WO2008069561A1 - Vnanocapsule creuse en oxyde métallique et procédé d'élaboration - Google Patents

Vnanocapsule creuse en oxyde métallique et procédé d'élaboration Download PDF

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WO2008069561A1
WO2008069561A1 PCT/KR2007/006269 KR2007006269W WO2008069561A1 WO 2008069561 A1 WO2008069561 A1 WO 2008069561A1 KR 2007006269 W KR2007006269 W KR 2007006269W WO 2008069561 A1 WO2008069561 A1 WO 2008069561A1
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iron oxide
oxide hollow
hollow
nanocapsules
oxyhydroxide
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PCT/KR2007/006269
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English (en)
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Taeghwan Hyeon
Yuanzhe Piao
Jaeyun Kim
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Seoul National University Industry Foundation
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/04—Ferrous oxide [FeO]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/5115—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5192—Processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/02—Magnesia
    • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
    • C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/90—Other morphology not specified above
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Definitions

  • the present invention relates to a metal oxide hollow nanocapsule which is able to disperse well in aqueous systems and a method for preparing thereof.
  • said method is not economical in respect to the costs of the manufacturing equipment due to the autoclave.
  • the iron oxide nanomaterials produced by said method have limited applicability to the biomedical field since said iron oxide nanomaterials are of tubular form with a length of 300nm or have surfactants at the surface of said nanoparticles when produced with surfactants.
  • the report does not mention the water-dispersability of said nanomaterials.
  • Chem. 2004, 43, 6540. discloses the manufacture of hollow metal oxide nano- structures, wherein ⁇ -FeOOH undergoes pryolysis in a vacuum for a method of producing tubular metal oxide nano-structures.
  • the diameters of the produced tubes are relatively as large as 50nm and thus, the surface area of said tubes are as small as 19.06m 2 /g.
  • Xi Yei et. al. does not disclose the water-dispersability of said nanotubes.
  • the method for preparing iron oxide nanotubes disclosed by Chongwu Zhou et. al. ('Single crystalline magnetite nanotubes', J. Am. Chem. Soc. 2005, 127, 6.) is shown in Fig. 1.
  • a MgO nanorod is used as a template and is coated epitaxially with Fe 3 O 4 , and then MgO, the core material, is removed.
  • the nanotubes obtained from the above method have limited application in the biomedical field such as drug delivery etc. due to their sizes which are up to micrometers.
  • the traditional technique involves the use of specific equipment such as an autoclave in the manufacturing method, which is not economical in view of the equipment costs for manufacture, and thus is not only unsuitable for large-scale production, but there are also limitations in the applicability in the biomedical field due to the size of the synthesized nanomaterials, and furthermore, there is no progress in the research for dispersion in aqueous systems.
  • An object of the present invention is to provide a method for preparing metal oxide hollow nanocapsules with aqueous dispersablity which has superior uniform size distribution.
  • Another object of the present invention is to provide a method for preparing metal oxide hollow nanocapsules with aqueous dispersablity and superior uniform size distribution without the required use of an autoclave and which is economically applicable for large-scale production.
  • Yet another object of the present invention is to provide a metal oxide hollow nanocapsule with superior dispersion in aqueous systems and suitable size and shape for applications in the biomedical field.
  • Yet another object of the present invention is to provide an iron oxide hollow nanocapsule in which said metal oxide hollow nanocapsule acts as a delivery vehicle which carries physiologically active materials inside the nanocapsule.
  • the present invention provides a method for preparing metal oxide hollow nanocapsules, which comprises:
  • the type of nanomaterial prepared by the method of the present invention depends on the metal of the metal oxyhydroxide used, thus, the metal oxyhydroxide used in the method of the present invention is selected from ⁇ -FeOOH (akaganeite), ⁇ - AlOOH (boehmite), CoOOH (heterogenite), ⁇ -CrOOH (chromia aerogel), InOOH (indium oxyhydroxide), MnOOH (manganite), NiOOH (nickel oxyhydroxide), WOOH (tungsten oxyhydroxide), etc..
