CN113881435B - Rare earth doped silver selenide quantum dot and synthesis method thereof - Google Patents

Rare earth doped silver selenide quantum dot and synthesis method thereof Download PDF

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CN113881435B
CN113881435B CN202111188492.8A CN202111188492A CN113881435B CN 113881435 B CN113881435 B CN 113881435B CN 202111188492 A CN202111188492 A CN 202111188492A CN 113881435 B CN113881435 B CN 113881435B
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rare earth
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organic phosphine
reaction
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CN113881435A (en
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徐丽广
丁棋
胥传来
匡华
马伟
孙茂忠
刘丽强
吴晓玲
郝昌龙
宋珊珊
胡拥明
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Jiangnan University
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
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    • C09K11/886—Chalcogenides with rare earth metals

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Abstract

The invention provides a rare earth doped silver selenide quantum dot and a synthesis method thereof, belonging to the technical field of material chemistry. The synthesis method comprises the following steps: adding selenium powder into the organic phosphine solution, and stirring and mixing uniformly under the condition of keeping out of the sun to obtain a selenium-organic phosphine solution; adding rare earth metal salt into an organic phosphine solution to obtain a rare earth element precursor; mixing octadecylene, mercaptan and silver acetate, and heating in inert gas for reaction to obtain a clear reaction solution; adding the selenium-organic phosphine solution and a chiral ligand into the reaction solution, uniformly mixing, heating and reacting in an inert atmosphere, adding the rare earth element precursor after the reaction is finished, and heating and reacting to obtain the rare earth element doped silver selenide quantum dots. The invention utilizes the means of transmission electron microscope, absorption spectrum, chiral circular dichroism analysis and the like to carry out corresponding physical characterization and deep research on the optical fiber. The quantum dots obtained by the method can be well compatible with cells, and have good application prospects in the biological field.

