CN104513664A - Near-infrared silver-indium-selenium quantum dot and preparation method thereof - Google Patents
Near-infrared silver-indium-selenium quantum dot and preparation method thereof Download PDFInfo
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- CN104513664A CN104513664A CN201310452250.4A CN201310452250A CN104513664A CN 104513664 A CN104513664 A CN 104513664A CN 201310452250 A CN201310452250 A CN 201310452250A CN 104513664 A CN104513664 A CN 104513664A
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Abstract
The invention discloses a near-infrared silver-indium-selenium quantum dot and a preparation method thereof. The preparation method comprises the following steps: (1) dissolving cupric chloride or silver acetate, indium acetate, sodium hydrogen selenide and 3-mercaptopropionic acid according to the molar ratio of 1:1-5:10-20:34-36, so as to obtain a mixed solution, wherein the concentration of cupric chloride or silver acetate is 0.7-0.9 mmol/L; and (2) adjusting the pH value of the mixed solution obtained in the step (1) to 8-9, then heating the mixed solution at 93-98 DEG C for reaction for 55-65 min, and cooling to room temperature, so as to obtain the near-infrared silver-indium-selenium quantum dot. The prepared quantum dot has the advantages of being nontoxic, simple in method, mild and controllable in reaction conditions, short in reaction time, good in reappearance and the like. The prepared quantum dot is widely applicable to cell and tissue imaging as a fluorescent marker, and also is applicable to in vivo imaging research.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to a kind of near infrared silver indium selenium quantum dot and preparation method thereof.
Background technology
Quantum dot (quantumdots, QDs) is also called semiconductor nanocrystal, is a kind of nanocrystal be made up of II-IV race or III-group Ⅴ element.Quantum dot due to its excellent physicochemical property, as quantum size effect, luminescent properties and chemical process, and application in fields such as biomarker, bio-sensing, photoelectronics and solar cells and receiving much concern.
Compared with traditional organic fluorescence reagent, quantum dot has the spectrum property of many excellences, wide application prospect is shown at biology, medical field, especially the near infrared fluorescence quantum point that gets up of development in recent years, owing to there is strong penetration power to tissue, be particularly suitable for Noninvasive visible in body.Imaging uses in vivo, and the most important can not produce toxicity and destroy normal cell exactly.The cytotoxicity of cadmium content point derives from its cadmium ion dissociating or be present in surface, and quantum dot greatly have impact on its cytotoxicity in intracellular distribution, strongly limit the application of near-infrared quantum dots in living imaging.
At present, mainly elementary composition with Cu, Ag, Mn, Zn, Se, S etc. without cadmium quantum dot, and chemically synthesize, the synthesis of quantum dot uses more method to be organometallic synthesis method and aqueous phase synthesis method at present.Though the quantum dot stability of organometallic synthesis, surface modifyingly better there is the shortcomings such as poorly water-soluble, preparation is complicated, cost is higher, limit its application.The advantages such as water phase synthesis method has low cost, simple to operate, reaction conditions is gentle, easy regulation and control.Have bibliographical information to adopt high temperature organic procedures to prepare silver sulfide quantum dot, owing to adopting high temperature oil phase method, the quantum dot of gained is oil soluble, needs further modification just can be applied to living things system; Adopt microwave irradiation to prepare water-soluble near infrared cadmium telluride quantum dot, the reaction times that the acquisition in its tellurium source needs longer and reaction needed oxygen-free environment protection, meanwhile, cadmium element contains higher toxicity; Employing Aqueous phase has synthesized the zinc selenide quantum dot launching the additive Mn of yellow visible light, but adjustable wavelength is limited, is unfavorable for that living imaging is studied.
Summary of the invention
Based on this, the object of this invention is to provide the preparation method of a kind of near infrared silver indium selenium quantum dot.
Concrete technical scheme is as follows:
A preparation method near infrared silver indium selenium quantum dot, comprises the steps:
(1) Silver Nitrate or Silver monoacetate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid are pressed the mol ratio of 1:1-5:10-20:34-36 soluble in water mixing solutions, the concentration of wherein said Silver Nitrate or Silver monoacetate is 0.7-0.9mmol/L;
(2) pH value of mixing solutions that obtains of regulating step (1) is to 8-9, then by mixing solutions reacting by heating 55-65min at 93-98 DEG C, is down to room temperature, obtains described near infrared silver indium selenium quantum dot.
Wherein in an embodiment, in described step (1), the mol ratio of Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:1-5:10-20:35.
Wherein in an embodiment, in described step (1), the mol ratio of Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:1:10:35 or 1:2.5:20:35 or 1:5:20:35.
Wherein in an embodiment, mixing solutions reacting by heating 60min at 95 DEG C in described step (2).
Another object of the present invention is to provide the near infrared silver indium selenium quantum dot that above-mentioned preparation method prepares.
Concrete technical scheme is as follows:
The near infrared silver indium selenium quantum dot that above-mentioned preparation method prepares.