  • ⁇ -FeOOH akaganeite
  • ⁇ - AlOOH boehmite
  • CoOOH heteroOOH
  • ⁇ -CrOOH chromia aerogel
  • InOOH indium oxyhydroxide
  • MnOOH mangaganite
  • NiOOH nickel oxyhydroxide
  • WOOH tungsten oxyhydroxide
  • particulate metal oxyhydroxide which is relatively unstable compared to stoichiometrically stable metal oxide is used to form a silica coating layer around the metal oxyhydroxide particle by sol-gel reaction, and then, via heat treatment, a layer of metal oxide made from metal oxyhydroxide, with uniform thickness is formed inside the silica coating layer with its shape maintained by the silica coating layer, and consequently the hollow space is formed with the metal oxide layer.
  • the metal oxyhydroxide becomes pryolized and converts to a metal oxide which causes a decrease in volume, however, because the formed metal oxide adheres to the inner wall of the silica coating layer, it maintains the shape of the metal oxyhydroxide and thus the hollow nanocapsule is formed.
  • the desirable thickness of said silica coating layer is 2nm to 200nm for the reason that if the outer shell is too thin then it is difficult to maintain its shape integrity. If the outer shell is too thick then subsequent removal thereof may be difficult.
  • the metal oxide hollow nanocapsules can then be obtained by removing the silica coating layer.
  • the metal oxide hollow nanocapsule prepared according to the present invention has the unique characteristics of regulated particle size uniformity and good dispersion in aqueous systems.
  • the present invention provides metal oxide hollow nanocapsules prepared by method of the present invention
  • the present invention provides a metal oxide hollow nanocapsule which is made of hematite ((X-Fe 2 O 3 ) or magnetite (Fe 3 O 4 ).
  • said iron oxide hollow nanocapsules have the unique characteristics of a diameter of IOnm to 20nm and a length of 50nm to lOOnm wherein the shell thickness of spindle form is 5nm to 15nm.
  • said metal oxide hollow nanocapsule is able to carry physiologically active material and thus is suitable for use as a drug delivery vehicle.
  • the present invention provides a method for preparing metal oxide hollow nanocapsules, which comprises:
  • the metal oxyhydroxide is selected from the group consisting of ⁇ -FeOOH
  • ⁇ -FeOOH may be used to produce iron oxide hollow nanocapsules with high industrial applicability. More preferably, in the case when using the spindle form of ⁇ -FeOOH, since it can carry physiologically active materials it is suitable for use in the biomedical field.
  • FeOOH ferric-ferrous salt
  • the ⁇ -FeOOH according to the method of the present invention has the advantage of having a uniform size distribution, and as a result, the uniform size distribution of hollow nanocapsules was able to be aquired.
  • the particulate metal oxyhydroxide can be directly synthesized or can be used commercially. Said metal oxyhydroxide is dispersed in a mixture solution of water and alcohol, and then a silica precursor agent is added to the dispersed solution.
  • said alcohol is low alcohol since low alcohol has good miscibility with water and makes it easier to form the silica coating layer by sol-gel reaction of the silica precursor.
  • the silica precursor is added, in the presence of base catalyst, into the metal oxyhydroxide particle dispersed solution, the silica coating layer is formed around the metal oxyhydroxide particle by sol-gel reaction.
  • the silica precursor used in the step of forming the silica coating layer is at least one selected from the group consisting of TEOS (tetraethyl orthosilicate), TMOS (tetramethyl orthosilicate), or TBOS (tetrabutyl orthosilicate).
  • the basic catalysts used in the sol- gel reaction of step b) can be selected from the group consisting of ammonium hydroxide, potassium hydroxide, or sodium hydroxide.
  • the desirable thickness of said silica coating layer is 2nm to 200nm, for the reason that if the outer shell is too thin it is difficult to maintain its shape integrity, and if the outer shell is too thick then removal of the outer shell may be difficult.
