CN100572500C - The aqueous phase preparation method of cyclodextrin modified CdTe quantum dot - Google Patents
The aqueous phase preparation method of cyclodextrin modified CdTe quantum dot Download PDFInfo
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- CN100572500C CN100572500C CNB200710150113XA CN200710150113A CN100572500C CN 100572500 C CN100572500 C CN 100572500C CN B200710150113X A CNB200710150113X A CN B200710150113XA CN 200710150113 A CN200710150113 A CN 200710150113A CN 100572500 C CN100572500 C CN 100572500C
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Abstract
A kind of aqueous phase preparation method of cyclodextrin modified CdTe quantum dot.At first synthetic CdTe nanocrystal, the aqueous solution of the cyclodextrin of adding sulfydryl modification in the CdTe nanocrystal reacts certain hour and can form cyclodextrin modified CdTe quantum dot again, and its emission wavelength is adjustable in 500～650 nanometer range.Method of the present invention is simple to operate, mild condition, and cost is low, and toxicity is little.Synthetic cyclodextrin modified water-soluble, the good stability of CdTe quantum dot that obtains, fluorescence quantum yield is higher, and emmission spectrum is adjustable in visible region.
Description
[technical field]:
The present invention relates to a kind of preparing technical field of quantum dot, particularly the method for synthetic high-quality water-soluble CdTe/CD quantum dot under simple and easy mild conditions.The fluorescence of this quantum dot is adjustable at visible region, and quantum yield is higher, stable in properties.
[background technology]:
Quantum dot is a kind of semiconductor nanocrystal or crystallite, is made up of II-VI, III-V or IV-VI period element, and diameter is at the spherical material of 1-12 nanometer.What research was more at present is II-VI type quantum dots such as CdS, CdSe, CdTe, ZnS.These nanoparticles show the character different with macroscopic material, comprise high quantum emission productive rate, the size adjustable of emmission spectrum, narrow spectrum band etc.In addition, the controlling dimension size can be regulated the position of emmission spectrum.The character of quantum dot uniqueness is based on it self quantum effect, when particle size reaches nanometer scale, because the size confinement causes dimensional effect, quantum confined effect, macro quanta tunnel effect and surface effects, thereby derive nanometer system and have the normal sight system low-dimensional rerum natura different with microsystem, show many electronics and optical characteristics that are different from macroscopic material, it is had broad application prospects at aspects such as luminescent material, photosensors.
Adopt the synthetic quantum dot of chemical process to mainly contain Organometallic Chemistry method and aqueous phase synthesis method at present.
The Organometallic Chemistry method is a kind of chemical process of synthetic quantum dot commonly used.This method is normally under the anhydrous and oxygen-free condition, with TOP, TOPO etc. is part, organic coordination compound with component is a precursor, it is synthetic to reflux under 200～300 ℃ condition, the shortcoming that this method prepares quantum dot is the preparation condition harshness, the reactions steps complexity, the reagent cost height, toxicity is bigger; For further application, the quantum dot that the organic synthesis method need be made is transferred to water, and its complex steps, the quantum yield of the quantum dot aqueous solution that obtains after the processing and stability all reduce greatly.
In recent years, the direct quantum dot that synthesizes excellent property in the aqueous solution became the research focus.The ultimate principle of aqueous phase synthesis method is to add stablizer (as sulfhydryl compound etc.) in water, obtains nanoparticle by the water ion exchange reaction.Its reaction conditions gentleness, simple to operate, toxicity is little, cost is low.Because quantum dot is at the aqueous phase synthetic, has directly solved the water-soluble problem of nanoparticle.But water synthetic quantum dot has shortcomings such as emmission spectrum is wide, distribution of sizes is inhomogeneous, fluorescence quantum yield is low.
In II-VI type quanta point material, the fluorescence spectrum with it of CdTe quantum dot is narrow, and the variable range of fluorescent emission is wide, and quantum yield is higher, is subjected to extensive concern.But cause stability very poor because Te wherein is oxidized easily, thereby influenced the application in later stage.
Utilize the quantum dot after macromole such as crown ether, cyclodextrin, calixarene are modified, reduced surface imperfection, its fluorescence quantum yield and stability all be improved significantly.Present this modifying method is that precursor is modified with organic synthesis method synthetic quantum dot still, and its water-soluble and bio-compatibility is all had a greatly reduced quality.
