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WO2004065306A1 - Particules composites et procede de production correspondant - Google Patents

Particules composites et procede de production correspondant Download PDF

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Publication number
WO2004065306A1
WO2004065306A1 PCT/JP2004/000293 JP2004000293W WO2004065306A1 WO 2004065306 A1 WO2004065306 A1 WO 2004065306A1 JP 2004000293 W JP2004000293 W JP 2004000293W WO 2004065306 A1 WO2004065306 A1 WO 2004065306A1
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WO
WIPO (PCT)
Prior art keywords
particles
target substance
composite
composite particles
iron oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2004/000293
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English (en)
Japanese (ja)
Inventor
Satoko Tsuboi
Mikio Kishimoto
Yoshiaki Nishiya
Masahiro Kusumoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Maxell Ltd
Original Assignee
Toyobo Co Ltd
Hitachi Maxell Ltd
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Priority to JP2005508047A priority Critical patent/JPWO2004065306A1/ja
Publication of WO2004065306A1 publication Critical patent/WO2004065306A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3071—Washing or leaching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles

Definitions

  • the present invention relates to a composite particle and a method for producing the same, and more particularly, to a composite particle mainly intended for capturing bacteria, viruses, proteins, and the like present in a gas or a liquid, a method for producing the composite particle, and the composite particle. It relates to a method for capturing, collecting, removing or detecting a target substance using particles. Background art
  • calcium phosphate compounds such as hydroxyaperite have been known as materials with excellent biocompatibility, including artificial bones and artificial teeth, and utilizing this property, bacteria, viruses, animal and plant cells, etc. Used as a trapping material.
  • Calcium phosphate compounds are known to be used, for example, as one filter material (Japanese Patent Application Laid-Open No. 2002-248307, Japanese Patent Application Laid-Open No. 2002-14859). Report). This is one in which a calcium phosphate compound layer is formed on the surface of an organic polymer base material. Specifically, an organic polymer substrate containing a calcium-containing compound is immersed in an aqueous solution containing phosphate ions and Z or a derivative thereof to form a calcium phosphate compound layer on the surface of the substrate.
  • a calcium phosphate compound is used not only in the form of a filter but also as an adsorbent in the form of particles.
  • the target substance is present in the solution, calcium phosphate compound particles are added thereto, and the target substance is specifically adsorbed on the calcium phosphate compound particles to be captured.
  • hydroxyapatite particles are used as an adsorbent for oily substances contained in edible oils and the like (see pages 2-3 of Japanese Patent Application Laid-Open No. 11-207175).
  • These particles are aggregates of hydroxyapatite whose primary particles have a particle size of l / m or less. It has been shown that the particle size of the aggregate must be 50 m or more in order to quickly recover the particles adsorbing the oily substance. To increase adsorption performance Hydroxyapatite particles having a small particle size are preferred as far as possible, but those having a large particle size are preferred from the viewpoint of operability during recovery. In addition, a storage and filtration process is required to recover the particles after adsorbing oily substances.
  • Hydroxyapatite is also known to be used as a bacterial separating agent (see pages 2 to 3 of JP-A-9-136030). This utilizes the fact that hydroxyapatite is a hexagonal columnar crystal to selectively separate bacteria. If this hydroxyaperite is used alone in the form of a slurry, it must be left for a certain period of time when it is collected, so it takes time. For this reason, hydroxyapatite is used in a layered or filed form.
  • Adding a hydroxyapatite particle is a simple and excellent method to capture the target substance present in the solution.
  • recovery of the hydroxyapatite particles that have captured the target substance requires a standing time and, in some cases, a filtration step, which has been a major drawback because of poor recovery after capture. .
  • a composite of a magnetic substance and hydroxyapatite can be used as a heating element for hyperthermia.
  • Kokoku 5 4 3 3 9 3 No. ferromagnetic ferrite particles and hydroxyl Apataito, such as magnetite Ya Li Ji um ferrite, further a sintered body of mixed powder of the sub-components of the L i 2 ⁇ and N a 2 0 Has been shown to be effective as a ceramic heating element for hyperthermia.
  • the treatment of diseased parts such as cancer is performed by utilizing the biocompatibility of apatite and the heat generation of a magnetic substance by applying an alternating magnetic field.
  • Patent Publication No. 2822997 describes an example of using hydroxyapatite as a ceramic heating element for hyperthermia.
  • hydroxyapatite as a ceramic heating element for hyperthermia.
  • the present invention avoids the disadvantage that the recovery step of the calcium phosphate-based compound capturing the target substance is complicated in the above-mentioned conventional materials, and provides composite particles having not only a high target substance capturing performance but also a significantly improved recovery performance. It is intended to be.