Description

Rare earth doped silver selenide quantum dot and synthesis method thereof
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a synthetic method of a chiral near-infrared two-region fluorescent silver selenide quantum dot.
Background
Because the light with long wavelength is low in scattering and good in penetration depth in the living body tissue, the near-infrared two-zone (1000-. Moreover, with the rapid development of the biological imaging field, more and more near-infrared quantum dots are widely used in a plurality of fields such as biological macromolecules and cell markers, tissue and living cell imaging, tumor model positioning, clinical diagnosis and the like, and have made breakthrough progress.
Silver selenide (Ag) 2 Se) is taken as a novel near-infrared binary silver-containing quantum dot, and is increasingly paid attention by researchers due to the advantages of low toxicity, small size, excellent near-infrared optical property and the like. The appearance of the quantum dots is a beneficial supplement to the limitation of the alloy quantum dots in the biological field. On one hand, the method makes up the problem that the quantum dots containing heavy metal elements (cadmium or lead) have high toxicity to the environment and biological systems, and can effectively reduce the biological toxicity of the quantum dots. On the other hand, the quantum dots are near infrared band quantum dots, so that the quantum dots can be well distinguished from autofluorescence of biological tissues, the cell resolution capability is improved, the penetration depth is deeper, and the biological application can be better carried out. The preparation of chiral near-infrared two-region fluorescent silver selenide quantum dots is technically challenging and has attracted considerable attention in different interdisciplinary fields. At present, the structures of alloy quantum dots CdSeS, CdHgTe, CdSexTe1 and the like are mostly reported by a plurality of scholars, and the alloy quantum dots have the defect that the quantum dots contain heavy metal Cd, so that the application of the alloy quantum dots in the biological field has certain limitation. However, the chiral near-infrared silver selenide quantum dot structure is a cadmium-free fluorescent quantum dot, so that the application of the near-infrared quantum dot in the field of biomarkers is necessarily expanded.
Disclosure of Invention
In order to solve the technical problems, the invention provides a rare earth doped silver selenide quantum dot and a synthesis method thereof.
A synthesis method of rare earth doped silver selenide quantum dots comprises the following steps:
(1) adding selenium powder into the organic phosphine solution, and stirring and mixing uniformly under the condition of keeping out of the sun to obtain a selenium-organic phosphine solution;
(2) adding rare earth metal salt into an organic phosphine solution for reaction to obtain a rare earth element precursor;
(3) mixing Octadecylene (ODE), mercaptan and silver acetate, heating to 160-180 ℃ in inert gas, and reacting for 10-40min to obtain a clear reaction solution;
(4) and (2) adding the selenium-organic phosphine solution and the chiral ligand in the step (1) into the reaction solution in the step (3), uniformly mixing, heating to 160-.
In one embodiment of the present invention, in the step (1), the organic phosphine is one or more of trioctylphosphine, tri-n-octylphosphine oxide and tributyloxyphosphorus.
In one embodiment of the present invention, in the step (2), the rare earth metal salt is selected from neodymium chloride, ytterbium chloride and erbium chloride.
In one embodiment of the invention, the molar ratio of neodymium chloride, ytterbium chloride and erbium chloride is 1:3-5: 4-5.
In one embodiment of the present invention, in step (3), the volume ratio of Octadecene (ODE) to thiol is 15-5: 17-3.
In one embodiment of the present invention, in the step (3), the silver acetate concentration is 0.2mM-1 mM.
In one embodiment of the present invention, in the step (3), the thiol is dodecyl mercaptan or/and tert-dodecyl mercaptan.
In one embodiment of the present invention, in the step (4), the chiral ligand is one or more of binaphthylamine, binaphthol, and naphthylethylamine.
In one embodiment of the invention, in step (4), the chiral ligand is at a concentration of 2mM to 10 mM.
The invention also provides the rare earth element doped silver selenide quantum dot prepared by the synthesis method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention realizes the preparation of Ag by a high-temperature oil phase synthesis method 2 Se quantum dots are prepared, and Ag with different sizes is obtained by changing the ratio of Ag to Se 2 Se quantum dots, and carrying out comparative analysis on the prepared quantum dots from the aspects of optical characteristics and structural characteristics so as to find the optimal Ag-Se ratio for preparing the quantum dots. Then, the fluorescence intensity is greatly enhanced by doping rare earth elements, the position of a fluorescence emission peak is red-shifted, quantum dots are chirally modified by dinaphthylamine, dinaphthol, naphthyl ethylamine and the like to have chirality, and the modified quantum dots are subjected to physicochemical characteristic characterization analysis, so that the verification is that Ag is used for verifying 2 The feasibility of Se applied to the field of biomarkers provides reliable basis for the application of the quantum dots in the field of biology.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a flow chart of a preparation method of the chiral near-infrared two-region fluorescent silver selenide quantum dot.
FIG. 2 is a transmission electron micrograph of the chiral near-infrared two-region fluorescent silver selenide quantum dots.
FIG. 3 is a Circular Dichroism (CD) diagram of the chiral near infrared two-region fluorescent silver selenide quantum dot of the invention.
FIG. 4 is an ultraviolet diagram of the chiral near-infrared two-region fluorescent silver selenide quantum dots of the invention.
FIG. 5 is a graph of the fluorescence enhancement effect of the chiral near-infrared two-region fluorescent silver selenide quantum dots of the invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
Adding 191mg of selenium powder into 2mL of tributylphosphine solution, stirring for 3h in a dark place to obtain selenium-tributylphosphine solution, and adding 0.5mmol of neodymium chloride, ytterbium chloride and erbium chloride into 5mL of tributylphosphine solution respectively to obtain neodymium-tributylphosphine solution, ytterbium-tributylphosphine solution and erbium-tributylphosphine solution.
2, adding 16mL of octadecene, 4mL of dodecyl mercaptan and 60mg of silver acetate into a three-neck flask, heating to 160 ℃ under the protection of nitrogen, and continuing to react for 10min at the preset temperature to obtain a clear reaction solution.
And 3, injecting 200 mu L of selenium-tributylphosphine solution and bi-2 naphthol into the reaction solution, heating to 160 ℃ under the protection of nitrogen, and continuously reacting for 30min at the preset temperature.
And 4, injecting 20 mu L of neodymium-tributylphosphine solution, 80 mu L of ytterbium-tributylphosphine solution and 120 mu L of erbium-tributylphosphine solution into the reaction solution, and continuing the reaction for 2 hours at the preset temperature under the protection of nitrogen.
And 5, after the reaction is finished, cooling to room temperature, and adding trichloromethane to prevent solidification.
And 6, carrying out centrifugal washing treatment by using acetone.
And adding trichloromethane into the reaction solution to obtain a silver selenide fluorescent quantum dot solution dispersed in the trichloromethane.
Example 2
1, adding 179mg of selenium powder into 3mL of tributylphosphine solution, and stirring for 4h in the dark to obtain selenium-tributylphosphine solution.
2, adding 17mL of octadecene, 3mL of dodecyl mercaptan and 65mg of silver acetate into a three-neck flask, heating to 170 ℃ under the protection of nitrogen, and continuing to react for 8min at the preset temperature to obtain a clear reaction solution.
And 3, injecting 200 mu L of selenium-tributylphosphine solution and bi-2 naphthol into the reaction solution, heating to 160 ℃ under the protection of nitrogen, and continuously reacting for 20min at the preset temperature.
And 4, injecting 10 mu L of neodymium-tributylphosphine solution, 100 mu L of ytterbium-tributylphosphine solution and 100 mu L of erbium-tributylphosphine solution into the reaction solution, and continuing to react for 2 hours at the preset temperature under the protection of nitrogen.
And 5, after the reaction is finished, cooling to room temperature, and adding trichloromethane to prevent solidification.
And 6, carrying out centrifugal washing treatment by using acetone.
And 7, adding trichloromethane into the reaction solution to obtain a silver selenide fluorescent quantum dot solution dispersed in the trichloromethane.
Example 3
1, adding 188mg of selenium powder into 2mL of tributylphosphine solution, and stirring for 4h in a dark place to obtain selenium-tributylphosphine solution.
2, adding 16mL of octadecene, 3mL of dodecyl mercaptan and 67mg of silver acetate into a three-neck flask, heating to 165 ℃ under the protection of nitrogen, and continuing to react for 8min at the preset temperature to obtain a clear reaction solution.
And 3, injecting 200 mu L of selenium-tributylphosphine solution and bi-2 naphthol into the reaction solution, heating to 160 ℃ under the protection of nitrogen, and continuously reacting for 20min at the preset temperature.
And 4, injecting 20 mu L of neodymium-tributylphosphine solution, 90 mu L of ytterbium-tributylphosphine solution and 90 mu L of erbium-tributylphosphine solution into the reaction solution, and continuing the reaction for 2 hours at the preset temperature under the protection of nitrogen.
And 5, after the reaction is finished, cooling to room temperature, and adding trichloromethane to prevent solidification.
And 6, carrying out centrifugal washing treatment by using acetone.
And 7, adding trichloromethane into the reaction solution to obtain a silver selenide fluorescent quantum dot solution dispersed in the trichloromethane.
Performance testing
The doped material passes through a fluorescence test, and can achieve stronger fluorescence intensity under the excitation of 808nm with the same power, the intensity can be enhanced by 120 times, and the position of an emission peak is red-shifted from 1100nm to 1500nm, so that the infrared two-region fluorescence imaging effect can be stronger. (the experimental results are shown in FIG. 5).
In conclusion, the high-temperature oil phase synthesis method is used for preparing Ag 2 Se quantum dots are prepared, and Ag with different sizes is obtained by changing the ratio of Ag to Se 2 Se quantum dots, andthe prepared quantum dots are compared and analyzed from the aspects of optical characteristics and structural characteristics, so that the optimal Ag to Se ratio for preparing the quantum dots is searched. Thereafter, Nd is doped in an optimum ratio 3+ 、Yb 3+ 、Er 3+ Greatly enhancing the luminous efficiency of fluorescence, carrying out chiral modification on the quantum dots by using binaphthylamine, binaphthol, naphthyl ethylamine and the like to enable the quantum dots to have chirality, and carrying out physicochemical characteristic characterization analysis on the modified quantum dots to verify that Ag is used for 2 The feasibility of Se applied to the field of biomarkers provides reliable basis for the application of the quantum dots in the field of biology.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (9)

