WO2020218869A1 - Nanoagrégats d'or, leur procédé de préparation et capteur optique les comprenant - Google Patents

Nanoagrégats d'or, leur procédé de préparation et capteur optique les comprenant Download PDF

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WO2020218869A1
WO2020218869A1 PCT/KR2020/005424 KR2020005424W WO2020218869A1 WO 2020218869 A1 WO2020218869 A1 WO 2020218869A1 KR 2020005424 W KR2020005424 W KR 2020005424W WO 2020218869 A1 WO2020218869 A1 WO 2020218869A1
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formula
group
gold
present
carbon atoms
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이동일
표경림
한상명
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연세대학교 산학협력단
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    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances

Definitions

  • the present invention relates to a gold nanocluster, a method for manufacturing the same, and an optical sensor including the same.
  • a nanocluster or superatom composed of a certain number of metal atoms and ligands follows the macroatomic orbital theory, in which the valence electrons of the particles are newly defined, and this is considered to be one giant atom. It is a theory.
  • Nanoclusters are stable compared to one atom or nanoparticles, and have strong molecular properties than metallic properties, and thus have optical and electrochemical properties that are completely different from nanoparticles.
  • optical, electrical and catalytic properties of nanoclusters are sensitively changed depending on the number of metal atoms, types of metal atoms, and ligands, research on nanoclusters is actively in progress in a wide variety of fields.
  • Korean Patent Publication No. 10-1845153 is proposed as a similar prior document.
  • an object of the present invention is to provide a gold nanocluster capable of controlling the number of substances bound to an amino group, which is a terminal group, a method of manufacturing the same, and an optical sensor including the same.
  • an object of the present invention is to provide a method for producing a gold nanocluster in which a binding reaction to an amino group, which is a terminal group, is performed in an organic solvent.
  • One aspect of the present invention relates to a gold nanocluster satisfying the following Formula 1.
  • the hydrocarbon skeleton in Formula 1 may have any one or two or more substituents selected from -OH, -COOH and -NH 2 .
  • L 1 is or And R 11 is an alkylene group having 2 to 6 carbon atoms, and Ar 1 may be an aryl having 6 to 30 carbon atoms.
  • Another aspect of the present invention relates to an optical sensor including the gold nanoclusters described above.
  • R 1 is each independently hydrogen or -R 11 -Ar 1
  • y is 1, said R is at least one of the units is -R 11 -Ar 1, wherein R 11 is an alkylene group having 1 to 6 carbon atoms
  • Ar 1 may be an aryl group having 6 to 50 carbon atoms
  • R 2 is hydrogen or a leaving group
  • x is 18, 22, 25, 38, 67, 102, 144 or 333
  • y is 14, 18, 24, 35, 44, 60 or 79.
  • steps b) and c) may be performed in an organic solvent.
  • the hydrocarbon skeleton may have any one or two or more substituents selected from -OH, -COOH and -NH 2 , and the primary bonded compound and the following
  • the molar ratio of the compound of Formula 3 may be 1:5 to 25.
  • step c) may be performed with tetraalkylammonium (C1-C20)alkylcarboxylic acid or trialkylammonium (C1-C20)alkylcarboxylic acid.
  • the gold nanocluster according to the present invention has the advantage of remarkably increasing fluorescence with excellent light emission characteristics and stability.
  • the method for preparing gold nanoclusters according to the present invention has the advantage that the gold nanoclusters soluble only in water can be reacted in an organic solvent, and the number of bonds of substances that bind to an amino group, which is a terminal group, can be easily controlled.
  • Example 1 shows a method of manufacturing a gold nanocluster according to Example 1 of the present invention.
  • ESI-MS electrospray ionization mass spectrometry
  • Example 3 is a diagram showing a 1 H-NMR graph of the Au 22 GS 18 BPy 18 material prepared in Example 1 of the present invention.
  • 5 is a result of PL characteristics for a wavelength band measured after excitation of the gold nanoclusters of an example and a comparative example of the present invention at 350 nm.
  • 6 is a result of PL characteristics for the number of end group bonds measured at wavelengths of 380 nm, 480 nm and 650 nm of the gold nanocluster of an embodiment of the present invention.