  • the present inventors have conducted intensive studies in order to achieve the above-mentioned object, and as a result, by using a ferromagnetic iron oxide particle as a base material and forming a calcium phosphate-based compound layer thereon as a composite particle, the target substance can be efficiently used.
  • the present inventors have found that excellent capture properties can be obtained at the same time as good capture and adsorption, and the present invention has been accomplished.
  • the composite particles of the present invention comprise ferromagnetic iron oxide particles and a calcium phosphate compound, and can be collected using a magnet or the like after trapping and adsorbing the target substance to the calcium phosphate compound. Since the calcium phosphate compound is formed near the surface of the ferromagnetic iron oxide particles, it exhibits high adsorption performance for the target substance.On the other hand, since the inside of the particles is ferromagnetic iron oxide particles, it reacts with a magnetic field. It can be easily collected with a magnet.
  • the calcium phosphate compound can be present as a mixture with the ferromagnetic iron oxide particles, but it is more preferable to form a film on the surface of the ferromagnetic iron oxide particles because the trapping performance is improved.
  • the film formed on the surface of each ferromagnetic iron oxide particle as a film having a uniform thickness can provide a desired biological substance.
  • the structure is optimal for achieving both capture and recovery of substances.
  • the calcium phosphate compound is particularly hydroxyapatite
  • [C a 5 (P 0 4) 3 (OH) ] is preferably.
  • the ratio of phosphorus atoms to calcium atoms is preferably from 1.4 to 1.8.
  • the ratio of phosphorus atoms to potassium atoms is within this range, the target substance can be adsorbed more efficiently.
  • the content of the calcium phosphate compound is preferably in the range of 5 to 150% by weight, particularly preferably in the range of 10 to 120% by weight, based on the ferromagnetic iron oxide particles. . If the amount is less than the above range, the capture of the target substance may be insufficient.On the other hand, if the amount is too large, particularly when a calcium phosphate compound is formed on the surface of the ferromagnetic iron oxide particles, the compound may be applied to portions other than the surface of the particles. Easy to precipitate, agglomeration of particles Is likely to occur, and conversely, the efficiency of capturing the target substance may decrease.
  • Ferromagnetic iron oxide particles is not particularly limited, magnesite evening I DOO (F e 3 0 4) Grain child, chromite into mug (y- F e 2 0 3) particles, chromite intermediate acid iron particles into magnetite over Mug and at least one particle selected from manganese zinc ferrite (Mn Z n F e 2 0 4) consisting of particles group is preferably used.
  • the magnetite particles are most suitable because of their large saturation magnetization and good magnetic field sensitivity when collected by a magnet or the like.
  • the ferromagnetic iron oxide particles may be in various shapes such as needles, plates, spheres, particles, ellipses, and cubes, and the particles having a spherical or granular shape have the best dispersibility. Yes, with excellent target substance capture performance.
  • the particle size of the ferromagnetic iron oxide particles is not particularly limited, but is preferably from 0.05 to 10 m. If the particle size is smaller than this, it is difficult to obtain a uniform dispersion, and as a result, it may be difficult to form a uniform film of the calcium phosphate compound. On the other hand, if the particle size is larger than the above three ranges, the specific surface area tends to be small, and the trapping performance tends to decrease.
  • the particle size of the composite particles depends on the particle size of the ferromagnetic iron oxide particles and the amount of the calcium phosphate-based compound to be deposited, but is preferably in the range of 0.1 to 10 ⁇ m. When the particle size is within the above range, the composite particles have a good balance between the capture performance and the recovery performance. If the particle size is smaller than the above range, the trapping amount of the target substance is improved, but the trapping property by the magnetic field tends to be low. Further, when the particle size is larger than the above range, the specific surface area of the particles becomes smaller, so that the adsorption efficiency of the target substance tends to decrease.
  • the composite particles combined with the target substance are collected by a magnet or the like, and the trapping property is improved as the saturation magnetization of the composite particles is larger as compared with those having the same particle size.
  • the content of the calcium phosphate compound is in the range of 5 to 150% by weight with respect to the ferromagnetic iron oxide particles, even if the saturation magnetization is reduced, it substantially has no effect on the trapping ability by the magnet. It turned out there was no.
  • the content of the calcium phosphate compound is less than the above range, the capturing performance of the target substance is insufficient, and when the content is more than the above range, the particles are easily aggregated and the saturation magnetization as the composite particles is small. It tends to decrease, and the trapping ability by the magnet tends to decrease.
