to have solved general magnetic target medicine preparation particle diameter, is difficult to control the imperfect problem that affects pharmacology stability of particle size and nucleocapsid structure.
The present invention adopts solvent-thermal method to prepare the ferriferrous oxide nano-particle that particle diameter is controlled and be evenly distributed in advance, coats the organic carbon that one deck is rich in hydroxyl on its surface then.Further coat the inorganic anion intercalated houghite of different-thickness on its surface by the co-precipitation self assembly, obtain having the magnetic control target medicine carrier of nucleocapsid structure through appropriate roasting, then by the recoverability load anti-inflammatory agent or the anticarcinogen (ibuprofen of hydrotalcite structure, or diclofenac, or doxifluridine) obtains a kind of novel magnetic Nano medicine carrying particle with nucleocapsid structure and magnetic targeting sustained and controlled release performance.
Magnetic nano-composite particle has typical nucleocapsid structure.Shell is medicament intercalated houghite (drug-LDH), and crystal structure is the supramolecular crystal structure of houghite material, and its thickness can be via changing Fe 3O 4In the 20-50nm scope, carry out modulation with the content of magnalium hydrotalcite.Stratum nucleare is Fe 3O 4Nano particle, its particle diameter can carry out modulation to adapt to different requirements in the 100-430nm scope.
The composition of magnetic nano-composite particle of the present invention is:
Fe 3O 4@drug-LDH, Fe 3O 4Be ferriferrous oxide nano-particle, drug-LDH is medicament intercalated houghite.
Its quality percentage composition is: Fe 30 4: 50%～85%; Drug-LDH:15%～50%; Drug:6%～15% is mass percent.Wherein drug-LDH is IBU-LDH, any one among DIC-LDH and the DFUR-LDH.(IBU represents the brufen anion, and DIC represents the diclofenac anion, and DFUR represents the doxifluridine anion; )
The slow release lasting period of magnetic nano-composite particle is 1.5～8.5 hours.Specific saturation magnetization is 8.7～20.4AM 2/ Kg.
The concrete preparation process of hydrotalcite doxifluridine slow release formulation of the present invention is:
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.0125～0.2mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle size range be 100～430nm, specific saturation magnetization σ sBe 54.3～88.7Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C is re-dispersed in the ethanol and is kept in the port grinding bottle stand-byly, and wherein C represents the carbon decorative layer.The Fe that above-mentioned steps obtains 3O 4The particle size range of@C is 120～470nm, and wherein carbon decorative layer thickness is 10～20nm, specific saturation magnetization σ sBe 48.4～75.6Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.0875～0.35mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.025～0.1mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Deionized water washing three times (adopting magnetic to separate in the washing process), resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH, wherein LDH is the nitrate anion hydrotalcite.The Fe that above-mentioned steps obtains 3O 4The particle size range of@C@LDH is 160～570nm, and wherein the LDH layer thickness is 20～50nm, specific saturation magnetization σ sBe 40.5～70.7Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 1～5 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO, wherein LDO is resulting composite oxides after the LDH roasting.The Fe that above-mentioned steps obtains 3O 4The particle size range of@LDO is 130～510nm, and wherein the LDO layer thickness is 15～40nm, specific saturation magnetization σ sBe 10.9～25.2Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g medicine (ibuprofen, or diclofenac, or doxifluridine) and place four-hole boiling flask, logical in advance N 2Add 100ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 7.2～12.8, N 2Under the protective condition, 60～70 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@Drug-LDH, wherein Drug-LDH is medicament intercalated houghite.The Fe that above-mentioned steps obtains 3O 4The particle size range of@Drug-LDH is 150～530nm, and wherein the Drug-LDH layer thickness is 20～50nm, and the medicine carrying amount is 6～15%, specific saturation magnetization σ sBe 8.7～20.4Am 2/ kg, the slowly-releasing lasting period is 1.5～8.5 hours.
Magnetic nano-composite particle Fe among the present invention 3O 4@Drug-LDH has that particle diameter is controlled and be evenly distributed, and magnetic is stronger, and good dispersion and medicine carrying amount high are highly suitable for the transmission of magnetic target medicine location and magnetic control drug release, are expected to obtain practical application in magnetic target therapy tumour and other disease.
Advantage of the present invention is:
[1] prepared a kind of novel magnetic nano-composite particle, its particle diameter is controlled and be evenly distributed, and nucleocapsid structure is complete.Its surface has coated one deck medicament intercalated houghite, has given its preferably biocompatibility and sustained drug release effect; Its stratum nucleare is by ferromagnetic Fe 3O 4Nano particle forms, and makes it be expected to become good magnetic target medicine system, and obtain practical application in magnetic target therapy tumour and other disease.