  • Example 7 is a result of PL characteristics for the number of end group bonds measured at wavelengths of 380 nm, 480 nm and 650 nm of the gold nanocluster of Example 11 of the present invention.
  • first, second, A, B, (a) and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term.
  • alkyl refers to a monovalent linear or branched saturated hydrocarbon radical composed of only carbon and hydrogen atoms, and may have 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of such alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and the like.
  • alkylene refers to a divalent organic radical derived from a saturated hydrocarbon.
  • aryl in the present specification is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms suitably in each ring It includes a system, and includes a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, pyrenyl, and chrysenyl.
  • arylene used herein refers to an aromatic ring divalent organic radical derived from an aromatic hydrocarbon.
  • halo or halogen used herein refers to a halogen element, and includes, for example, fluoro (F), chloro (Cl), bromo (Br), and iodo (I).
  • the inventors of the present invention not only can easily bind various substances to the ligands of the gold nanoclusters stably in an organic solvent, but also finely control the number of bonds to realize various luminescence and fluorescence properties, and a method of manufacturing the same. It is intended to provide an optical sensor including this.
  • the present invention relates to a gold nanocluster that satisfies the following Formula 1, and by satisfying the following Formula 1, it may have excellent light-emitting properties and stability.
  • the gold nanocluster according to the present invention contains gold (Au), has a shape in which gold (Au) is coordinated with sulfur (S) in the y-unit, which is a ligand, and satisfies Formula 1.
  • the gold nanocluster is a core composed of a gold (Au) atom and a core composed of a ligand, which is GS, surrounding the core- It can have a shell structure.
  • GS is an abbreviation of the y unit in Chemical Formula 1.
  • the gold nanocluster has a gold (Au) atom at the center as a core (nucleus), and [GS-Au-GS-Au-GS-Au-GS ], and two chains such as [GS-Au-GS-Au-GS-Au-GS-Au-GS] form a ring with each other to form a cluster in a structure surrounding the core (shell).
  • Au gold
  • L 1 may be a trivalent linking group consisting of three bonds, preferably a hydrocarbon skeleton including or not including any one or two or more selected from -CONH- . More preferably, it may have one or two or more substituents selected from -OH, -COOH and -NH 2 in the hydrocarbon skeleton. More preferably, it may be one having a -COOH substituent in the hydrocarbon skeleton.
  • L 1 in Formula 1 may be a glutathione skeleton, and the glutathione skeleton has two carboxyl groups (-COOH) and It is derived from a compound represented by the following formula (4) having one amino group (-NH 2 ).
  • the gold nanocluster can be easily bonded with various materials to the terminal groups, thereby increasing the luminous intensity and yield, as well as finely adjusting the number of bonds, thereby implementing various luminous intensities. have.
  • each of R 1 is independently hydrogen or -R 11 -Ar 1 , and at least one of the y units R 1 is -R 11 -Ar 1 .
  • at least two of R 1 may be -R 11 -Ar 1 .
  • R 11 is an alkylene group having 1 to 6 carbon atoms
  • Ar 1 may be an aryl group having 6 to 50 carbon atoms
  • R 11 is an alkylene group having 2 to 6 carbon atoms
  • Ar 1 may be an aryl group having 6 to 50 carbon atoms.
  • R 11 is propylene, isopropylene, butylene, pentylene or hexylene
  • Ar 1 may be a polycyclic aromatic group, and specifically, phenyl, naphthyl, biphenyl, anthryl, pyrenyl, or It could be Senil.
  • R 11 is a direct bond, energy transfer disappears, whereas when the end group bonds as described above are formed, more energy transfer occurs, thereby implementing excellent fluorescence.
  • the gold nanocluster according to the present invention when at least one of the y units of R1 is bonded to -R 11 -Ar 1 as described above, fluorescence can be imparted, and as the number of bonds increases, strong fluorescence can be implemented. . Moreover, when all of the R 1s in the y unit are combined with -R 11 -Ar 1 , the fluorescence in the three wavelength bands of 380 nm, 480 nm and 650 nm is dramatically increased, and white light may be realized. As described above, the combination of all of the R 1s in the y unit is an effect that cannot be implemented by conventional manufacturing methods.
