CN102127446A - 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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CN102127446A
CN102127446A CN2011100066293A CN201110006629A CN102127446A CN 102127446 A CN102127446 A CN 102127446A CN 2011100066293 A CN2011100066293 A CN 2011100066293A CN 201110006629 A CN201110006629 A CN 201110006629A CN 102127446 A CN102127446 A CN 102127446A
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selenium
znse
high purity
potassium hydride
aqueous phase
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CN102127446B (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 quantum dot as green quantum dot and have the toxic limitation of heavy metal ion.But all the time, be that part is consuming time longer with the ZnSe quantum dot that Hydrothermal Preparation goes out with simple sulfhydryl compound, exist bigger surface imperfection, fluorescence emission peak exists tangible 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), (GSH, Japan), all the other are the aqueous solution to reduced glutathion.
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 value of solution value 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, stopper beyond the Great Wall.In-3--5 ℃ following 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, in the stirring of 150 ~ 300 commentaries on classics/min with constantly feed 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 jar of 50ml, in 93-97 ℃ of following 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, record its fluorescence quantum yield greater than 40% with 300nm.
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 to the average price influence.
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 value of solution value 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 0.03006g POTASSIUM BOROHYDRIDE (KBH respectively 4) and the selenium powder (Se) of 0.00789g in tool plug test tube, to wherein adding 2mL high purity water, stopper beyond the Great Wall.In-3 or-4 or-5 ℃ of down reactions 0.5 or 1 or 1.5h, colourless transparent liquid, be the selenium potassium hydride KH (KH of 0.05mol/L 4Se).
2. take by weighing 0.16463g zinc acetate (Zn (Ac) respectively 22H 2O) crystal and 0.41489g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
3. in the stirring of 150 ~ 300 commentaries on classics/min with constantly feed 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 following 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 value of solution value 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 0.03006g POTASSIUM BOROHYDRIDE (KBH respectively 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 reactions 0.5 or 1 or 1.5h down, colourless transparent liquid, be the selenium potassium hydride KH (KH of 0.05mol/L 4Se).
2. take by weighing 0.10975 zinc acetate (Zn (Ac) respectively 22H 2O) crystal and 0.24586g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
3. in the stirring of 150 ~ 300 commentaries on classics/min with constantly feed 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 jar of 50ml afterwards, make the ZnSe/ZnS nuclear shell structure quantum point in 95 ℃ of following 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 0.03006g POTASSIUM BOROHYDRIDE (KBH respectively 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 reactions 0.5 or 1 or 1.5h down, colourless transparent liquid, be the selenium potassium hydride KH (KH of 0.05mol/L 4Se);
2. take by weighing 0.10975 zinc acetate (Zn (Ac) respectively 22H 2O) crystal and 0.24586g reduced glutathion (GSH) are dissolved in the 200mL anaerobic high purity water.
3. in the stirring of 150 ~ 300 commentaries on classics/min with constantly feed 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 jar of 50ml afterwards, make the ZnSe/ZnS nuclear shell structure quantum point in 95 ℃ of following 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 sodium 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 powder in tool plug test tube respectively, to wherein adding the 2mL high purity water, stopper beyond the Great Wall, in-3--5 ℃ of reaction 0.5 ~ 1.5h down, colourless transparent liquid, be the selenium potassium hydride KH of 0.05mol/L;
C, take by weighing 0.10975 ~ 0.16463g zinc acetate crystal and 0.24586 ~ 0.41489g reduced glutathion respectively, be dissolved in the 200mL anaerobic high purity water;
D, in the stirring of 150 ~ 300 commentaries on classics/min with constantly feed under the condition of high-purity argon gas, add the selenium potassium hydride KH of 1mL0.05mol/L, be 10-11 with the sodium hydroxide solution regulator solution pH value of 5mol/L, treat its mixing;
E, be sub-packed in the tetrafluoroethylene counteracting tank with every jar of 50ml, in 93-97 ℃ of following 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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CN102517024A (en) * 2011-12-19 2012-06-27 武汉大学 Method for water-phase microwave preparation of CdSeS quantum dots
CN102517025A (en) * 2011-12-19 2012-06-27 武汉大学 Preparation method of ZnSe/ZnS core-shell quantum dots
CN102798724A (en) * 2012-08-07 2012-11-28 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
CN104403670A (en) * 2014-11-03 2015-03-11 南京化工职业技术学院 Preparation method of cadmium-ytterbium-codoped zinc sulfide quantum point
CN104531141A (en) * 2014-12-16 2015-04-22 南京化工职业技术学院 Microwave aqueous phase preparation method of cerium and erbium co-doped ZnS quantum dot
CN104927868A (en) * 2015-06-09 2015-09-23 湖北荆楚理工科技开发有限公司 Preparation method for CdHgTe/CdS core-shell quantum dot
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
CN106423265A (en) * 2016-09-23 2017-02-22 安徽理工大学 Peptide quantum dot and ultrasonic microwave synthesis method thereof
CN115710016A (en) * 2022-11-28 2023-02-24 西华大学 Surface-vulcanized metal compound composite material MS @ MX and preparation method thereof

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CN102517025A (en) * 2011-12-19 2012-06-27 武汉大学 Preparation method of ZnSe/ZnS core-shell quantum dots
CN102517024A (en) * 2011-12-19 2012-06-27 武汉大学 Method for water-phase microwave preparation of CdSeS quantum dots
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
CN102798724A (en) * 2012-08-07 2012-11-28 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
CN104403670A (en) * 2014-11-03 2015-03-11 南京化工职业技术学院 Preparation method of cadmium-ytterbium-codoped zinc sulfide quantum point
CN104531141A (en) * 2014-12-16 2015-04-22 南京化工职业技术学院 Microwave aqueous phase preparation method of cerium and erbium co-doped ZnS quantum dot
CN104927868A (en) * 2015-06-09 2015-09-23 湖北荆楚理工科技开发有限公司 Preparation method for CdHgTe/CdS core-shell quantum dot
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
CN106423265A (en) * 2016-09-23 2017-02-22 安徽理工大学 Peptide quantum dot and ultrasonic microwave synthesis method thereof
CN106423265B (en) * 2016-09-23 2019-04-12 安徽理工大学 A kind of polypeptide quantum dot and its ultrasonic-microwave synthetic method
CN115710016A (en) * 2022-11-28 2023-02-24 西华大学 Surface-vulcanized metal compound composite material MS @ MX and preparation method thereof
CN115710016B (en) * 2022-11-28 2024-05-14 西华大学 Surface vulcanized metal compound composite material MS@MX and preparation method thereof

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