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WO2007138851A1 - Nanoparticule de semi-conducteur III-V/SiO2 et agent de marquage de substances biologiques - Google Patents

Nanoparticule de semi-conducteur III-V/SiO2 et agent de marquage de substances biologiques Download PDF

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Publication number
WO2007138851A1
WO2007138851A1 PCT/JP2007/059937 JP2007059937W WO2007138851A1 WO 2007138851 A1 WO2007138851 A1 WO 2007138851A1 JP 2007059937 W JP2007059937 W JP 2007059937W WO 2007138851 A1 WO2007138851 A1 WO 2007138851A1
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WO
WIPO (PCT)
Prior art keywords
iii
type semiconductor
nanoparticle
nanoparticles
type
Prior art date
Application number
PCT/JP2007/059937
Other languages
English (en)
Japanese (ja)
Inventor
Naoko Furusawa
Kazuya Tsukada
Original Assignee
Konica Minolta Medical & Graphic, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Priority to JP2008517824A priority Critical patent/JP5200931B2/ja
Publication of WO2007138851A1 publication Critical patent/WO2007138851A1/fr

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Classifications

    • 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
    • G01N33/588—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with semiconductor nanocrystal label, e.g. quantum dots
    • 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

Definitions

  • the present invention relates to III V-type semiconductor ZSiO-type nanoparticles, and the III V-type semiconductor ZSiO-type
  • semiconductor nanoparticles have a nanometer size, they exhibit quantum size effects such as an increase in bandgap energy, and exhibit, for example, good optical absorption characteristics and optical characteristics such as light emission characteristics. It is known to show. Therefore, in recent years, research reports on semiconductor nanoparticles have only been actively made. Semiconductor nanoparticles such as CdSeZZnS type semiconductor nanoparticles and Si ZSiO type semiconductor nanoparticles can be used for various purposes such as displays and LEDs.
  • the marker substances such as organic fluorescent dyes conventionally used in the above method have the disadvantages that they are severely deteriorated when irradiated with ultraviolet rays and have a short lifetime, and the sensitivity with low luminous efficiency is sufficient.
  • a method using semiconductor nanoparticles as the marker substance has attracted attention.
  • a polymer having a polar functional group is physically and
  • the semiconductor nanoparticles disclosed in Patent Document 1 substantially including the effects thereof are CdSeZZnS type semiconductor nanoparticles, but when used as a biological material labeling agent, the surface is organic. Although it is covered with molecules, the materials used with these semiconductor nanoparticles, especially CdSe, have been pointed out to be inherently biotoxic and environmentally friendly. There was a problem.
  • the SiZSiO type semiconductor nanoparticle used in Patent Document 2 has Si as its core material.
  • Si may be too reactive with other substances, such as oxygen.For example, deterioration of luminescence characteristics when UV irradiation is continued in an aqueous dispersion. There was a problem.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-329686
  • Patent Document 2 JP 2005-172429 A
  • the present invention provides a luminescent material with high emission intensity and little deterioration using III VI type semiconductor nanoparticles with low toxicity, and further, a biological material label using the III VI type semiconductor nanoparticles.
  • the purpose is to provide an agent.
  • III-V type semiconductor / SiO type nanoparticle characterized by having a particle size in the range of 1 to 50 nm.
  • III V-type semiconductor ZSiO-type nanoparticle according to any one of 1 to 4 above and a molecular marker
  • Bio substance labeling agent characterized in that it is bound to a recognition substance via an organic molecule.
  • the present invention it is possible to provide a light emitting material with high emission intensity and low deterioration using III-VI type semiconductor nanoparticles with low toxicity. Further, the III V type semiconductor ZSiO type
  • Bio substance labeling agent could be provided using nanoparticles.
  • the present invention may use the expression AZB-type nanoparticle.
  • a doublet means a nanoparticle with a core formed of InP and a shell formed of SiO.
  • Akira has one feature that the shell is SiO. Core material as shell material
  • SiO has a band gap of 9eV
  • SiO is very cheap as a compound.
  • the thickness of the shell is in the range of 0.2 to 50 nm, and more preferably in the range of 1 to 20 nm. If the thickness of the shell is larger than the lower limit of the above range, the thickness of the shell is sufficient, and it does not cause a chemical reaction between the core and other substances or a decrease in light emission intensity when light irradiation is continued. . In addition, it is preferable that the shell thickness is smaller than the upper limit of the above range because the optical properties of the nanoparticles can be sufficiently exhibited.
  • the m-V semiconductor is a semiconductor using an m-group element and a V-group element.
  • Group m (group 13) elements include aluminum (A1), gallium (Ga), and indium (In) forces.
