CN101921593A - Preparation method of amino-containing aqueous CdSeS quantum dot - Google Patents

Preparation method of amino-containing aqueous CdSeS quantum dot Download PDF

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Publication number
CN101921593A
CN101921593A CN2009100692054A CN200910069205A CN101921593A CN 101921593 A CN101921593 A CN 101921593A CN 2009100692054 A CN2009100692054 A CN 2009100692054A CN 200910069205 A CN200910069205 A CN 200910069205A CN 101921593 A CN101921593 A CN 101921593A
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China
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quantum dot
amino
cdses
preparation
cdses quantum
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CN2009100692054A
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Chinese (zh)
Inventor
郑超
赵国锋
曹世东
谢伟
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TIANJIN URA QUANTUM DOT TECHNOLOGY DEVELOPMENT Co Ltd
Nankai University
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TIANJIN URA QUANTUM DOT TECHNOLOGY DEVELOPMENT Co Ltd
Nankai University
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Priority to CN2009100692054A priority Critical patent/CN101921593A/en
Publication of CN101921593A publication Critical patent/CN101921593A/en
Pending legal-status Critical Current

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Abstract

The invention discloses a preparation method of an amino-containing aqueous CdSeS quantum dot. In the method, a hydrophobic CdSeS quantum dot is adopted; an organic solvent and an amino-containing silane coupling agent serve as raw materials; and in alkaline aqueous solution, the hydrophobic CdSeS quantum dot, the organic solvent and the amino-containing silane coupling agent are reacted to prepare the amino-containing hydrophilic silicone-clad CdSeS quantum dot by a method at the normal temperature. The method is simple and feasible and has good repeatability. The obtained quantum dot has the advantages of high stability, uniform texture, high fluorescence intensity and long fluorescence lifetime. The silicone clad has no toxic effect at the same time. Furthermore, because the amino is introduced, the amino-containing aqueous CdSeS quantum dot serving as a biological fluorescent probe is applied to multiple fields of biomedicine.

Description

A kind of preparation method who contains amino water-soluble CdSeS quantum dot
Technical field:
The present invention relates to a kind of preparation method who is prepared into the hydrophilic CdSeS quantum dots that contains amino by hydrophobic CdSeS quantum dot through the silicon covering.
Background technology:
(quantum dots QDs) claims semiconductor nano crystallite (semiconductor nanocrystal) again to quantum dot, is a kind of by the elementary composition nano microcrystalline of II-VI family or III-V family.The ultra micro size of quantum dot has caused a kind of quantum scale effect, has given its unique electronics and optical property.Quantum dot can be launched the fluorescence more superior than conventional fluorescent material under the exciting of light, its optical property has quantum dot and uses widely.Quantum dot varies in size owing to it or forms the fluorescence that difference can be sent different colours, and can be with the quantum dot of the multiple different colours of light de-excitation of single wavelength, compare with traditional organic fluorescent substance, has good spectrum property, caused people's extensive concern in recent years, particularly had the water-soluble quantum dot of functional group, in biological chemistry, biocytology, research fields such as molecular biology have shown very application prospects.Nie etc. utilize the coordination between sulfydryl and the Zn atom to realize CdSe/ZnS QDs surface and Thiovanic acid (thioglycolic acid, TGA) connection, it is water-soluble that the polar carboxyl has QDs, and free carboxyl group can be covalently bound with various biomolecules (as protein, peptide, nucleic acid etc.).Mitchell etc. are earlier with QDs and 3-thiohydracrylic acid (3-mereaptopropionic acid, MPA) connect, again with 4-(dimethylamino). the pyridine complexing, the wetting ability of QDs increases considerably, this method can prepare the QDs of number gram at every turn, but TGA is not very stable, easily from the QDs surface desorption, thereby causes QDs to reunite and precipitation.Usefulness 3-such as A1ivisatos (sulfydryl propyl group) Trimethoxy silane disperses the ZnS of TOPO protection or the CdSe core/shell structure QDs that CdS coats again, the TOPO molecule is substituted, again solution is adjusted to alkalescence, make the methoxy silane hydrolysis, just formed the shell of layer of silicon dioxide/siloxanes on the QDs surface, make QDs have better water solubility, very stable in the aqueous solution or damping fluid, and still can keep higher quantum yield; Use further reaction of bifunctional methoxylation compound (as TSL 8330, trimethoxy propyl group urea) then, just can with the biomolecules coupling.The QDs of this method preparation has certain stability, but each experiment only can obtain the QDs of microgram magnitude, and under the pH neutral condition, the siloxy of QDs remained on surface forms gel or precipitation through regular meeting.We adopt and have amino silane coupling agent, form the shell that has silica/silicon oxygen alkane on the quantum dot surface, and among the amino introducing, not only ensured the stability and the spectral quality of quantum dot, can carry out various functionalization and carry out coupling simultaneously with biomacromolecule.Application relates to biomolecules, cell and living imaging etc.
Summary of the invention:
The present invention adopts hydrophobicity CdSeS quantum dot, and organic solvent is a raw material with having amino silane coupling agent, is dissolved in the organic solvent, reaction for some time, with the solvent evaporate to dryness, in alkaline aqueous solution, adds Na 2SiO 3.The reaction of normal temperature method makes and contains amino wetting ability silicon covering CdSeS quantum dot.
Quantum dot of the present invention comprises that wavelength is 510nm, 564nm, the CdSeS quantum dot of 620nm.
The silane coupling agent that contains amino of the present invention is (3-aminopropyl) triethoxyl silane, (3-aminopropyl) Trimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-TSL 8330, (3-aminopropyl) methoxyl group diethoxy silane.
Buffer reagent of the present invention is NaHCO 3, perhaps Na 2HPO 4Solution.
Temperature of reaction of the present invention is a room temperature, and adjustment PH is 8-10.
This invention is simple, good reproducibility, and the quantum dot that obtains stability is high, and quality is even, the fluorescence intensity height, fluorescence lifetime is long.The silicon covering has played the nontoxic usefulness that turns into simultaneously, and owing to introduced amino, can be used as a kind of biological fluorescent labeling and be applied to biomedical many-sided field.
Embodiment:
It is as follows to be prepared into the experimental procedure that contains amino hydrophilic CdSeS quantum dots by hydrophobic CdSeS quantum dot through the silicon covering:
Specific examples 1:
(1) in the round-bottomed flask of 25ml, adds hydrophobic CdSeS (wavelength is 542nm) quantum dot 2.0mg, add (3-aminopropyl) Trimethoxy silane 200ul and chloroform 5ml.Sealing, lucifuge, stirring at room 2h.
(2) under 50 ℃ of temperature, boil off the chloroform in the system, in the triangular flask of the 100ml of transfer, add the Na of concentration 60mmol/L 2SiO 3, 35ml, sealing, lucifuge, stirring at room 2 days.Reaction is finished, and obtains the transparent amino CdSeS quantum dot aqueous solution that contains.
Specific examples 2:
(1) in the round-bottomed flask of 25ml, adds hydrophobic CdSeS (wavelength is 512nm) quantum dot 2.0mg, add (N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane 200ul and chloroform 5ml.Sealing, lucifuge, stirring at room 2h.
(2) under 50 ℃ of temperature, boil off the chloroform in the system, in the triangular flask of the 100ml of transfer, add the Na of concentration 60mmol/L 2SiO 3, 35ml, sealing, lucifuge, stirring at room 2 days.Reaction is finished, and obtains the transparent amino CdSeS quantum dot aqueous solution that contains.