  • the desirable temperature applied for heat treatment in step c) is between 400 to 1600 0 C, for the reason that in case the temperature of less than 400 0 C is applied in said heat treatment, the metal oxide does not form properly and thus crystallization of the metal oxide is difficult, and in the case that said temperature exceeds 1600 0 C, the silica coating will melt and cause extreme aggregation which will be a problem during removal.
  • the method of the present invention may further comprise a step of reduction during or after said heat treatment stage, and the metal oxide may be changed into the other material via reduction. For example, hematite metal oxide may be converted to magnetite via reduction. In this case, hydrogen gas or NaBH 4 etc. may be used as the reducing agent.
  • an inorganic base such as NaOH or KOH, or aqueous HF solution is used for the removal of the silica coating layer and it is much preferred to use supersonic wave treatment in combination with said inorganic base or hydrofluoric acid for the purpose of curtailing removal process time. After the silica coating layer is removed, iron oxide hollow nanocapsule is produced.
  • hollow nanocapsules may be prepared by coating metal oxide oxyhydroxide with silica and using the heat treatment method.
  • the prepared hollow nanocapsules have the advantages of good dispersibility in aqueous systems and uniform size distribution.
  • the iron oxide hollow nanocapsules prepared by the method of the present invention is simple and can be produced economically on a large scale.
  • the iron oxide hollow nanocapsules of the present invention have a large surface area of at least 100 m 2 /g and narrow mesopore size distribution which allows physiologically active material carrying capability which brings great expectations for a wide range of industrial uses such as drug delivery vehicles for biomedical applications, gas sensors, lithium ion batteries, etc.
  • FIG. 1 is a schematic diagram of the conventional method for preparing tubular iron oxide nanoparticles.
  • FIG. 2 is a process diagram of the method of the present invention for preparing the iron oxide hollow nanoparticles
  • Fig. 3(a) is an SEM (Scanning electron Microscopy) image of prepared ⁇ -FeOOH
  • Fig. 3(b) is a TEM (Transmission electron Microscopy) image of ⁇ -FeOOH.
  • Fig. 4(a) is a SEM image of silica coated ⁇ -FeOOH according to the method of the present invention
  • Fig. 4(b) is a TEM image thereof.
  • Fig. 5(a) is a SEM image of the obtained nanocapsules after heat treatment was administered to the silica coated ⁇ -FeOOH
  • Fig. 5(b) and Fig. 5(c) is a TEM image thereof.
  • Fig. 6(a) and Fig. 6(b) are TEM images of the iron oxide hollow nanocapsules according to the method of the present invention
  • Fig.6(c) and Fig.6(d) are high resolution TEM images of the prepared hematite iron oxide hollow nanocapsules.
  • the inset at the upper-right corner of Fig. 6(a) is an image of the hematite iron oxide nanocapsules dispersed in an aqueous solution.
  • Fig. 7 is X-ray diffraction spectra of (a) ⁇ -FeOOH and (b) hematite nanocapsules prepared by the method of the present invention.
  • Fig. 8(a) is a TEM image of silica coated iron oxide hollow nanocapsules after reduction with hydrogen
  • Fig. 8 (a) is a TEM image after removal of silica from said iron oxide hollow nanocapsule
  • Fig. 8(c) and Fig. 8(d) are high resolution TEM images of magnetite iron oxide hollow nanocapsules.
  • the inset on Fig. 8(d) is an image of said magnetite iron oxide nanocapsules dispersed in aqueous solution.
  • Fig. 9 is an X-ray diffraction spectra of the magnetite iron oxide hollow nanocapsules prepared by the method of the present invention.
  • Fig. 10 is a SEM imag (a) and TEM image (b) of obtained ⁇ -FeOOH after undergoing heat treatment without silica coating.
  • FIG. 11 shows images of the effects of magnetic attraction on hematite (left) and magnetite (right) iron oxide nanocapsules prepared by the method of the present invention.
  • Fig. 12 shows N2 adsorption isotherms of (a) bulky state, (b) ⁇ -FeOOH, (c) hematite hollow nanocapsules, and (d) magnetite hollow nanocapsules.