  • the saturation magnetization of the composite particles is determined by the saturation magnetization of the ferromagnetic iron oxide particles and the amount of the calcium phosphate-based compound to be deposited, but 20 to 80 ⁇ 2 kg (20 to 80 emu / g ) Range is optimal. If the saturation magnetization is smaller than 2 OA'm 2 / kg, the trapping ability by the magnet tends to decrease. On the other hand, in order to make the saturation magnetization larger than 8 OA ⁇ m 2 / kg, it is necessary to reduce the content of the calcium phosphate compound, and there is a tendency that the trapping characteristics of the target substance are reduced.
  • the coercive force of the composite particles generally, as the coercive force increases, the cohesive force between the magnetic particles increases, and the dispersibility decreases. As a result, the active surface to be adsorbed with the target substance decreases, and the trapping efficiency tends to decrease.
  • the individual ferromagnetic oxide particles are coated with a calcium phosphate-based compound that does not exhibit magnetism, so that the coercive force of the composite particles is limited to that of the ferromagnetic iron oxide particles. It is almost determined by the magnetic force.
  • the present inventors have studied the optimum coercive force range that does not affect the trapping characteristics. As a result, if the range is 0.80 to 15.92 kA / m (10 to 200 Oe), there is a practical problem. I found nothing.
  • FIG. 1 is a scanning electron micrograph of the composite particles of the present invention shown in Example 1.
  • FIG. 2 is a powder X-ray diffraction diagram of the composite particles of the present invention shown in Example 1.
  • FIG. 3 is a powder X-ray diffraction chart of the composite particles of the present invention shown in Example. BEST MODE FOR CARRYING OUT THE INVENTION
  • the composite particles of the present invention include a ferromagnetic iron oxide particle and a calcium phosphate-based particle. It is characterized by comprising a compound.
  • the calcium phosphate compound is hydroxyapatite, and at least one particle selected from the group consisting of magnetite particles, maghemite particles, magnetite-maghemite intermediate particles, and manganese zinc ferrite particles as ferromagnetic iron oxide particles.
  • the shape of the ferromagnetic iron oxide particles is preferably spherical or granular, and the average particle size is preferably in the range of 0.05 to 10 m.
  • the coercive force and the saturation magnetization of the composite particles are in the range of 0.80 to 15.92 kA / m (10 to 200 réelled) and 20 to 80 A'm 2 Zkg (20 to 80 emu / g), respectively. Is preferred.
  • the magnetite particles can be synthesized by the following method using an oxidation reaction of an iron salt in an aqueous solution.
  • the air blowing speed and the suspension holding temperature have a significant effect on the size of the magnetite particles.
  • the air blowing speed should be adjusted to 100-400 liters / hour, and the holding temperature of the suspension should be adjusted to 50-90 ° C. If the air blowing speed is high, the crystal growth of magnesite will be faster and the particle size will be smaller. If the air blowing speed is too low or too high, substances other than magnesite may be mixed. Precipitation tends to occur. Furthermore, the higher the holding temperature, the easier the magnesite is to crystallize and the larger the particle size. On the other hand, if the holding temperature is too low, it becomes easy to generate goethite (Hi-FeOOH) particles.
  • magnetite particles having an average particle size of 0.05 to 0.5 m can be synthesized.
  • the average particle size is determined from the average value of the sizes of 300 particles measured on a scanning electron micrograph.
  • Ferromagnetic iron oxide particles having a larger particle diameter can be obtained, for example, by producing an ingot of alpha-hematite by a firing method, pulverizing the ingot, adjusting the particle diameter to an arbitrary particle diameter, and then performing a reduction treatment. be able to.
  • the magnetite particles After sufficiently washing the magnetite particles with pure water, without drying, the magnetite particles are dispersed in water such that the content of the magnetite particles in the water is 1 to 10% by weight.
  • An aqueous solution of a calcium salt is added to the dispersion, and the pH is adjusted to 7 to 13 with an alkali.
  • An aqueous phosphate solution is added to the dispersion while maintaining the pH. By stirring this mixed solution at room temperature for 2 to 6 hours, hydroxyapatite is deposited near the surface of the magnesite particles.
  • a hydroxyapatite film was formed under a constant pH condition by simultaneously adding an alkaline aqueous solution and a phosphoric acid aqueous solution such that the pH always became a constant value.
  • the above-mentioned calcium salt is not particularly limited, but salted calcium, calcium hydroxide, calcium nitrate, calcium bromide, calcium chlorate dihydrate and the like are used.
  • the above alkali is an aqueous solution of sodium hydroxide, lithium hydroxide An aqueous solution, ammonia gas, or the like is used. pH? If the cp H is less than 7, calcium and phosphorus compounds may not be precipitated, which is not preferred.