  • Group V (group 15) elements include nitrogen (N), phosphorus (P), and arsenic ( As) and antimony (Sb) are often used.
  • GaAs gallium 'arsenic
  • InP indium' phosphorus
  • InGaAs InGaAs
  • GaInNAs gainus
  • InP Ga (0 ⁇ x ⁇ 1), etc. are produced.
  • the gap is close to and located in the visible light region, it is mainly used as a light-emitting device material.
  • many of the current red, green and blue light emitting diodes are III-V
  • the material is semiconductor.
  • the particle size of the core formed of the III V semiconductor is in the range of 1 to 50 nm, preferably in the range of 1 to 20 nm, and more preferably in the range of 2 to 12 nm. If the particle size of the core is not less than the lower limit of the above range, the particle size can be easily adjusted, and the variation in the particle size is reduced. Further, if the core particle size is not more than the upper limit of the above range, it has good optical characteristics. In the present invention, InP Ga (0 ⁇ x ⁇ 1) is preferred among III-V semiconductors.
  • the surface of the nanoparticle shell is preferably subjected to a hydrophilization treatment because there are problems such as aggregation of particles having poor water dispersibility.
  • Examples of the hydrophilization treatment method include a method in which the surface lipophilic group is removed with pyridine and the like, and then the surface modifier is chemically and Z-bound or physically bonded to the particle surface.
  • the surface modifier those having a carboxyl group or an amino group as a hydrophilic group are preferably used, and specific examples include mercaptopropionic acid, mercaptodecanoic acid, and amaminopropanethiol.
  • the biological material labeling agent of the present invention includes the above-described hydrophilic treatment III V type semiconductor ZSiO
  • the biological substance labeling agent of the present invention can label a biological substance by specifically binding and Z-reacting with the target biological substance.
  • the molecular labeling substance include nucleotide chains, antibodies, antigens and cyclodextrins.
  • the biological substance labeling agent of the present invention comprises a hydrophilic IIIV type semiconductor ZSiO type nanoparticle.
  • the two molecules and the molecular labeling substance are bound by an organic molecule.
  • the organic molecules include III-V type half Conductor Zsio-type nanoparticles are not particularly limited as long as they are organic molecules that can bind to the molecular labeling substance.
  • Strength For example, among proteins, albumin, myoglobin, casein and the like, and avidin which is a kind of protein are also preferably used together with piotin.
  • the form of the bond is not particularly limited, and examples thereof include a covalent bond, an ionic bond, a hydrogen bond, a coordination bond, a physical adsorption, and a physic adsorption. Bond stability strength Bonds with strong binding strength such as covalent bonds are preferred.
  • mV type semiconductor Zsio type nanoparticles are hydrophilized with mercaptodecanoic acid.
  • avidin and piotin can be used as organic molecules.
  • the carboxyl group of the hydrophilized III V semiconductor Zsio nanoparticle is avid.
  • the avidin is further selectively bonded to piotin, and the biotin is further bonded to the biomaterial labeling agent to form a biomaterial labeling agent.
  • the glovebox is deoxygenated in an Ar atmosphere, and synthesis is performed in this environment.
  • TOPO tri-n-octylphosphine oxide
  • TOP tri-n-octylphosphine
  • 4.5g is put in a three-necked flask, and the temperature is raised to 290 ° C.
  • Nanoparticle dispersion liquid 1 could be obtained.
  • Nanoparticle dispersion 2 could be obtained.
  • a particle dispersion 4 could be obtained.
  • a child dispersion 5 could be obtained.
  • lnm obtained in the preparation of the nanoparticle dispersion 1 were dispersed in pyridine, and this dispersion was heated to 100 ° C.
  • Dimethylzinc, 0.0041 g, tributylthiophosphine, A mixed solution of 0. 0053 g, tributylphosphine, and 10 g was added.
  • methanol was added to aggregate the particles, and the aggregate was separated by centrifugation.
  • Nanoparticle dispersion 2 94% Present invention
  • Nanoparticle dispersion 5 99% comparison
  • Avidin-conjugated nanoparticles were produced by adding 25 mg of avidin to 10 ml of the nanoparticle dispersion 10 obtained by hydrophilizing the nanoparticle dispersion 2 of Example 1 and stirring at 40 ° C. for 10 minutes.
  • the resulting avidin-conjugated nanoparticle solution was mixed and stirred with an oligonucleotide having a known piotinated base sequence to prepare an oligonucleotide labeled with nanoparticles.
  • An oligonucleotide having a base sequence complementary to the labeled oligonucleotide is obtained by dropping and washing the labeled oligonucleotide on a DNA chip on which oligonucleotides having various base sequences are immobilized. Only these spots emitted light by UV irradiation. This confirmed the labeling of the oligonucleotides on the nanoparticles.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Molecular Biology (AREA)
  • Hematology (AREA)
  • General Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Biomedical Technology (AREA)
  • Immunology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cell Biology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Materials Engineering (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Luminescent Compositions (AREA)