1. A synthesis method of rare earth doped silver selenide quantum dots is characterized by comprising the following steps:
(1) adding selenium powder into the organic phosphine solution, and stirring and mixing uniformly under the condition of keeping out of the sun to obtain a selenium-organic phosphine solution;
(2) adding rare earth metal salt into an organic phosphine solution for reaction to obtain a rare earth element precursor; the rare earth metal salt is a mixture of neodymium chloride, ytterbium chloride and erbium chloride;
(3) mixing octadecylene, mercaptan and silver acetate, and heating in inert gas for reaction to obtain a clear reaction solution;
(4) adding the selenium-organic phosphine solution obtained in the step (1) and a chiral ligand into the reaction solution obtained in the step (3), uniformly mixing, heating and reacting in an inert atmosphere, adding the rare earth element precursor obtained in the step (2) after the reaction is finished, and heating and reacting to obtain the rare earth element doped silver selenide quantum dots.
2. The synthesis method according to claim 1, wherein in step (1), the organic phosphine is one or more of trioctylphosphine, tri-n-octylphosphine oxide and tributyloxyphosphorus.
3. The synthesis method according to claim 1, characterized in that the molar ratio of neodymium chloride, ytterbium chloride and erbium chloride is between 1:3 and 5:4 and 5.
4. The synthesis method according to claim 1, wherein in the step (3), the volume ratio of the octadecene to the mercaptan is 15-5: 17-3.
5. The method of synthesis according to claim 1, wherein in step (3), the silver acetate is at a concentration of 0.2mM to 1 mM.
6. The synthesis method according to claim 1, wherein in the step (3), the mercaptan is dodecyl mercaptan or/and tert-dodecyl mercaptan.
7. The synthesis method according to claim 1, wherein in the step (4), the chiral ligand is one or more of binaphthylamine, binaphthol and naphthylethylamine.
8. The method of claim 1, wherein in step (4), the chiral ligand is present at a concentration of 2mM to 10 mM.
9. The rare earth element doped silver selenide quantum dot prepared by the synthesis method of any one of claims 1-8.
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CN104449737A (en) * 2013-09-25 2015-03-25 海洋王照明科技股份有限公司 Holmium-ytterbium co-doped silver selenium salt up-conversion luminescent material as well as preparation method and application thereof
CN103840034B (en) * 2014-01-17 2016-02-17 南昌航空大学 The preparation of rare earth selenide quantum dots solar cell and application thereof
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