Claims (5)

1. preparation method who contains amino water-soluble CdSeS quantum dot, it is characterized in that, with hydrophobic CdSeS quantum dot, parcel one deck silane coupling agent, then under the effect of buffer reagent, wrap silicon layer again to determine to generate the nontoxicity of quantum dot, finally to change into the hydrophilic quantum dot that has amino.Temperature of reaction is a room temperature, and PH is 8-10.
2. a kind of preparation method who contains amino water-soluble CdSeS quantum dot according to claim 1 is characterized in that, employed quantum dot is multi-wavelength's a CdSeS quantum dot, and wavelength region comprises 510nm, 564nm, 620nm from 490 to 640nm.
3. a kind of preparation method who contains amino water-soluble CdSeS quantum dot according to claim 1, it is characterized in that, the employed silane coupling agent that contains amino is (3-aminopropyl) triethoxyl silane, (3-aminopropyl) Trimethoxy silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-TSL 8330, (3-aminopropyl) methoxyl group diethoxy silane.
4. a kind of preparation method who contains amino water-soluble CdSeS quantum dot according to claim 1 is characterized in that used buffer reagent is NaHCO 3, perhaps Na 2HPO 4Solution.
5. a kind of preparation method who contains amino water-soluble CdSeS quantum dot according to claim 1 is characterized in that temperature of reaction is a room temperature, and PH is 8-10.
CN2009100692054A 2009-06-10 2009-06-10 Preparation method of amino-containing aqueous CdSeS quantum dot Pending CN101921593A (en)

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CN101921593A true CN101921593A (en) 2010-12-22

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105623644A (en) * 2016-01-12 2016-06-01 苏州英芮诚生化科技有限公司 Amino-modified water-soluble fluorescent quantum dot and preparation method thereof
CN108998004A (en) * 2018-08-01 2018-12-14 北京苏瑞同创科技有限公司 A kind of preparation method of high stability quantum dot microsphere
CN109929540A (en) * 2017-12-15 2019-06-25 Tcl集团股份有限公司 A kind of nano particle and preparation method thereof and solar battery
WO2022242130A1 (en) * 2021-05-18 2022-11-24 深圳先进技术研究院 Nano-fluorescent probe, preparation method therefor and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105623644A (en) * 2016-01-12 2016-06-01 苏州英芮诚生化科技有限公司 Amino-modified water-soluble fluorescent quantum dot and preparation method thereof
CN109929540A (en) * 2017-12-15 2019-06-25 Tcl集团股份有限公司 A kind of nano particle and preparation method thereof and solar battery
CN108998004A (en) * 2018-08-01 2018-12-14 北京苏瑞同创科技有限公司 A kind of preparation method of high stability quantum dot microsphere
WO2022242130A1 (en) * 2021-05-18 2022-11-24 深圳先进技术研究院 Nano-fluorescent probe, preparation method therefor and application thereof

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Application publication date: 20101222