WO2011071167A1 - Particules à nanotiges cœur-écorce au-ag et leur procédé de production - Google Patents

Particules à nanotiges cœur-écorce au-ag et leur procédé de production Download PDF

Info

Publication number
WO2011071167A1
WO2011071167A1 PCT/JP2010/072288 JP2010072288W WO2011071167A1 WO 2011071167 A1 WO2011071167 A1 WO 2011071167A1 JP 2010072288 W JP2010072288 W JP 2010072288W WO 2011071167 A1 WO2011071167 A1 WO 2011071167A1
Authority
WO
WIPO (PCT)
Prior art keywords
gold
shell
nanorod
silver
polymerizable monomer
Prior art date
Application number
PCT/JP2010/072288
Other languages
English (en)
Japanese (ja)
Inventor
英典 大塚
俊彦 黒澤
美宏 齋藤
好一 沓沢
Original Assignee
学校法人東京理科大学
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 学校法人東京理科大学 filed Critical 学校法人東京理科大学
Priority to US13/514,838 priority Critical patent/US9156088B2/en
Priority to EP10836086.8A priority patent/EP2511028A4/fr
Priority to JP2011545270A priority patent/JP5709219B2/ja
Publication of WO2011071167A1 publication Critical patent/WO2011071167A1/fr

Links

Images

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0547—Nanofibres or nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/001—Preparation for luminescence or biological staining
    • A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
    • A61K49/0065—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the luminescent/fluorescent agent having itself a special physical form, e.g. gold nanoparticle

