CN100395306C - Process of water-solubility for oil-soluble quantum - Google Patents
Process of water-solubility for oil-soluble quantum Download PDFInfo
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- CN100395306C CN100395306C CNB200410013332XA CN200410013332A CN100395306C CN 100395306 C CN100395306 C CN 100395306C CN B200410013332X A CNB200410013332X A CN B200410013332XA CN 200410013332 A CN200410013332 A CN 200410013332A CN 100395306 C CN100395306 C CN 100395306C
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Abstract
The present invention discloses a method for causing high-quality quantum dots to be water soluble. An amphipathicity surfactant is adopted as a modifying reagent; hydrophobic interaction in a non-polar ligand existing between the surfactant and the surface of an oil soluble quantum dot is utilized; the water solubility of an oil soluble quantum dot is successfully realized by an extremely simple and practical polishing method; therefore, a high quality product of a water soluble quantum dot can be obtained. The water soluble quantum dot product prepared by the modification method has an extremely excellent photoluminescent property, water solubility and stability. The product has the characteristics of high fluorescence intensity, long fluorescence lifetime, high quantum yield, high light stability and good light-resistant blanching performance, and the stability of a water solution can last for a plurality of months and is still very high for a salt intensive solution. The preparation method has the characteristics of simple practice, high operability, good repeatability and low cost for the adopted modifying reagent. The obtained product can be widely applied to the bioanalysis fields of biological tagging, cell image forming, development, etc.
Description
Technical field
The invention discloses a kind of method of high-quality water-solubleization of quantum dot.Affiliated technical field is analytical chemistry, nano science, surface chemistry, bioanalysis chemistry.
Background technology
Fluorescent reagent is used for biomarker and cell imaging always is an active research field, but detect used luciferase assay reagent at biology laboratory and clinical medicine now and mostly be traditional organic dye class fluorescent reagent and bioluminescence protein etc., these fluorescent reagents have significant disadvantages such as fluorescence intensity is little, excitation spectrum is narrow, fast light whitening capacity difference.Quantum dot is a kind of novel inorganic nano material, have very excellent photoluminescent property, fluorescence intensity is big, fluorescence emission peak is narrow and symmetrical, fluorescence color be form and controllable size, excitation spectrum is continuous bands of a spectrum, is easy to realize that the unit excites polynary emission.These character make quantum dot have the potentiality that the traditional organic fluorescence reagent of replacement is applied to the bio-imaging analysis field.Because present high-quality quantum dot all prepares by the organic phase high-temperature cracking method, product is an oil soluble, and all living things systems all are the polarity aqueous environment, so means and method by surface chemistry are modified the quantum dot surface, water-solubleization that realizes the oil soluble quantum dot then is the bottleneck that the restriction quantum dot truly is widely used in the bioanalysis field.
M.Dahan and X.Wu etc. adopt phosphatide and amphipathic superpolymer respectively, utilize the hydrophobic interaction between the organic molecule of they and quantum dot surface, successfully are modified into the oil soluble quantum dot water miscible.And modified outcome is applied to cell marking and tracking test, obtains very ideal experimental result.But the problem of its existence is, products therefrom La directly becomes greatly, modifies raw material and is difficult for obtaining, and product is not easy to biologically-derivedization.
Summary of the invention
Problem to be solved by this invention provides a kind of method of water-solubility of oil soluble quantum dotsization, and this method is easy to operation, the modification raw material is easy to get, cost is low, good reproducibility.The products therefrom particle diameter is constant substantially, is easy to biologically-derivedization.
Technical scheme provided by the invention is: a kind of method of water-solubility of oil soluble quantum dotsization, the oil soluble quantum dot is dissolved in the solution that is mixed with 0.5～4mg/mL in the non-polar organic solvent, in above-mentioned 0.5～2ml solution, add 4～180mg amphiphilic surfactant then, mixed grinding treats promptly to obtain after the non-polar organic solvent volatilization oil soluble quantum dot of water-solubleization.
Above-mentioned oil soluble quantum dot is CdSe, CdSe/ZnS, CdSe/CdS quantum dot.
Above-mentioned non-polar organic solvent is hexane or chloroform.
Above-mentioned amphiphilic surfactant is cetyl trimethylammonium bromide CTAB or sodium lauryl sulphate.