  • Fig. 13 shows the pore size distributions calculated from nitrogen absorption experiments of (a) hematite hollow nanocapsules and (b) magnetite hollow nanocapsules. Best Mode for Carrying Out the Invention
  • FIG. 1 the conventional process for preparing the tubular iron oxide nanoparticle is illustrated, wherein a MgO nanorod is used as a template, and after a metal oxide layer is shaped around the exterior of the molding material, the MgO is etched to prepare the tubular iron oxide nanoparticle.
  • Fig. 2. shows the preparation process of the iron oxide hollow nanocapsules as one example of the present invention.
  • the ⁇ -FeOOH prepared by the method of the present invention is used as the metal oxide oxyhydroxide.
  • the ⁇ - FeOOH used in the present invention is uniquely characterized is that said ⁇ -FeOOH is in a spindle form.
  • the silica coating layer is formed on the spindle ⁇ -FeOOH, and after administering heat treatment, as space is formed inside, hematite layer is formed within the inner wall of the silica coating layer. When the silica is removed, a hematite iron oxide hollow nanocapsule is produced.
  • FIG. 3 shows SEM and TEM pictures of the ⁇ -FeOOH in the examples of the present invention, which allow confirmation of the uniform shape and size of the prepared ⁇ - FeOOH.
  • Fig. 4 shows SEM and TEM pictures after silica coating layer is formed around said ⁇ -FeOOH, which allow confirmation of the uniform formation of the silica coating layer.
  • Fig. 5 shows SEM and TEM pictures after heat treatment of silica coating layer formed ⁇ -FeOOH
  • Fig. 6 shows TEM pictures after removal of said silica coating layer which can confirm that the lattice spacing of the crystalline hematite iron oxide is 0.21nm, and that hollow crystalline metal oxide nanocapsules are produced.
  • the prepared spindle-shaped iron oxide hollow nanocapsule with a diameter of IOnm to 20nm and a length of 50nm to lOOnm, is characterized in that the thickness of the shell of said nanocapsule is 5nm to 15nm.
  • the inset at the upper-right corner of Fig. 6(a) is an image which shows that there is almost no precipitation of the iron oxide hollow nanocapsules after dispersion in water for 2 months afer ultrasonic treatment of the hematite iron oxide hollow nanoparticles.
  • Fig. 7 (a) is the x-ray diffraction spectra of ⁇ -FeOOH prepared by hydrolysis of
  • Fig. 8 (a) is a Transmission Electron Microscope image of silica coated iron oxide hollow nanocapsules after reduction with hydrogen
  • Fig 8(b) is a Transmission Electron Microscope image taken after said silica has been removed
  • Fig.8(c) and Fig.8(d) are high resolution transmission electron microscope images of magnetite iron oxide hollow nanocapsules, and the inset at the upper-right corner of Fig. 8(d) shows an image of magnetite iron oxide nanocapsules dispersed in an aqueous system.
  • Fig. 9 is the X-ray diffraction spectra of the magnetite iron oxide hollow nanocapsules prepared by the method of the present invention. With reference to Fig. 8 and Fig.
  • Fig. 10 shows a Scanning Electron Microscope image of a sample of ⁇ -FeOOH after undergoing heat treatment without silica coating (a), and a Transmission Electron Microscope image(b).
  • the images show that because ⁇ -FeOOH is normally unstable, heat treatment without undergoing the silica coating process results in the ⁇ -FeOOH adhering together and forming into a bulky state, and thus is not able to produce nanocapsules with uniform size and shape.
  • FIG. 11 shows images of the effects of magnetic attraction on hematite (left) and magnetite(right) iron oxide nanocapsules prepared by the method of the present invention, which indicates ferromagnetism of magnetite iron oxide hollow nanocapsules.
  • Fig. 12 shows N 2 adsorption isotherms of (a) bulky state, (b) ⁇ -FeOOH, (c) hematite hollow nanocapsules, and (d) magnetite hollow nanocapsules, and Fig. 13 shows the pore size distributions calculated from nitrogen absorption experiments of hematite hollow nanocapsules(a) and magnetite hollow nanocapsules(b).