[summary of the invention]:
Purpose of the present invention is exactly the easy oxidation of quantum dot that solves the aqueous phase synthesis method preparation, and there are a large amount of defectives on the surface, has a strong impact on the problem of its quantum yield and stability.A kind of aqueous phase preparation method of CdTe quantum dot of water soluble Beta-cyclodextrin modification is provided.
The aqueous phase preparation method of the CdTe quantum dot that water soluble Beta-cyclodextrin provided by the invention is modified comprises successively:
The first, in closed reaction vessel, the adding mol ratio is 2: 1～3: 1 NaBH
4Or KBH
4With the Te powder, add the deionized water of 1～5mL, normal-temperature reaction is 45～90 minutes under the magnetic agitation, makes colourless transparent liquid, i.e. the NaHTe of fresh anaerobic or the KHTe aqueous solution;
The second, the preparation of the cadmium salt and the sulfhydryl compound aqueous solution: in beaker, in sulfhydryl compound, add 15～135mL deionized water and 0.02～0.1mol/L cadmium salt aqueous solution, wherein, the mol ratio of cadmium and sulfydryl is 1: 1.5～1: 5, regulates pH to 10.0～12.0 with the NaOH aqueous solution;
Add the solution of second step preparation in third and fourth mouthful bottle, argon shield was stirred 20～30 minutes;
Four, the NaHTe or the KHTe aqueous solution with the fresh anaerobic for preparing in the first step joined in the 3rd step, and make Cd: Te: the mol ratio of sulfydryl is 2: 1: 3～4: 1: 20;
Five, with the mixing solutions reflux in the 4th step, reacted 10～30 minutes, can obtain the CdTe quantum dot;
Six, get an amount of the 5th step solution as observation fluorescence and characterization sample;
Seven, in the 5th step solution, add the cyclodextrin that 200～1000mg has sulfydryl, the temperature maintenance of reaction soln makes part generation part permutoid reaction at 50～60 ℃, reacts 1～5 hour, obtain cyclodextrin modified CdTe quantum dot, the fluorescence maximum emission wavelength is in 500～650 nanometers.
Described cadmium salt is Cadmium chloride fine powder, cadmium bromide, cadmium iodide, cadmium nitrate, cadmium chlorate, cadmium acetate, cadmium perchlorate, Cadmium Sulphate or cadmium carbonate.
Described sulfhydryl compound is halfcystine, Gelucystine, Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, sulfydryl butyrates, mercaptoethanol, mercaptoethylamine, Methyl Thioglycolate, Thiovanic acid second fat, mercapto-propionate or gsh.
Advantage of the present invention and effect: the inventive method combines the advantage of superior photoluminescent property of CdTe itself and macromole modification, in the aqueous solution, synthesized cyclodextrin modified CdTe quantum dot, its water-soluble, stable and all obviously raising of fluorescence quantum yield.
The inventive method does not need harsh equipment, condition; simple and safe operation; toxicity is little, cost is low; used plant and instrument is common equipment; as: induction stirring well heater, nitrogen protection device, four-hole bottle, reflux condensing tube, thermometer and syringe, its production cost is low, and reaction conditions is simple; reflux gets final product, and does not have the exacting terms requirement.
Adopt the method for ligand moiety permutoid reaction to realize under the alkaline condition by being controlled at the stable cyclodextrin modified CdTe quantum dot of aqueous phase controlledly synthesis, the fluorescence maximum emission wavelength is at the quantum dot of 500～650 nanometers, realized the adjustable of the composition of quantum dot and fluorescence spectrum.After adding cyclodextrin, modification has to a certain degree been carried out on the quantum dot surface, reduced exciting defective, improved the resistance of oxidation of quantum dot, thereby the stability of quantum dot is strengthened greatly, and fluorescence quantum yield is compared with the quantum dot that does not add cyclodextrin, has improved 5～10 times.Utilize the hydrophobic cavity of cyclodextrin can carry out some micromolecular identification work.