The present invention just can realize water-solubleization of oil soluble quantum dot by simple polishing, and the product after the modification has the photoluminescent property of almost identical with oil soluble quantum dot excellence.It is existing to levy by instrumentation tables such as transmission electron microscope, fluorescence inverted microscope, fluorescence spectrophotometer, and the quantum dot distribution of sizes is constant substantially after modifying, monodispersity is good, fluorescence intensity is big, quantum yield is high, fluorescence peak is narrow and symmetrical.Has tangible advantage with present existing other water-soluble quantum dot modifying method ratio.And the amphiphilic surfactant can make product after the modification selectively with going up different electric charges, and this surface exists enriches electric charge and can make this quantum dot by electrostatic interaction and biomolecule action formation quantum dot/biomolecular science conjugated body (biologically-derivedization).As mentioned above, the present invention provides a simple road for quantum dot is widely used in the bioanalysis field.
Adopt method of the present invention to realize that water-solubleization of quantum dot has the following advantages: 1) You Yi photoluminescent property and stability.Because the hydrophobic interaction that this method is based between tensio-active agent and the surperficial stabilization organic reagent that exists of quantum dot is modified successfully.Do not destroy stabilization reagent and the interatomic coordination of bare quantum spot surface metal.Thereby the crystalline structure that so almost completely keeps quantum dot is not damaged its photoluminescent property is not changed.This advantage is that the most frequently used small numerator modified method of sulfydryl is beyond one's reach now.The light stability of products therefrom of the present invention, fast light bleaching, fluorescence quantum yield (more than 65%), aqueous stability character such as (depositing more than four months still stable) all will be much better than the small numerator modified product of sulfydryl (fluorescence quantum yield about 15%, its aqueous solution are deposited about a week and promptly reunited); 2) simple and convenient, workable, the good reproducibility of modifying method, raw materials used safety are easy to get.Adopt with low cost and amphiphilic surfactant (eg.CTAB, SDS etc.) that be easy to get just can obtain high-quality water-soluble quantum dot by simple Ginding process.Making processes is simple far beyond other water-solubleization of quantum dot method; 3) modification back quantum dot distribution of sizes is constant substantially; 4) this method prepares the product surface and optionally enriches electric charge and can make this quantum dot by electrostatic interaction and biologically-derivedization.Though the electrostatic interaction specificity is not strong, that other the chemical functional group coupled reaction of comparing then has is simple to operate, reaction efficiency is high, can control characteristics such as reversibility.In sum, the present invention is easy to operation, cost is low, good reproducibility, all can finish at general chemistry and Biochemistry Experiment chamber, may for applying that quantum dot provides.
Embodiment
Embodiment 1
02139152.1 number patent application discloses the preparation (5-25 is capable referring to this application Instructions Page 3) of CdSe, CdSe/CdS or CdSe/ZnS core/shell type quantum dot: (a) in glove box, the selenium powder of 0.1g is dissolved in the tri-n-octyl phosphine (TOP) and 2.1g dioctylamine of 0.54g, make the storing solution of selenium, [(TMS) with 50ul sulfuration two (trimethyl silyl)
2S] be dissolved in the tri-n-octyl phosphine (TOP) and 1.6g dioctylamine of 0.4g, make the storing solution of sulfide; (b) take by weighing 0.0165gCdO and 0.28g stearic acid and put into four-hole Schlenk reaction vessel A, adopt the Schlenk technology, charge into Ar gas after vacuumizing with vacuum pump, outgas so repeatedly six times so that be full of Ar gas in the reaction vessel, then be heated to 150 ℃ and keep about 25min, CdO is fully dissolved; Cool to then about 50 ℃, add 2.43g oxidation tri-n-octyl phosphine (TOPO) and 2.43g cetylamine (HDA), after adopting the degassing of Schlenk technology again, stir, be heated to 320 ℃, then from glove box, take out rapidly, it is injected reaction vessel with fast as far as possible speed with the storing solution of syringe with selenium in (a); After keeping 5min about 280 ℃, remove heating unit rapidly and make product be cooled to 30-50 ℃, promptly make the CdSe quantum dot, take out the product (making the contrast sample) of a small amount of CdSe quantum dot with syringe after, remaining part is heated to 200 ℃; (c) take by weighing 0.285g cadmium acetate (perhaps 0.0241g zinc acetate), 1.06gTOPO and 1.06gHDA put into three mouthfuls of Schlenk reaction vessel B, adopt to be stirred and heated to 200 ℃ and keep more than the 30min after the degassing of Schlenk technology; (d) with syringe the solution in (c) is transferred in the constant pressure funnel that is connected on the reaction vessel A, with syringe sulfide storing solution in (a) is transferred to from glove box in this constant pressure funnel again, stir by syringe, after two portions solution is mixed, splash into equably in the intensively stirred reactor A with per two seconds one speed; (e) dropwise, lower the temperature and make solution temperature be stabilized in 90 ℃ keep 1h after, stop heating, make the solution cool to room temperature; (f) in the solution of (e), add chloroform, centrifugal, after discarding upper strata suspended substance and lower sediment, in solution, add methyl alcohol, leaving standstill 1h precipitates product, centrifugal, remove behind the solution the CdSe/CdS of orange red flow-like or CdSe/ZnS resolution of precipitate in hexane, promptly get required CdSe/CdS or CdSe/ZnS quantum dot product; The product that obtains is the transparent salmon solution of hyperfluorescence.
