CN102127446B - Aqueous phase preparation method of ZnSe/ZnS core-shell structure quantum dots - Google Patents

Aqueous phase preparation method of ZnSe/ZnS core-shell structure quantum dots Download PDF

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CN102127446B
CN102127446B CN 201110006629 CN201110006629A CN102127446B CN 102127446 B CN102127446 B CN 102127446B CN 201110006629 CN201110006629 CN 201110006629 CN 201110006629 A CN201110006629 A CN 201110006629A CN 102127446 B CN102127446 B CN 102127446B
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selenium
znse
high purity
aqueous phase
shell structure
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CN102127446A (en
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周培疆
陈驰
丁玲
何振宇
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Wuhan University WHU
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Wuhan University WHU
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Abstract

The invention discloses an aqueous phase preparation method of ZnSe/ZnS core-shell structure quantum dots. The aqueous phase preparation method comprises the following steps of: A, preparing KH4Te solution, namely preparing by reducing tellurium powder with sodium borohydride; B, respectively weighing potassium borohydride and selenium powder and adding into a test tube with a stopper, adding high purity water into the test tube, and plugging the stopper to obtain colorless and transparent liquid, namely selenium potassium hydride; C, weighing zinc acetate crystals and reduced glutathione respectively, and dissolving in anaerobic high purity water; D, adding the selenium potassium hydride under the condition of stirring at the speed of 150 to 300 revolutions/min and continuously introducing high purity argon, adjusting a pH value of the solution by using sodium hydroxide solution, and mixing; and E, packaging in a polytetrafluoroethylene digestion tank, and performing microwave heating, wherein a molar ratio of KH4Se to Zn(Ac)2.2H2O to the reduced glutathione is (1/15-1/10):1:(1.6-1.8). The preparation process of the quantum dots is easy, and is high in biocompatibility and fluorescent quantum yield, heavy metal ion toxicity is avoided, fluorescence labeling can be performed on organisms without the aftertreatment process, and process parameters are easy to control.