Definitions

  • the present invention relates to gold-silver core-shell nanorod particles and a method for producing the same.
  • Gold nanorod particles are rod-shaped (rod-shaped) gold nanoparticles and have absorption in two wavelength regions, a visible light region ( ⁇ 520 nm) and a near infrared region ( ⁇ 900 nm). These are derived from surface plasmon resonance in the short axis direction and the long axis direction, respectively, and absorption in the near infrared region is specific to gold nanorod particles. Also, the absorbed light energy is converted into heat, which is called the photothermal effect. Since the near-infrared region has high biological permeability, the gold nanorod particles are expected to be applied to bioimaging utilizing its strong near-infrared absorption ability and photothermal treatment utilizing generated heat (non-patented) References 1, 2).
  • Non-patent Document 3 gold-silver core-shell nanorod particles having gold nanorod particles as a core and having a surface coated with a shell layer made of silver have also been reported (Non-patent Document 3).
  • the absorption region of the particles is blue-shifted.
  • the photothermal effect can be enhanced by coating with silver.
  • the gold nanorod particles are usually produced in a micelle of a cationic surfactant such as CTAB (cetyltrimethylammonium bromide), the surface exists in a state where the surface is protected by CTAB or the like. Further, since the gold-silver core-shell nanorod particles are also produced by depositing silver on the surface of the gold nanorod particles protected by CTAB or the like, the surface of the shell layer exists in a state protected by CTAB or the like.
  • a cationic surfactant such as CTAB has a very high cytotoxicity, and as such, there is a problem in medical application.
  • the gold nanorod particles can be medically applied by replacing a cationic surfactant such as CTAB with a compound (SH-PEG) in which a thiol group is bonded to the end of a polyethylene glycol chain (PEG chain). It has been reported (Non-Patent Documents 1 and 2). However, for gold-silver core-shell nanorod particles, there has been no report of replacing cationic surfactants such as CTAB with other compounds. According to the experiments by the present inventors, when CTAB on the surface of the gold nanorod particles was replaced with SH-PEG, a shell layer made of silver could not be formed.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a gold-silver core-shell nanorod particle in which a cationic surfactant such as CTAB is replaced with another compound and a method for producing the same. Is to provide.
  • Gold-silver core-shell nanorod particles in which a gold nanorod particle is used as a core, a shell layer made of silver is coated on the surface of the gold nanorod particle, and a copolymer is adsorbed on the surface of the shell layer, Gold-silver core-shell nanorod particles characterized in that the copolymer is a block copolymer or graft copolymer obtained by polymerizing at least the polymerizable monomer (A) having a group represented by the general formula (I) . (In the formula, R a represents an alkylene group having 2 to 7 carbon atoms.)
  • the copolymer is a block copolymer or graft copolymer of the polymerizable monomer (A) and a polymerizable monomer (B) having a repeating structure represented by the general formula (II).
  • the gold-silver core-shell nanorod particle according to (1) In the formula, R b represents an alkylene group having 2 to 5 carbon atoms, and n represents an arbitrary integer of 5 to 2000.
  • a photothermal therapeutic agent containing the gold-silver core-shell nanorod particles according to any one of (1) to (6) above.
  • a method for producing nanorod particles comprising forming a gold nanorod particle using a cationic surfactant as a template, and replacing the cationic surfactant with a block copolymer or a graft copolymer to form a block.
  • R a represents an alkylene group having 2 to 7 carbon atoms.
  • a cationic surfactant such as CTAB is replaced by a block copolymer or graft copolymer obtained by polymerizing at least the polymerizable monomer (A) having a group represented by the general formula (I).
  • A polymerizable monomer having a group represented by the general formula (I).
  • Produced gold-silver core-shell nanorod particles can be produced. Since the copolymer does not show toxicity to cells, a treatment utilizing the photothermal effect of the gold-silver core-shell nanorod particles can be expected.
  • FIG. 2 is a diagram showing dispersion stability (in salt solution) of Py-g-PEG protected gold-silver core-shell nanorod particles (addition amount of 1 mM AgNO 3 solution: (A) 120 ⁇ l, (B) 240 ⁇ l).
  • FIG. 6 shows the dispersion stability (in DMEM with 10% FBS) of Py-g-PEG protected gold-silver core-shell nanorod particles.
  • FIG. 3 is a graph showing an absorption spectrum of a Py-b-PEG protected gold-silver core-shell nanorod particle dispersion.
  • Py-b-PEG protection Gold - amount of FIG. (1 mM of AgNO 3 solution was observed silver core-shell nanorod particles with a transmission electron microscope (TEM): (A) 120 ⁇ l , (B) 240 ⁇ l, (C) 360 ⁇ l, ( D) 480 ⁇ l). It is a figure ((A) Py-g-PEG protection gold-silver core shell nanorod particle, (B) CTAB protection gold-silver core shell nanorod particle) which shows the evaluation result of cytotoxicity.
  • FIG. 6 is a view of cell uptake of Py-g-PEG protected gold-silver core-shell nanorod particles observed with a phase contrast microscope and a fluorescence microscope.
  • FIG. 3 is a diagram of the photothermal effect on cells of Py-g-PEG protected gold-silver core-shell nanorod particles observed with a phase contrast microscope and a fluorescence microscope.
  • the gold-silver core-shell nanorod particles of the present invention have gold nanorod particles as a core, the surface of the gold nanorod particles is coated with a shell layer made of silver, and the copolymer is adsorbed on the surface of the shell layer. is there.
  • the copolymer is a block copolymer or graft copolymer obtained by polymerizing at least a polymerizable monomer (A) having a group represented by the general formula (I).
  • the gold nanorod particle is a nanoscale gold particle having a rod (rod) shape in which the ratio of the length in the major axis direction (aspect ratio) to the length in the minor axis direction is greater than 1.
  • the particle diameter of the gold nanorod particles the length of the major axis is preferably 10 to 500 nm, and more preferably 20 to 200 nm.
  • the minor axis length is preferably 1 to 500 nm, and more preferably 1 to 50 nm.
  • the particle size of the gold nanorod particles can be controlled by the concentration of gold ions in the preparation solution. If the length of the major axis and the minor axis is in the above range, good dispersion stability is exhibited.
  • the gold nanorod particles preferably have an aspect ratio of 1 to 10, more preferably 1 to 5. If the aspect ratio is in the above range, good dispersion stability is exhibited.
  • the gold nanorod particles may be synthesized by a conventionally known method such as a seed method, or a commercially available product may be used.
  • the surface of the gold nanorod particles that are the core is coated with a shell layer made of silver.
  • the thickness of the shell layer to be coated is not particularly limited as long as the surface of the gold nanorod particles is uniformly coated, but is usually 1 to 100 nm in the major axis direction and 1 in the minor axis direction. ⁇ 100 nm. Further, it is preferably 1 to 50 nm in the major axis direction and 1 to 50 nm in the minor axis direction.
  • the thickness of the shell layer can be controlled by the concentration of silver ions in the gold nanorod particle dispersion, the aspect ratio of the gold nanorod particles, and the like.
  • the wavelength and intensity of plasmon absorption can be controlled by changing the thickness of the shell layer, and the near-infrared light can be increased by increasing the thickness of the shell layer.
  • the photothermal effect of converting the absorbed light into thermal energy can be enhanced, so that it may be appropriately adjusted depending on the application while considering dispersion stability.
  • the polymerizable monomer (A) is a polymerizable monomer having a group represented by the general formula (I).
  • Ra is an alkylene group having 2 to 7 carbon atoms, and preferably an alkylene group having 3 to 5 carbon atoms.
  • the hydrophobic cohesion between gold-silver core-shell nanorod particles can be controlled by changing the carbon number of the alkylene group of the copolymer. By setting the carbon number of the alkylene group within the above range, gold-silver core-shell nanorod particles having a small and stable particle size can be obtained.