  • the gold nanocluster has the number of ligands that can be bound according to the number of gold atoms, and specifically, x in Formula 1 is 18, 22, 25, 38, 67, 102, 144 or 333, , y is 14, 18, 24, 35, 44, 60 or 79.
  • x in Formula 1 is 18, 22, 25, 38, 67, 102, 144 or 333,
  • y is 14, 18, 24, 35, 44, 60 or 79.
  • x is preferably 18, 22 or 25, and y may be 14 or 18.
  • (x,y), (18,14), ( 22,18) or (25,18) may be satisfied, but is not limited thereto.
  • the gold nanoclusters may have an average size of 10 nm or less, preferably 0.1 to 5 nm, more preferably 0.5 to 3 nm, but are limited thereto. It does not become.
  • the gold nanocluster according to the present invention has the above configuration, so that remarkably excellent fluorescence can be realized, and a fluorescence effect maximized even with a small amount can be realized.
  • the gold nanoclusters according to the present invention can achieve water solubility because the carboxyl group is present as it is. By having water solubility in this way, it can be applied in various ways in the field of biotechnology such as biopsy.
  • the optical sensor refers to a sensor having optical characteristics capable of expressing light emission and fluorescence characteristics, and may be specifically a fluorescence sensor or a light emission sensor. Depending on the application used, for example, it may be selected from a bio sensor, an energy harvesting sensor, and a gas sensor, and in more detail, it may be applied in a field selected from bio-imaging, bio-diagnosis, disease diagnosis and gas detection, etc. It is not limited thereto.
  • the gold nanocluster may be used as an optical sensor by itself, and may be used in combination with various parts, materials, systems, etc., but is not limited thereto.
  • Another aspect of the present invention relates to a method for preparing a gold nanocluster as described above, and in detail, to a method for preparing a gold nanocluster represented by the following Chemical Formula 1, a) a compound represented by the following Chemical Formula 2 and a quaternary ammonium salt Reacting to first bond a quaternary ammonium salt to the carboxyl group of the compound represented by Formula 2, b) secondary bonding the compound represented by the following Formula 3 to the amino group of the primary bonded compound; and c) the And removing the quaternary ammonium salt primary bonded to the carboxyl group of the secondary bonded compound.
  • Chemical Formula 1 a) a compound represented by the following Chemical Formula 2 and a quaternary ammonium salt Reacting to first bond a quaternary ammonium salt to the carboxyl group of the compound represented by Formula 2, b) secondary bonding the compound represented by the following Formula 3 to the amino group of the primary bonded compound; and c) the And removing the qua
  • R 1 is each independently hydrogen or -R 11 -Ar 1, wherein R 1 is at least one of y units -R 11 -Ar 1, wherein R 11 is alkyl of 1 to 6 carbon atoms Is a ren group
  • Ar 1 may be an aryl group having 6 to 50 carbon atoms
  • R 2 is hydrogen or a leaving group
  • x is 18, 22, 25, 38, 67, 102, 144 or 333
  • y is 14, 18 , 24, 35, 44, 60, or 79.
  • the description of Chemical Formulas 1 to 3 will be omitted for the same overlapping description as derived from the description of the gold nanocluster.
  • the reaction steps b) and c), which are the reaction steps of binding the substance to the end group of the ligand, can be performed in an organic solvent without water, and the reaction activity and stability are excellent.
  • the number of bonds can be precisely adjusted as desired, and the gold nanoclusters yield of the reaction performed in organic solvent conditions is 3 times or more compared to the reaction performed in water-containing conditions. can do.
  • the method of manufacturing a gold nanocluster according to the present invention may sequentially perform steps a) to c), and is specifically as follows.
  • the compound represented by Formula 2 in step a) includes a carboxyl group and an amino group as terminal groups, and may be primary bonded by reacting a quaternary ammonium salt with the carboxyl group.
  • the compound represented by Formula 2 is a material that is soluble only in water, but after passing through step a) as described above, it loses solubility in water and becomes solubility in an organic solvent.