  • the pH is higher than 13, a compound composed of calcium and phosphorus is rapidly precipitated, and it is difficult to uniformly coat the surface of the magnetite particles, which is not preferable.
  • the phosphate diammonium hydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate and the like are used.
  • a uniform hydroxyapatite coating can be formed on the surface of each magnetite particle.However, the coating strength of glacial apatite can be increased or crystallinity can be imparted. In order to perform this, a heating and stirring process or a hydrothermal treatment as described below may be continuously performed.
  • the lower the crystallinity of hydroxyapatite the better the ability to capture biological substances.
  • the reason for this is unknown, but it is believed that the lower the crystallinity, the easier it is to bind to specific functional groups of the biological material.
  • a heat treatment is further applied after the formation of the hydroxyapatite film, the binding property with the magnetite particles is improved, so that the composite particles of the present invention are used under severe conditions such as vigorous stirring or vibration. In this case, heat treatment is preferably performed.
  • the temperature of the crystalline control it is the temperature of the crystalline control, but the temperature of the suspension when forming a hydroxyapatite film on the surface of the magnetite particles should be 60 ° C or less as described later. Is preferred. By reacting at a temperature of 60 ° C. or less, composite particles having a low hydroxyapatite crystallinity and excellent in capturing biological substances can be obtained.
  • the dispersion liquid of magnetite particles to which the above-mentioned calcium phosphate compound is applied is By performing heating and stirring under normal pressure, composite particles having a low crystalline hydroxyapatite film formed near the surface of the magnetite particles can be prepared.
  • the processing temperature is preferably from 30 to 100 ° C. If the temperature is lower than 30 ° C, it is difficult to obtain the effect of the heat treatment, and the processing exceeding 100 ° C under normal pressure is difficult. For obtaining hydroxyapatite having low crystallinity, the temperature is particularly preferably from 30 to 60 ° C.
  • the stirring time is preferably 1 to 6 hours. If the treatment time is shorter than 1 hour, the effect of the stirring treatment is small. On the other hand, if the treatment time exceeds 6 hours, there is no particular problem, but the effect of the stirring treatment is saturated, so there is little merit.
  • the magnetite particles coated with the calcium phosphate compound are placed in an autoclave and subjected to hydrothermal treatment to prepare composite particles having a highly crystalline hydroxyapatite film formed near the surface of the magnetite particles. That is, by this hydrothermal treatment, highly crystalline hydroxyapatite can be uniformly generated near the surface of the magnetite particles.
  • the hydrothermal treatment temperature is preferably from 120 to 300 ° C. Below 120 ° C, the temperature is too low and the hydrothermal treatment effect is small. Even if the temperature exceeds 300 ° C., there is no particular problem.However, from the viewpoint of improving the crystallinity of hydroxyapatite, the merit of processing at a temperature higher than 300 ° C. is that only the equipment becomes expensive. Few.
  • the hydrothermal treatment time is preferably 1 to 6 hours. If the hydrothermal treatment temperature is too short, it is difficult to obtain a sufficient hydrothermal effect. If it is too long, there is no particular problem. However, even if the treatment is performed for more than 6 hours, the effect of the hydrothermal treatment is saturated, so that the production cost is increased and there is little merit.
  • the coercive force and saturation magnetization are values measured using a vibrating sample magnetometer (manufactured by Toei Kogyo Co., Ltd.).
  • the saturation magnetization is obtained from the amount of magnetization when a magnetic field of 797 kA / m (10 kE) is applied.
  • the coercive force is determined by applying a magnetic field of 797 kA / m, magnetizing, returning the magnetic field to zero, and gradually increasing the magnetic field in the opposite direction. From the value of
  • the particle shape and average particle size were measured by the following methods.
  • the obtained composite particles were sufficiently dispersed in water in a diluted state until individual particles were isolated, and this dispersion was dropped on a mesh for observation with an electron microscope to prepare a sample for observation with an electron microscope.
  • the sample was photographed with an electron microscope, and the shape and average particle size of the particles were determined.
  • the average particle size was determined as an average value of 300 particle sizes.
  • the calcium phosphate compound is preferably hydroxyapatite having a ratio of phosphorus atoms to calcium atoms in the range of 1.4 to 1.8,
  • the ferromagnetic iron oxide particles are preferably spherical or granular, and are preferably magnetite particles having a particle size of 0.05 to 10 / m,
  • the particle size of the composite particles after the application of the calcium phosphate compound is preferably in the range of 0:!
  • a calcium salt and a phosphate are added to a dispersion of the ferromagnetic iron oxide particles, and the pH is adjusted to a constant value to adjust the pH to a value close to the surface of the particles. It is preferable to precipitate a compound consisting of calcium and phosphorus on the surface and to deposit hydroxyapatite near the surface of the ferromagnetic iron oxide particles.