  • the polymerizable monomer (A) is a polymerizable monomer and needs to have a polymerizable group in its structure, but the type thereof is not particularly limited, and examples thereof include a vinyl group, an allyl group, a styryl group, and a methacryloyl group. An acryloyl group or the like may be used. It can superpose
  • the copolymer preferably has the polymerizable monomer (A) represented by the general formula (III).
  • R 1a is an alkylene group having 2 to 7 carbon atoms, and preferably an alkylene group having 3 to 5 carbon atoms.
  • R 2a is a hydrogen atom or a methyl group.
  • the polymerizable monomer (B) is a polymerizable monomer having a repeating structure represented by the general formula (II).
  • R b is an alkylene group having 2 to 5 carbon atoms, and preferably 2 to 3 carbon atoms. By setting the number of carbon atoms of the alkylene group in the above range, the hydrophilicity and flexibility of the molecule are increased.
  • n is an arbitrary integer of 5 to 2000, and preferably 10 to 500. By setting n within the above range, hydrophilicity and flexibility are enhanced.
  • it does not specifically limit as a unit of the repeating structure represented by general formula (II) For example, ethylene oxide, propylene oxide, etc. are mentioned.
  • the polymerizable monomer (B) is a polymerizable monomer and needs to have a polymerizable group in its structure, but the type of the functional group is not particularly limited.
  • a vinyl group, an allyl group, a styryl group It may be a methacryloyl group, an acryloyl group, or the like. It can superpose
  • the copolymer preferably has the polymerizable monomer (B) represented by the general formula (IV).
  • R 1b is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 2 to 5 carbon atoms.
  • R 2b is an alkylene group having 2 to 5 carbon atoms, and R 3b is a hydrogen atom or a methyl group.
  • n is an arbitrary integer of 5 to 2000, and preferably 10 to 500.
  • the polymerizable monomer (C) has a ligand.
  • ligand for example, molecular recognition showing a specific interaction with a specific target substance such as a nucleic acid such as a sugar chain, sugar, glycoprotein, glycolipid, protein, antigen, antibody, peptide, oligo DNA, oligo RNA, etc. An element is mentioned. By binding these ligands, various functions can be added to the copolymer.
  • a specific target substance such as a nucleic acid such as a sugar chain, sugar, glycoprotein, glycolipid, protein, antigen, antibody, peptide, oligo DNA, oligo RNA, etc.
  • the polymerizable monomer (C) is a polymerizable monomer and needs to have a polymerizable group in its structure, but the type thereof is not particularly limited, and examples thereof include a vinyl group, an allyl group, a styryl group, and a methacryloyl group. An acryloyl group or the like may be used. It is possible to polymerize with the polymerizable monomer (A) through this polymerizable group.
  • the copolymer is preferably such that the polymerizable monomer (C) is represented by the following general formula (V).
  • R 1c is a hydrogen atom or a methyl group
  • R 2c is —O— or —NH—
  • X is a spacer
  • Z is a ligand.
  • the spacer is not particularly limited as long as the above-described ligand can be introduced, and examples thereof include an oligoalkyleneoxy group having 1 to 200 repeating units, an alkylene group, and the like, and preferably repeating units.
  • the alkylene group may be linear or branched.
  • the number of carbon atoms of the alkylene group is not particularly limited, but is preferably C1 to C8.
  • An ethyleneoxy group having 1 to 50 repeat units or a C1 to C8 alkylene group is preferred because the mobility of the copolymer is improved.
  • the above-mentioned ligand may couple
  • the copolymer in the present invention is a block copolymer or graft copolymer obtained by polymerizing at least the polymerizable monomer (A).
  • the polymerization method of the copolymer in the present invention is not particularly limited, and a conventionally known method can be used. Living radical polymerization methods such as addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) can be used. preferable. According to the living radical polymerization method, the molecular weight and molecular weight distribution of the copolymer to be synthesized can be controlled.
  • RAFT addition-fragmentation chain transfer
  • ATRP atom transfer radical polymerization
  • the synthesis method in case the copolymer in this invention is a copolymer which copolymerized the polymerizable monomer (A) and the polymerizable monomer (B) is illustrated.
  • the polymerization method is a living radical polymerization method.
  • RAFT the case of using RAFT is illustrated.
  • the polymerizable monomer (B) After the polymerizable monomer (B), the chain transfer agent, and the polymerization initiator are dissolved in a predetermined solvent and oxygen in the reaction vessel containing dissolved oxygen is completely removed, the polymerization initiator is at a temperature higher than the cleavage temperature.
  • a macro chain in which a chain transfer agent is introduced into the terminal of a polymer obtained by polymerizing the polymerizable monomer (B) hereinafter referred to as B block) by heating at a temperature of 100 ° C. or lower for 24 to 48 hours. Synthesize transfer agent.
  • the macro chain transfer agent and the polymerizable monomer (A) are dissolved in a predetermined solvent and heated at a temperature not lower than the temperature at which the polymerization initiator is cleaved and not higher than 100 ° C. for 24 to 300 hours.
  • the copolymer (block copolymer) in the present invention in which the B block and a polymer obtained by polymerizing the polymerizable monomer (A) (hereinafter referred to as A block) are coupled in series can be synthesized. it can.
  • the polymerizable monomer (A), the polymerizable monomer (B), the chain transfer agent, and the polymerization initiator are dissolved in a predetermined solvent, and the temperature is equal to or higher than the temperature at which the polymerization initiator is cleaved, and 100 A copolymer (graft copolymer) according to the present invention in which the B block and the A block are combined in a comb shape can be synthesized by heating for 24 to 300 hours at a temperature of 0 ° C. or lower.
  • the polymerization initiator is not particularly limited, and examples thereof include azo polymerization initiators such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis (2-methylbutyronitrile), Examples thereof include sulfate polymerization initiators such as ammonium sulfate and potassium persulfate, and organic peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide.
  • azo polymerization initiators such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis (2-methylbutyronitrile)
  • sulfate polymerization initiators such as ammonium sulfate and potassium persulfate
  • organic peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide.
  • a suitable amount of the polymerization initiator is 0.1 to 10% by mass with respect to the total amount of the polymerizable monomer (A) and the polymerizable monomer (B).
  • a chain transfer agent such as mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, or 1-butanethiol may be added to adjust the molecular weight.
  • the polymerization temperature and polymerization time are exemplified as described above, but depend on the temperature and the properties of the desired final product.
  • the temperature is preferably 30 to 90 ° C., more preferably 50 to 70 ° C., and 1 to 96 hours.
  • a macrohalogenated alkyl agent in which a halogenated alkyl agent is introduced at the end of the B block is prepared by dissolving a polymerizable monomer (B), a halogenated alkyl agent, and a catalyst in a predetermined solvent and reacting them. Synthesize.
  • the macrohalogenated alkyl initiator and the polymerizable monomer (A) are dissolved in a predetermined solvent, a catalyst is further added, and the temperature is higher than room temperature and lower than 100 ° C. for 6 to 50 hours.
  • the copolymer (block copolymer) in the present invention in which the B block and the A block are bonded in series can be synthesized.
  • the halogenated alkyl initiator used for ATRP is not particularly limited, and examples thereof include 2-bromoisobutyryl bromide, 2-chloroisobutyryl chloride, bromoacetyl bromide, bromoacetyl chloride, and benzyl bromide.
  • transition metal complexes such as monovalent copper and divalent ruthenium can be used.
  • the solvent used in the polymerization reaction is not particularly limited.
  • water, methanol, ethanol, propanol, t-butanol, benzene, toluene, N, N-dimethylformamide, tetrahydrofuran, chloroform, 1,4-dioxane, dimethyl examples thereof include sulfoxide and a mixed solution thereof.