  • the reaction can proceed.
  • the number of bonds during the end group bonding reaction can be precisely controlled as desired with excellent reaction activity and stability, and gold nanoclusters can be obtained with excellent yield. Further, it is possible to more stably bind the compound represented by Formula 3 to the amino group of the compound represented by Formula 2.
  • step a) a solution obtained by dispersing or dissolving a quaternary ammonium salt in an organic solvent is added to an aqueous solution obtained by dispersing or dissolving the compound represented by Chemical Formula 2 in water, and is then first bonded to the product. It may be to induce a phase shift to the phase. Accordingly, it is possible to induce a subsequent reaction in the organic solvent as described above.
  • the first bonding in step a) may be performed under basic conditions, and preferably may be reacted under conditions of pH 8 to 10.
  • the primary bond may have a form of an ionic complex between the carboxyl group of the compound represented by Formula 2 and a quaternary ammonium salt. Having the form of the ionic complex is preferable because it loses solubility in water and has solubility in organic solvents, and it is possible to easily separate the quaternary ammonium salt from the gold nanocluster again in step c).
  • the organic solvent may be a non-water miscible non-polar solvent. Specifically, it may be selected from an aliphatic alkyl-based solvent, a substituted alkyl-based solvent, and an aromatic-based solvent. For example, toluene, xylene, benzene, dichloromethane, dichlorobenzene, chloroform, cyclohexane, methylcyclohexane, heptane, hexane, octane, decane, undecane, dodecane, tetradecane, pentadecane and hexadecane ) It may be any one or a mixture of two or more selected from.
  • the compound represented by Chemical Formula 2: quaternary ammonium salt may be performed in a weight ratio of 1: 1.5 to 3.
  • the quaternary ammonium salt may be an ammonium salt having a tetraalkyl substituted structure, and specifically, may be a tetra(C4-C20)alkylammonium salt.
  • TBACl Tetrabutyl ammonium bromide
  • TPABr Tetrabutylammonium bromide
  • THXABr Tetrahexyl ammonium bromide
  • THXABr Tetrahexylammonium bromide
  • TOABr Tetraoctylammonium bromide
  • TODABr Tetrahexadecylammonium bromide
  • TODABr Tetraoctadecyl ammonium bromide
  • TODABr Tetraoctadecyl ammonium bromide
  • TODABr Tetraoctadecyl ammonium bromide
  • TODABr Tetraoctadecyl ammonium bromide
  • TBACl Tetrabutyl ammonium chloride
  • the compound represented by Formula 3 may be secondary bonded to the amino group of the primary bonded compound.
  • the secondary bond may be a coupling reaction between the carboxyl group of the compound represented by Formula 3 and the amino group of the compound represented by Formula 2 through DCC/NHS coupling reaction as an example of a coupling reagent.
  • DCC dicyclohexylcarbodiimide
  • NHS N-hydroxysuccinimide
  • a leaving group according to an embodiment of the present invention is a fragment of a compound that has an electron pair when a compound is disproportionately decomposed in a chemical reaction, and stabilizes an electron pair that is additionally taken out as an anion or a neutral molecule. The ability is important to break away from the original molecule.
  • the leaving group according to an embodiment of the present invention may be any functional group recognized by those skilled in the art, but may be, for example, a halogen group, an N-succinylimide group, or the like.
  • the dicyclohexylcarbodiimide and N-hydroxysuccinimide may be included in a molar ratio of 1:0.1 to 1:5, and preferably, for smooth secondary bonding, from 1:1 to It may be included in a 1:4 molar ratio, but is not limited thereto.
  • the secondary bonding in step b) may be performed under a basic catalyst.
  • the basic catalyst may further comprise any one or a mixture of two or more selected from, for example, pyridine, pyrimidine, triethylamine, diethylamine, diisopropylamine, diisopropylethylamine and dimethylaminopyridine. I can.
  • the reaction solution is adjusted to a basic condition, so that the secondary bonding reaction can be performed more effectively.
  • the compound represented by Formula 3 can be covalently bonded to the gold nanoclusters very uniformly and stoichiometrically.