Advantage of the present invention is as follows:
The near infrared silver indium selenium quantum dot that the present invention prepares is with Silver Nitrate, the inorganic metal water-soluble cpdss such as indium acetate and 3-thiohydracrylic acid are raw material, the regulation and control of quantum dot spectrum are realized with the molar ratio of indium by regulating silver, emmission spectrum covers near infrared light region, have nontoxic, method be easy, reaction conditions gentle controlled, the reaction times is short, high repeatability and other advantages.Eliminate due to the toxicity that the use of heavy metal element brings in traditional quantum dot, and preparation can be repeated in a large number.Can be used as fluorescent marker and be widely used in cell, imaging of tissue, and can be applicable to living imaging research.At molecular biology, cytobiology, medical diagnostics, particularly biomedical living imaging research aspect has great application prospect.
Accompanying drawing explanation
Fig. 1 is the synthesis schematic diagram of preparation method of the present invention;
Fig. 2 is the product abosrption spectrogram (in figure, 1,2,3 represent embodiment 1,2,3) that embodiment 1-3 prepares;
Fig. 3 is the product utilizing emitted light spectrogram (in figure, 1,2,3 represent embodiment 1,2,3) that embodiment 1-3 prepares.
Embodiment
By the following examples the present invention is further elaborated.
Embodiment 1
The preparation method of a kind of near infrared silver of the present embodiment indium selenium quantum dot, comprises the steps:
(1) precursor storing solution A: take Silver Nitrate 0.195g, is dissolved in 10ml ultrapure water;
(2) precursor storing solution B: take indium acetate 0.0583g, is dissolved in 10ml ultrapure water;
(3) precursor storing solution C: take 3-thiohydracrylic acid 0.212g, is dissolved in 10ml ultrapure water;
(4) precursor storing solution D: take sodium borohydride 0.04g, selenium powder 0.0395g, be dissolved in 1ml ultrapure water, and ice bath is to colourless;
(5) 0.08ml precursor storing solution A is got, add the precursor storing solution B of 2ml, add 1.4ml precursor storing solution C, be settled to 10ml, adjust ph is 8.5, pass into argon gas deoxygenation 30min, the mol ratio adding 0.32ml precursor storing solution D(Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:5:20:35);
(6) the mixing solutions reacting by heating 60min at 95 DEG C then step (5) obtained, is down to room temperature, obtains near infrared silver indium selenium quantum dot (synthesis schematic diagram as shown in Figure 1) described in the present embodiment.
The result that the near infrared silver indium selenium that above-mentioned preparation method obtains becomes quantum dot ultimate analysis is as follows:
| Ag/In mol ratio | Ag/Se mol ratio | Particle diameter |
| 0.19 | 0.05 | 4.5nm |
As shown in Figure 2, emmission spectrum as shown in Figure 3 for absorption spectrum.
Embodiment 2
The preparation method of a kind of near infrared silver of the present embodiment indium selenium quantum dot, comprises the steps:
(1) precursor storing solution A: take Silver Nitrate 0.195g, is dissolved in 10ml ultrapure water;
(2) precursor storing solution B: take indium acetate 0.0583g, is dissolved in 10ml ultrapure water;
(3) precursor storing solution C: take 3-thiohydracrylic acid 0.212g, is dissolved in 10ml ultrapure water;
(4) precursor storing solution D: take sodium borohydride 0.04g, selenium powder 0.0385g, be dissolved in 1ml ultrapure water, and ice bath is to colourless;
(5) 0.08ml precursor storing solution A is got, add the precursor storing solution B of 1ml, add 1.4ml precursor storing solution C, be settled to 10ml, adjust ph is 8.5, pass into argon gas deoxygenation 30min, the mol ratio adding 0.32ml precursor storing solution D(Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:2.5:20:35);
(6) the mixing solutions reacting by heating 60min at 95 DEG C then step (5) obtained, is down to room temperature, obtains near infrared silver indium selenium quantum dot (synthesis schematic diagram as shown in Figure 1) described in the present embodiment.
The result that the near infrared silver indium selenium that above-mentioned preparation method obtains becomes quantum dot ultimate analysis is as follows:
| Ag/In mol ratio | Ag/Se mol ratio | Particle diameter |
| 0.39 | 0.05 | 4.5nm |
As shown in Figure 2, emmission spectrum as shown in Figure 3 for absorption spectrum.
Embodiment 3
The preparation method of a kind of near infrared silver of the present embodiment indium selenium quantum dot, comprises the steps:
(1) precursor storing solution A: take Silver Nitrate 0.195g, is dissolved in 10ml ultrapure water;
(2) precursor storing solution B: take indium acetate 0.0583g, is dissolved in 10ml ultrapure water;
(3) precursor storing solution C: take 3-thiohydracrylic acid 0.212g, is dissolved in 10ml ultrapure water;
(4) precursor storing solution D: take sodium borohydride 0.04g, selenium powder 0.0395g, be dissolved in 1ml ultrapure water, and ice bath is to colourless;
(5) 0.08ml precursor storing solution A is got, add the precursor storing solution B of 0.4ml, add 1.4ml precursor storing solution C, be settled to 10ml, adjust ph is 8.5, pass into argon gas deoxygenation 30min, the mol ratio adding 0.16ml precursor storing solution D(Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:1:10:35);
(6) the mixing solutions reacting by heating 60min at 95 DEG C then step (5) obtained, is down to room temperature, obtains near infrared silver indium selenium quantum dot (synthesis schematic diagram as shown in Figure 1) described in the present embodiment.