[2] adopt the roasting restoring method to prepare magnetic nano-composite particle first, with respect to reported method in the document, simpler the method for the layer assembly that the preparation technology of resulting magnetic nano-composite particle reports in document in this patent, easy operating is applicable to large-scale production.
[3] by adjusting the Fe in the magnetic nano-composite particle 3O 4The size of nano particle and the thickness of Drug-LDH can be realized easily that structure, magnetic, particle diameter, medicine carrying amount, the medicament slow release lasting period to this magnetic nano-composite particle carried out modulation, thereby satisfy different actual demands.
The specific embodiment
Embodiment 1
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.0125mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle diameter be 100nm, specific saturation magnetization σ sBe 54.3Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after the Magnetic Isolation 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C is about 120nm, and wherein carbon decorative layer thickness is about 10nm, specific saturation magnetization σ sBe 48.4Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.0875mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.025mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Deionized water washing three times (adopting magnetic to separate in the washing process), resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C@LDH is about 160nm, and wherein the LDH layer thickness is about 20nm, specific saturation magnetization σ sBe 40.5Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 5 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO.The Fe that above-mentioned steps obtains 3O 4The particle size range of @LDO is about 130nm, and wherein the LDO layer thickness is about 15nm, specific saturation magnetization σ sBe 10.9Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g doxifluridine (DFUR) and place four-hole boiling flask, logical in advance N 2Add 100ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 7.2, N 2Under the protective condition, 60 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@DFUR-LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @DFUR-LDH is about 150nm, and wherein the DFUR-LDH layer thickness is about 25nm, and drug loading is 6%, specific saturation magnetization σ sBe 8.7Am 2/ kg, the slow release lasting period is about 3 hours.
Embodiment 2
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.025mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle diameter be 150nm, specific saturation magnetization σ sBe 77.1Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, Magnetic Isolation went out Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C is about 190nm, and wherein carbon decorative layer thickness is about 20nm, specific saturation magnetization σ sBe 68.8Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.35mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.1mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Three times (adopting Magnetic Isolation in the washing process) of deionized water washing, resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C@LDH is about 290nm, and wherein the LDH layer thickness is about 50nm, specific saturation magnetization σ sBe 54.7Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 2 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO.The Fe that above-mentioned steps obtains 3O 4The particle size range of @LDO is about 210nm, and wherein the LDO layer thickness is about 40nm, specific saturation magnetization σ sBe 13.7Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g diclofenac (DIC) and place four-hole boiling flask, logical in advance N 2Add 100ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 12.8, N 2Under the protective condition, 70 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@DIC-LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @DIC-LDH is about 250nm, and wherein the DIC-LDH layer thickness is 50nm, and drug loading is 15%, specific saturation magnetization σ sBe 8.9Am 2/ kg, the slow release lasting period is about 8.5 hours.
Embodiment 3
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.1mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle diameter be 260nm, specific saturation magnetization σ sBe 85.4Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C is about 280nm, and wherein carbon decorative layer thickness is about 10nm, specific saturation magnetization σ sBe 72.8Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.175mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.05mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Deionized water washing three times (adopting magnetic to separate in the washing process), resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C@LDH is about 340nm, and wherein the LDH layer thickness is about 30nm, specific saturation magnetization σ sBe 54.7Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 1 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO.The Fe that above-mentioned steps obtains 3O 4The particle size range of @LDO is about 330nm, and wherein the LDO layer thickness is 25nm, specific saturation magnetization σ sBe 14.9Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g doxifluridine (DFUR) and place four-hole boiling flask, logical in advance N 2Add 100ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 7.2, N 2Under the protective condition, 60 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@DFUR-LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @DFUR-LDH is about 350nm, and wherein the DFUR-LDH layer thickness is 45nm, and drug loading is 9.7%, specific saturation magnetization σ sBe 10.1Am 2/ kg, the slow release lasting period is about 6 hours.