  • ferromagnetic iron oxide particles are dispersed in an aqueous solution of a calcium salt, and an aqueous solution of an aqueous solution and an aqueous solution of a phosphate are added to the suspension so that the pH is constant. Form a uniform hydroxyapatite coating on the surface of the ferromagnetic iron oxide particles,
  • a heating and stirring treatment or a hydrothermal treatment under normal pressure may be performed in order to impart any crystallinity.
  • the composite particles of the present invention may be used as a composition to which a solvent such as water or another additive substance is added as necessary.
  • the composite particles of the present invention it is possible to capture bacteria, viruses, proteins, and the like present in a gas or a liquid.
  • (b) (1) a step of mixing the sample containing the target substance with the composite particles; (2) a step of isolating the target substance bound to the composite particles from the sample, for example, by applying a magnetic field; Separating the separated biological material bound to the target substance from the composite particles.
  • a method for detecting the target substance from a sample containing the target substance using the composite particles can be provided. For example, the following steps are effective. (1) mixing the sample containing the target substance with the composite particles; (2) isolating the target substance bound to the composite particles from the sample, for example, by applying a magnetic field; A step of separating the isolated biological substance bound to the target substance from the composite particles, and a step of detecting the target substance.
  • Example 1 Example 1
  • ferrous sulfate (630 4 '711 2 0) was dissolve in pure water 1, 0000 c. 28.8 g of sodium hydroxide was dissolved in 500 cc of pure water so as to have a molar amount equal to that of the ferrous sulfate.
  • an aqueous sodium hydroxide solution was added dropwise over 1 hour to produce a precipitate of ferrous hydroxide.
  • the temperature of the suspension containing the precipitate of ferrous hydroxide is lowered.
  • the temperature was raised to 75 ° C. After the temperature of the suspension reached 75 ° C., it was oxidized for 8 hours at a rate of 250 liters / hour while blowing air using an air pump to produce magnetite particles.
  • the magnetite particles were almost spherical, with an average particle size of about 0.22 m.
  • the particle size of magnetite particles was determined from the average particle size by measuring about 300 particle sizes on a transmission electron micrograph.
  • the dispersion of the magnetite particles was thoroughly washed with pure water, and then dried without drying so that the weight or volume of the magnetite and pure water became 10 g and 100 ml, respectively.
  • the content of magnetite in the dispersion after washing with water was obtained by partially collecting and drying.
  • the composite particles thus obtained should have hydroxyapatite deposited near the surface of the magnetite particles by the scanning electron micrograph shown in Fig. 1 and the powder X-ray diffraction shown in Fig. 2. I understood.
  • These composite particles are spherical or granular with an average particle size of 0.27 zm, have a coercive force of 4.94 kA / m (62 Oersteds), and have a saturation magnetic field of 52.3 A ⁇ m 2 / kg (52 3 emu / g-).
  • the amount of calcium atoms in the deposited hydroxyapatite was 1.67 atomic% with respect to the amount of phosphorus atoms. Further, the content of hydroxyapatite was 60% by weight based on the magnetite particles.
  • BSA bovine serum albumin
  • 500 883 was dissolved in 1 ml of 1 mmol / liter sodium phosphate buffer (pH 6.8) to prepare a biological material sample.
  • 50 mg of the composite particles were washed several times with 1 mmol / liter sodium phosphate buffer (pH 6.8).
  • the BSA solution is added to the composite particles, and the BSA is adsorbed on the composite particles. I let you.
  • the supernatant that is, the non-adsorbed fraction was collected, and the absorbance (OD 280 nm) was measured with an absorptiometer to determine the amount of BSA contained in the non-adsorbed fraction.
  • the amount of BSA adsorbed on the composite particles was calculated by subtracting the amount of BSA contained in the non-adsorbed fraction from the amount of BSA that had been added.
  • the composite particles from which the non-adsorbed fraction was removed were washed several times with 1 mM Z-little sodium phosphate buffer. Thereafter, 200 mM of sodium phosphate buffer was added and mixed to elute the BSA adsorbed on the composite particles. The eluate was collected and the absorbance (OD 28 Onm) was measured to determine the amount of BSA eluted.
  • the BSA elution efficiency was calculated by the following equation.
