WO2008078970A1 - Préparation in situ de substrats présentant des nanoparticules d'or dispersées - Google Patents
Préparation in situ de substrats présentant des nanoparticules d'or dispersées Download PDFInfo
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- WO2008078970A1 WO2008078970A1 PCT/KR2007/006895 KR2007006895W WO2008078970A1 WO 2008078970 A1 WO2008078970 A1 WO 2008078970A1 KR 2007006895 W KR2007006895 W KR 2007006895W WO 2008078970 A1 WO2008078970 A1 WO 2008078970A1
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- substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00646—Making arrays on substantially continuous surfaces the compounds being bound to beads immobilised on the solid supports
- B01J2219/00648—Making arrays on substantially continuous surfaces the compounds being bound to beads immobilised on the solid supports by the use of solid beads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/0072—Organic compounds
- B01J2219/00725—Peptides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to a process for in situ preparation of substrates with dispersed gold nanoparticles, substrate and biochip.
- a portable biosensor is one of micro devices in the field of biotechnology. It enables avoid complex and time-consumable processes in medical centers, thereby contributing to realization of handy self diagnosis in time-effective manner. In this regard, researches to develop earlier and more accurate diagnosis have been intensively made. Such technology developments could be expected to produce high value-added products and impose large influence on the human society.
- Medical biosensors may be classified into a DNA sensor and a protein sensor according to biological molecules used.
- protein sensors have been intensively studied for diagnosis of diseases by analyzing protein-protein interactions.
- the core technologies for protein sensors include protein immobilization onto a definite region, contributing to development of protein chip technologies. Since subunits and functional groups of proteins are affected by surrounding circumstances and substances, their bioactive configuration is extremely important in proper performance of biosensors.
- SAMs self-assembled monolayer
- proteins immobilized on substrates via short spacers are very likely to denaturation since they are greatly affected by properties of substrate surface, resulting in a sharp decrease in sensitivity of sensors. Therefore, protein integration and activity are very essential considerations for fabricating biosensors with higher efficiency.
- Korean Pat. No. 443256 discloses processes for preparing molecular electronic devices comprising the steps of preparing a monolayer by fabricating organic molecules having different functionalities at their both termini to gold (Au) electrodes, attaching gold nanoparticles onto the surface of the monolayer, and depositing gold (Au) onto the gold nanoparticles.
- Korean Pat. No. 578747 discloses a metal nanoparticle chemical sensor, comprising metal nanoparticle of gold, silver, platinum or copper; and at least two kinds of ligand molecules encapsulated on a surface of the metal nanoparticle and having a relatively lower conductivity than the metal nanoparticle, wherein electrical properties are reversibly changed by contact or interaction between an analyte and the ligand molecules.
- U.S. Pat. No. 680594 describes a process of forming a multilayer nanoparticle thin film assembly by use of stabilizers located on nanoparticles.
- the present inventors have made intensive researches to develop a novel process for accomplishing high dense integration of immobilized proteins and overcoming protein inactivation.
- immobilized proteins could be successfully controlled and protein inactivation could be prevented by a novel process in which ionic polymer thin films are formed in substrates and then gold nanoparticles are generated and dispersed in situ in the ionic polymer thin films.
- a process for in situ preparation of a substrate with dispersed gold nanoparticles which comprises the steps of: (a) immersing the substrate in a polycationic polymer solution to form a polycationic thin film on the substrate; (b) immersing the substrate in a polyanionic polymer solution to form a polymeric thin film of the polycationic polymer and the polyanionic polymer; (c) immersing the substrate with the polymeric thin film formed in a solution of a reducible-gold compound; and (d) reducing the reducible- gold compound to disperse gold nanoparticles in the polymeric thin film, whereby the substrate with dispersed gold nanoparticles is prepared.
- the present inventors have made intensive researches to develop a novel process for accomplishing high dense integration of immobilized proteins and overcoming protein inactivation.
- the integration of immobilized proteins could be successfully controlled and protein inactivation could be prevented by a novel process in which ionic polymer thin films are formed in substrates and then gold nanoparticles are generated and dispersed in situ in the ionic polymer thin films.
- the present invention is directed to providing a process for in situ preparation of a substrate with dispersed gold nanoparticles.
- in situ preparation means a preparative process in which gold nanoparticles are formed and dispersed directly in polymeric thin films on substrates to obtain substrates with stably dispersed gold nanoparticles.
- the gold nanoparticles are stably bound to polyionic polymers per se, functional groups of polyionic polymers and/or substrate surface, thereby providing binding sites for proteins or nucleic acid molecules or surface for formation of self assembled monolayer.
