WO2012115151A1 - 粒子集積体、粒子集積体の製造方法、光増強素子及び光化学反応を利用する装置 - Google Patents
粒子集積体、粒子集積体の製造方法、光増強素子及び光化学反応を利用する装置 Download PDFInfo
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- WO2012115151A1 WO2012115151A1 PCT/JP2012/054279 JP2012054279W WO2012115151A1 WO 2012115151 A1 WO2012115151 A1 WO 2012115151A1 JP 2012054279 W JP2012054279 W JP 2012054279W WO 2012115151 A1 WO2012115151 A1 WO 2012115151A1
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- metal core
- segment
- carbon atoms
- fluorinated
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- KLDLLRZCWYKJBD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCCOCCO)C=C1 KLDLLRZCWYKJBD-UHFFFAOYSA-N 0.000 description 1
- WKWBAMQUPVUBKY-UHFFFAOYSA-N 2-[2-[2-(1,1-difluoro-2-undec-10-enoxyethoxy)-1,1,2,2-tetrafluoroethoxy]-1,1,2,2-tetrafluoroethoxy]-2,2-difluoroethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)COCCCCCCCCCC=C WKWBAMQUPVUBKY-UHFFFAOYSA-N 0.000 description 1
- FGDJUEZBMFELRW-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCCOCCOCCOCCO)C=C1 FGDJUEZBMFELRW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- WRZXKWFJEFFURH-UHFFFAOYSA-N dodecaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO WRZXKWFJEFFURH-UHFFFAOYSA-N 0.000 description 1
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- UJLXKYSGBFPPAD-UHFFFAOYSA-N gold;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Au].OC(=O)CC(O)(C(O)=O)CC(O)=O UJLXKYSGBFPPAD-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
- B22F1/0655—Hollow particles
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/12—Gold compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
Definitions
- the present invention relates to a particle assembly, a method for manufacturing the particle assembly, a light enhancement element, and an apparatus using a photochemical reaction.
- metal nanoparticles having a nanometer level size have properties different from those of the bulk.
- the metal nanoparticles have properties such as a melting point reduction, a quantum effect, and a specific surface area increase.
- Non-Patent Document 1 describes that a three-dimensional aggregate of zinc oxide fine particles enhances light scattering and increases photoelectric conversion efficiency in a solar cell.
- Non-Patent Document 2 describes that the three-dimensional superlattice structure of gold nanoparticle remarkably enhances the Raman scattering spectrum.
- Patent Document 1 describes that by arranging colloidal particles regularly, infrared rays are efficiently reflected and visible light transmittance is increased.
- Non-Patent Document 3 describes the use of colloidal fine particles encapsulating a drug as a drug delivery system.
- Non-Patent Document 4 discloses a method of collecting metal nanoparticles on a substrate with a polymer interposed therebetween.
- Non-Patent Document 5 discloses a method of collecting metal nanoparticles by using a template (template) made of silica particles.
- the nanoparticle integration method described in Non-Patent Document 4 is limited to integration on a flat substrate, and a plurality of processing steps are required, so that the operation tends to be complicated. Further, in the nanoparticle integration method described in Non-Patent Document 5, a template is required for integration, and after nanoparticle integration, an operation of removing the template by dissolving with hydrogen fluoride is required. Easy to get complicated.
- the present invention has been made in view of the above circumstances, and provides a particle assembly, a light enhancement element, and an apparatus utilizing a photochemical reaction, which can be manufactured by a simple operation and have an excellent light enhancement effect.
- an object of this invention is to provide the manufacturing method of the particle
- the metal core may be a fluorinated alkylene glycol group that may be branched, a fluorinated alkylene group that may be branched, or a branched structure.
- a first segment comprising an optionally fluorinated azaalkylene group, a second segment having at least one hydrophilic group and bound to one end of the main chain of the first segment, and the first segment Self-assembled, characterized by being modified with a metal core surface modifier that is directly or indirectly bonded to the other end of the main chain of the segment and has a functional group capable of binding to the metal core It is a hollow particle aggregate in which a plurality of particles are accumulated.
- the surface modifier of the metal core is represented by the general formula R t — (R h —O) 1 —R f —R a —X.
- R t represents a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms
- R h represents an alkylene group which may have 2 to 6 carbon atoms which may be branched.
- R f represents the following general formulas (1) and (2)
- R a represents a straight-chain alkyl having 3 to 18 carbon atoms, a branched alkyl having 3 to 18 carbon atoms, or an aralkyl having 3 to 18 carbon atoms
- X is a thiol group, a cyano group, a dithiol group
- Y 1 and Y 2 represent a hydrogen atom or a fluorine atom, and at least one of Y 1 and Y 2 represents a fluorine atom
- l represents an integer of 1 to 12
- m represents Represents an integer of 1 to 12
- n represents an integer of 1 to 6
- — (R h —O) l — includes a cyclic group. It may be represented by
- the hollow particle assembly may be a substantially spherical body.
- the diameter of the substantially spherical body may be 30 to 400 nm.
- the coverage of the surface modifier of the metal core on the surface of the metal core may be 20% or more.
- the metal core may contain gold, platinum, silver, copper, iron or semiconductor quantum dots.
- the method for producing a particle assembly according to the second aspect of the present invention includes a metal core having a ligand on its surface, a fluorinated alkylene glycol group which may be branched, and a fluorinated alkylene group which may be branched. Or a first segment containing a fluorinated azaalkylene group which may be branched, and a second segment having at least one hydrophilic group and bonded to one end of the main chain of the first segment; A step of mixing a surface modifier of the metal core, which is directly or indirectly bonded to the other end of the main chain of the first segment and has a functional group capable of binding to the metal core, in a solvent. It is characterized by that.
- the surface modifier of the metal core is represented by the general formula R t — (R h —O) 1 —R f —R a —X.
- R t represents a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms
- R h represents an alkylene group which may have 2 to 6 carbon atoms which may be branched.
- R f represents the following general formulas (1) and (2)
- R a represents a straight-chain alkyl having 3 to 18 carbon atoms, a branched alkyl having 3 to 18 carbon atoms, or an aralkyl having 3 to 18 carbon atoms
- X is a thiol group, a cyano group, a dithiol group
- Y 1 and Y 2 represent a hydrogen atom or a fluorine atom, and at least one of Y 1 and Y 2 represents a fluorine atom
- l represents an integer of 1 to 12
- m represents Represents an integer of 1 to 12
- n represents an integer of 1 to 6
- — (R h —O) l — includes a cyclic group. It may be represented by
- the method for producing the particle assembly may further include a step of replacing the solvent with a substitution solvent after the step.
- the light enhancement element according to the third aspect of the present invention includes the hollow particle assembly.
- An apparatus using a photochemical reaction according to the fourth aspect of the present invention includes the light enhancement element.