  • the mass average molecular weight of the copolymer is preferably from 1,000 to 500,000, and more preferably from 2,000 to 100,000. In the above range, interface stability can be imparted to the gold-silver core-shell nanorod particles.
  • the mass average molecular weight of the polymerizable monomer (B) is preferably 200 to 80000, more preferably 500 to 20000.
  • the dispersion stability of the gold-silver core-shell nanorod particles in the solvent can be controlled. In the above range, the gold-silver core-shell nanorod particles can be stably dispersed in the solvent.
  • the molar ratio of the polymerizable monomer (A) to the polymerizable monomer (B) in the copolymer is preferably 1:99 to 99: 1, and preferably 10:90 to 90:10. Is more preferable.
  • the hydrophilicity / hydrophobicity balance can be controlled by changing the molar ratio of the polymerizable monomer (A) to the polymerizable monomer (B). In addition, by setting it as the said range, it can adsorb
  • the gold-silver core-shell nanorod particles of the present invention a cationic surfactant such as cytotoxic CTAB is replaced by a non-cytotoxic copolymer. Is possible. Further, the gold-silver core-shell nanorod particles of the present invention exhibit excellent dispersion stability in a solution containing a salt or a solution containing serum. Therefore, application to the treatment of tumor tissue using the photothermal effect of the gold-silver core-shell nanorod particles can be expected.
  • the gold-silver core-shell nanorod particles of the present invention can be used as a photothermal therapeutic agent.
  • Examples of the administration method of the photothermal therapeutic agent containing the gold-silver core-shell nanorod particles of the present invention include surgical means and the like in addition to subcutaneous injection and intravenous injection to the affected area to be treated.
  • the gold-silver core-shell nanorod particles of the present invention are used as a photothermal therapeutic agent, after the gold-silver core-shell nanorod particles of the present invention are administered, the affected area is irradiated with light for a certain period.
  • the wavelength range of light is preferably 500 to 1500 nm, more preferably 700 to 900 nm.
  • the gold-silver core-shell nanorod particles of the present invention effectively generate heat.
  • the light irradiation method include light sources such as a laser and a pulse laser.
  • examples of diseases to be treated include cancer.
  • the method for producing gold-silver core-shell nanorod particles of the present invention comprises a step of forming gold nanorod particles using a cationic surfactant as a template, and the cationic surfactant is converted into a block copolymer or a graft copolymer.
  • the gold-silver core-shell nanorod particles of the present invention can be specifically produced by the following method.
  • gold nanorod particles are produced by a conventionally known method such as a seed method.
  • a gold nanoparticle dispersion is obtained by adding a reducing agent to a solution containing a cationic surfactant and a halogenated gold acid and stirring to precipitate gold.
  • the reducing agent is further added and stirred.
  • a dispersion of gold nanorod particles protected by a cationic surfactant is obtained by adding and stirring the above dispersion of gold nanoparticles to the obtained solution.
  • the gold nanorod particles commercially available products may be used.
  • quaternary ammonium salts such as hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride (CTAC) and the like can be suitably used.
  • CTAB hexadecyltrimethylammonium bromide
  • CAC hexadecyltrimethylammonium chloride
  • halogenated gold acid for example, chloroauric acid can be preferably used.
  • the reducing agent for example, sodium borohydride can be suitably used.
  • the dispersion of gold nanorod particles protected by a cationic surfactant is subjected to centrifugation, and the resulting precipitate is dispersed in the solution containing the copolymer and stirred, and then a dialysis membrane is used. Dialyze. The dispersion after dialysis is subjected to centrifugation, and then the precipitate is dispersed in water to obtain a dispersion of gold nanorod particles protected by the copolymer.
  • the centrifugation is preferably performed at 20000 to 140,000 rpm.
  • the dialysis membrane is preferably a regenerated cellulose membrane having a molecular weight cut-off of 2000 to 10,000.
  • the supernatant containing a highly toxic cationic surfactant is removed by the centrifugation, and the copolymer is adsorbed on the surface of the gold nanorod particles by dialysis using the dialysis membrane.
  • a reducing agent and a base are sequentially added and stirred, and then dialyzed using a dialysis membrane.
  • the dispersion after dialysis is subjected to centrifugation, and the precipitate is dispersed in water to obtain a dispersion of gold-silver core-shell nanorod particles protected by the copolymer.
  • examples of the inorganic silver salt include silver nitrate and silver acetate, and silver nitrate is preferable in view of excellent dispersion stability, toxicity, and the like.
  • the amount of the inorganic silver salt used is usually 0.1 to 5 equivalents, preferably 0.1 to 1 equivalent, relative to the gold nanorods. Within the above range, gold-silver core-shell nanorod particles having excellent dispersion stability can be obtained.
  • the thickness of a shell layer can be controlled by adjusting the usage-amount of the said inorganic silver salt.
  • Examples of the reducing agent include sodium borohydride, ascorbic acid, and citric acid, and ascorbic acid is preferable in terms of excellent controllability of the reduction reaction.
  • Examples of the base include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferable in terms of availability and low cost.
  • the number average molecular weight (Mn) of the obtained Py-g-PEG is 113,180, the dispersity (Mw / Mn) is 1.634, and copolymerization of polyethylene glycol (PEG) and pyridine (Py)
  • the ratio (PEG / Py) was 10.3%.
  • the molecular weight was measured by gel filtration chromatography (GPC).
  • CTAB protected gold nanorod particles [Preparation of gold-silver core-shell nanorod particles protected with Py-g-PEG] ⁇ Preparation of CTAB protected gold nanorod particles>
  • CTAB hexadecyltrimethylammonium bromide
  • the dialyzed solution is centrifuged (rotation speed: 18000 rpm, time: 30 minutes, number of times: 1) with an ultracentrifuge, and then the resulting precipitate is sterilized water so that the total amount becomes 100 ml.
  • Rotation speed: 18000 rpm, time: 30 minutes, number of times: 1 with an ultracentrifuge, and then the resulting precipitate is sterilized water so that the total amount becomes 100 ml.
  • metal nanoparticles having a size of several tens of nanometers exhibit characteristic optical absorption due to surface plasmon excitation depending on the type and shape of the metal.
  • a dispersion of spherical gold nanoparticles exhibits absorption near 520 nm, and in the case of a rod shape, in addition to absorption near 520 nm due to the short axis of the rod, long wavelength due to the long axis of the rod. It is known to show absorption on the side (near 900 nm).
  • the dispersion after dialysis is sterilized by ultracentrifugation (rotation speed: 18000 rpm, time: 30 minutes, number of times: 1), and the resulting precipitate is sterilized so that the total amount becomes 100 ml. Re-dispersed in water to obtain a test solution.
  • the prepared solution was put into a 1 cm plastic cell, and irradiated with an 800 nm laser beam (irradiation energy: 450 mW / cm 2 , irradiation area: 1 mm) using an OPO laser (SL454G pulsed Nd: YAG laser, manufactured by Spectron Laser System). 2 ).
  • OPO laser S454G pulsed Nd: YAG laser, manufactured by Spectron Laser System. 2
  • a cut filter was used to cut off the Signal light or Idler light.
  • the emitted laser light was condensed using a lens (SLB-30-50PM, spherical plano-convex lens, manufactured by Sigma Koki Co., Ltd.). Note that the cell was placed in a thermostatic bath at 25 ° C. until the laser beam was irradiated, and the starting temperature was kept constant. As a result, it was confirmed that the photothermal effect of Py-g-PEG protected gold-silver core-shell nanorod particles depends on the
  • each dispersion 2 ml of each dispersion is put in a 1 cm plastic cell, and an OPO laser (SL454G pulsed Nd: YAG laser, manufactured by Spectron Laser System) is used to oscillate a triple wave (355 nm) as an excitation light source.
  • the laser beam becomes a wavelength-tunable laser beam by changing the angle of the BBOtype nonlinear optical crystal ( ⁇ -BaB 2 O 4 ) in the midband OPO VisIR2 device (manufactured by GWU lasertechnik).
  • the repetition frequency is 10 Hz and the pulse width is 2-3 ns.
  • a cut filter was used to cut off the Signal light or Idler light.