[embodiment]:
Embodiment 1
The first, airtight, have in the reaction vessel of needle applicator, add 80mg (1.5mmol) KBH
4, the deionized water of 95mg (0.75mmol) Te powder and 5mL, normal-temperature reaction is 90 minutes under the magnetic agitation, makes colourless transparent liquid, i.e. the KHTe aqueous solution of fresh anaerobic;
The second, the preparation of the Cadmium chloride fine powder and the L-halfcystine aqueous solution: in beaker, add the 132ml deionized water and 15mL (0.1mol/L) the Cadmium chloride fine powder aqueous solution, regulate pH to 12.0 with the NaOH aqueous solution of 1mol/L to 365mg (3mmol) stablizer L-halfcystine;
Three, add the aqueous solution 150mL that contains Cadmium chloride fine powder and L-halfcystine that second step prepared in the four-hole bottle of 250mL, argon shield was stirred 30 minutes;
Four, the KHTe aqueous solution 5mL with the fresh anaerobic for preparing in the first step all joined in the 3rd step;
Five, the mixing solutions in the 4th step is heated to 100 ℃, back flow reaction 10 minutes;
Six, get CdTe solution that 5mL the 5th step prepares as observation fluorescence and characterization sample.
Seven, airtight, have in the reaction vessel of needle applicator, add the cyclodextrin (40mg/mL) that 25mL has sulfydryl, under 60 ℃, magnetic agitation reaction 1 hour makes red transparent liquid, the promptly cyclodextrin modified CdTe aqueous solution.
Embodiment 2
The first, airtight, have in the reaction vessel of needle applicator, add 22mg (0.4mmol) KBH
4, the deionized water of 20mg (0.15mmol) Te powder and 1mL, normal-temperature reaction is 45 minutes under the magnetic agitation, makes colourless transparent liquid, i.e. the KHTe aqueous solution of fresh anaerobic;
The second, the preparation of Cadmium chloride fine powder and gsh (GSH) aqueous solution: in beaker, add the 18mL deionized water and 30mL (0.02mol/L) the Cadmium chloride fine powder aqueous solution, regulate pH to 10.0 with the NaOH aqueous solution of 1mol/L to 766mg (2.5mmol) stablizer gsh;
Three, add the aqueous solution 50mL that contains Cadmium chloride fine powder and gsh that second step prepared in the four-hole bottle of 100mL, argon shield was stirred 20 minutes;
Four, the KHTe aqueous solution 1mL with the fresh anaerobic for preparing in the first step all joined in the 3rd step;
Five, the mixing solutions in the 4th step is heated to 100 ℃, back flow reaction 30 minutes;
Six, get CdTe solution that 5mL the 5th step prepares as observation fluorescence and characterization sample.
Seven, airtight, have in the reaction vessel of needle applicator, add the cyclodextrin that 10mL (40mg/mL) has sulfydryl, under 50 ℃, magnetic agitation reaction 2 hours makes orange-yellow transparent liquid, the promptly cyclodextrin modified CdTe aqueous solution.
Embodiment 3
The first, airtight, have in the reaction vessel of needle applicator, add 24mg (0.6mmol) NaBH
4, the deionized water of 40mg (0.3mmol) Te powder and 3mL, normal-temperature reaction is 60 minutes under the magnetic agitation, makes colourless transparent liquid, i.e. the NaHTe aqueous solution of fresh anaerobic;
The second, the preparation of the cadmium acetate and the Thiovanic acid aqueous solution: in beaker, add the 24mL deionized water and 15mL (0.04mol/L) the cadmium acetate aqueous solution, regulate pH to 11.5 with the NaOH aqueous solution of 1mol/L to 92mg (1mmol) stablizer Thiovanic acid;
Three, add the aqueous solution 40mL that contains cadmium acetate and Thiovanic acid that second step prepared in the four-hole bottle of 100mL, argon shield was stirred 30 minutes;
Four, the NaHTe aqueous solution 3mL with the fresh anaerobic for preparing in the first step all joined in the 3rd step;
Five, the mixing solutions in the 4th step is heated to 100 ℃, back flow reaction 20 minutes;
Six, get CdTe solution that 5mL the 5th step prepares as observation fluorescence and characterization sample.
Seven, airtight, have in the reaction vessel of needle applicator, add the cyclodextrin that 5mL (40mg/mL) has sulfydryl, under 60 ℃, magnetic agitation reaction 1.5 hours makes the scarlet transparent liquid, the promptly cyclodextrin modified CdTe aqueous solution.