The result that the near infrared silver indium selenium that above-mentioned preparation method obtains becomes quantum dot ultimate analysis is as follows:
| Ag/In mol ratio | Ag/Se mol ratio | Particle diameter |
| 0.98 | 0.1 | 5.0nm |
As shown in Figure 2, emmission spectrum as shown in Figure 3 for absorption spectrum.
Comparative example 1
A kind of CuInSe of yellow copper structure has been synthesized in prior art
2and CuInSe
2/ ZnS core-shell structured quantum dot, a kind of zincblende lattce structure and wurtzite structure CuInS
2quantum dot, its preparation method all adopts high temperature oil to be combined to, and the copper indium system used, do not have the quantum dot patent of silver-colored indium system at present.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (5)
1. a preparation method near infrared silver indium selenium quantum dot, is characterized in that, comprise the steps:
(1) Silver Nitrate or Silver monoacetate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid are pressed the mol ratio of 1:1-5:10-20:34-36 soluble in water mixing solutions, the concentration of wherein said Silver Nitrate or Silver monoacetate is 0.7-0.9mmol/L;
(2) pH value of mixing solutions that obtains of regulating step (1) is to 8-9, then by mixing solutions reacting by heating 55-65min at 93-98 DEG C, is down to room temperature, obtains described near infrared silver indium selenium quantum dot.
2. the preparation method of near infrared silver indium selenium quantum dot according to claim 1, it is characterized in that, in described step (1), the mol ratio of Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:1-5:10-20:35.
3. the preparation method of near infrared silver indium selenium quantum dot according to claim 2, it is characterized in that, in described step (1), the mol ratio of Silver Nitrate, indium acetate, sodium hydrogen selenide and 3-thiohydracrylic acid is 1:1:10:35 or 1:2.5:20:35 or 1:5:20:35.
4. the preparation method of the near infrared silver indium selenium quantum dot according to any one of claim 1-3, is characterized in that, mixing solutions reacting by heating 60min at 95 DEG C in described step (2).
5. the near infrared silver indium selenium quantum dot that described in any one of claim 1-4, preparation method prepares.
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Cited By (6)
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| CN105154084A (en) * | 2015-07-21 | 2015-12-16 | 东华大学 | Preparation method for color-adjustable ternary AgInSe2 fluorescent quantum dots through aqueous-phase synthesis |
| CN108291143A (en) * | 2016-01-19 | 2018-07-17 | 株式会社村田制作所 | Illuminator, the manufacturing method of illuminator and organism mass signatures agent |
| CN113684022A (en) * | 2021-09-29 | 2021-11-23 | 陕西煤业化工技术研究院有限责任公司 | AgInS2Quantum dot and preparation method and application thereof |
| CN114606003A (en) * | 2022-03-25 | 2022-06-10 | 青岛科技大学 | Water phase preparation method of near-infrared luminescence enhanced low-toxicity quantum dots |
| WO2022156467A1 (en) * | 2021-01-20 | 2022-07-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Fluorescent quantum dots and preparation method therefor and use thereof |
| CN114854416A (en) * | 2021-01-20 | 2022-08-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver-gold-selenium fluorescent quantum dot and preparation method and application thereof |
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| CN102660288A (en) * | 2012-04-16 | 2012-09-12 | 天津大学 | Method for preparing chalcopyrite structure CuInSe2 or/and CuInSe2/ZnS core-shell structure quantum dots |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105154084A (en) * | 2015-07-21 | 2015-12-16 | 东华大学 | Preparation method for color-adjustable ternary AgInSe2 fluorescent quantum dots through aqueous-phase synthesis |
| CN108291143A (en) * | 2016-01-19 | 2018-07-17 | 株式会社村田制作所 | Illuminator, the manufacturing method of illuminator and organism mass signatures agent |
| CN108291143B (en) * | 2016-01-19 | 2021-04-09 | 株式会社村田制作所 | Light-emitting body, method for producing light-emitting body, and biological substance labeling agent |
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| WO2022156467A1 (en) * | 2021-01-20 | 2022-07-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Fluorescent quantum dots and preparation method therefor and use thereof |
| CN114854416A (en) * | 2021-01-20 | 2022-08-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver-gold-selenium fluorescent quantum dot and preparation method and application thereof |
| CN114854416B (en) * | 2021-01-20 | 2023-06-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Near-infrared silver-gold-selenium fluorescent quantum dot and preparation method and application thereof |
| CN113684022A (en) * | 2021-09-29 | 2021-11-23 | 陕西煤业化工技术研究院有限责任公司 | AgInS2Quantum dot and preparation method and application thereof |
| CN114606003A (en) * | 2022-03-25 | 2022-06-10 | 青岛科技大学 | Water phase preparation method of near-infrared luminescence enhanced low-toxicity quantum dots |
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