  • the emitted laser light was condensed using a lens (SLB-30-50PM, spherical plano-convex lens, manufactured by Sigma Koki Co., Ltd.).
  • a laser beam of 800 nm was irradiated (irradiation energy: 0.5 mW / cm 2 ⁇ pulse, irradiation area: 1 mm 2 ). Note that the cell was placed in a constant temperature bath at 20 ° C. until the start temperature was constant until just before the laser beam irradiation.
  • the measurement sample includes a Py-g-PEG protected gold nanorod particle dispersion obtained by the above method (addition amount of 1 mM AgNO 3 solution: 0 ⁇ l) and the Py-g-PEG protected gold-silver obtained by the above method.
  • a core-shell nanorod particle dispersion (addition amount of 1 mM AgNO 3 solution: 80 ⁇ l, 180 ⁇ l) was used.
  • the irradiation energy of the 800 nm laser light was set to 450 mW / cm 2 and the temperature of the thermostatic chamber containing the cell was set to 25 ° C., and the same method as in the comparison with the gold nanorod particles (1) was performed. It was. As a result, it was clearly shown that the Py-g-PEG protected gold-silver core-shell nanorod particles had a higher photothermal effect than the Py-g-PEG protected gold nanorod particles (FIG. 12).
  • the acid chloride is dissolved in 7 ml of dehydrated benzene, and further 400 ⁇ l of triethylamine (2.88 mmol, 1.2 equivalents relative to the RAFT agent) dissolved in dehydrated benzene, and the monomer (B) of the present invention.
  • PEG polyethylene glycol
  • the obtained precipitate was dissolved in chloroform, concentrated and freeze-dried to obtain a PEG-macro-RAFT agent in which the RAFT agent was introduced at the end of the polymer obtained by polymerizing the monomer (B) (yield: 1060 mg, yield: 83.3%, terminal modification rate: 85%).
  • Py-b-PEG has a theoretical number average molecular weight (Mw (th)) of 5530 and a polydispersity (Mw / Mn) of 0.2878.
  • the particle size distribution (histogram particle size) was 28.0 ⁇ 18.0 nm, and the average particle size (cumulant particle size) was 19.2 nm.
  • the theoretical number average molecular weight was calculated from the number of Py chains based on the ethylene oxide chain of PEG by 1 H-NMR.
  • the particle size distribution (histogram particle size) was calculated by dynamic light scattering, the average particle size (cumulant particle size) was calculated by dynamic light scattering, and the polydispersity (Mw / Mn) was calculated by dynamic light scattering.
  • ⁇ Precipitation of Ag on the surface of Py-b-PEG protected gold nanorod particles A 1 mM AgNO 3 solution (120 ⁇ l, 240 ⁇ l, 360 ⁇ l, 480 ⁇ l) was added to 5 ml of the Py-b-PEG protected gold nanorod particle dispersion obtained by the above method. To these solutions, 0.1 ml of a 0.1 M aqueous solution of ascorbic acid was added, and then 0.2 ml of a 0.1 M aqueous solution of NaOH was added.
  • the mixture was placed in a dialysis membrane (fraction molecular weight: about 10,000) and dialyzed against 3000 ml of water for 3 days.
  • the dispersion after dialysis is centrifuged (rotation speed: 18000 rpm, time: 30 minutes, number of times: 1) with an ultracentrifuge, and then the resulting precipitate is sterilized so that the total amount becomes 50 ml.
  • the mixture was placed in a dialysis membrane (fraction molecular weight: about 10,000) and dialyzed against 3000 ml of water for 3 days.
  • the dispersion after dialysis is centrifuged (rotation speed: 18000 rpm, time: 30 minutes, number of times: 1) with an ultracentrifuge, and then the resulting precipitate is sterilized so that the total amount becomes 50 ml.
  • CTAB Redispersion in water yielded CTAB protected gold-silver core-shell nanorod particle dispersions with concentrations of 8.5 ⁇ g / ml, 11.3 ⁇ g / ml, 17 ⁇ g / ml, 22.6 ⁇ g / ml, and 34 ⁇ g / ml.
  • the Py-g-PEG protected gold-silver core / shell nanorod particle dispersion obtained by the above method and the CTAB protected gold / silver core / shell nanorod particle dispersion obtained by the above method were used. After 20 ml of each dispersion was centrifuged with an ultracentrifuge (rotation speed: 18000 rpm, time: 30 minutes, number of times: 1), the resulting precipitate was fetal bovine so that the total amount became 100 ml. DMEM containing 10% serum (FBS) was added and redispersed. Next, this redispersion was purified by a filter (Mirex-GV filter, 0.22 ⁇ m, manufactured by Millipore).
  • HeLa cells (cell number: 5 ⁇ 10 4 ) were added to 0.5 ml of each redispersed liquid after purification, and incubated at 37 ° C. for 30 minutes. Then, cytotoxicity was evaluated using a cell proliferation measurement kit (MTT, manufactured by Calbiochem Novabiochem Novagen). As a result, it was confirmed that the CTAB protected gold-silver core-shell nanorod particle dispersion was highly toxic to cells. In contrast, it was confirmed that the dispersion of Py-g-PEG protected gold-silver core-shell nanorod particles of the present invention was not toxic to cells (FIG. 15).
  • MTT cell proliferation measurement kit
  • the re-dispersed liquid was stirred in a cool dark place for 3 days and then centrifuged (rotation speed: 18000 rpm, time: 15 minutes, number of times: 1) to obtain a precipitate.
  • the precipitate was redispersed in DMEM containing 10% FBS, and the concentrations of FITC-labeled Py-g-PEG protected gold-silver core-shell nanorod particles were 30 ⁇ g / ml, 40 ⁇ g / ml, 50 ⁇ g / ml, 60 ⁇ g / ml. A redispersion was obtained.
  • HeLa cells (cell number: 2 ⁇ 10 5 ) were added to 1 ml of the redispersion after the purification, Incubated at 37 ° C. for 4 hours. Then, after exchanging with a new DMEM containing 10% FBS, the cells were observed with a phase contrast microscope (Observer. D1, Carl Zeiss) and a fluorescence microscope (Observer. D1, Carl Zeiss). It was confirmed that the prepared Py-g-PEG protected gold-silver core-shell nanorod particles were taken up by cells depending on the concentration of the particles (FIG. 16).
  • the re-dispersed liquid was stirred in a cool dark place for 3 days and then centrifuged (rotation speed: 18000 rpm, time: 15 minutes, number of times: 1) to obtain a precipitate.
  • the precipitate was re-dispersed in DMEM containing 10% FBS to obtain a re-dispersed liquid having a Py-g-PEG protected gold-silver core-shell nanorod particle concentration of 60 ⁇ g / ml and 100 ⁇ g / ml.
  • BAEC cells (cell number: 3 ⁇ 10 5 ) were seeded on a microfabricated substrate for spheroid preparation, and after culturing for 1 day, HepG2 cells (cell number: 5 ⁇ 10 5 ) were seeded to form spheroids.
  • 1 ml of a re-dispersion solution (particle concentration: 60 ⁇ g / ml, 100 ⁇ g / ml) of the above Py-g-PEG protected gold-silver core-shell nanorod particles was added thereto, incubated at 37 ° C.
  • the gold-silver core-shell nanorod particles of the present invention As described above, according to the gold-silver core-shell nanorod particles of the present invention, excellent dispersion stability is exhibited not only in a salt solution but also in a solution containing serum, and is not toxic to cells. It became clear that safety was high. In addition, since the gold-silver core-shell nanorod particles of the present invention are taken up into cells and efficiently generate heat by light irradiation, application as a medical device such as photothermal treatment using the heat can be expected.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne : des particules à nanotiges cœur-écorce Au-Ag dans lesquelles un tensioactif cationique comme le CTAB est substitué par un autre composé ; et un procédé de production des particules à nanotiges cœur-écorce Au-Ag. Elle concerne spécifiquement des particules à nanotiges cœur-écorce Au-Ag qui sont caractérisées en ce que chacune des particules à nanotiges comprend une particule à nanotige d'or qui sert de cœur, une couche d'écorce qui recouvre la surface de la particule à nanotige et est constituée d'argent, et un copolymère qui adsorbe sur la surface de la couche d'écorce. Les particules à nanotiges cœur-écorce Au-Ag sont aussi caractérisées en ce que le copolymère est un copolymère séquencé ou un copolymère greffé qui est obtenu en polymérisant au moins un monomère polymérisable (A) qui comporte un groupe représenté par la formule générale (I). Dans la formule Ra représente un groupe alcoylène comportant 2-7 atomes de carbone.
PCT/JP2010/072288 2009-12-11 2010-12-10 Particules à nanotiges cœur-écorce au-ag et leur procédé de production WO2011071167A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/514,838 US9156088B2 (en) 2009-12-11 2010-12-10 Au—Ag core-shell nanorod particles and method for producing same
EP10836086.8A EP2511028A4 (fr) 2009-12-11 2010-12-10 Particules à nanotiges c ur-écorce au-ag et leur procédé de production
JP2011545270A JP5709219B2 (ja) 2009-12-11 2010-12-10 金−銀コアシェルナノロッド粒子及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-282312 2009-12-11
JP2009282312 2009-12-11