- this invention it is possible to provide a hollow particle assembly, a light enhancement element, and a device utilizing a photochemical reaction, which can be manufactured by a simple operation and have an excellent light enhancement effect. Moreover, this invention can provide the manufacturing method of the hollow particle assembly which can be implemented by simple operation.
- the self-organizable particle according to the present invention comprises a metal core having an optionally branched fluorinated alkylene glycol group, an optionally branched fluorinated alkylene group, or an optionally branched fluorinated azaalkylene group.
- the metal core refers to metal nanoparticles having a nanometer-level diameter.
- a constituent element of the metal core for example, gold, platinum, silver, copper, iron, semiconductor quantum dots, zinc oxide fine particles, titanium oxide fine particles, or a mixture thereof is used.
- gold, platinum, silver, or copper as a constituent element of the metal core, the effect of enhancing light absorption by the localized surface plasmon resonance described later is enhanced.
- the constituent elements of the metal core can be appropriately selected as long as they have the effects of the present invention.
- the diameter of the metal core is about 1 to 200 nm, for example, 5 nm, 10 nm, 20 nm, 50 nm, 100 nm, 200 nm, and the like. With regard to the diameter of the metal core, for example, at 20 nm to 100 nm, the effect of enhancing light absorption by the localized surface plasmon resonance described later is enhanced.
- the first segment provided in the surface modifier of the metal core may be a fluorinated alkylene glycol group that may be branched, a fluorinated alkylene group that may be branched, or a fluorinated azaalkylene group that may be branched
- fluorinated alkylene glycol group examples include two fluorinated tetraethylene glycol (FTEG), fluorinated triethylene glycol, fluorinated diethylene glycol, fluorinated monoethylene glycol, fluorinated propylene glycol, and fluorinated butylene glycol.
- FTEG fluorinated tetraethylene glycol
- examples include a group obtained by removing one hydroxyl group from the hydroxyl group and removing one hydrogen atom from the other hydroxyl group.
- the fluorinated alkylene glycol group may be represented by the following general formula.
- Y 1 and Y 2 represent a hydrogen atom or a fluorine atom, and at least one of Y 1 and Y 2 is a fluorine atom, m represents an integer of 1 to 12, and n represents an integer of 1 to 6 Represents.
- fluorinated alkylene glycol group for example, one hydroxyl group of two hydroxyl groups of fluorinated tetraethylene glycol (FTEG), fluorinated triethylene glycol, or fluorinated diethylene glycol is excluded and the other 1 A group obtained by removing one hydrogen atom from one hydroxyl group is preferably used.
- FTEG fluorinated tetraethylene glycol
- FTEG fluorinated triethylene glycol
- fluorinated alkylene group examples include groups in which part or all of the hydrogen atoms of an alkylene group having 2 to 12 carbon atoms are substituted with fluorine atoms.
- the fluorinated alkylene group may have an ether bond, for example.
- Examples of the fluorinated alkylene group having an ether bond include 1H, 1H, 4H, 4H-perfluoro-1,4-butanediol, 1H, 1H, 5H, 5H-perfluoro-1,5-pentanediol, 1H, 1H, 6H, 6H-perfluoro-1,6-hexanediol, 1H, 1H, 8H, 8H-perfluoro-1,8-octanediol, 1H, 1H, 9H, 9H-perfluoro-1,9-nonanediol, 1H, 1H , 10H, 10H-perfluoro-1,10-decanediol, 1H, 1H, 12H, 12H-perfluoro-1,12-dodecanediol, etc. except for one hydroxyl group and the other And a group obtained by removing one hydrogen atom from one hydroxyl group.
- fluorinated azaalkylene group examples include groups in which part or all of the hydrogen atoms of the azaalkylene group having 2 to 12 carbon atoms are substituted with fluorine atoms.
- fluorine atoms For example, -CH 2 -CF 2 -NH -, - CF 2 -CF 2 -NH -, - CF 2 -CH 2 -NH -, - CH 2 -CF 2 -NH-CF 2 -CH 2 -NH-, —CF 2 —CF 2 —NH—CF 2 —CH 2 —NH—, —CH 2 —CF 2 —NH—CH 2 —CF 2 —NH—, or the like is used.
- the fluorinated azaalkylene group may be represented by the following general formula.
- Y 1 and Y 2 represent a hydrogen atom or a fluorine atom, and at least one of Y 1 and Y 2 is a fluorine atom, m represents an integer of 1 to 12, and n represents an integer of 1 to 6 Represents.
- the fluorinated alkylene glycol group which may be branched the fluorinated alkylene group which may be branched, or the fluorinated azaalkylene group which may be branched, the first segment has the effect of the present invention. Any group that plays can be selected as appropriate.
- the first segment has a fluorinated alkylene glycol group that may be branched, a fluorinated alkylene group that may be branched, or a fluorinated azaalkylene group that may be branched.
- a fluorinated alkylene glycol group that may be branched
- a fluorinated alkylene group that may be branched
- a fluorinated azaalkylene group that may be branched.
- the second segment provided in the surface modifier of the metal core has at least one hydrophilic group.
- a 2nd segment has a hydroxyl group, an ether group, etc. as a hydrophilic group, for example.
- ether groups include tetraethylene glycol (PEG4), triethylene glycol (PEG3), diethylene glycol (PEG2), ethylene glycol, pentaethylene glycol, hexaethylene glycol, nonaethylene glycol, heptaethylene glycol, decaethylene glycol, and dodecaethylene.
- Examples include a group obtained by removing one hydrogen atom from one hydroxyl group out of two hydroxyl groups possessed by glycol or the like.
- the ether group for example, a group containing 12-crown 4-ether, 15-crown 5-ether, 18-crown 6-ether, or the like can be used.
- the second segment may be represented by the general formula R t — (R h —O) 1 —.
- R t represents a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms
- R h represents an optionally branched alkylene group having 2 to 6 carbon atoms.
- 1 represents an integer of 1 to 12
- — (R h —O) 1 — includes a cyclic group.
- the alkoxyl group includes, for example, a methoxy group, an ethoxy group, and the like.
- Examples of the second segment include PEG4, PEG3, PEG2, ethylene glycol, pentaethylene glycol, hexaethylene glycol, nonaethylene glycol, heptaethylene glycol, decaethylene glycol, and dodecaethylene glycol.
- a group obtained by removing one hydrogen atom from one hydroxyl group is preferably used, for example, one hydrogen from one hydroxyl group of two hydroxyl groups possessed by PEG4, PEG3, or PEG2.
- a group excluding atoms is more preferably used.
- the hydrophilic group of the second segment can be appropriately selected as long as the group has the effects of the present invention.
- the second segment has at least one hydrophilic group, and thus has a low affinity for a hydrophobic organic solvent and a high affinity for water.
- the second segment is bonded to one end of the main chain of the first segment, for example, by a covalent bond.
- the functional group provided in the surface modifier of the metal core is a functional group that can bind to the metal core. Any functional group capable of binding to the metal core can be used. Examples of the functional group include a thiol group, a cyano group, a dithiol group, an amino group, and an isocyano group. For example, a thiol group is preferably used. be able to. With respect to this functional group, any group that exhibits the effects of the present invention can be selected as appropriate.