The method of CdSe water-solubility of oil soluble quantum dotsization:
1) be that the CdSe oil soluble quantum dot of 2nm-6nm (can adopt above-mentioned No. 02139152.1 patent application disclosed method preparation with particle diameter, during with this method, need not prepare and use the storing solution of sulfide) be dissolved in the hexane, making concentration is the hexane solution of the oil soluble quantum dot of 1mg/mL.
2) get the hexane solution of the above-mentioned oil soluble quantum dot of 1mL, add the methanol extraction oil soluble quantum dot of 5 times of hexane volumes, with hexane throw out is dissolved into the solution for later use of 2mL at last.
3) take by weighing amphiphilic surfactant's cetyl trimethylammonium bromide 150mg and be put in the agate mortar,, ground 2～3 minutes, be positioned over and treat the hexane volatilization in the stink cupboard fully the quantum dot hexane solution adding of above-mentioned 2mL.
4) add about 2mL hexane again in mortar, ground 2～3 minutes, be positioned over and treat the hexane volatilization in the stink cupboard fully.
5) mortar is positioned under 80 ℃ of conditions dry 10 minutes, obtains the CdSe oil soluble quantum dot (particle diameter is 2nm-6nm, fluorescence quantum yield 66%) of water-solubleization.
Embodiment 2
The method of CdSe/ZnS water-solubility of oil soluble quantum dotsization:
1) be that the CdSe/ZnS oil soluble quantum dot of 4nm-8nm is (as adopting the CdSe/ZnS oil soluble quantum dot of No. 02139152.1 patent application disclosed method preparation with particle diameter, see embodiment 1) and be dissolved in the hexane, making concentration is the hexane solution of the oil soluble quantum dot of 1mg/mL.
2) get the hexane solution of the above-mentioned oil soluble quantum dot of 2mL, add the methanol extraction oil soluble quantum dot of 5 times of hexane volumes, with hexane throw out is dissolved into the solution for later use of 2mL at last.
3) take by weighing amphiphilic surfactant's sodium lauryl sulphate 150mg and be put in the agate mortar,, ground 2-3 minute, be positioned over and treat the hexane volatilization in the stink cupboard fully the quantum dot hexane solution adding of above-mentioned 2mL.
4) add about 2mL hexane again in mortar, ground 2-3 minute, be positioned over and treat the hexane volatilization in the stink cupboard fully.
5) mortar is positioned under 80 ℃ of conditions dry 10 minutes.
6) in mortar, add 8mL water, stir, collect, in ultrasonic cleaner ultrasonic 15 minutes with centrifuge tube.
7) centrifugal under the 12000rpm/10min condition, removing post precipitation (generally speaking not precipitation) collects clear liquid and is the CdSe/ZnS oil soluble quantum dot of water-solubleization of final product (particle diameter is 4nm-8nm, fluorescence quantum yield 65% is deposited not have more than four months and is reunited).
The method of embodiment 3:CdSe/CdS water-solubility of oil soluble quantum dotsization:
1) be that the CdSe/CdS oil soluble quantum dot of 4nm-8nm is (as adopting the CdSe/CdS oil soluble quantum dot of No. 02139152.1 patent application disclosed method preparation with particle diameter, see embodiment 1) and be dissolved in the chloroform, making concentration is the chloroformic solution of the oil soluble quantum dot of 2mg/mL.
2) get the chloroformic solution of the above-mentioned oil soluble quantum dot of 2mL, add the methanol extraction oil soluble quantum dot of 3 times of chloroform volumes, with chloroform throw out is dissolved into the solution for later use of 2mL at last.