  • BSA elution efficiency (83 eight elution amount) / (83 eight adsorption amount) 100
  • hydroxyapatite In the process of applying hydroxyapatite to magnetite particles, the concentration of aqueous calcium chloride solution was changed from 540 mmol / liter to 1,080 mmol / liter, and the concentration of diammonium hydrogen phosphate aqueous solution was changed from 324 mmol / little to 648 mmol. Hydroxyapatite was applied in the same manner as in Example 1 except that the amount was changed to / liter. Subsequent hydrothermal treatment was performed in the same manner as in Example 1. Scanning electron micrographs and powder X-ray diffraction showed that the obtained composite particles had hydroxyapatite deposited near the surface of the magnesite particles.
  • the composite particles are spherical or granular with an average particle size of 0.31 zm, a coercive force of 4.78 kA / m (60 Oersteds), and a saturation magnetization of 41.8 A ⁇ m 2 / kg (41.8 emu / g).
  • the amount of calcium atoms was 1.63 at% with respect to the amount of phosphorus atoms. Further, the content of hydroxyapatite was 101% by weight based on the magnetite particles.
  • the composite particles were subjected to a dispersion treatment in pure water using an ultrasonic disperser and a subsequent measurement of the sedimentation time using a magnet in the same manner as in Example 1, and the sedimentation time was 8 seconds. there were.
  • the elution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated. This The elution efficiency of the particles was 74%.
  • Example 2 In the hydrothermal treatment step, the same procedure as in Example 1 was performed, except that the pH was changed from 10 to 11, and the hydrothermal treatment temperature was changed from 180 ° C to 220 ° C. Scanning electron micrographs and powder X-ray diffraction showed that the obtained composite particles had hydroxyapatite deposited near the surface of the magnetite particles.
  • the composite particles are spherical or granular with an average particle size of 0.28 ⁇ m, have a coercive force of 5.58 kA / m (70 Oersteds), and have a saturation magnetic field of 55.6 A ⁇ m 2 / k ( 55.6 emu / g).
  • the amount of calcium atoms was 1.70 atomic% with respect to the amount of phosphorus atoms. Further, the content of hydroxyapatite was 51% by weight based on the magnetite particles.
  • the composite particles were subjected to dispersion treatment in pure water using an ultrasonic disperser and subsequent sedimentation time measurement using a magnet, as in Example 1, and the sedimentation time was 53 ⁇ 4>.
  • Example 1 the sedimentation time was 53 ⁇ 4>.
  • the elution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated.
  • the elution efficiency of these particles was 65%.
  • Example 2 After the step of applying hydroxyapatite to the magnetite particles, the same procedure as in Example 1 was performed, except that a heating and stirring treatment was performed at 60 ° C. for 3 hours instead of performing a hydrothermal treatment at 180 ° C. for 4 hours. Scanning electron micrographs and powder X-ray diffraction showed that the obtained composite particles had hydroxyapatite deposited near the surface of the magnetite particles.
  • the composite particles are spherical or granular with an average particle size of 0.30 zm, have a coercive force of 5.17 kA / m (65 Oersteds), and have a saturation magnetization of 53.6 A ⁇ m 2 / kg (53. 6 emu / g).
  • the amount of calcium atoms was 1.68 atomic% based on the amount of phosphorus atoms. Further, the content of hydroxyapatite was 56% by weight based on the magnetite particles. Further, the composite particles were subjected to dispersion treatment in pure water using an ultrasonic disperser and subsequent measurement of the sedimentation time using a magnet in the same manner as in Example 1, and the sedimentation time was 6 seconds. Was.
  • the dissolution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated.
  • the elution efficiency of these particles was 75%.
  • Example 2 After the step of applying hydroxyapatite to the magnetite particles, the same procedure as in Example 1 was performed except that the hydrothermal treatment was not performed at 180 ° C. for 4 hours. Scanning electron micrographs and powder X-ray diffraction showed that the obtained composite particles had hydroxyapatite deposited near the surface of the magnetite particles.
  • the composite particles are spherical or granular with an average particle size of 0.28 m, have a coercive force of 5.09 kA / m (64 réelled), and have a saturation magnetization of 51.5 A ⁇ m 2 kg. (51.5 emu /).
  • the amount of calcium atoms was 1.66 at% with respect to the amount of phosphorus atoms. Further, the content of hydroxyapatite was 63% by weight based on the magnetic particles.
  • the composite particles were subjected to dispersion treatment in pure water using an ultrasonic disperser and subsequent measurement of the sedimentation time using a magnet in the same manner as in Example 1, and the sedimentation time was 7 seconds.
  • the sedimentation time was 7 seconds.
  • the dissolution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated.
  • the elution efficiency of these particles was 78%.
  • the calcium phosphate compound particles were hydroxyapatite particles having an average particle size of about 0.1 ⁇ m. Further, in the hydroxyapatite particles, the amount of calcium atoms was 1.66 at% with respect to the amount of phosphorus atoms.