- the functional group provided in the surface modifier of the metal core is directly or indirectly bonded to the other end of the main chain of the first segment with respect to one end to which the second segment is bonded.
- the case where the functional group is directly bonded to the other end of the main chain of the first segment refers to the case where the functional group is bonded to the other end of the main chain of the first segment by, for example, a covalent bond. .
- the case where the functional group is indirectly bonded to the other end of the main chain of the first segment is, for example, via the third segment bonded to the other end of the main chain of the first segment.
- the third segment for example, straight-chain alkyl having 3 to 18 carbon atoms, branched alkyl having 3 to 18 carbon atoms or aralkyl having 3 to 18 carbon atoms is used.
- a functional group is bonded to the other end of the main chain of the third segment with respect to one end to which the first segment is bonded, for example, by a covalent bond.
- the metal core surface modifier includes the aforementioned first segment, the aforementioned second segment, and the aforementioned functional group.
- the surface modifier of the metal core may be represented by the general formula R t — (R h —O) 1 —R f —R a —X, wherein R t is a hydrogen atom, a hydroxyl group, a carbon number of 1 Represents an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, R h represents an alkylene group having 2 to 6 carbon atoms which may be branched, and R f represents the following general formulas (1) and (2) R a represents a straight-chain alkyl having 3 to 18 carbon atoms, a branched alkyl having 3 to 18 carbon atoms, or an aralkyl having 3 to 18 carbon atoms, X is a thiol group, a cyano group, a dithiol group, Represents an amino group or an isocyano group, Y 1 and Y 2 represent a hydrogen atom or a fluorine atom, and at least
- R t — (R h —O) 1 — represents the first 2 represents a segment
- R f represents a first segment
- R a represents a third segment
- X represents a functional group
- the surface modifier for the metal core for example, 14, 14, 16, 16, 17, 17, 19, 19, 20, 20, 22, 22-dodecafluoro-35-mercapto-3, 6, 9, 12, 15 , 18,21,24-octaoxapentatriacontan-1-ol (PEG4-FTEG-C11-SH), 11, 11, 13, 13, 14, 14, 16, 16, 17, 17, 19, 19- Dodecafluoro-32-mercapto-3,6,9,12,15,18,21-heptoxadotriacontan-1-ol (PEG3-FTEG-C11-SH), 8, 8, 10, 10, 11, 11, 13, 13, 14, 14, 16, 16-dodecafluoro-29-mercapto-3,6,9,12,15,18-hexaoxanonacosan-1-ol (PEG2-F) EG-C11-SH)
- the first segment may be referred to as a fluorinated segment
- the second segment may be referred to as a fluorinated segment
- the self-organizable particles according to the present invention are characterized in that the metal core is modified with the surface modifier of the metal core described above.
- modification refers to a state in which the surface modifier and the metal core are bonded to each other by, for example, coordinate bonding of the functional group provided on the surface modifier of the metal core to the metal core.
- the coverage of the surface modifier on the surface of the metal core is, for example, 5 nm for the metal core.
- gold nanoparticles having a diameter it may be 20% or more, for example, about 50 to 60% is preferable.
- the coverage of the surface modifier on the surface of the metal core can be measured using an ICP emission analyzer (for example, ICPE-9000 (manufactured by Shimadzu Corporation)).
- ICP emission analyzer for example, ICPE-9000 (manufactured by Shimadzu Corporation)
- gold as the constituent element of the metal core
- PEG4-FTEG-C11-SH, PEG3-FTEG-C11-SH or PEG2-FTEG-C11-SH as the surface modifier
- the obtained hollow particle aggregate By dissolving (described later) in aqua regia and combusting with high frequency inductively coupled plasma, the component ratio of gold atoms and sulfur atoms can be obtained and calculated.
- a metal core composed of gold nanoparticles removes one of the two hydroxyl groups of FTEG and removes hydrogen from the other hydroxyl group.
- a first segment comprising a group excluding one atom
- a second segment comprising a group obtained by removing one hydrogen atom from one hydroxyl group of two hydroxyl groups of PEG4, and a thiol
- Fluorinated thiol-presenting gold particles coated with a metal core surface modifier PEG4-FTEG-C11-SH comprising a functional group comprising a group and a third domain comprising an alkyl chain having 11 carbon atoms be able to.
- the fluorinated thiol-presenting gold particles are represented as follows.
- the particle aggregate according to the present invention is a hollow particle aggregate in which a plurality of the aforementioned self-organizable particles are accumulated. Self-organizable particles are accumulated in three dimensions.
- the hollow particle assembly according to the present invention includes, for example, about 100 to 200 particles that can be self-assembled.
- the hollow particle aggregate according to the present invention can improve the dispersibility of the hollow particle aggregate in a solvent by having a space inside. Further, by enclosing a drug or the like in the space inside the hollow particle assembly, the hollow particle assembly can be used for an in-vivo diagnostic agent, a drug delivery system, and the like described later.
- the hollow particle aggregate according to the present invention is a hollow body
- TEM image the electron microscope
- SAXS X-ray small angle scattering
- the measured value of the X-ray scattering intensity of the hollow particle aggregate is compared with that of the core-shell model to examine whether the SAXS scattering profile matches. Can be confirmed. Any confirmation method that exhibits the effects of the present invention can be selected as appropriate.
- the hollow particle aggregate according to the present invention can be formed into, for example, a substantially spherical shape, a substantially elliptical spherical shape, a dome shape, a flat plate shape, etc., but is preferably formed in a substantially spherical shape.
- the shape (substantially spherical body etc.) of the hollow particle aggregate of the present invention can be confirmed by observation with an electron microscope (SEM image or TEM image), for example. Any shape confirmation method that exhibits the effects of the present invention can be selected as appropriate.
- the hollow particle aggregate according to the present invention is a substantially spherical body
- its diameter is 30 to 400 nm.
- the diameter can be appropriately adjusted depending on the application, but generally 30 to 200 nm is preferable.
- the diameter is preferably 50 to 200 nm, more preferably 80 to 120 nm from the viewpoint of light enhancement.
- the diameter is preferably 30 to 200 nm, more preferably 50 to 100 nm from the viewpoint of delivery efficiency.
- the average diameter of the hollow particle aggregate (substantially spherical body) is about 60 nm when there is a distribution of 70 to 80 nm, for example.
- the diameter of the hollow particle assembly (substantially spherical body) of the present invention can be measured, for example, by observation with an electron microscope (SEM image or TEM image). Any diameter measuring method that exhibits the effects of the present invention can be selected as appropriate.
- a plurality of self-organizable particles are arranged on the substantially spherical surface by, for example, a one-layer structure or a two-layer structure, preferably a one-layer structure, A spherical space exists inside the sphere.
- the inner diameter of the spherical space inside the sphere can be, for example, about 50 to 60 nm.