3) take by weighing amphiphilic surfactant's sodium lauryl sulphate 150mg and be put in the agate mortar,, ground 2-3 minute, be positioned over and treat the chloroform volatilization in the stink cupboard fully the quantum dot chloroformic solution adding of above-mentioned 2mL.
4) add about 2mL chloroform again in mortar, ground 2-3 minute, be positioned over and treat the chloroform volatilization in the stink cupboard fully.
5) mortar is positioned under 80 ℃ of conditions dry 10 minutes.
6) in mortar, add 7mL water, stir, collect, in ultrasonic cleaner ultrasonic 15 minutes with centrifuge tube.Centrifugal under the 12000rpm/10min condition, removing post precipitation (generally speaking not precipitation) collects clear liquid and is the CdSe/CdS oil soluble quantum dot of water-solubleization of final product (particle diameter is 4nm-8nm, fluorescence quantum yield 66% is deposited not have more than four months and is reunited).
Adopt the aforesaid method of the present invention can be with other water-solubility of oil soluble quantum dotsization.
Obviously,, adopt other amphiphilic surfactant, also can obtain similar result by method of the present invention.
Claims (4)
1. the method for a water-solubility of oil soluble quantum dotsization, it is characterized in that: the oil soluble quantum dot is dissolved in the solution that is mixed with 0.5～4mg/mL in the non-polar organic solvent, in above-mentioned 0.5～2ml solution, add 4～180mg amphiphilic surfactant then, mixed grinding treats promptly to obtain after the non-polar organic solvent volatilization oil soluble quantum dot of water-solubleization.
2. method according to claim 1 is characterized in that: above-mentioned oil soluble quantum dot is CdSe, CdSe/ZnS, CdSe/CdS quantum dot.
3. method according to claim 1 and 2 is characterized in that: non-polar organic solvent is hexane or chloroform.
4. method according to claim 1 and 2 is characterized in that: the amphiphilic surfactant is cetyl trimethylammonium bromide or sodium lauryl sulphate.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1328351C (en) * | 2005-09-23 | 2007-07-25 | 上海大学 | Method for preparing II-VI family fluorescent mark semiconductor quantum point MX |
| CN100413938C (en) * | 2006-07-07 | 2008-08-27 | 中国科学技术大学 | Au/CdSe heterostructure quantum point and its preparation method |
| CN102304361B (en) * | 2011-07-04 | 2013-10-23 | 江苏大学 | Aqueous synthesis method of cadmium telluride quantum dot with hydrophobic surface |
| CN102516996A (en) * | 2011-12-13 | 2012-06-27 | 北京理工大学 | Method for transferring oil phase quantum dots to aqueous phase |
| CN103911141B (en) * | 2012-12-31 | 2017-10-31 | 深圳先进技术研究院 | A kind of method that oil-soluble quantum dot is converted into water-soluble quantum dot |
| CN106085417A (en) | 2016-06-14 | 2016-11-09 | 深圳市华星光电技术有限公司 | water-soluble quantum dot, preparation method and quantum dot film preparation method |
| CN110724412B (en) * | 2019-10-12 | 2022-10-04 | 纳晶科技股份有限公司 | Printing method of quantum dot ink |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174080A (en) * | 1997-09-05 | 1998-02-25 | 张玉杰 | Chinese medicine granule for asthma |
| WO1998019963A1 (en) * | 1996-11-08 | 1998-05-14 | Spectra Science Corporation | Synthesis of metal chalcogenide quantum dots from aqueous media |
| WO2000029617A2 (en) * | 1998-09-24 | 2000-05-25 | Advanced Research And Technology Institute, Inc. | Water-soluble luminescent quantum dots and bioconjugates thereof |
| WO2003037788A1 (en) * | 2001-11-01 | 2003-05-08 | Oxonica Limited | Water soluble luminescent nanoparticles |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998019963A1 (en) * | 1996-11-08 | 1998-05-14 | Spectra Science Corporation | Synthesis of metal chalcogenide quantum dots from aqueous media |
| CN1174080A (en) * | 1997-09-05 | 1998-02-25 | 张玉杰 | Chinese medicine granule for asthma |
| WO2000029617A2 (en) * | 1998-09-24 | 2000-05-25 | Advanced Research And Technology Institute, Inc. | Water-soluble luminescent quantum dots and bioconjugates thereof |
| WO2003037788A1 (en) * | 2001-11-01 | 2003-05-08 | Oxonica Limited | Water soluble luminescent nanoparticles |
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