Description

A kind of aqueous phase preparation method of ZnSe/ZnS nuclear shell structure quantum point
Technical field
The present invention relates to the novel fluorescence nano material, more specifically relate to a kind of aqueous phase preparation method of ZnSe/ZnS nuclear shell structure quantum point, can be used for biomarker and detection.
Background technology
The ZnSe quantum dot can overcome the limitation that quantum dot has heavy metal ion toxicity as green quantum dot.But all the time, consuming time longer for the ZnSe quantum dot that goes out with the hydro-thermal legal system take simple sulfhydryl compound as part, exist larger surface imperfection, fluorescence emission peak exists obvious conditions of streaking, and fluorescence quantum yield is lower, can't be applied to biomarker.Therefore, with reductive glutathione as part, the mode of microwave heating prepares quantum dot, can shorten its generated time, and outside the nuclear structure of ZnSe quantum dot, form one deck ZnS shell, effectively reduce the surface imperfection of quantum dot, and increased its fluorescence quantum yield, overcome the limitation of the synthetic ZnSe quantum dot of hydrothermal method.
Summary of the invention
The objective of the invention is to be to provide a kind of aqueous phase preparation method of ZnSe/ZnS nuclear shell structure quantum point, preparation technology is simple fast, need not last handling process, has good biocompatibility, and cheap.This quantum dot quantum yield higher (〉 40%), peak width at half height narrower (about 25nm), and nontoxic, pollution-free.
In order to realize above-mentioned purpose, the present invention adopts following technical measures:
Its technical conceive is: a kind of ZnSe/ZnS nuclear shell structure quantum point, it consists of: selenium powder (Se, Tianjin section close europeanized reagent development centre), zinc acetate (Zn (Ac) 22H 2O, Meixing Chemical Co., Ltd., Shanghai), reduced glutathion (GSH, Japan), all the other are the aqueous solution.
In the described ZnSe/ZnS nuclear shell structure quantum point, selenium powder (Se), zinc acetate (Zn (Ac) 22H 2O), the molar ratio of reduced glutathion (GSH) is respectively under ℃ condition of 1/15 ~ 1/10:1:1.6 ~ 1.8,95 and heats 45 ~ 60min.
Described pH is 10-11.
A kind of aqueous phase preparation method of ZnSe/ZnS nuclear shell structure quantum point the steps include:
A, preparation selenium potassium hydride KH (KH 4Se) solution: by POTASSIUM BOROHYDRIDE (KBH 4) reduction selenium powder (Se) preparation, reaction equation is as follows:
4KBH 4?+?2Se?+?7H 2O?→?2KH 4Se?+?K 2B 4O 7?+11H 2↑
B, take by weighing 0.03006g POTASSIUM BOROHYDRIDE (KBH respectively 4) and 0.00789g selenium powder (Se) powder in tool plug test tube, to wherein adding 2mL high purity water, beyond the Great Wall stopper.In-3--5 ℃ lower reaction 0.5 ~ 1.5h, get colourless transparent liquid, be the selenium potassium hydride KH (KH of 0.05mol/L 4Se);
C, take by weighing 0.10975 ~ 0.16463g zinc acetate (Zn (Ac) respectively 22H 2O) crystal and 0.24586 ~ 0.41489g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
D, turn 150 ~ 300/stirring of min and constantly passing under the condition of high-purity argon gas (Ar), add the selenium potassium hydride KH (KH of 1mL0.05mol/L 4Se), using sodium hydroxide solution (NaOH) the regulator solution pH value of 5mol/L is 10-11, treats that it mixes fully.
E, be sub-packed in the tetrafluoroethylene counteracting tank with every tank 50ml, in 93-97 ℃ of lower microwave heating 60 ~ 75min.KH 4Se, Zn (Ac) 22H 2O, the molar ratio of reduced glutathion is respectively 1/15 ~ 1/10:1:1.6 ~ 1.8.
Make reference with quinoline sulfate solution, measure uv-absorbing in the 300nm place, and excite mensuration fluorescence excitation peak-to-peak area with 300nm, record its fluorescence quantum yield greater than 40%.
The present invention compared with prior art has the following advantages and effect:
1. the most of source of this quantum dot main raw material is abundant, cheap; Reduced glutathion (GSH) is though price is more expensive, and addition is few, and is little on the average price impact.
2. this quantum dot preparation technology is simple, processing parameter (mol ratio 1/15 ~ 1/10:1:1.6 ~ 1.8, pH=10.5, heat-up time 60-75min, Heating temperature 93-97 ℃) easy to control, and generated time (60min) is than hydrothermal method (〉 3h) shorten dramatically.
3. this quantum dot is nontoxic, pollution-free, has higher fluorescence quantum yield (〉 40%), and good biocompatibility is arranged.
Embodiment
Embodiment 1:
Below by embodiment, further illustrate outstanding feature of the present invention, only be the present invention is described and never limit the present invention.
A kind of ZnSe/ZnS nuclear shell structure quantum point, it consists of: selenium powder (Se), zinc acetate (Zn (Ac) 22H 2O), reduced glutathion (GSH), all the other are the aqueous solution.
In the described ZnSe/ZnS nuclear shell structure quantum point, selenium powder (Se), zinc acetate (Zn (Ac) 22H 2O), the molar ratio of reduced glutathion (GSH) is respectively under ℃ condition of 1/15 ~ 1/10:1:1.6 ~ 1.8,95 and heats 45 ~ 60min.
Described pH is 10-11.
A kind of aqueous phase preparation method of ZnSe/ZnS nuclear shell structure quantum point the steps include:
1. take by weighing respectively 0.03006g POTASSIUM BOROHYDRIDE (KBH 4) and the selenium powder (Se) of 0.00789g in tool plug test tube, to wherein adding 2mL high purity water, beyond the Great Wall stopper.In-3 or-4 or-5 ℃ of lower reactions 0.5 or 1 or 1.5h, get colourless transparent liquid, be the selenium potassium hydride KH (KH of 0.05mol/L 4Se).
2. take by weighing respectively 0.16463g zinc acetate (Zn (Ac) 22H 2O) crystal and 0.41489g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
3. turn 150 ~ 300/stirring of min and constantly passing under the condition of high-purity argon gas (Ar), add the selenium potassium hydride KH (KH of 1mL0.05mol/L 4Se), be 10 or 10.3 or 10.5 or 10.7 or 11 with sodium hydroxide solution (NaOH) the regulator solution pH value of 5mol/L, treat that it mixes fully, selenium potassium hydride KH (KH 4Se), zinc acetate (Zn (Ac) 22H 2O), the molar ratio of reduced glutathion (GSH) is respectively 1/15:1:1.8.
4. be sub-packed in afterwards in the tetrafluoroethylene counteracting tank, make the ZnSe/ZnS nuclear shell structure quantum point in 93 ℃ or 95 ℃ or 97 ℃ of lower microwave heating 60min or 65min or 70min or 75min, recording its fluorescence quantum yield is 20 ~ 35.7%.
Embodiment 2:
A kind of ZnSe/ZnS nuclear shell structure quantum point, it consists of: selenium powder (Se), zinc acetate (Zn (Ac) 22H 2O), reduced glutathion (GSH), all the other are the aqueous solution.
In the described ZnSe/ZnS nuclear shell structure quantum point, selenium powder (Se), zinc acetate (Zn (Ac) 22H 2O), the molar ratio of reduced glutathion (GSH) is respectively under ℃ condition of 1/15 ~ 1/10:1:1.6 ~ 1.8,95 and heats 45 ~ 60min.
Described pH is 10.5
A kind of aqueous phase preparation method of ZnSe/ZnS nuclear shell structure quantum point the steps include:
1. take by weighing respectively 0.03006g POTASSIUM BOROHYDRIDE (KBH 4) and the selenium powder (Se) of 0.00789g in tool plug test tube, to wherein adding the 2mL high purity water, stopper beyond the Great Wall in-4 ℃ of lower reactions 0.5 or 1 or 1.5h, gets colourless transparent liquid, is the selenium potassium hydride KH (KH of 0.05mol/L 4Se).
2. take by weighing respectively 0.10975 zinc acetate (Zn (Ac) 22H 2O) crystal and 0.24586g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
3. turn 150 ~ 300/stirring of min and constantly passing under the condition of high-purity argon gas (Ar), add the selenium potassium hydride KH (KH of 1mL0.05mol/L 4Se), be 10.5 with sodium hydroxide (NaOH) the regulator solution pH value of 5mol/L, treat that it mixes fully, selenium potassium hydride KH (KH 4Se), zinc acetate (Zn (Ac) 22H 2O), the molar ratio of reduced glutathion (GSH) is respectively 1/10:1:1.6.
4. be sub-packed in the tetrafluoroethylene counteracting tank with every tank 50ml afterwards, make the ZnSe/ZnS nuclear shell structure quantum point in 95 ℃ of lower microwave heating 45min, recording its fluorescence quantum yield is 39.7%.
Other implementation step is identical with embodiment 1.
Embodiment 3:
1. take by weighing respectively 0.03006g POTASSIUM BOROHYDRIDE (KBH 4) and the selenium powder (Se) of 0.00789g in tool plug test tube, to wherein adding the 2mL high purity water, stopper beyond the Great Wall in-4 ℃ of lower reactions 0.5 or 1 or 1.5h, gets colourless transparent liquid, is the selenium potassium hydride KH (KH of 0.05mol/L 4Se);
2. take by weighing respectively 0.10975 zinc acetate (Zn (Ac) 22H 2O) crystal and 0.24586g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
3. turn 150 ~ 300/stirring of min and constantly passing under the condition of high-purity argon gas (Ar), add the selenium potassium hydride KH (KH of 1mL0.05mol/L 4Se), be 10 or 10.5 or 11 with sodium hydroxide (NaOH) the regulator solution pH value of 5mol/L, treat that it mixes fully, selenium potassium hydride KH (KH 4Se), zinc acetate (Zn (Ac) 22H 2O), the molar ratio of reduced glutathion (GSH) is respectively 1/10:1:1.6.
4. be sub-packed in the tetrafluoroethylene counteracting tank with every tank 50ml afterwards, make the ZnSe/ZnS nuclear shell structure quantum point in 95 ℃ of lower microwave heating 60min, recording its fluorescence quantum yield is 41.2%.
Other implementation step is identical with embodiment 1.