  • the number of moles of the compound of Formula 3 that is secondary bonded according to the number of moles of the compound represented by Formula 3 can be finely adjusted according to the characteristics of a uniform and stoichiometric reaction, so that a light emission intensity suitable for a purpose can be realized.
  • the molar ratio of the primary bonded compound and the compound of Formula 3 may be adjusted according to the light emission intensity corresponding to the purpose, but it may be preferably 1: 5 to 25, more preferably 1: 10 to 20. have.
  • the compound represented by the formula 3 is preferably characterized in that said R 11 is an alkylene group having 2 to 6 carbon atoms, wherein Ar 1 may be aryl having 6 to 50 carbon atoms in the date. More preferably, R 11 is propylene, isopropylene, butylene, pentylene or hexylene, and Ar 1 may be a polycyclic aromatic group, and specifically, phenyl, naphthyl, biphenyl, anthryl, pyrenyl, or It could be Senil. When the end group bonds as described above are formed, excellent fluorescence can be implemented.
  • the secondary bond may bind one or more of the y units of the compound represented by Formula 1, thereby imparting fluorescence, and increasing the number of bonds, resulting in stronger fluorescence. Can be implemented. Moreover, when all of the y units are secondary-coupled, the fluorescence intensity in the three wavelength bands of 380 nm, 480 nm and 650 nm increases dramatically, and white light can be realized. Combining all of the y units as described above is an effect that cannot be realized by conventional manufacturing methods.
  • step c) is a step of removing the quaternary ammonium salt primary bonded to the carboxyl group among the secondary bonded compounds.
  • an ammonium salt of an alkylcarboxylic acid may be used to remove the primary bonded quaternary ammonium salt, and specifically tetraalkylammonium (C1-C20)alkylcarboxylic acid or trialkylammonium (C1-C20)alkylcar It can be carried out using an acid, preferably tetra(C1-C5)alkylammonium (C1-C20)alkylcarboxylic acid or tri(C1-C5)alkylammonium (C1-C20)alkylcarboxylic acid.
  • the ammonium salt of the alkylcarboxylic acid may be a tetraammonium salt of the alkylcarboxylic acid, and preferably R 3 COO - N + (R 4 R 5 R 6 R 7 ) may be satisfied.
  • R 3 is an alkyl group having 1 to 20 carbon atoms, and R 4 to R 7 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms. More preferably, R 3 may be an alkyl group having 10 to 20 carbon atoms, and R 4 to R 7 may each independently be hydrogen or an alkyl group having 1 to 3 carbon atoms.
  • a carboxyl group is formed in the final gold nanocluster to lose solubility in an organic solvent and may have water solubility again.
  • water solubility By having water solubility in this way, it can be used in the bio field as it is compatible with the biological environment where water exists. In addition to this, it can be applied in various fields in fields requiring excellent fluorescence.
  • the solvent was completely removed by rotary evaporation, and then the Au 22 GS 18 nanoclusters were separated through a recrystallization process in which a solid formed by adding 12 ml of isopropanol was dissolved in 10 ml of water and precipitated using a centrifuge.
  • a solid produced by adding 2 ml of isopropanol to the supernatant was separated through a centrifuge, and this process was continued until the supernatant became transparent.
  • the separated solid was washed with an excess of isopropanol and methanol to remove impurities remaining without reaction to obtain a gold nanocluster (Au 22 GS 18 ), which is an Au 22 cluster protected by glutathione ligand (GS).
  • FIG. 2 shows the mass spectrometry results of the gold nanocluster (Au 22 GS 18 ) prepared in Preparation Example 1. From this, it can be seen that gold nanoclusters (Au 22 GS 18 ) were synthesized.
  • HAuCl 4 ⁇ 3H 2 O dissolved in 80 ml of methanol and 1.23 g of glutathione (GS) dissolved in 40 ml of water were simultaneously mixed, stirred vigorously for 30 minutes, and the color of the solution When it turned to a turbid white color, 0.374 g NaBH 4 dissolved in 10 ml of water was added and stirred vigorously for 1 hour and 30 minutes. After evaporation of all solvents, 10 ml of water was added to dissolve them. Each 5 ml each was transferred to a Falcon tube, and 1 ml of methanol was added, shaken, and centrifuged. The supernatant was transferred to another Falcon tube and a solid that fell below was obtained.