  • the surface area of the hematite hollow nanocapsules and magnetite hollow nanocapsules prepared by the method of the present invention are l ⁇ Sitfg 1 and 17 Im ⁇ 1 respectively, and gross pore volumes are 0.40cm 3 g 1 and O ⁇ lcrrPg 1 respectively, and the pore size calculated from the adsorption curves are both 15nm.
  • the iron oxide hollow nanocapsules according to the present invention have wide applicability in the fields of catalysts, lithium ion batteries, gas sensors, etc. due to their large surface area and pore volume, and the size and shape of said iron oxide hollow nanocapsules allow for suitable applicability in the biomedical field in applications such as production of extended release formulation of physiologically active materials since said iron oxide nanocapsules have good water-dispersability and can carry physiologically active materials therewithin.
  • the iron oxide hollow nanocapsules have low toxicity, are inexpensive, and can be monitored using their magnetic properties.
  • the obtained silica coated ⁇ -FeOOH was heated up 500 0 C at a rate of 1.5°C/min and maintained at that temperature for 5 hours. After heat treatment, the obtained nano- structure materials were added to 0. IM NaOH and ultrasonic wave treatment was administered for 2 hours to dissolve the silica in order to produce the hematite hollow nanocapsules. The obtained nanomaterials were repeatedly dispersed in distilled water and underwent centrifugation until pH was 7.
  • the prepared iron oxide hollow nanocapsules are crystalline hematite with crystal lattice spacing of 0.21nm and a spindle shape with a diameter of IOnm to 20 nm, length of 50nm to 100 nm and shell thickness of 9nm to 1 lnm.
  • the inset in the upper-right corner of Fig. 6(a) is an image which shows that there is almost no precipitation of the metal oxide hollow nanocapsules after 2 months from dispersion in water by way of ultrasonic treatment of the hematite iron oxide hollow nanoparticles.
  • iron oxide was prepared by the same process described in Example 1. With reference to Fig. 9, the iron oxide nanoparticles did not form nanostructures, and the ⁇ -FeOOH became coagulated with each other which resulted in a bulky formation
  • Fig. 12 shows the N 2 adsorption isotherms
  • Fig. 13 shows the pore size distribution calculated from N 2 adsorption test of hematite hollow nanocapsules (a) and magnetite hollow nanocapsules(b).
  • the surface areas (Brunauer-Emmett-Teller, BET) of the bulky nanocapsules (Comparative Example 1), ⁇ -FeOOH, hematite nanocapsules (Example 1), and magnetite nanocapsules (Example 2) were 16.6, 82.3, 165, and 17 Im ⁇ 1 respectively.
  • Doxorubicin solution total used amount of Doxorubicin used separately was 0.6mg
  • the Doxorubicin solution total used amount of Doxorubicin used separately was 0.6mg
  • 0.5mL(1.15 mg Fe used) of iron oxide nanocapsule solution was added to said Doxorubicin solution and then stirred for 24 hours in a darkroom. After 1 hour of centrifugation, the remaining Doxorubicin was measured using UV absorption spectra.

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Abstract

Nanocapsule creuse en oxyde métallique à dispersion satisfaisante dans des systèmes aqueux et procédé d'élaboration, lequel est caractérisé par la dispersion d'oxyhydroxyde métallique dans une solution aqueuse et le revêtement de cet oxyhydroxyde avec une couche de revêtement de silice puis un traitement thermique permettant de former une couche d'oxyde métallique autour de l'espace interne creux de la couche de revêtement de silice, et enfin l'élimination de cette silice pour donner la nanocapsule décrite. Les nanoparticules creuses d'oxyde de fer élaborées selon le procédé ont à la fois un potentiel de dispersion supérieur dans des solutions aqueuses et une distribution de taille supérieure, et cette nanocapsule peut aussi porter des matériaux physiologiquement actifs dans son espace creux. De plus, les nanocapsules creuses en oxyde de fer considérées ont une large aire spécifique d'au moins 100 m2/g et une distribution de taille de nanopore réduite qui leur confére une capacité porteuse de matériau physiologiquement actif donnant des grands espoirs pour une large gamme d'applications industrielles du type véhicules de délivrance de médicaments en liaison avec des applications biomédicales, capteurs de gaz, batteries aux ions litihum, etc.