Publications (1)

Publication Number Publication Date
WO2011071167A1 true WO2011071167A1 (fr) 2011-06-16

Family

ID=44145710

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/072288 WO2011071167A1 (fr) 2009-12-11 2010-12-10 Particules à nanotiges cœur-écorce au-ag et leur procédé de production

Country Status (4)

Country Link
US (1) US9156088B2 (fr)
EP (1) EP2511028A4 (fr)
JP (1) JP5709219B2 (fr)
WO (1) WO2011071167A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015079788A1 (fr) * 2013-11-29 2015-06-04 学校法人東京理科大学 Procédé de préparation de nanoparticules métalliques et nanoparticule métallique
WO2015108183A1 (fr) * 2014-01-20 2015-07-23 公立大学法人滋賀県立大学 Procédé de production d'un nanofil d'argent
WO2015133524A1 (fr) * 2014-03-07 2015-09-11 学校法人東京理科大学 Support polymère pour une administration intracellulaire
JP2016060811A (ja) * 2014-09-17 2016-04-25 国立研究開発法人産業技術総合研究所 近赤外光応答性ゲル材料及び該ゲル材料を用いた自己修復性材料並びに自己修復方法
KR101752541B1 (ko) * 2015-04-08 2017-06-30 서울대학교산학협력단 화학적 환원방법을 통한 금/은 코어/셀 금속 나노입자를 표면에 포함하는 이산화티타늄 중공구조 나노입자의 제조방법
KR20180035530A (ko) * 2016-09-29 2018-04-06 고려대학교 산학협력단 이종금속 나노 입자의 합성 방법
CN108311709A (zh) * 2018-02-23 2018-07-24 上海双洳生物科技有限公司 一种金纳米刺及其制备方法和应用
JP2019090111A (ja) * 2017-11-13 2019-06-13 国立大学法人北海道大学 修飾金属ナノ粒子及び医薬組成物
CN110293231A (zh) * 2019-07-11 2019-10-01 中国科学院广州能源研究所 一种以非贵金属元素为核且贵金属元素为壳的核壳结构纳米颗粒阵列的制备方法
JP2020046506A (ja) * 2018-09-18 2020-03-26 住友金属鉱山株式会社 金属ナノロッド含有樹脂、近赤外線遮蔽レンズ、近赤外線遮蔽眼鏡、保護具、近赤外線遮蔽窓材、近赤外線遮蔽器具、近赤外線遮蔽フィルム、近赤外線遮蔽ガラス、及び金属ナノロッド集合体の製造方法
CN111258091A (zh) * 2018-12-03 2020-06-09 波音公司 用于促进孔保护的***和方法以及制造***的方法
CN111888342A (zh) * 2020-07-02 2020-11-06 南方医科大学南方医院 一种载药纳米复合物及其制备方法和应用