- the hollow particle aggregate according to the present invention can be developed on a solid substrate by, for example, a drop casting method.
- the hollow particle aggregate according to the present invention can stably maintain the state in which the hollow particle aggregate is formed even in a dry state such as when it is spread on a solid substrate.
- the hollow particle aggregate according to the present invention can exist in a state of being stably and uniformly dispersed in the polymer, for example, even in a state of being embedded in the polymer.
- the polymer for example, epoxy resin, agarose gel, methacrylate resin, isopropylacrylamide, and the like can be used. Any polymer that exhibits the effects of the present invention can be selected as appropriate.
- the method for embedding the hollow particle aggregate in the polymer include a method in which the hollow particle aggregate and the polymer are mixed and thermally cured or photocured. Any method can be selected as appropriate.
- the method for producing a particle assembly according to the present invention includes a step of mixing a metal core having a ligand on its surface and the above-described surface modifier of the metal core in a solvent (hereinafter referred to as a mixing step).
- Examples of the ligand that the metal core has on the surface include organic acids such as citric acid, ascorbic acid, and tannic acid, polyvinylpyrrolidone, polyvinyl alcohol, cetyltrimethylammonium bromide, and the like.
- organic acids such as citric acid, ascorbic acid, and tannic acid
- polyvinylpyrrolidone polyvinyl alcohol
- cetyltrimethylammonium bromide and the like.
- the material constituting the metal core include gold, platinum, silver, copper, iron, semiconductor quantum dots, zinc oxide fine particles, and titanium oxide fine particles.
- a commercially available gold citrate colloid solution or the like may be used as a metal core having a ligand on its surface.
- the metal core having a ligand on the surface and the surface modifier of the metal core are mixed in a solvent, so that the functional group provided in the surface modifier of the metal core is added to the surface of the metal core.
- they can be bonded by a coordinate bond.
- self-organization of particles occurs.
- self-organization means that particles are organized and assembled by a natural order without depending on external guidance or control.
- the self-assembly of particles proceeds in parallel with the above-described ligand exchange reaction.
- the particle aggregate according to the present invention is formed by self-organization of particles. By self-organization, for example, a hollow particle aggregate having a uniform diameter can be obtained.
- the self-assembly in the mixing step involves a balance between the hydrophobic organic solvent affinity of the first segment and the hydrophobic organic solvent non-affinity of the second segment provided in the surface modifier of the metal core. It is conceivable that. Self-organization is considered to occur spontaneously due to the repulsive action of the second segments in the solvent. Furthermore, for example, by using the surface modifier having the above-described third segment, the third segment becomes a spacer between the metal core and the first segment, and the self-assembly proceeds well. is there.
- a solvent having an ether bond for example, a solvent having an ether bond, a solvent having an SP value of about 8 to 10 (cal / ml), or a mixture thereof is used.
- the SP value as used in the present specification is a numerical value representing a solubility parameter by Hildebrand et al., And a cohesive energy density (cohesive energy density: evaporation energy per unit area of one molecule) is raised to the power of 1/2. It is a value representing the magnitude of polarity per unit volume.
- solvent having an ether bond examples include tetrahydrofuran (THF), dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane.
- THF tetrahydrofuran
- dimethyl ether diethyl ether
- diisopropyl ether di-n-butyl ether
- methyl tert-butyl ether methyl tert-butyl ether
- the solvent having an SP value of about 8 to 10 for example, cyclohexane, carbon tetrachloride, xylene, ethyl acetate, toluene, benzene, chloroform, trichloroethylene, methyl ethyl ketone, acetone or the like, or a mixture thereof is used.
- a solvent having an ether bond can be suitably used, and for example, THF can be more suitably used.
- the solvent used in the mixing step can be appropriately selected as long as it is a solvent that exhibits the effects of the present invention.
- stirring may be performed when the metal core having the ligand on the surface and the surface modifier are mixed in a solvent.
- a ligand exchange reaction and self-organization can be advanced more favorably.
- you may perform an ultrasonic treatment. By performing the ultrasonic treatment, the solubility of the metal core having the ligand on the surface in the solvent can be improved, and the ligand exchange reaction and the self-assembly can be promoted better.
- a mixture of different types of surface modifiers may be used as the surface modifier of the metal core.
- a particle aggregate can be obtained.
- the particle aggregate obtained in this step may contain self-organizable particles. For example, when the ligand exchange reaction and the self-assembly proceed well in the mixing step, more particle aggregates can be obtained.
- the mixing step for example, the mixed solution of the metal core having the ligand on the surface and the surface modifier is centrifuged, the supernatant is removed, and the solvent is added to the pellet.
- it may further include a step (hereinafter referred to as a redispersion step) in which stirring and sonication are performed, followed by centrifugation and removal of the supernatant.
- a redispersion step By performing the redispersion step, impurities in the mixed solution may be removed and self-organization may proceed well. By doing so, it becomes possible to obtain more particle aggregates.
- the solvent used in the redispersion step the same solvent as used in the mixing step can be used.
- the series of operations in the mixing step can be performed simply by simply mixing a metal core having a ligand on the surface and a surface modifier in a solvent.
- the method for producing a particle aggregate according to the present invention can be carried out by a simple operation.
- the formation of the particle aggregate is, for example, measured by measuring the absorbance of the reaction solution after the mixing step, compared with the absorbance of the reaction solution before the mixing step or the absorbance of the solution not forming the particle aggregate. This can be confirmed by observing the shift to the wavelength side.
- the formation of the particle aggregate can also be confirmed by, for example, observing a change in the color of the reaction solution. The color of the reaction solution changes from, for example, red to purple before and after the mixing step.
- the method for producing a particle aggregate according to the present invention may further include a step of replacing the solvent with a substitution solvent after the mixing step or the redispersion step.
- a substituted solvent the thing similar to the solvent used at a mixing process or a redispersion process may be used, and the thing different from the solvent used at a mixing process or a redispersion process may be used.
- the substitution solvent for example, THF, ethyl acetate, dichloromethane, butanol, methanol, acetone, dimethylformamide (DMF) and the like can be used.
- the particle aggregate according to the present invention can stably maintain the state in which the particle aggregate is formed even in a substitution solvent. Even when the particle aggregate according to the present invention is formed in a solvent in the mixing step or the redispersion step and then replaced with a substitution solvent, the state where the particle aggregate is formed can be stably maintained.
- ligand exchange reaction and self-assembly in the mixing step is shown below. This is an example in which a gold citrate colloidal solution is used as a metal core having a ligand on its surface, and PEG4-FTEG-C11-SH is used as a surface modifier for the metal core.
- the light enhancement element according to the present invention includes the aforementioned hollow particle assembly.
- the light enhancement element refers to an element that enhances light absorption by localized surface plasmon resonance.
- the light absorption by the localized surface plasmon resonance means that the energy of light or the electric field generated thereby is accumulated in the particles and the particle aggregates by the particles and the particle aggregates absorbing light of a specific wavelength.