Embodiment 4
The first, airtight, have in the reaction vessel of needle applicator, add 19mg (0.5mmol) NaBH
4, the deionized water of 25mg (0.2mmol) Te powder and 2mL, normal-temperature reaction is 70 minutes under the magnetic agitation, makes colourless transparent liquid, i.e. the NaHTe aqueous solution of fresh anaerobic;
The second, the preparation of the cadmium nitrate and the mercaptoethanol aqueous solution: in beaker, add the 73mL deionized water and 15mL (0.05mol/L) the cadmium nitrate aqueous solution, regulate pH to 10.0 with the NaOH aqueous solution of 1mol/L to 160mg (2.5mmol) stablizer mercaptoethanol;
Three, add the aqueous solution 90mL that contains cadmium nitrate and mercaptoethanol that second step prepared in the four-hole bottle of 250mL, argon shield was stirred 30 minutes;
Four, the NaHTe aqueous solution 2mL with the fresh anaerobic for preparing in the first step all joined in the 3rd step;
Five, the mixing solutions in the 4th step is heated to 100 ℃, back flow reaction 20 minutes;
Six, get CdTe solution that 5mL the 5th step prepares as observation fluorescence and characterization sample.
Seven, airtight, have in the reaction vessel of needle applicator, add the cyclodextrin that 15mL (40mg/mL) has sulfydryl, under 50 ℃, magnetic agitation reaction 2 hours makes orange transparent liquid, the promptly cyclodextrin modified CdTe aqueous solution.
Claims (3)
1, a kind of aqueous phase preparation method of cyclodextrin modified CdTe quantum dot is characterized in that this method comprises the steps:
The first, in closed reaction vessel, the adding mol ratio is 2: 1～3: 1 NaBH
4Or KBH
4With the Te powder, add the deionized water of 1～5mL, normal-temperature reaction is 45～90 minutes under the magnetic agitation, makes colourless transparent liquid, i.e. the NaHTe of fresh anaerobic or the KHTe aqueous solution;
The second, the preparation of the cadmium salt and the sulfhydryl compound aqueous solution: in beaker, in sulfhydryl compound, add 15～135mL deionized water and 0.02～0.1mol/L cadmium salt aqueous solution, wherein, the mol ratio of cadmium and sulfydryl is 1: 1.5～1: 5, regulates pH to 10.0～12.0 with the NaOH aqueous solution;
Add the solution of second step preparation in third and fourth mouthful bottle, argon shield was stirred 20～30 minutes;
Four, the NaHTe or the KHTe aqueous solution with the fresh anaerobic for preparing in the first step joined in the 3rd step, and make Cd: Te: the mol ratio of sulfydryl is 2: 1: 3～4: 1: 20;
Five, with the mixing solutions reflux in the 4th step, reacted 10～30 minutes, can obtain the CdTe quantum dot;
Six, get an amount of the 5th step solution as observation fluorescence and characterization sample;
Seven, in the 5th step solution, add the cyclodextrin that 200～1000mg has sulfydryl, the temperature maintenance of reaction soln makes part generation part permutoid reaction at 50～60 ℃, reacts 1～5 hour, obtain cyclodextrin modified CdTe quantum dot, the fluorescence maximum emission wavelength is in 500～650 nanometers.
2, synthetic method according to claim 1 is characterized in that cadmium salt is Cadmium chloride fine powder, cadmium bromide, cadmium iodide, cadmium nitrate, cadmium chlorate, cadmium acetate, cadmium perchlorate, Cadmium Sulphate or cadmium carbonate.
3, synthetic method according to claim 1 is characterized in that sulfhydryl compound is halfcystine, Gelucystine, Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, sulfydryl butyrates, mercaptoethanol, mercaptoethylamine, Methyl Thioglycolate, Thiovanic acid second fat, mercapto-propionate or gsh.
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| DK1828772T3 (en) * | 2004-12-06 | 2010-08-23 | Biogen Idec Inc | Detection and quantification of cyclodextrins |
| CN101704507B (en) * | 2009-12-04 | 2012-07-04 | 华东师范大学 | Method for synthesizing quantum dot with core-shell-shell structure in aqueous phase |
| CN101864003B (en) * | 2010-06-11 | 2012-05-02 | 漆又毛 | Synthesis method of 6-deoxy thioether amino acid cyclodextrin derivative |
| CN102086397A (en) * | 2010-12-10 | 2011-06-08 | 南开大学 | Method for fast preparing soluble near infrared CdTe quantum dots covered with mercaptan in aqueous phase |
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| CN105062489A (en) * | 2015-07-20 | 2015-11-18 | 东南大学 | Method for synthesizing ZnSe quantum dots modified with beta-CD (cyclodextrin) ligands |
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