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2011093401A1 (ja) 2010-01-27 2013-06-06 三菱レイヨン株式会社 新規連鎖移動剤及びそれを用いた乳化重合
US20130261444A1 (en) 2012-03-28 2013-10-03 The Uab Research Foundation Photothermal nanostructures in tumor therapy
CN105833270A (zh) * 2016-03-30 2016-08-10 复旦大学附属肿瘤医院 纳米金属颗粒的制备方法和纳米探针的制备方法
CN107189314B (zh) * 2017-05-17 2019-03-12 宁波大学 一种金/聚合物/金三层核壳纳米哑铃材料及其制备方法和应用
CN108097981B (zh) * 2017-12-19 2021-02-09 安徽师范大学 一种核壳结构的Au@SnO2纳米颗粒及其制备方法
US11383298B1 (en) 2018-11-30 2022-07-12 United States Of America As Represented By The Secretary Of The Air Force Polarity inversion of gold nanorod materials
CN111036935B (zh) * 2019-12-13 2022-11-11 武汉工程大学 间隙可调的Au层和AgAu层的核与CdS壳的纳米材料及其制备方法和应用
CN111375760B (zh) * 2020-04-28 2022-06-28 中国科学院海洋研究所 一种以卡拉胶作还原剂的Au-Ag纳米核壳材料及其制备方法和应用
CN114131037B (zh) * 2021-12-07 2022-06-21 南京医科大学第二附属医院 一种高sers活性的金-银合金纳米壳的制备方法
CN114309633A (zh) * 2021-12-16 2022-04-12 杭州电子科技大学 一种亲油金纳米棒制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009084680A1 (fr) * 2007-12-28 2009-07-09 Shiga University Of Medical Science Composition de nanoparticules d'or, puce à adn, absorbant de rayonnement proche infrarouge, vecteur de médicament pour système de libération de médicament (dds), agent de coloration, biodétecteur, cosmétique, composition pour diagnostic in vivo et composition pour utilisation thérapeutique
WO2009096569A1 (fr) * 2008-02-01 2009-08-06 Kyushu University, National University Corporation Procédé pour produire un nanomatériau métallique et nanomatériau métallique obtenu par celui-ci

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007023143A (ja) * 2005-07-15 2007-02-01 Idemitsu Sartomer Kk アクリル酸エステル系共重合体および水性分散体
JP5243203B2 (ja) * 2008-08-20 2013-07-24 富士フイルム株式会社 複合金属ナノロッド、並びに複合金属ナノロッド含有組成物、及び偏光材料

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009084680A1 (fr) * 2007-12-28 2009-07-09 Shiga University Of Medical Science Composition de nanoparticules d'or, puce à adn, absorbant de rayonnement proche infrarouge, vecteur de médicament pour système de libération de médicament (dds), agent de coloration, biodétecteur, cosmétique, composition pour diagnostic in vivo et composition pour utilisation thérapeutique
WO2009096569A1 (fr) * 2008-02-01 2009-08-06 Kyushu University, National University Corporation Procédé pour produire un nanomatériau métallique et nanomatériau métallique obtenu par celui-ci

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEM. LETT., vol. 38, no. 1, pages 60 - 61
DRUG DELIV. SYST., vol. 24, no. 3, pages 260
J. AM. CHEM. SOC., vol. 130, no. 32, pages 10643 - 10647
See also references of EP2511028A4