Embodiment 4
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.2mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle diameter be 430nm, specific saturation magnetization σ sBe 88.7Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C is about 470nm, and wherein carbon decorative layer thickness is about 20nm, specific saturation magnetization σ sBe 75.6Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.35mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.1mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Deionized water washing three times (adopting magnetic to separate in the washing process), resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C@LDH is about 570nm, and wherein the LDH layer thickness is about 50nm, specific saturation magnetization σ sBe 64.1Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 1 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO.The Fe that above-mentioned steps obtains 3O 4The particle size range of @LDO is about 500nm, and wherein the LDO layer thickness is 35nm, specific saturation magnetization σ sBe 25.2Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g doxifluridine (DFUR) and place four-hole boiling flask, logical in advance N 2Add 100ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 7.2, N 2Under the protective condition, 60 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@DFUR-LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @DFUR-LDH is about 530nm, and wherein the DFUR-LDH layer thickness is about 50nm, and drug loading is 7.5%, specific saturation magnetization σ sBe 20.4Am 2/ kg, the slow release lasting period is about 5 hours.
Embodiment 5
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.1mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle diameter be 260nm, specific saturation magnetization σ sBe 85.4Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C is about 280nm, and wherein carbon decorative layer thickness is about 10nm, specific saturation magnetization σ sBe 72.8Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.175mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.05mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Deionized water washing three times (adopting magnetic to separate in the washing process), resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C@LDH is about 340nm, and wherein the LDH layer thickness is about 30nm, specific saturation magnetization σ sBe 54.7Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 1 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO.The Fe that above-mentioned steps obtains 3O 4The particle size range of @LDO is about 330nm, and wherein the LDO layer thickness is 15nm, specific saturation magnetization σ sBe 14.9Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g ibuprofen (IBU) and place four-hole boiling flask, logical in advance N 2Add 100ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 10.0, N 2Under the protective condition, 60 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@IBU-LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @IBU-LDH is about 330nm, and wherein the IBU-LDH layer thickness is about 35nm, and drug loading is 11.9%, specific saturation magnetization σ sBe 11.9Am 2/ kg, the slow release lasting period is about 7 hours.
Embodiment 6
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.1mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24.Resulting solution is added in the 500ml autoclave, then 200 ℃ of following crystallization 8 hours.The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid.The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4Particle diameter be 260nm, specific saturation magnetization σ sBe 85.4Am 2/ kg.
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, 180 ℃ of lower crystallization 8 hours.After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C is about 280nm, and wherein carbon decorative layer thickness is about 10nm, specific saturation magnetization σ sBe 72.8Am 2/ kg.
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.0875mol/L.Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask.Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.025mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2.At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of following vigorous stirring.Crystallization obtains the grey black suspension after 48 hours, with taking off CO 2Deionized water washing three times (adopting magnetic to separate in the washing process), resulting grey black solid is distributed in the methyl alcohol preserves called after Fe 3O 4@C@LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @C@LDH is about 320nm, and wherein the LDH layer thickness is about 20nm, specific saturation magnetization σ sBe 61.2Am 2/ kg.
With gained Fe 3O 4@C@LDH vacuum drying, the roasting pipe of packing into after the grinding, in advance logical N 230 minutes.At N 2Under the protective condition with 1 ℃ of min -1Be warming up to 500 ℃, constant temperature 2 hours is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO.The Fe that above-mentioned steps obtains 3O 4The particle size range of @LDO is about 310nm, and wherein the LDO layer thickness is about 15nm, specific saturation magnetization σ sBe 11.5Am 2/ kg.
(3) preparation of magnetic nano-composite particle
Take by weighing 0.5g doxifluridine (DFUR) and place four-hole boiling flask, logical in advance N 2Add 1O0ml after 20 minutes and take off CO 2Deionized water.Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 7.2, N 2Under the protective condition, 70 ℃ were stirred crystallization 24 hours.Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains dark gray powder under the vacuum then, called after Fe 3O 4@DFUR-LDH.The Fe that above-mentioned steps obtains 3O 4The particle diameter of @DFUR-LDH is about 300nm, and wherein the DFUR-LDH layer thickness is about 20nm, and drug loading is 7.2%, specific saturation magnetization σ sBe 9.4Am 2/ kg, the slow release lasting period is about 1.5 hours.

Claims (2)

1. based on Fe 3O 4Core-shell type magnetic nano-composite particle with hydrotalcite is characterized in that, magnetic nano-composite particle has typical nucleocapsid structure, and its composition is: Fe 3O 4@drug-LDH, its quality percentage composition is: Fe 3O 4: 50%～85%; Drug-LDH:15%～50%, drug:6%～15% is mass percent; Wherein drug-LDH is IBU-LDH, a kind of among DIC-LDH and the DFUR-LDH; Described IBU represents the brufen anion; DIC represents the diclofenac anion; DFUR represents the doxifluridine anion; The slowly-releasing lasting period of magnetic nano-composite particle is 1.5～8.5h; Specific saturation magnetization is 8.7～20.4AM 2/ Kg;
The shell of nucleocapsid structure is medicament intercalated houghite, and crystal structure is the supramolecular crystal structure of houghite material, and its thickness is by changing Fe 3O 4In the interval of 20-50nm, carry out modulation with the content of magnalium hydrotalcite; Stratum nucleare is Fe 3O 4Nano particle, its particle diameter carry out modulation in the interval of 100-430nm.