  • GS glutathione
  • TOABr tetraoctylammonium bromide
  • N-hydroxysuccinimide N-hydroxysuccinimide
  • BPy 1-pyrene valeric acid
  • impurities were removed to obtain a reaction intermediate (NHS-BPy) in which N-hydroxysuccinimide was bound to 1-pyrenevaleric acid.
  • Example 3 shows 1 H-NMR of the Au 22 GS 18 BPy 18 material prepared in Example 1, and it can be seen that the Au 22 GS 18 BPy 18 of Example 1 was prepared as FIG. 3 suggests.
  • Example 1 In Example 1, except that 0.007 mmol of the reaction intermediate (NHS-BPy) dissolved in 1 ml of dichloromethane was added to the TOA-Au 22 cluster dissolved in 0.001 mmol in 5 ml of dichloromethane.
  • Gold nanoclusters obtained by performing the same procedure as in Example 1 were obtained by separating Au 22 GS 18 BPy 7 material through polyacrylamide gel electrophoresis (PAGE).
  • Example 1 in place of Au 22 GS 18 , the same was carried out except that the Au 18 GS 14 prepared from Preparation Example 2 was used to obtain a gold nanocluster Au 18 GS 14 Bpy 14 .
  • Gold nanocluster Au 25 GS 18 Bpy 18 was obtained in the same manner as in Example 1, except that Au 25 GS 18 prepared from Preparation Example 3 was used instead of Au 22 GS 18 in Example 1.
  • Example 10 also had the same pattern as in Examples 1 and 11, and luminescence peaks were expressed at 380 nm, 480 nm and 650 nm, and the emission intensity was remarkably improved while emitting white light. I did.
  • the gold nanoclusters according to the present invention not only can easily control the number of end group bonds, but also induce end group bonds as much as the number of ligands, and thus can have strong luminescence intensity. It can be applied to various optical sensors due to its excellent luminescence and fluorescence properties, and the final material has water solubility, so it is excellent for application to bio fields such as living bodies.

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Abstract

La présente invention concerne des nanoagrégats d'or, un procédé de préparation associé, et un capteur optique le comprenant et, spécifiquement, la présente invention concerne des nanoagrégats d'or qui peuvent augmenter significativement la fluorescence avec des caractéristiques d'émission de lumière et une stabilité excellentes, un procédé de préparation associé, et un capteur optique comprenant les nanoagrégats d'or.
PCT/KR2020/005424 2019-04-26 2020-04-24 Nanoagrégats d'or, leur procédé de préparation et capteur optique les comprenant WO2020218869A1 (fr)

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KR1020200049583A KR102408347B1 (ko) 2019-04-26 2020-04-23 금 나노클러스터와 이의 제조방법 및 이를 포함하는 광학 센서

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WO2016022870A1 (fr) * 2014-08-07 2016-02-11 The Regents Of The University Of Michigan Nanoagrégats métalliques et leurs utilisations
KR20160134257A (ko) * 2015-05-15 2016-11-23 연세대학교 산학협력단 발광 특성이 뛰어난 금 클러스터 및 이의 제조방법
KR20170127794A (ko) * 2016-05-12 2017-11-22 연세대학교 산학협력단 고발광 금 나노 클러스터 및 그의 제조방법

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JP2007045791A (ja) * 2005-08-12 2007-02-22 Univ Of Tsukuba Ａｕ２５クラスターの選択的大量合成方法
WO2016022870A1 (fr) * 2014-08-07 2016-02-11 The Regents Of The University Of Michigan Nanoagrégats métalliques et leurs utilisations
KR20160134257A (ko) * 2015-05-15 2016-11-23 연세대학교 산학협력단 발광 특성이 뛰어난 금 클러스터 및 이의 제조방법
KR20170127794A (ko) * 2016-05-12 2017-11-22 연세대학교 산학협력단 고발광 금 나노 클러스터 및 그의 제조방법

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