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015079788A1 (fr) * 2013-11-29 2015-06-04 学校法人東京理科大学 Procédé de préparation de nanoparticules métalliques et nanoparticule métallique
JP2015105420A (ja) * 2013-11-29 2015-06-08 学校法人東京理科大学 金属ナノ粒子の調製方法及び金属ナノ粒子
WO2015108183A1 (fr) * 2014-01-20 2015-07-23 公立大学法人滋賀県立大学 Procédé de production d'un nanofil d'argent
JP2015137370A (ja) * 2014-01-20 2015-07-30 公立大学法人 滋賀県立大学 銀ナノワイヤの製造方法
US10213838B2 (en) 2014-01-20 2019-02-26 The University Of Shiga Prefecture Silver nanowire production method
CN105934297A (zh) * 2014-01-20 2016-09-07 公立大学法人滋贺县立大学 银纳米线的制造方法
WO2015133524A1 (fr) * 2014-03-07 2015-09-11 学校法人東京理科大学 Support polymère pour une administration intracellulaire
JP2015168653A (ja) * 2014-03-07 2015-09-28 学校法人東京理科大学 細胞内送達用高分子担体
JP2016060811A (ja) * 2014-09-17 2016-04-25 国立研究開発法人産業技術総合研究所 近赤外光応答性ゲル材料及び該ゲル材料を用いた自己修復性材料並びに自己修復方法
KR101752541B1 (ko) * 2015-04-08 2017-06-30 서울대학교산학협력단 화학적 환원방법을 통한 금/은 코어/셀 금속 나노입자를 표면에 포함하는 이산화티타늄 중공구조 나노입자의 제조방법
KR20180035530A (ko) * 2016-09-29 2018-04-06 고려대학교 산학협력단 이종금속 나노 입자의 합성 방법
KR102453907B1 (ko) * 2016-09-29 2022-10-12 고려대학교 산학협력단 이종금속 나노 입자의 합성 방법
JP2019090111A (ja) * 2017-11-13 2019-06-13 国立大学法人北海道大学 修飾金属ナノ粒子及び医薬組成物
JP7376901B2 (ja) 2017-11-13 2023-11-09 国立大学法人北海道大学 修飾金属ナノ粒子及び医薬組成物
CN108311709A (zh) * 2018-02-23 2018-07-24 上海双洳生物科技有限公司 一种金纳米刺及其制备方法和应用
JP2020046506A (ja) * 2018-09-18 2020-03-26 住友金属鉱山株式会社 金属ナノロッド含有樹脂、近赤外線遮蔽レンズ、近赤外線遮蔽眼鏡、保護具、近赤外線遮蔽窓材、近赤外線遮蔽器具、近赤外線遮蔽フィルム、近赤外線遮蔽ガラス、及び金属ナノロッド集合体の製造方法
JP7361326B2 (ja) 2018-09-18 2023-10-16 住友金属鉱山株式会社 金属ナノロッド含有樹脂、近赤外線遮蔽レンズ、近赤外線遮蔽眼鏡、保護具、近赤外線遮蔽窓材、近赤外線遮蔽器具、近赤外線遮蔽フィルム、近赤外線遮蔽ガラス、及び金属ナノロッド集合体の製造方法
CN111258091A (zh) * 2018-12-03 2020-06-09 波音公司 用于促进孔保护的***和方法以及制造***的方法
CN110293231B (zh) * 2019-07-11 2022-06-21 中国科学院广州能源研究所 一种以非贵金属元素为核且贵金属元素为壳的核壳结构纳米颗粒阵列的制备方法
CN110293231A (zh) * 2019-07-11 2019-10-01 中国科学院广州能源研究所 一种以非贵金属元素为核且贵金属元素为壳的核壳结构纳米颗粒阵列的制备方法
CN111888342A (zh) * 2020-07-02 2020-11-06 南方医科大学南方医院 一种载药纳米复合物及其制备方法和应用
CN111888342B (zh) * 2020-07-02 2022-03-15 南方医科大学南方医院 一种载药纳米复合物及其制备方法和应用

Also Published As

Publication number Publication date
EP2511028A4 (fr) 2017-05-24
EP2511028A1 (fr) 2012-10-17
JP5709219B2 (ja) 2015-04-30
JPWO2011071167A1 (ja) 2013-04-22
US20120244225A1 (en) 2012-09-27
US9156088B2 (en) 2015-10-13

Similar Documents

Publication Publication Date Title
JP5709219B2 (ja) 金−銀コアシェルナノロッド粒子及びその製造方法
Luesakul et al. Shape-controlled synthesis of cubic-like selenium nanoparticles via the self-assembly method
Deng et al. Theranostic gold nanomicelles made from biocompatible comb‐like polymers for thermochemotherapy and multifunctional imaging with rapid clearance
Bai et al. Cylindrical polymer brushes-anisotropic unimolecular micelle drug delivery system for enhancing the effectiveness of chemotherapy
Bagheri et al. Controlled direct growth of polymer shell on upconversion nanoparticle surface via visible light regulated polymerization
Gui et al. Recent advances in synthetic methods and applications of photo-luminescent molecularly imprinted polymers
Abbasian et al. Chemo-photothermal therapy of cancer cells using gold nanorod-cored stimuli-responsive triblock copolymer
Appold et al. Multi-stimuli responsive block copolymers as a smart release platform for a polypyridyl ruthenium complex
Nakal-Chidiac et al. Chitosan-stabilized silver nanoclusters with luminescent, photothermal and antibacterial properties
CN109453378B (zh) 一种光控纳米粒子组装体及其制备方法与应用
Farjadian et al. Thermo-responsive nanocarrier based on poly (N-isopropylacrylamide) serving as a smart doxorubicin delivery system
Song et al. Preparation of plasmonic vesicles from amphiphilic gold nanocrystals grafted with polymer brushes
Liu et al. Smart “on-off” responsive drug delivery nanosystems for potential imaging diagnosis and targeted tumor therapy
Li et al. Preparation of PEG-modified PAMAM dendrimers having a gold nanorod core and their application to photothermal therapy
Wang et al. Thermal and photo dual-responsive core–shell polymeric nanocarriers with encapsulation of upconversion nanoparticles for controlled anticancer drug release
Wang et al. Synthesis of yolk–shell polymeric nanocapsules encapsulated with monodispersed upconversion nanoparticle for dual-responsive controlled drug release
Wang et al. Gold nanostar@ polyaniline theranostic agent with high photothermal conversion efficiency for photoacoustic imaging-guided anticancer phototherapy at a low dosage
WO2013134089A1 (fr) Nanoparticules enduites avec des copolymères à blocs amphiphiles
Poursalehi et al. A simple strategy for chemo-photothermal ablation of breast cancer cells by novel smart gold nanoparticles
Morfin-Gutierrez et al. Synthesis and characterization of poly (N-vinycaprolactam)-grafted gold nanoparticles by free radical polymerization for using as chemotherapeutic delivery system
Rohleder et al. Near-infrared-triggered photothermal aggregation of polymer-grafted gold nanorods in a simulated blood fluid
CN112089838B (zh) 肿瘤微环境响应的黑磷纳米凝胶药物及其制备方法和应用
Mousavi et al. Doxorubicin-loaded biodegradable chitosan–graphene nanosheets for drug delivery applications
He et al. Thermal and pH responsive ZnO-based nanoparticles for efficient drug delivery
CN104888214B (zh) 一种金纳米粒子光热疗剂及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10836086

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011545270

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 13514838

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2010836086

Country of ref document: EP