CN102517339A - Method for controllably synthesizing near-infrared Ag2Se nano crystal - Google Patents
Method for controllably synthesizing near-infrared Ag2Se nano crystal Download PDFInfo
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- CN102517339A CN102517339A CN2011103856513A CN201110385651A CN102517339A CN 102517339 A CN102517339 A CN 102517339A CN 2011103856513 A CN2011103856513 A CN 2011103856513A CN 201110385651 A CN201110385651 A CN 201110385651A CN 102517339 A CN102517339 A CN 102517339A
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Abstract
The invention discloses a method for controllably synthesizing Ag2Se nano crystal. The method comprises the following steps of: obtaining low-valence Se in processes of simulating glutathione reductase in an organism outside cells and reducing sodium selenite (Na2SeO3) by using coenzyme, reacting the low-valence Se and Ag<+> coordinated with alanine in an inert atmosphere, and thus obtaining the Ag2Se nano crystal with good monodispersity, uniform particle size and different fluorescence emission wavelengths under the condition of aqueous phase. In the method, the size and the fluorescence emission wavelength of the product are controlled by controlling the ratio of the Se precursor to the Ag precursor. The method is easy and convenient, can be repeated for preparation, does not require inflammable, explosive and toxic metallic organic compounds, is good in safety, and can be applied in the fields of chemistry and material science more widely.
Description
Technical field
The present invention relates to a kind of through regulation and control biochemical reaction come controlledly synthesis Ag
2The preparation method of Se nanocrystal belongs to biology, chemistry and material science.
Background technology
Because the autofluorescence of organism blood and tissue is with to be absorbed near infrared region very low, therefore, the near infrared material is extremely important to bio-imaging and live body detection.In addition, the biocompatibility of near infrared material, toxicity, small size also are important problems in the biologic applications.Under green gentle condition in the nano materials, the size and the performance of nano material controlled well is the focus that this field receives much concern.Usually dangerous and expensive organometallics raw material or complicacy, unmanageable working method have all been adopted among the preparation method of quantum dot.The quantum dot size that obtains is bigger usually.
Qian had reported Ag in 2003
2CO
3Prepare Ag with Se Hybrid Heating in several kinds of different solvents
2The method of Se.After this, Cao has reported that elder generation is with AgNO
3And C
4H
4Se is respectively with C
6H
5NH
2Form solution A and B, solution B is added to removes to add hot preparation Ag in the solution A then
2Se.Li uses Na
2SeSO
3And AgNO
3Adopt micro emulsion method synthetic Ag
2Se particle diameter 7 to 12 nm.In addition with AgNO
3In ODA, heat the Ag that obtains particle diameter 8.5 nm with Se
2Se is assembled into meso-hole structure then.Fu with hydrothermal method with AgNO
3And Na
2SeSO
3At poly (vinyl pyrrolidone) Ag that (PVP) heating is made with KI
2Long 60 –, 80 nm of Se, wide 30 –, 40 nm.
Vittal is with single precursor [(Ph
3P)
3Ag
2(SeC{O}Ph)
2] thermal degradation prepares Ag in TOP and HAD
2Se, through the ratio of change HAD and precursor, temperature of reaction, the reaction times obtains the Ag of different sizes (11-70 nm) and form
2The Se nanocrystal.Norris uses AgNO
3Form reacting precursor with TOP respectively with Se, at oleic acid (OA), 1-octadecylamine (ODA) successively injects the Ag that TOP-Se and Ag-TOP obtain in 1-octadecene (ODE) mixing solutions
2Se particle diameter 7 nm.
First has reported the Ag that in organic phase, synthesizes small particle size (2-4nm) fluorescent emission wavelength 1030 and 1250 nm Heiss
2The Se quantum dot.
The controllability that how to realize near infrared nano material small particle size is the difficult problem in the material building-up process always.In biomarker, the necessary character of nano material depends on composition, size, shape, percent crystallinity and the structure of material.If can realize above these parameter control are promptly realized the controllability of nano material, characteristic that again can control material, thus obtain various desirable material.
In the method for above-mentioned various metallic compound/element organism route, though can use AgNO
3Prepare quantum dot with mineral compound such as Se, but prepared usually quantum point grain diameter is bigger, no photoluminescent property etc.Organometallic compound is made raw material; Need comparatively harsh reaction conditions, so, select raw material cheap, stable in properties if can these methods be improved; Under green, safe, gentle relatively condition, controllably prepare required nano material, undoubtedly with significant.
Summary of the invention
To above-mentioned deficiency, the present invention provides a kind of Ag that under green gentle condition, synthesizes to controllable size
2The method of Se nanocrystal.