- a polymeric thin film is formed on a solid substrate.
- polymer and “macromolecule”, and these terms will be used interchangeably.
- the substrate useful in the present invention include any solid substrates known to one of skill in the art, preferably glass, silicon wafer, quartz, fused silica, metal, plastic and polymers [e.g, cycloolefin copolymers, poly(methyl methacrylate), polystyrene, polyethylene and polypropylene]. More preferably, the substrate used in the present invention is glass, silicon wafer, quartz, fused silica or metal except gold.
- the step for forming polymeric thin films on substrates is carried out in accordance with LbL method (layer-by-layer method) (Investigations of New Self- Assembled Multilayer Thin Films Based on Alternatively Absorbed Layers of Polyelectrolytes and Functional Dye Molecules, D. Yoo, et al., Material Resource, Soc. Symp. Proc. vol. 413, 1996, Materials Research Society).
- LbL method layer-by-layer method
- Polymers having different charges are used: polycationic polymer and
- polycationic polymer refers to polymers having a plurality of positive-charged groups in their chains.
- the polycationic polymer useful in this invention include any polymers having a plurality of positive-charged groups, preferably PAH [poly(allylamine hydrochloride)], PEI [poly(ethyleneimine)], PVBT [poly(vinylbenzyltriamethylamine)], PAN (polyaniline), PPY (polypyrrole) or poly(pyridinium acetylene), most preferably PAH.
- PAH poly(allylamine hydrochloride)
- PEI poly(ethyleneimine)
- PVBT poly(vinylbenzyltriamethylamine)
- PAN polyaniline
- PPY polypyrrole
- poly(pyridinium acetylene) most preferably PAH.
- the substrate is immersed in a polyanionic polymer solution to form a polyanionic thin film on the polycationic thin film, resulting in the generation of a bilayer composed of two typed polymers with different charges from each other.
- polyanionic polymer refers to polymers having a plurality of negative-charged groups in their chains.
- the polyanionic polymer useful in this invention include any polymers having a plurality of negative-charged groups, preferably PMA (polymethacrylic acid), PAA (polyacrylic acid), PTAA [poly(thiophene-3-acetic acid)], PSS [poly(4-styrene sulfoinc acid)], SPS [sodium poly(4-styrene sulfonate)] or PSSS [poly(sodium styrene sulfonate)], most preferably PAA.
- the present process further comprises a washing step before performing the immersion step in two types of polyionic polymers.
- a washing step before performing the immersion step in two types of polyionic polymers. For example, after the thin film is formed with the polycationic polymer on the substrate, the substrate is washed and then immersed in the polyanionic polymer solution.
- the thin films of polycationic and polyanionic polymers on the substrate are electrostatically interacted with each other, leading to the formation of stable thin films.
- the steps (a) and (b) are repeated several times.
- the immersion step with two types of polyionic polymer solutions is repeatedly performed to produce a plurality of a polycation/polyanion bilayer.
- the thickness of the final thin film can be adjusted with help of the production of a plurality of the bilayer, which enables the amount of gold nanoparticles bound to polymeric thin films to be controlled.
- the substrate with thin films formed is then immersed in a solution of a reducible-gold compound and a reduction is carried out, whereby the substrate with dispersed gold nanoparticles is prepared in situ.
- reducible-gold compound useful in the present invention includes any reducible-gold compounds known to those skilled in the art.
- reducible-gold compound means compounds capable of generating gold nanoparticles by reduction, e.g., including acids or salts of gold.
- the reducible-gold compound includes sodium tetrachloroaurate, sodium tetrabromoaurate, tetrachloroauric acid, tetrabromoauric acid, potassium tetrachloroaurate and potassium tetrabromoaurate, more preferably tetrachloroauric acid ⁇ i.e., hydrogen tetrachloroaurate).
- Hydrogen tetrachloroaurate trihydrate is most preferably.
- the substrate with thin films immersed in the solution of the reducible-gold compound undergoes reduction for in situ preparation of the substrate with gold nanoparticles dispersed in thin films. More preferably, where the substrate with polymeric thin films is immersed in the solution of the reducible-gold compound, gold ions are bound to chemically activated groups of polycationic and polyanionic polymers to form polymeric thin films. Afterwards, gold nanoparticles are formed from gold ions by reduction. In the present process, the polymeric thin films serve as substrates for nanoparticle synthesis.
- the reducing agent may include any reducing agent known to one of skill in the art, preferably formaldehyde, sodium citrate, sodium borohydride, white phosphorus, lithium ammonium hydride, sodium cyanoborohydride, sodium hypophosphide and boran-dimethylamine complex, most preferably boran-dimethylamine complex.