  • the hydroxyapatite particles were subjected to dispersion treatment in pure water using an ultrasonic disperser and subsequent sedimentation time measurement using a magnet, as in Example 1, and the sedimentation time was about 5 minutes. However, compared to the composite particles of Examples 1 to 5, it was clearly found that the composite particles required a longer time. This is because the hydroxyapatite particles do not have magnetism and do not respond to a magnetic field, and as a result, settle only by gravity-induced sedimentation.
  • the elution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated. The elution efficiency of these particles was 62%.
  • Example 2 The same magnesite particles used in Example 1 were used. 10 g of the magnetite particles were dispersed in 300 ml of distilled water to form a suspension. Next, 11.10 g of calcium chloride dihydrate, 12.19 g of ammonium phosphate, and 60.06 g of urea were separately dissolved in 200 ml of distilled water, and the suspension was treated with magnesite. The suspension was added. The suspension was heated to 80 ° C at a heating rate of 4 ° 0 minutes with gentle stirring, kept at that temperature for 4 hours, and then cooled to room temperature. The precipitate was washed with distilled water and dried at 40 ° C.
  • the particles are spherical or granular average particle Saizu is 0.5 33 ⁇ m, the coercive force is 7. 95kAZm (100 oersted) and a saturation magnetization 62. OA - m 2 / kg ( 62. 0 emu / g )Met.
  • the amount of calcium atoms was 1.66 at% with respect to the amount of phosphorus atoms. Further, the content of hydroxyapatite was 35% by weight based on the magnetite particles. Further, the particles were subjected to dispersion treatment in pure water using an ultrasonic disperser and subsequent measurement of the sedimentation time using a magnet in the same manner as in Example 1, and the sedimentation time was 4 seconds. .
  • the dissolution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated.
  • the elution efficiency of the particles was 38%.
  • hydroxyapatite was precipitated in the same manner as in Comparative Example 2, except that the reaction temperature of the suspension was 35 ° C., and the suspension was maintained at this temperature for 4 hours while stirring. From the scanning electron micrograph and the powder X-ray diffraction, the obtained hydroxyapatite precipitated particles were found to have hydroxyapatite deposited so as to cover a plurality of magnetite particles.
  • the particles are spherical or granular with an average particle size of 0.32 ⁇ m, have a coercive force of 7.16 kA / m (90 Oersted), and have a saturation magnetization of 58.1 A-m 2 / m. kg (58. le mu / g).
  • the amount of calcium atoms in the deposited hydroxyapatite was 1.65 atomic% with respect to the amount of phosphorus atoms. Further, the content of hydroxyapatite was 44% by weight based on the magnetite particles.
  • the particles were subjected to dispersion treatment in pure water using an ultrasonic disperser and subsequent measurement of the sedimentation time using a magnet in the same manner as in Example 1, and the sedimentation time was 4 seconds. .
  • the dissolution efficiency of BSA was measured in the same manner as in Example 1, and the trapping performance was evaluated.
  • the elution efficiency of the particles was 42%.
  • each of the composite particles of Examples 1 to 5 in which a uniform coating of hydroxyapatite was formed on the surface of the magnetite particles by using a magnetic field compared to the hydroxyapatite particles of Comparative Example 1.
  • the target substance can be efficiently captured and adsorbed by the hydroxyapatite uniformly adhered to the surface of the ferromagnetic iron oxide particles, and the magnetic field reaction of the ferromagnetic iron oxide particles It shows that it is possible to capture and recover quickly using the property.
  • the composite particles prepared according to the present invention are particles having a good balance between the capturing performance and the recovering performance of a biological substance.
  • the composite particles of the present invention can capture and adsorb biological substances such as bacteria, viruses, and proteins and heavy metal ions present in gases and liquids, they are used for applications such as removal of bacteria and viruses from blood and body fluids and sewage treatment. be able to. It can also be used for crude protein purification from biological samples such as blood and body fluids. Since these composite particles easily react to a magnetic field, they can be quickly recovered by a very simple method using a magnet or the like.
  • the composite particles of the present invention can be applied to the treatment and regeneration of bones and teeth, because the calcium phosphate compound is equivalent to the components of bones and teeth and has excellent biocompatibility.
  • the composite particles of the present invention are based on ferromagnetic iron oxide particles, Since calcium phosphate-based compounds such as oxyapatite are uniformly deposited, the coating of the above compounds enables efficient capture and adsorption of biological substances such as bacteria, viruses, and proteins, and captures these biological substances. When recovering the adsorbed composite particles, if the particle size of the hydroxyapatite particles alone is reduced, the recoverability is significantly reduced.