One kind to prepare claim 1 described based on Fe 3O 4Method with the core-shell type magnetic nano-composite particle of magnalium hydrotalcite is characterized in that technology is:
(1) Fe 3O 4Preparation and finishing thereof
Take by weighing FeCl 36H 2O and sodium acetate add in the 400ml ethylene glycol and at room temperature are stirred to and dissolve formation finely dispersed yellow solution, wherein FeCl 36H 2The molar concentration of O is 0.0125～0.2mol/L, sodium acetate and FeCl 36H 2The molar concentration rate of O is 4.24; Resulting solution is added in the 500ml autoclave, then at 200 ℃ of lower crystallization 8h; The autoclave taking-up is naturally cooled to room temperature, with resulting Fe 3O 4Suspension respectively washs three times with ethanol and deionized water, adopts Nd-Fe-B permanent magnet to isolate Fe during washing 3O 4Solid; The washing finish after with resulting Fe 3O 4Solid is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by;
Take by weighing the above-mentioned Fe of 0.1g 3O 4Join the HNO of 150ml 0.1mol/L 3In, ultrasonic 10 minutes, with the deionized water washing once, magnetic was isolated Fe after magnetic separated 3O 4With resulting Fe 3O 4Be distributed in the glucose solution of 100ml 0.5mol/L, after ultrasonic 20 minutes resultant suspension added in the 100ml autoclave, at 180 ℃ of lower crystallization 8h; After finishing, crystallization respectively washs three times products obtained therefrom called after Fe with ethanol and deionized water 3O 4@C also is re-dispersed in the ethanol and is kept in the port grinding bottle stand-by;
(2) the synthetic and magnetic composite oxides of magnetic hydrotalcite precursor fires
Take by weighing 0.1g Fe 3O 4@C is distributed in the methanol solution of 60ml NaOH, and the molar concentration of NaOH is 0.0875～0.35mol/L; Above-mentioned suspension obtains solution A after ultrasonic 30 minutes and is transferred in the 250ml four-hole boiling flask; Other takes by weighing Mg (NO 3) 26H 2O and Al (NO 3) 29H 2O joins in the 60ml methyl alcohol, and ultrasonic the dissolving fully to solid obtains settled solution B, wherein Mg (NO 3) 26H 2The molar concentration of O is 0.025～0.1mol/L, Mg (NO 3) 26H 2O and Al (NO 3) 29H 2The molar concentration rate of O is 2; At N 2Under the protective condition solution B is slowly splashed in the solution A, and the HCl solution of the NaOH of employing 0.5mol/L or 0.5mol/L is adjusted the pH to 9.5 of above-mentioned reaction solution, 60 ℃ of lower vigorous stirring.Obtain the grey black suspension behind the crystallization 48h, with taking off CO 2Deionized water washing three times, resulting black solid is distributed in the methyl alcohol to be preserved, called after Fe 3O 4@C@LDH;
With gained Fe 3O 4The @C@LDH vacuum drying, the roasting pipe of packing into after the grinding, logical in advance N 230 minutes; At N 2Under the protective condition with 1～5 ℃ of min -1Be warming up to 500 ℃, constant temperature 2h is cooled to room temperature with furnace temperature then, obtains the magnetic Nano composite oxides and is designated as Fe 3O 4@LDO;
(3) preparation of magnetic nano-composite particle
Take by weighing the 0.5g medicine and place four-hole boiling flask, in advance logical N 2Add 100ml after 20 minutes and take off CO 2Deionized water; Other takes by weighing 0.1g Fe 3O 4@LDO adds in the flask, and adopting NaOH regulator solution pH value is 7.2～12.8, N 2Under the protective condition, 60～70 ℃ are stirred crystallization 24h; Product adopts and takes off CO 2Deionized water centrifuge washing to pH value is 7, and drying obtains black powder under the vacuum then, called after Fe 3O 4@Drug-LDH; Described medicine is brufen, or diclofenac, or doxifluridine.
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