- gold nanoparticle refers to particles composed of gold atoms with a diameter of 1-500 nm, preferably 10-300 nm.
- the size of gold nanoparticles may be dependent on various conditions, e.g., the content of reducing agents.
- the gold nanoparticles directly formed ⁇ i.e., formed in situ) on polymeric thin films bound to substrates are bound to functional groups of polycationic and polyanionic polymers and/or substrates.
- two-dimensional substrate surface is only used, which is responsible for low dense immobilization of biomolecules (particularly proteins) on substrate surface.
- the conventional technologies have serious problems of protein inactivation due to interaction between substrate surface and proteins.
- gold nanoparticles are bound to polymeric thin films other than two-dimensional substrates, which enables gold nanoparticles to be dispersed in a three- dimensional manner.
- the present invention permits the amount of gold nanoparticles bound to substrates to be adjusted by controlling the composition and thickness of polymeric thin films.
- the process further comprises the step of (be) forming pores in the polymeric thin film of the polycationic polymer and the polyanionic polymer.
- the pores formed in the polymeric thin films increase the surface area of thin films and permits gold nanoparticles to be bound to thin films-contained functional groups positioned at three-dimensionally various sites.
- the step (be) is performed by immersing the polymeric thin film in an acid aqueous solution for phase separation.
- the acids for pore formation include any acids known to one of skill in the art.
- the acid includes inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as carboxylic acids.
- the acid for pore formation is hydrochloric acid or sulfuric acid, most preferably hydrochloric acid. It is preferable that the reaction for pore formation is carried out at acidic pH, more preferably pH 1.0-5.0, still more preferably pH 2.0-4.0 and most preferably pH 2.0-3.0.
- a substrate for biochips which comprises (a) a substrate; (b) a polymeric thin film on the substrate in which the a polymeric thin film is formed by alternative formation of a polycationic thin film and a polyanionic thin film; and (c) gold nanoparticles bound to functional groups of the polymeric thin film.
- biochip comprising the present substrate described hereinabove.
- biomolecules may be immobilized on substrates by linking to gold nanoparticles or by binding to linkers linked to gold nanopartides.
- the biomolecules immobilized on substrates may include a wide variety of biomolecules known to one of skill in the art, e.g., nucleic acid molecules (e.g., DNA, RNA and aptamer), proteins, peptides, peptide nucleic acid (PNA), lectin and avidin (or streptavidin), but not limited to. Most preferably, the biomolecules immobilized on substrates include proteins and peptides.
- the biochip is a protein chip.
- the protein chip of the present invention may proteins immobilized via linkers on solid substrates.
- the general descriptions applied to the biochip of the present invention are found in U.S. Pat. Nos. 5,143,854, 5,242,974, 5,252,743, 5,324,633, 5,384,261, 5,405,783, 5,412,087, 5,424,186, 5,451,683, 5,482,867, 5,491,074, 5,527,681, 5,550,215, 5,571,639, 5,578,832, 5,593,839, 5,599,695, 5,624,711, 5,631,734, 5,795,716, 5,831,070, 5,837,832, 5,856,101, 5,858,659, 5,889,165, 5,936,324, 5,959,098, 5,968,740, 5,974,164, 5,981,185, 5,981,956, 6,025,601, 6,033,860, 6,040,193, 6,090,555, 6,136,2
- Exemplary proteins immobilized include, but not limited to, hormones, hormone analogues, enzymes, enzyme inhibitors, signal transduction proteins or fragments thereof, antibodies or fragments thereof, single chain antibodies, binding proteins or fragments thereof, peptides, antigens, adhesive proteins, structural proteins, regulatory proteins, toxin proteins, cytokines, transcription regulatory proteins, blood clotting proteins and plant defense-inducing proteins.
- the present invention permits gold nanoparticles to be dispersed in substrates in a three-dimensional manner.
- hydrophilic polymeric films used in this invention protects proteins to decrease their denaturation.
- the amount of gold nanoparticles can be adjusted by controlling the composition and thickness of polymeric thin films formed on substrates.
- Fig. 1 schematically represents the process of the present invention.
- Hg. 2 is AFM (atomic force microscope) images of PAH [poly(allylamine hydrochloride)]/PAA[poly(acrylic acid)] porous polyelectrolyte thin film formed according to the present process.
- the left panel is a height image of tapping mode and the right panel is a phase image of tapping mode.
- Fig. 3 represents UV-vis spectra showing that the absorbance values increase as the reaction cycle of gold nanoparticle synthesis increases.
- Fig. 4 represents AFM images demonstrating the polyelectrolyte multilayer with gold nanoparticles.