  • the base material contains a ferromagnetic material and easily reacts to a magnetic field. Can be quickly recovered by a very simple method.

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Power Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Peptides Or Proteins (AREA)
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Abstract

L'invention concerne des particules composites présentant d'excellentes propriétés en matière de piégeage et de récupération de substances cibles, telles que des biosubstances. L'invention concerne notamment des particules composites comprenant des particules d'oxyde de fer ferromagnétiques et un composé phosphate de calcium, ainsi qu'un procédé permettant de produire lesdites particules et un procédé de piégeage, de récupération, d'élimination et de détection d'une substance cible à l'aide desdites particules composites.
PCT/JP2004/000293 2003-01-17 2004-01-16 Particules composites et procede de production correspondant Ceased WO2004065306A1 (fr)

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WO2008023853A1 (fr) * 2006-08-25 2008-02-28 National University Corporation Nagoya University Absorbeur chimique magnétique, procédé pour produire celui-ci, procédé de régénération de celui-ci et procédé de traitement des déchets liquides
EP1942508A1 (fr) 2007-01-04 2008-07-09 Korea University Foundation Nanocristaux à coeur magnétique-coque céramique et leur procédé de fabrication
JP2010154777A (ja) * 2008-12-26 2010-07-15 Aichi Prefecture 醸造酒用タンパク質除去剤
EP2136379A4 (fr) * 2007-03-14 2011-12-28 Toda Kogyo Corp Poudre de ferrite et composition de résine pour aimant lié et corps moulé constitué de ces matières
JP2012144401A (ja) * 2011-01-14 2012-08-02 Dowa Electronics Materials Co Ltd フェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤
CN104549127A (zh) * 2015-01-29 2015-04-29 宁波大学 磁性复合羟基磷灰石纳米微粒及其制备方法和应用
EP3438054A4 (fr) * 2016-03-31 2020-01-22 Powdertech Co., Ltd. Particules de ferrite, composition de résine et film de résine
CN111001388A (zh) * 2019-12-30 2020-04-14 中国科学院城市环境研究所 一种竹基生物炭除磷吸附剂的制备方法及其应用

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JPS63147858A (ja) * 1986-07-28 1988-06-20 オオタケセラム株式会社 活性無機質材料及びその製造法
JPS6364308A (ja) * 1986-09-05 1988-03-22 Rigaku Keisoku Kk 磁性流体
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WO2008023853A1 (fr) * 2006-08-25 2008-02-28 National University Corporation Nagoya University Absorbeur chimique magnétique, procédé pour produire celui-ci, procédé de régénération de celui-ci et procédé de traitement des déchets liquides
US8557337B2 (en) 2007-01-04 2013-10-15 Korea University Foundation Magnetic core—ceramic shell nanocrystals and manufacturing method thereof
EP1942508A1 (fr) 2007-01-04 2008-07-09 Korea University Foundation Nanocristaux à coeur magnétique-coque céramique et leur procédé de fabrication
JP2008162884A (ja) * 2007-01-04 2008-07-17 Korea Univ Foundation 磁性体コア−セラミックシェルナノ結晶及びその製造方法
EP2136379A4 (fr) * 2007-03-14 2011-12-28 Toda Kogyo Corp Poudre de ferrite et composition de résine pour aimant lié et corps moulé constitué de ces matières
US9249033B2 (en) 2007-03-14 2016-02-02 Toda Kogyo Corporation Ferrite particles for bonded magnets, resin composition for bonded magnets, and molded product comprising the same
JP2010154777A (ja) * 2008-12-26 2010-07-15 Aichi Prefecture 醸造酒用タンパク質除去剤
JP2012144401A (ja) * 2011-01-14 2012-08-02 Dowa Electronics Materials Co Ltd フェライト粒子並びにそれを用いた電子写真現像用キャリア及び電子写真用現像剤
CN104549127A (zh) * 2015-01-29 2015-04-29 宁波大学 磁性复合羟基磷灰石纳米微粒及其制备方法和应用
EP3438054A4 (fr) * 2016-03-31 2020-01-22 Powdertech Co., Ltd. Particules de ferrite, composition de résine et film de résine
US11014826B2 (en) 2016-03-31 2021-05-25 Powdertech Co., Ltd. Ferrite particles, resin composition and resin film
CN111001388A (zh) * 2019-12-30 2020-04-14 中国科学院城市环境研究所 一种竹基生物炭除磷吸附剂的制备方法及其应用
CN111001388B (zh) * 2019-12-30 2022-05-03 中国科学院城市环境研究所 一种竹基生物炭除磷吸附剂的制备方法及其应用

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