PCT/KR2007/006269 2006-12-05 2007-12-05 Vnanocapsule creuse en oxyde métallique et procédé d'élaboration WO2008069561A1 (fr)

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EP2366387A1 (fr) 2009-12-21 2011-09-21 Instituto Presbiteriano Mackenzie Matrice céramique pour incorporer la libération contrôlée de médicaments, comprimé, procédé d'obtention de la matrice céramique et procédé de production d'un comprimé
WO2013087405A3 (fr) * 2011-12-13 2014-03-20 Basf Se Capsules de libération, procédé de fabrication et utilisations correspondants
CN107096039A (zh) * 2017-04-27 2017-08-29 武汉理工大学 一种磁靶向双载药递释系统及其制备方法
CN110194457A (zh) * 2019-05-20 2019-09-03 重庆科技学院 一种SiO2中空纳米棒的制备方法和尺寸调控方法
CN112897595A (zh) * 2021-03-04 2021-06-04 重庆科技学院 一种水相中制备中空棒状纳米Fe3O4的方法
CN113979466A (zh) * 2021-10-27 2022-01-28 烟台佳隆纳米产业有限公司 ZnO@SiO2纳米胶囊的制备方法

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KR101187872B1 (ko) 2009-08-31 2012-10-05 서울대학교산학협력단 미세다공성 마그네타이트 및 이의 제조 방법
KR101419982B1 (ko) * 2011-06-22 2014-07-15 울산대학교 산학협력단 균일한 중공형의 리튬이차전지용 양극 활물질의 제조방법
CN104548114B (zh) * 2014-12-23 2017-04-26 西安交通大学 一种无机‑有机复合气凝胶药物载体的制备方法
KR101703958B1 (ko) * 2015-04-08 2017-02-08 공주대학교 산학협력단 내부에 구리나노입자를 포함하는 중공 나노입자 및 이의 제조방법
KR101711168B1 (ko) 2015-10-14 2017-02-28 김경란 폐드럼통 압축장치
KR102530072B1 (ko) 2018-01-10 2023-05-08 삼성전자주식회사 이미지 센서, 촬상 장치 및 이미지 센서 칩 패키지의 제조 방법
CN110152569B (zh) * 2018-04-28 2022-07-08 浙江大学 一种纳米FeO(OH)复合气凝胶、其制备方法和用途
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2366387A1 (fr) 2009-12-21 2011-09-21 Instituto Presbiteriano Mackenzie Matrice céramique pour incorporer la libération contrôlée de médicaments, comprimé, procédé d'obtention de la matrice céramique et procédé de production d'un comprimé
WO2013087405A3 (fr) * 2011-12-13 2014-03-20 Basf Se Capsules de libération, procédé de fabrication et utilisations correspondants
CN107096039A (zh) * 2017-04-27 2017-08-29 武汉理工大学 一种磁靶向双载药递释系统及其制备方法
CN107096039B (zh) * 2017-04-27 2019-11-26 武汉理工大学 一种磁靶向双载药递释系统及其制备方法
CN110194457A (zh) * 2019-05-20 2019-09-03 重庆科技学院 一种SiO2中空纳米棒的制备方法和尺寸调控方法
CN112897595A (zh) * 2021-03-04 2021-06-04 重庆科技学院 一种水相中制备中空棒状纳米Fe3O4的方法
CN113979466A (zh) * 2021-10-27 2022-01-28 烟台佳隆纳米产业有限公司 ZnO@SiO2纳米胶囊的制备方法
CN113979466B (zh) * 2021-10-27 2023-04-28 烟台佳隆纳米产业有限公司 ZnO@SiO2纳米胶囊的制备方法

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