- the left panel is a height image of tapping mode at pH 4.5/3.0 and the right panel is a height image of tapping mode at pH 7.5/3.5.
- the polymeric thin films with functional groups capable of binding to gold ions were prepared according to LbL method (layer-by-layer method) (Investigations of New Self-Assembled Multilayer Thin Films Based on Alternatively Absorbed Layers of Polyelectrolytes and Functional Dye Molecules, D. Yoo, et al., Material Resource, Soc. Symp. Proc. vol. 413, 1996, Materials Research Society), as depicted in Fig. 1.
- PAH poly(allylamine hydrochloride), Polysciences]
- PAA[poly(acrylic acid), Polysciences] were used as a pair of polyionic polymers in 1:1 mole ratio of PAH to PAA.
- the glass or silicon wafer was immersed in a PHA solution for several minutes to form films, and washed. Afterwards, the substrate was immersed in a PAA solution to form a bilayer through electrostatic interactions. These processes were repeated to obtain a polymeric thin film with thickness of interest.
- Example 2 The thin film prepared in Example 1 was immersed in an aqueous solution with pH 2.5 (pH was adjusted using 0.1 M HCI solution) for phase separation, thereby forming pores with a diameter of 0.5 ⁇ m. The formation of pores was verified using AFM (atomic force microscope, Digital Instruments).
- Fig. 2 shows polyelectrolyte thin film having pores.
- EXAMPLE 3 Preparation of Polymeric Thin Film with Gold Nanoparticles
- the polyelectrolyte multilayer with pores prepared in Example 2 was immersed in 5 mM gold salt solution (Hydrogen tetrachloroaurate(III) trihydrate, Sigma-Aldrich) and then immersed in 1 mM reducing solution (Borane-dimethylamine complex, Sigma-Aldrich), resulting in the production of thin films with dispersed gold nanoparticles.
- the thin film with dispersed gold nanoparticles was determined by UV-vis spectroscopy (Fig. 3) and AFM (Fig. 4).
- Fig. 3 represents UV-vis spectra showing that the absorbance values increase as the reaction cycle of gold nanoparticle synthesis increases, demonstrating that gold nanoparticles were formed in polymeric thin films.
- Fig. 4 represents AFM images demonstrating the polyelectroiyte multilayer with gold nanoparticles. The AFM images clearly show that gold nanoparticles were dispersed in the polyelectrolyte multilayer.
- the present invention provides a novel process for in situ preparation of a substrate with dispersed gold nanoparticles.
- the present invention provides a substrate with dispersed gold nanoparticles and a biochip comprising the substrate.
- the present invention permits gold nanoparticles to be dispersed in substrates in a three-dimensional manner. Such three-dimensional dispersion enables biomolecules (particularly proteins) to be immobilized with higher density.
- the present invention effectively prevents inactivation of proteins due to interaction with substrate surface and the hydrophilic polymeric film sused in this invention protects proteins to decrease their denaturation.
- the amount of gold nanoparticles can be adjusted by controlling the composition and thickness of polymeric thin films formed on substrates.
Abstract
La présente invention concerne une méthode de préparation in situ d'un substrat présentant des nanoparticules d'or dispersées, qui consiste à: a) immerger le substrat dans une solution de polymère polycationique pour former une couche mince polycationique sur le substrat; b) immerger le substrat dans une solution de polymère polyanionique pour former une couche mince polymérique du polymère polycationique et du polymère polyanionique; c) immerger le substrat comportant la couche mince polymérique ainsi formée dans un composé d'or réductible en solution; et d) réduire le composé d'or réductible afin de disperser les nanoparticules d'or dans la couche mince polymérique, ce qui permet de préparer le substrat présentant des nanoparticules d'or dispersées. L'invention concerne en outre un substrat et une biopuce comprenant le substrat.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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KR10-2006-0135415 | 2006-12-27 | ||
KR1020060135415A KR100887530B1 (ko) | 2006-12-27 | 2006-12-27 | 금 나노입자가 분산되어 결합된 기질의 인 시투 제조 |
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WO2008078970A1 true WO2008078970A1 (fr) | 2008-07-03 |