Claims (1)

1. the aqueous phase preparation method of a ZnSe/ZnS nuclear shell structure quantum point the steps include:
A, preparation selenium potassium hydride KH solution: by the preparation of potassium borohydride reduction tellurium powder, reaction equation is as follows:
4KBH 4?+?2Se?+?7H 2O?→?2KH 4Se?+?K 2B 4O 7?+11H 2↑
B, take by weighing 0.03006g POTASSIUM BOROHYDRIDE and 0.00789g selenium powder in tool plug test tube respectively, to wherein adding the 2mL high purity water, stopper beyond the Great Wall, in-3--5 ℃ lower reaction 0.5 ~ 1.5h, get colourless transparent liquid, be the selenium potassium hydride KH of 0.05mol/L;
C, take by weighing 0.10975 ~ 0.16463g crystal of zinc acetate and 0.24586 ~ 0.41489g reduced glutathion respectively, be dissolved in the 200mL anaerobic high purity water;
D, turning 150 ~ 300/stirring of min and constantly passing under the condition of high-purity argon gas, add the selenium potassium hydride KH of 1mL0.05mol/L, is 10-11 with the sodium hydroxide solution regulator solution pH value of 5mol/L, treats its mixing;
E, be sub-packed in the tetrafluoroethylene counteracting tank with every tank 50ml, in 93-97 ℃ of lower microwave heating 60 ~ 75min, KH 4Se, Zn (Ac) 22H 2O, the molar ratio of reduced glutathion is respectively 1/15 ~ 1/10:1:1.6 ~ 1.8.
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CN102517024B (en) * 2011-12-19 2013-11-27 武汉大学 Method for water-phase microwave preparation of CdSeS quantum dots
CN102517025B (en) * 2011-12-19 2013-11-27 武汉大学 Preparation method of ZnSe/ZnS core-shell quantum dots
CN102798724B (en) * 2012-08-07 2014-11-19 深圳先进技术研究院 Method for measuring breast cancer HER2 gene expression and kit thereof
CN102965113A (en) * 2012-11-08 2013-03-13 上海大学 Water-phase preparation method for ZnSe: Cu quantum dot coated by Zns
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CN104531141B (en) * 2014-12-16 2017-09-26 南京科技职业学院 A kind of microwave aqueous phase preparation method of cerium, erbium-codoped ZnS quantum dot
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CN104974742A (en) * 2015-07-06 2015-10-14 天门市天宝化工科技有限公司 Method for microwave-assisted preparation of CdTeSeS/ZnTe core-shell quantum dot in water
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