- Light absorption due to localized surface plasmon resonance occurs also in the particles, but may be enhanced by the accumulation of a plurality of particles into an aggregate. This is because when a plurality of particles are accumulated to form an aggregate, a gap (gap) is generated between the particles, and light is accumulated in the gap.
- Raman spectroscopy can be used as a method for confirming light absorption by localized surface plasmon resonance. In Raman spectroscopy, the measurement of the Raman spectrum becomes easier by utilizing the electric field enhancement by localized surface plasmon resonance.
- the light enhancement element according to the present invention includes, for example, a photoreaction catalyst. Since this photoreaction catalyst includes the hollow particle assembly according to the present invention, light can be integrated. For example, a chemical reaction can be advanced by the energy.
- the light enhancement element according to the present invention includes, for example, an in-vivo diagnostic agent.
- a drug or the like that can be visualized by the light enhancement effect is sealed in the space inside the hollow particle assembly.
- the hollow particle aggregate in which such a drug is encapsulated is administered to the patient, and light is irradiated from outside the patient's body when the hollow particle aggregate has gathered at the lesion (for example, cancer tissue).
- the drug encapsulated in the hollow particle assembly can be visualized by the light enhancement effect, and the diagnosis of the lesioned part of the patient can be performed.
- the light enhancement element according to the present invention includes, for example, a drug delivery system.
- a drug or the like is first sealed in the space inside the hollow particle assembly.
- the hollow particle aggregate in which the drug is encapsulated is administered to a patient, and control is performed so that the hollow particle aggregate is collapsed when the hollow particle aggregate is collected at a lesion (for example, cancer tissue).
- medical agent can be discharge
- the diameter of the medium used in the drug delivery system is desirably 100 nm or less, particularly from the viewpoint of delivery efficiency when targeting cancer cells.
- the diameter of the hollow particle aggregate (substantially sphere) can be 50 to 100 nm, a drug delivery system with higher delivery efficiency can be provided.
- a higher Raman activity scattering enhancement effect can be obtained by encapsulating a drug or the like inside the hollow particle assembly according to the present invention. Therefore, for example, by encapsulating an anticancer agent in a hollow particle assembly (which may further contain a Raman probe), the detection sensitivity of the cancer tissue can be improved, and at the same time, the hollow tissue assembly is hollow in the target cancer tissue. It is possible to release the anticancer agent from inside the particle assembly.
- diagnosis and treatment of a lesion can be performed simultaneously.
- An apparatus using a photochemical reaction according to the present invention includes the above-described light enhancement element.
- Examples of the device include a light sensing device, a light sensing material, and a solar cell.
- the optical sensing device includes the above-described light enhancement element, light can be integrated. For this reason, in this optical sensing device, sensing can be performed with high sensitivity. In addition, for example, sensing can be performed using a drug or the like enclosed in the space inside the hollow particle assembly as a probe.
- the light sensing material according to the present invention includes the above-described light enhancement element.
- the light enhancement element has the property that the color changes as the distance between the particles changes. For this reason, for example, by mixing (embedding) the optical sensing material according to the present invention with a polymer, it is possible to detect the expansion / contraction, strain, etc. of the polymer caused by temperature change, humidity change, etc. by color change. It is. Further, as described above, the light sensing material according to the present invention is also useful in that it can exist in a polymer in a stable and uniformly dispersed state.
- the solar cell according to the present invention includes the above-described light enhancement element, sunlight can be integrated. For this reason, this solar cell can efficiently convert light energy into electric power.
- C11-OTs 10-undecene-1-tosylate (C11-OTs)
- C11-OTs was synthesized as follows. In a 300 mL Erlenmeyer flask, 5.0 g (29.4 mmol) of 10-undecen-1-ol was dissolved in 20 mL of dichloromethane.
- PEG3-OTs (7.94 g, 26.1 mmol, 39%) and PEG2-OTs (9.71 g, 36%) were synthesized in the same manner as described above using triethylene glycol di and ethylene glycol instead of tetraethylene glycol. .9 mmol, 32%).
- FTEG-C11 2,2,4,4,5,5,7,7,8,8,10,10-dodecafluoro-3,6,9,12-tetraoxatricos-22-en-1-ol Synthesis of (FTEG-C11)
- FTEG-C11 was synthesized as follows. In a 300 mL eggplant flask, 7.59 g (18.5 mmol) of fluorinated tetraethylene glycol (FTEG) and 7.59 g (13.9 mmol) of potassium carbonate were dissolved in 5 mL of N, N-dimethylformamide (DMF).
- FTEG fluorinated tetraethylene glycol
- DMF N, N-dimethylformamide
- the fluorinated thiol (PEG4) -presented gold particle aggregate THF solution obtained as described above was spread on a TEM electron microscope grid mesh (elastic carbon support film, STEM100Cu grid, grid pitch 100 ⁇ m) and allowed to air dry. Fluorinated thiol (PEG4) -presented gold particle aggregates were observed with an electron microscope (HD-2000, manufactured by Hitachi, Ltd.) at an acceleration voltage of 200 kV. The results are shown in FIGS. 2A-D.
- the SEM image of FIG. 2B confirmed that the spherical structure surface was covered with particles, and it was confirmed that a three-dimensional spherical structure was formed.
- the TEM image in FIG. 2C confirms that the inside of the spherical structure is seen through, and it is confirmed that a hollow spherical structure is formed by combining with the result of the SEM image described above. confirmed.
- the diameter of this spherical structure was about 100 nm.
- the presence of a spherical structure having a diameter of about 200 to 400 nm was confirmed by the TEM image in FIG. 2D. From this, it was confirmed in a dry state that the fluorinated thiol (PEG4) -presenting particle assembly formed a three-dimensional spherical structure.
- the dodecanethiol presentation gold particle does not have a fluorinated segment and a PEG segment.
- the results are shown in FIG. Fluorinated thiol (PEG4) presenting gold particle aggregate THF solution, fluorinated thiol (PEG3) presenting gold particle aggregate THF solution, and fluorinated thiol (PEG2) presenting compared to the absorbance of the dodecanethiol presenting gold particle THF solution It was confirmed that the absorbance of the gold particle aggregate THF solution was shifted to the longer wavelength side. From this, it was confirmed that a particle aggregate was formed in the solution.
- the fluorinated thiol (PEG2) -presented gold particle aggregate THF solution obtained as described above was dissolved in aqua regia and burned by high frequency inductively coupled plasma, to determine the component ratio of gold atoms and sulfur atoms. From the component ratio, the coverage was calculated based on the number of gold atoms presented on the surface. As a result, the coverage was 58.1%.
- SAXS X-ray small angle scattering
- NANO-Viewer manufactured by Rigaku Corporation
- NANO-Solver Ver3.4
- the X-ray scattering intensity (I (q)) depends on the shape and size of the scatterer (reflecting the shape factor (F (q))) and the distance between the scatterers (reflecting the structure factor (S (q))).