Abstract

L'invention concerne un matériau luminescent utilisant des nanoparticules de semi-conducteur III-V moins toxiques et présentant une intensité lumineuse élevée. Ce matériau luminescent se détériore difficilement. L'invention concerne également un agent de marquage de substances biologiques qui utilise les nanoparticules de semi-conducteur III-V. L'invention concerne spécifiquement une nanoparticule de semi-conducteur III-V/SiO2 qui est caractérisée par un cœur constitué d'un semi-conducteur III-V et ayant un diamètre de particules dans la gamme de 1-50 nm, et par une coquille constituée de SiO2.
PCT/JP2007/059937 2006-05-26 2007-05-15 Nanoparticule de semi-conducteur III-V/SiO2 et agent de marquage de substances biologiques WO2007138851A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008517824A JP5200931B2 (ja) 2006-05-26 2007-05-15 ＩＩＩ−Ｖ型半導体／ＳｉＯ２型ナノ粒子、及び生体物質標識剤

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006146344 2006-05-26
JP2006-146344 2006-05-26

Publications (1)

Publication Number Publication Date
WO2007138851A1 true WO2007138851A1 (fr) 2007-12-06

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JP (1) JP5200931B2 (fr)
WO (1) WO2007138851A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010128604A1 (fr) * 2009-05-08 2010-11-11 コニカミノルタエムジー株式会社 Nanoparticule de silice présentant des points quantiques encapsulés dans celle-ci, son procédé de production et agent de marquage biologique l'utilisant
US9281447B2 (en) 2011-05-30 2016-03-08 Fujifilm Corporation Method for synthesizing indium phosphide nanoparticles
JP2017160078A (ja) * 2016-03-09 2017-09-14 三菱マテリアル株式会社 ＩｎＡｓコロイド粒子の製造方法
JP2018131685A (ja) * 2017-02-17 2018-08-23 三菱マテリアル株式会社 ＩｎＡｓコロイド粒子の合成方法

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JP2002544488A (ja) * 1999-05-07 2002-12-24 クアンタム ドット コーポレイション 半導体ナノクリスタルを用いて分析物を検出する方法
JP2003524147A (ja) * 1998-09-18 2003-08-12 マサチューセッツ インスティテュート オブ テクノロジー 半導体ナノ結晶の生物学的用途
JP2003287498A (ja) * 2002-03-27 2003-10-10 Hitachi Software Eng Co Ltd 半導体ナノ粒子蛍光試薬及び蛍光測定方法
JP2003532898A (ja) * 2000-05-05 2003-11-05 バイエル アクチェンゲゼルシャフト 生体標識としてのドープ処理されたナノ粒子
JP2005172429A (ja) * 2003-12-05 2005-06-30 Sony Corp 生体物質蛍光標識剤及び生体物質蛍光標識方法、並びにバイオアッセイ方法及び装置
JP2005189237A (ja) * 2003-12-05 2005-07-14 Sekisui Chem Co Ltd 光学的測定方法

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JP2003524147A (ja) * 1998-09-18 2003-08-12 マサチューセッツ インスティテュート オブ テクノロジー 半導体ナノ結晶の生物学的用途
JP2002544488A (ja) * 1999-05-07 2002-12-24 クアンタム ドット コーポレイション 半導体ナノクリスタルを用いて分析物を検出する方法
JP2003532898A (ja) * 2000-05-05 2003-11-05 バイエル アクチェンゲゼルシャフト 生体標識としてのドープ処理されたナノ粒子
JP2003287498A (ja) * 2002-03-27 2003-10-10 Hitachi Software Eng Co Ltd 半導体ナノ粒子蛍光試薬及び蛍光測定方法
JP2005172429A (ja) * 2003-12-05 2005-06-30 Sony Corp 生体物質蛍光標識剤及び生体物質蛍光標識方法、並びにバイオアッセイ方法及び装置
JP2005189237A (ja) * 2003-12-05 2005-07-14 Sekisui Chem Co Ltd 光学的測定方法

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YANG Y.: "Preparation of Fluorescent SiO2 Particles with Single CdTe Nanocrystal Cores by the Reverse Microemulsion Method", ADV. MATER., vol. 17, no. 19, 2005, pages 2354 - 2357, XP003019397 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010128604A1 (fr) * 2009-05-08 2010-11-11 コニカミノルタエムジー株式会社 Nanoparticule de silice présentant des points quantiques encapsulés dans celle-ci, son procédé de production et agent de marquage biologique l'utilisant
US9023659B2 (en) 2009-05-08 2015-05-05 Konica Minolta Medical & Graphic, Inc. Silica nanoparticle embedding quantum dots, preparation method thereof and biosubstance labeling agent by use thereof
US9281447B2 (en) 2011-05-30 2016-03-08 Fujifilm Corporation Method for synthesizing indium phosphide nanoparticles
JP2017160078A (ja) * 2016-03-09 2017-09-14 三菱マテリアル株式会社 ＩｎＡｓコロイド粒子の製造方法
JP2018131685A (ja) * 2017-02-17 2018-08-23 三菱マテリアル株式会社 ＩｎＡｓコロイド粒子の合成方法

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JP5200931B2 (ja) 2013-06-05
JPWO2007138851A1 (ja) 2009-10-01

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