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PCT/KR2007/006895 WO2008078970A1 (fr) | 2006-12-27 | 2007-12-27 | Préparation in situ de substrats présentant des nanoparticules d'or dispersées |
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WO (1) | WO2008078970A1 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009081386A3 (fr) * | 2007-12-21 | 2009-09-11 | The Provost Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Procédé de préparation de nanoparticules |
WO2010031890A1 (fr) * | 2008-09-22 | 2010-03-25 | Consejo Superior De Investigaciones Científicas (Csic) | Synthèse de particules subnanométriques de au catalytiques portées sur des surfaces comportant des groupes amine |
CN102031566A (zh) * | 2010-09-20 | 2011-04-27 | 哈尔滨工业大学 | 基于表面等离子体效应的全有机一维光子晶体及制备方法 |
CN101602279B (zh) * | 2009-07-15 | 2012-07-25 | 中国石油大学(北京) | 原位银纳米粒子/聚合物复合分子薄膜及其制备方法 |
EP2792410A1 (fr) * | 2013-04-15 | 2014-10-22 | Goldemar Solutions, S.L. | Procédé de préparation d'un catalyseur comprenant des nanoparticules d'or, le catalyseur et son utilisation |
Citations (4)
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WO2002085500A1 (fr) * | 2001-04-18 | 2002-10-31 | Florida State University Research Foundation, Inc. | Procede de fabrication de membranes libres en polyelectrolyte |
KR20030007024A (ko) * | 2001-07-11 | 2003-01-23 | 조진한 | 회전 코팅을 이용한 단층/다층 초박막의 제조방법 |
JP2003522621A (ja) * | 1998-03-19 | 2003-07-29 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | 分解性コロイド原型上のナノ複合多層の静電的自己集成体による多層被覆粒子及び中空シェルの製造 |
KR20030089545A (ko) * | 2002-05-16 | 2003-11-22 | 한국화학연구원 | 금 나노입자를 이용한 유기분자 소자 및 이의 제조방법 |
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2006
- 2006-12-27 KR KR1020060135415A patent/KR100887530B1/ko not_active IP Right Cessation
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2007
- 2007-12-27 WO PCT/KR2007/006895 patent/WO2008078970A1/fr active Application Filing
Patent Citations (4)
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JP2003522621A (ja) * | 1998-03-19 | 2003-07-29 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | 分解性コロイド原型上のナノ複合多層の静電的自己集成体による多層被覆粒子及び中空シェルの製造 |
WO2002085500A1 (fr) * | 2001-04-18 | 2002-10-31 | Florida State University Research Foundation, Inc. | Procede de fabrication de membranes libres en polyelectrolyte |
KR20030007024A (ko) * | 2001-07-11 | 2003-01-23 | 조진한 | 회전 코팅을 이용한 단층/다층 초박막의 제조방법 |
KR20030089545A (ko) * | 2002-05-16 | 2003-11-22 | 한국화학연구원 | 금 나노입자를 이용한 유기분자 소자 및 이의 제조방법 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009081386A3 (fr) * | 2007-12-21 | 2009-09-11 | The Provost Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth Near Dublin | Procédé de préparation de nanoparticules |
US8808420B2 (en) | 2007-12-21 | 2014-08-19 | The Provost, Fellows And Scholars Of The College Of The Holy And Undivided Trinity Of Queen Elizabeth, Near Dublin | Process for preparing nanoparticles |
WO2010031890A1 (fr) * | 2008-09-22 | 2010-03-25 | Consejo Superior De Investigaciones Científicas (Csic) | Synthèse de particules subnanométriques de au catalytiques portées sur des surfaces comportant des groupes amine |
ES2335467A1 (es) * | 2008-09-22 | 2010-03-26 | Consejo Superior De Investigaciones Cientificas (Csic) (10%) | Sintesis de particulas subnanometricas de au cataliticas soportadas en superficies con grupos amino. |
CN101602279B (zh) * | 2009-07-15 | 2012-07-25 | 中国石油大学(北京) | 原位银纳米粒子/聚合物复合分子薄膜及其制备方法 |
CN102031566A (zh) * | 2010-09-20 | 2011-04-27 | 哈尔滨工业大学 | 基于表面等离子体效应的全有机一维光子晶体及制备方法 |
EP2792410A1 (fr) * | 2013-04-15 | 2014-10-22 | Goldemar Solutions, S.L. | Procédé de préparation d'un catalyseur comprenant des nanoparticules d'or, le catalyseur et son utilisation |
WO2014170191A1 (fr) * | 2013-04-15 | 2014-10-23 | Goldemar Solutions S.L. | Procédé de fabrication d'un catalyseur comprenant des nanoparticules d'or, catalyseur ainsi obtenu et son utilisation |
US9795946B2 (en) | 2013-04-15 | 2017-10-24 | Goldemar Solutions S.L. | Method of manufacturing a catalyst comprising gold nanoparticles, the catalyst and its use |
Also Published As
Publication number | Publication date |
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KR100887530B1 (ko) | 2009-03-06 |
KR20080060841A (ko) | 2008-07-02 |
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