- Q scattering vector
- ⁇ X-ray wavelength
- ⁇ half of the angle between the scattered beam and the incident beam
- the shape factor is expressed by the following equation.
- R Shell inner radius
- d Shell thickness
- ⁇ 0 Shell outer density
- ⁇ 1 Shell density
- ⁇ 2 Shell inner density
- FIG. 5 shows a curve comparing the measured value of the X-ray scattering intensity of the particle aggregate and the fitting. The actually measured curve and the fitting curve almost coincided. From this, it was confirmed that the particle aggregate was a hollow body.
- FTEG-C11-SH having no PEG segment or PEG4-C11-SH having no fluorinated segment and a 5 nm gold citrate colloid solution are mixed, and a ligand exchange reaction is performed in the same manner as described above.
- a gold particle solution having no segment or a gold particle solution having no fluorinated segment was obtained.
- Gold particles without PEG segments and gold particles without fluorinated segments are each shown below.
- FIGS. 6A and 6B Each particle was observed using an electron microscope in the same manner as described above. The results are shown in FIGS. 6A and 6B.
- FIG. 6A is an electron microscope image of a gold particle having no PEG segment
- FIG. 6B is an electron microscope image of a gold particle having no fluorinated segment. It was confirmed that neither particle formed a particle aggregate. From this, self-assembly of particles can be realized and a particle aggregate can be obtained by using a surface modifier comprising a fluorinated segment (first segment) and a PEG segment (second segment). It became clear that.
- the Raman active scattering enhancing action on the substrate of the hollow particle assembly according to the present invention was examined.
- the fluorinated thiol (PEG4) -presenting gold particle aggregate THF solution obtained in Example 1 was centrifuged at 10,000 rpm and 4 ° C. for 5 minutes. After removing the supernatant with a micropipettor, each displacement solvent of ethyl acetate, dichloromethane, acetone, butanol, methanol, dimethylformamide (DMF) was added to the pellet and exposed to ultrasound for about 10 seconds in the same manner as described above. Substitution with substitution solvent. This was dropped onto a grid mesh for a TEM electron microscope similar to that described above, dried for more than half a day, and observed with an electron microscope as described above. The results are shown in Table 2.
- the fluorinated thiol (PEG2) -presented gold particle aggregate can stably maintain the state in which the particle aggregate is formed even when embedded in the epoxy resin, and is uniform in the epoxy resin. It became clear that it was distributed. From these facts, it is considered that this resin can be used as an optical sensing material.
- the hollow particle assembly, the light enhancement element, and the apparatus using the photochemical reaction according to the present invention can be manufactured by a simple operation and have an excellent light enhancement effect. Further, the method for producing a hollow particle assembly according to the present invention can be carried out by a simple operation.
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Abstract
Description
〔式中、Rtは水素原子、ヒドロキシル基、炭素数1~4のアルコキシル基又は炭素数1~4のアルキル基を表し、Rhは炭素数2~6の分岐していてもよいアルキレン基を表し、Rfは下記一般式(1)及び(2)
で表されてもよい。
〔式中、Rtは水素原子、ヒドロキシル基、炭素数1~4のアルコキシル基又は炭素数1~4のアルキル基を表し、Rhは炭素数2~6の分岐していてもよいアルキレン基を表し、Rfは下記一般式(1)及び(2)
で表されてもよい。
金属コアの構成元素としては、例えば、金、白金、銀、銅、鉄、半導体量子ドット、酸化亜鉛微粒子、酸化チタン微粒子等、又はこれらの混合物が用いられる。金属コアの構成元素としては、例えば、金、白金、銀、銅を用いることで、後述の局在表面プラズモン共鳴による光吸収を増強させる効果が高くなる。金属コアの構成元素に関しては、本発明の効果を奏する元素であれば、適宜選択され得る。
金属コアの直径は、1~200nm程度であり、例えば、5nm、10nm、20nm、50nm、100nm、200nm等である。金属コアの直径については、例えば20nm~100nmにおいて、後述の局在表面プラズモン共鳴による光吸収を増強させる効果が高くなる。
金属コアの構成材料としては、例えば、金、白金、銀、銅、鉄、半導体量子ドット、酸化亜鉛微粒子、酸化チタン微粒子等が挙げられる。
配位子を表面に有する金属コアとして、例えば、市販の金クエン酸コロイド溶液等を用いてもよい。
エーテル結合を有する溶媒として、例えば、テトラヒドロフラン(THF)、ジメチルエーテル、ジエチルエーテル、ジイソプロピルエーテル、ジ-n-ブチルエーテル、メチル-tert-ブチル-エーテル、アニソール、1,4-ジオキサン、1,2-ジメトキシエタン、ビス(2-メトキシエチル)エーテル、テトラヒドロピラン等、又はこれらの混合物が挙げられる。
SP値8~10(cal/ml)程度を有する溶媒として、例えば、シクロヘキサン、四塩化炭素、キシレン、酢酸エチル、トルエン、ベンゼン、クロロホルム、トリクロロエチレン、メチルエチルケトン、アセトン等、又はこれらの混合物が用いられる。
混合工程で用いる溶媒としては、例えば、エーテル結合を有する溶媒を好適に用いることができ、例えば、THFをより好適に用いることができる。
混合工程で用いられる溶媒に関しては、本発明の効果を奏する溶媒であれば、適宜選択され得る。
C11-OTsは以下の通り合成された。
PEG4-OTs、PEG3-OTs、PEG2-OTsは以下の通り合成された。
テトラエチレングリコールの代わりにトリエチレングリコールジ及びエチレングリコールを用いて上述と同様に合成することにより、PEG3-OTs(7.94g,26.1mmol,39%)及びPEG2-OTs(9.71g,36.9mmol,32%)を得た。得られたPEG3-OTsの1H-NMRスペクトルデータ(400MHz,CDCl3)は、δ/ppm=2.44(s,3H,methyl),3.53-3.58(br,6H,-CH2-O-),3.68(t,4H,J=9.2Hz,-CH2-O-),4.16(t,2H,J=8.68Hz,-CH2-O-S),7.35(d,2H,J=7.32Hz,phenyl),7.79(d,2H,J=7.32Hz,phenyl)であり、MALDI-TOF MS分析の結果(m/z)は、[M+H]calcd for C13H21O6S,305.36;found,305.2,[M+Na]calcd for C13H20O6SNa,327.35;found,327.20,[M+K]calcd for C13H20O6K,343.46;found,343.1であった。得られたPEG2-OTsの1H-NMRスペクトルデータ(400MHz,CDCl3)は、δ/ppm=2.45(s,3H,methyl),3.54-3.71(br,6H,-CH2-O-),4.20(t,2H,J=8.60Hz,-CH2-O-S),7.35(d,2H,J=7.66Hz,phenyl),7.80(d,2H,J=7.66Hz,phenyl)であり、MALDI-TOF MS分析の結果(m/z)は、[M+H]calcd for C11H17O5S,261.31;found,261.5,[M+Na]calcd for C11H16O5SNa,283.3;found, 283.6であった。
FTEG-C11は、以下の通り合成された。
PEG4-FTEG-C11、PEG3-FTEG-C11、PEG2-FTEG-C11は以下の通り合成された。
PEG4-OTsの代わりに、上述の通り得られたPEG3-OTs及びPEG2-OTsを用いて上述と同様に合成することにより、PEG3-FTEG-C11(1.19g,1.71mmol,45%)及びPEG2-FTEG-C11(490mg,0.75mmol,28%)を得た。得られたPEG3-FTEG-C11の1H-NMRスペクトルデータ(600MHz,CDCl3)は、δ/ppm=1.25-1.41(br,13H,alkyl chain),1.58-1.60(br,2H,alkyl chain),2.04(q,2H,J=7.56Hz,=CH-CH2-CH2),3.59-3.94(br,18H,-CH2-O-),4.91-5.00(br,2H,olefin),5.78-5.83(br,1H,olefin)であり、MALDI-TOF MS分析の結果(m/z)は、[M+H]calcd for C25H39F12O8,695.55;found,695.4,[M+Na] calcd for C25H38F12O8Na,717.54;found,717.4,[M+K]calcd for C25H38F12O8K,733.65;found, 733.4であった。得られたPEG2-FTEG-C11の1H-NMRスペクトルデータ(400MHz,CDCl3)は、δ/ppm=1.24-1.41(br,13H,alkyl chain),1.55-1.60(br,2H,alkyl chain),2.04(q,2H,J=7.68Hz,=CH-CH2-CH2),3.58-3.83(br,12H,-CH2-O-),3.91(t,2H,J=9.724,-CF2-CH2-O-),4.91-5.00(br,2H,olefin),5.78-5.83(br,1H,olefin)であった。
PEG4-FTEG-C11-SOMe、PEG3-FTEG-C11-SOMe、PEG2-FTEG-C11-SOMeは以下の通り合成された。
PEG4-FTEG-C11の代わりに、上述の通り得られたPEG3-FTEG-C11及びPEG2-FTEG-C11を用いて上述と同様に合成することにより、PEG3-FTEG-C11-SOMe 0.99g(1.28mmol,77%)及びPEG2-FTEG-C11-SOMe 520mg(0.71mmol,97%)を得た。
PEG4-FTEG-C11-SH,PEG3-FTEG-C11-SH,PEG2-FTEG-C11-SHは以下の通り合成された。
PEG4-FTEG-C11-SOMeの代わりに、PEG3-FTEG-C11-SOMe及びPEG2-FTEG-C11-SOMeを用いて上記と同様に合成することにより、PEG3-FTEG-C11-SH 360mg(0.494mmol,39%),又はPEG2-FTEG-C11-SH 140mg(0.204mmol,29%)を得た。
1.5mLマイクロチューブに、5nm金クエン酸コロイド溶液(Gold Colloid 5nm,British BioCell International社製)1mL(17pmol/mL)を入れ、10,000rpm、4℃で90分間遠心分離を行った。上清をマイクロピペッターを用いて取り除き、約100倍に濃縮された金クエン酸コロイド溶液を調製した。別の1.5mLマイクロチューブに、上述の通り得られたPEG4-FTEG-C11-SH(メタノール中に溶解)2μmolを入れ、メタノールを風乾させた。それに、THF490μLを加えて、PEG4-FTEG-C11-SHを溶解させた。PEG4-FTEG-C11-SHが入っている1.5mLマイクロチューブを水槽中で超音波(使用機器:超音波洗浄機 1510J-MT、ヤマト科学株式会社製)に暴露させつつ、上述の通り調製された金クエン酸コロイド溶液10μLを滴下した。さらに20分間、上述と同様に超音波に暴露させた後、2日間常温で撹拌した。このとき、反応溶液内の金濃度は濃縮前の金クエン酸コロイド溶液の濃度とほぼ同じ値(=17pmol/mL)であり、PEG4-FTEG-C11-SHの分子数は溶液内金微粒子の全結合サイト数に対して約75倍であった。なお、この際、溶液の色は、赤色から紫色に変化した。その後、10,000rpm、4℃で5分間遠心分離を行った。マイクロピペッターで上清を除いた後、ペレットにTHF500μLを加えた。再び遠心分離を行い、上清を除いた。ペレットにTHF200μLを加え、上述と同様に超音波に暴露させた。このようにして、フッ素化チオール(PEG4)提示金粒子集積体THF溶液を得た。
同様に、PEG4-FTEG-C11-SHの代わりに上述の通り得られたPEG3-FTEG-C11-SH及びPEG2-FTEG-C11-SHを用いて上述と同様に合成することにより、フッ素化チオール(PEG3)提示金粒子集積体THF溶液及びフッ素化チオール(PEG2)提示金粒子集積体THF溶液を得た。
上述の通り得られたフッ素化チオール(PEG4)提示金粒子集積体THF溶液、フッ素化チオール(PEG3)提示金粒子集積体THF溶液、及びフッ素化チオール(PEG2)提示金粒子集積体THF溶液を用いて、各粒子集積体の溶液中における動的光散乱(Dynamic Light Scattering:DLS)を測定した。Delsa Nano HC(ベックマンコールター社製)を用いて、THF中、摂氏20度で測定を行った。結果を図1に示す。DLSピーク値は、各集積体において50~70nm程度であることが確認された。
上述の通り得られたフッ素化チオール(PEG4)提示金粒子集積体THF溶液をTEM電子顕微鏡用グリッドメッシュ(エラスチックカーボン支持膜、STEM100Cuグリッド、グリッドピッチ100μm)に展開し、風乾させた。電子顕微鏡(HD-2000、日立製作所社製)により加速電圧200kVでフッ素化チオール(PEG4)提示金粒子集積体を観察した。結果を図2A-Dに示す。図2BのSEMイメージにより、球形構造体表面が粒子で覆われていることが確認され、3次元的な球形構造体が形成されていることが確認された。また、図2CのTEMイメージにより、球形構造体の内部が透けて見えていることが確認され、前述のSEMイメージの結果と併せることで、中空体状の球形構造体が形成されていることが確認された。また、この球形構造体の直径は、約100nmであった。さらに、図2DのTEMイメージにより、直径200~400nm程度の球形構造体の存在も確認された。このことから、フッ素化チオール(PEG4)提示粒子集積体が、3次元的な球形構造体を形成していることが、乾燥状態において確認された。
溶液中において粒子集積体が形成されているか確認するために、上述の通り得られたフッ素化チオール(PEG4)提示金粒子集積体THF溶液、フッ素化チオール(PEG3)提示金粒子集積体THF溶液、フッ素化チオール(PEG2)提示金粒子集積体THF溶液の吸光度、及びコントロールとして作成したドデカンチオール提示金粒子THF溶液の吸光度を、各溶液でほぼ同一の金ナノ粒子濃度において、紫外可視分光光度計(UV-1650PC、島津製作所社製)を用いて測定した。なお、ドデカンチオール提示金粒子は、フッ素化セグメント及びPEGセグメントを有しない。結果を図3及び表1に示す。ドデカンチオール提示金粒子THF溶液の吸光度に比して、フッ素化チオール(PEG4)提示金粒子集積体THF溶液、フッ素化チオール(PEG3)提示金粒子集積体THF溶液、及びフッ素化チオール(PEG2)提示金粒子集積体THF溶液の吸光度は、長波長側にシフトしていることが確認された。このことから、溶液中において粒子集積体が形成されていることが確認された。
上述の通り得られたフッ素化チオール(PEG2)提示金粒子集積体THF溶液を用いて、金属コアである金粒子表面におけるPEG2-FTEG-C11-SHの被覆率を、測定した。測定には、ICP発光分析装置(ICPE-9000、島津製作所製)を用いた。
前述で得られた粒子集積体が中空体であることをさらに確認するために、上述の通り得られたフッ素化チオール(PEG2)提示金粒子集積体THF溶液を用いて、X線小角散乱(SAXS:Small-angle X-ray scattering)分析を行った。具体的には、該粒子集積体のX線散乱強度の実測値と、コアーシェルモデルのX線散乱強度(フィッティング)とを比較して、SAXS散乱プロファイルが一致するか否かを検討した。該粒子集積体のX線散乱強度の測定には、X-ray diffractometer NANO-Viewer(リガク社製)を用いた(測定条件;カメラ長:600mm、露光時間:3時間、検出:イメージングプレート、X線波長:0.1542nm)。また、分析には、解析ソフトであるNANO-Solver(Ver3.4)(リガク社製)を用いた。
この場合、形状因子のみが考慮される。散乱体モデルがコアーシェルモデルの場合、形状因子は下記式で表される。
各パラメータは、以下の通り固定された;ρ0=0.89g/cm3(THF)、ρ1=19.32g/cm3(Au)、ρ2=0.89g/cm3(THF)、d=10nm。
PEGセグメントを有しないFTEG-C11-SH、又はフッ素化セグメントを有しないPEG4-C11-SHと5nm金クエン酸コロイド溶液とを各々混合して、上述と同様に配位子交換反応を行い、PEGセグメントを有しない金粒子溶液又はフッ素化セグメントを有しない金粒子溶液を得た。PEGセグメントを有しない金粒子及びフッ素化セグメントを有しない金粒子は、各々下記に示される。
(a):THFにCVのみを添加した(CV濃度:1×10-5μM)。
(b):実施例1で得られたドデカンチオール提示金粒子THF溶液にCVを添加した(CV濃度:1×10-5μM)。
(c):実施例1で得られたフッ素化チオール(PEG2)提示金粒子集積体THF溶液にCVを添加した(CV濃度:1×10-5μM)。
(d):フッ素化チオール(PEG2)提示金粒子集積体の中空部分にCVを内包させた、CV内包型粒子集積体を調製した。具体的には、実施例1(配位子交換反応及び自己組織化)で用いるTHFを、上述の(a)に換える以外は実施例1と同様にして、CV内包型粒子集積体を得た。
Claims (11)
- 金属コアが、分岐していてもよいフッ素化アルキレングリコール基、分岐していてもよいフッ素化アルキレン基又は分岐していてもよいフッ素化アザアルキレン基を含む第1のセグメントと、少なくとも1つの親水性基を有し前記第1のセグメントの主鎖の一端に結合している第2のセグメントと、前記第1のセグメントの主鎖の他端に直接又は間接に結合されかつ前記金属コアと結合可能な官能基と、を備える金属コアの表面修飾剤で修飾されている、
ことを特徴とする自己組織化可能な粒子が複数集積されてなる中空粒子集積体。 - 前記金属コアの表面修飾剤が、
一般式Rt-(Rh-O)l-Rf-Ra-X
〔式中、Rtは水素原子、ヒドロキシル基、炭素数1~4のアルコキシル基又は炭素数1~4のアルキル基を表し、Rhは炭素数2~6の分岐していてもよいアルキレン基を表し、Rfは下記一般式(1)及び(2)
で表される、
ことを特徴とする請求項1に記載の中空粒子集積体。 - 略球体である、
ことを特徴とする請求項1又は2に記載の中空粒子集積体。 - 前記略球体の直径は、30~400nmである、
ことを特徴とする請求項3に記載の中空粒子集積体。 - 前記金属コアの表面における前記金属コアの表面修飾剤の被覆率は、20%以上である、
ことを特徴とする請求項1乃至4のいずれか1項に記載の中空粒子集積体。 - 前記金属コアは、金、白金、銀、銅、鉄又は半導体量子ドットを含む、
ことを特徴とする請求項1乃至5のいずれか1項に記載の中空粒子集積体。 - 配位子を表面に有する金属コアと、分岐していてもよいフッ素化アルキレングリコール基、分岐していてもよいフッ素化アルキレン基又は分岐していてもよいフッ素化アザアルキレン基を含む第1のセグメントと、少なくとも1つの親水性基を有し前記第1のセグメントの主鎖の一端に結合している第2のセグメントと、前記第1のセグメントの主鎖の他端に直接又は間接に結合されかつ前記金属コアと結合可能な官能基と、を備える金属コアの表面修飾剤と、を溶媒中で混合させる工程を含む、
ことを特徴とする粒子集積体の製造方法。 - 前記金属コアの表面修飾剤が、
一般式Rt-(Rh-O)l-Rf-Ra-X
〔式中、Rtは水素原子、ヒドロキシル基、炭素数1~4のアルコキシル基又は炭素数1~4のアルキル基を表し、Rhは炭素数2~6の分岐していてもよいアルキレン基を表し、Rfは下記一般式(1)及び(2)
で表される、
ことを特徴とする請求項7に記載の粒子集積体の製造方法。 - 前記工程の後に、前記溶媒を置換溶媒に置換させる工程をさらに含む、請求項7又は8に記載の粒子集積体の製造方法。
- 請求項1乃至6のいずれか1項に記載の中空粒子集積体を含む光増強素子。
- 請求項10に記載の光増強素子を備える、光化学反応を利用する装置。
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JP2008285753A (ja) * | 2007-04-25 | 2008-11-27 | Samsung Electronics Co Ltd | ナノ結晶−金属酸化物複合体及びその製造方法 |
JP2009020437A (ja) | 2007-07-13 | 2009-01-29 | Toyota Central R&D Labs Inc | 赤外線反射材、赤外線反射積層体および赤外線反射構造体ならびにその製造方法 |
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JP2009020437A (ja) | 2007-07-13 | 2009-01-29 | Toyota Central R&D Labs Inc | 赤外線反射材、赤外線反射積層体および赤外線反射構造体ならびにその製造方法 |
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