The inventive method is through regulation and control organism glutathion inside reductase enzyme and codehydrogenase catalysis Sodium Selenite (Na
2SeO
3) the reduction process biochemical reaction comes controlledly synthesis Ag
2The Se nanocrystal.Concrete steps are following:
1) [Ag-Al]
+Preparation: under inert atmosphere, with Silver Nitrate (AgNO
3) solution joins in L-L-Ala (L-Al) solution of prepared fresh, solution A;
2)-Se
+Preparation: under inert atmosphere, with GSH, Na
2SeO
3, codehydrogenase (NADPH) and NADPH-GSSG reductase (GR) mix in the BR of pH6.5-8.5 solution (Britton-Robinson buffered soln), solution B;
3) solution A is warming up to 80-95 ℃, the solution B of prepared fresh is joined in the solution A, 80-95 ℃ of reaction 10-15min is cooled to room temperature, promptly obtains nanocrystal;
Wherein step 3) can be through regulating blended [Ag-Al]
+With-Se
+Mol ratio, the size of regulating nanocrystal.Especially at fixing [Ag-Al]
+With-Se
+The condition of solubility product under, through regulating blended [Ag-Al]
+With-Se
+Mol ratio, can obtain the nanocrystal of specific size.Preferably, solution A and solution B can be according to [Ag-Al]
+With-Se
+Mol ratio 7 ~ 3:1 mix.
Wherein, the mol ratio of Silver Nitrate and L-L-Ala reaction is 1:1 in the step 1), when actually operating, can add according to mol ratio 1:1 ~ 2.Reduced glutathion (GSH) solution can be through being dissolved in GSH in the basic soln of deoxygenation, to keep its reduced form.For example in embodiments of the present invention gsh is dissolved in the NaOH solution of 0.1M.
Wherein, gsh, Na step 2)
2SeO
3With the mol ratio of codehydrogenase be 3:1:1 ~ 5:1:1.NADPH-GSSG reductase adds 7 ~ 10U according to every mole of substrate.
Preferred steps 2) gsh, Na in
2SeO
3, codehydrogenase and NADPH-GSSG reductase mix in the BR of pH7.5 solution.
The preferred temperature of reaction of wherein said step 3) is 90 ℃, and the reaction times is 10min.
Method synthesis condition provided by the invention is gentle, and easy, the strong operability of method is not used as CF
3Virose organometallic compound such as COOAg, TOPO or organic reagent; Building-up process and product environmental pollution are little, need not to use synthetic precursor, stable, the difficult blast of building-up process; Requirement to equipment is not harsh, and the industriallization that helps to promote nano particle (containing quantum dot) is synthesized.
Description of drawings
Fig. 1, the prepared Ag of the present invention
2The high-resolution-ration transmission electric-lens photo that Se is nanocrystalline.
The Ag of Fig. 2, the present invention's preparation
2The X-ray diffractogram of Se quantum dot.
The Ag of Fig. 3, the present invention's preparation
2The fluorescence emission spectrogram of Se quantum dot.
The Ag of the different-grain diameter size of Fig. 4, the present invention's preparation
2The Se nanocrystal.A) particle size is: 1.5 ± 0.4 nm; B) particle size is: 1.6 ± 0.4 nm; C) particle size is: 2.4 ± 0.5 nm.
The Ag of Fig. 5, the present invention's preparation
2The X-ray energy spectrum figure of Se quantum dot.
The Ag of Fig. 6, the present invention's preparation
2The living imaging figure of Se quantum dot.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.Under the situation that does not deviate from the present invention's spirit and essence, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.If do not specialize the conventional means that used technique means is well known to those skilled in the art among the embodiment.
This example is with Ag
2Preparing method of the present invention is explained in the preparation of Se quantum dot.
1, [Ag-Al]
+Preparation
With 4.4 * 10
-6Mol L-L-Ala (L-Al) is dissolved in the NaOH solution of 6mL except that the 0.1M of peroxide, under inert atmosphere, adds 4.4 * 10
-6The mol silver nitrate solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in BR solution, successively with 4.4 * 10 near the pH7.5 of physiological condition
-6Mol GSH, 1.1 * 10
-6Mol Na
2SeO
3, 1.1 * 10
-6Mol codehydrogenase (NADPH) and NADPH-GSSG reductase (GR) are (by every mole of substrate Na
2SeO
3Add 8U) in the BR solution of the pH7.5 of 4mL, mix.
3, quantum dot generates
After the solution of step (1) is warming up to 90 ℃, the solution in the step (2) of prepared fresh is added in (1) fast,, be cooled to room temperature, can obtain required Ag at 90 ℃ of reaction 10min
2The Se quantum dot.
At fixing [Ag-Al]
+With-Se
+The condition of solubility product under, only change [Ag-Al] in the above-mentioned steps
+With-Se
+Mol ratio, can obtain the Ag of different emission
2Se quantum dot (Fig. 3) is realized Ag
2The control of the size of Se quantum dot.
Instance 2 Ag
2The preparation of Se quantum dot:
This example is with Ag
2Preparing method of the present invention is explained in the preparation of Se quantum dot.
1, [Ag-Al]
+Preparation
With 4.4 * 10
-6Mol L-L-Ala (L-Al) is dissolved in the NaOH solution of 6mL except that the 0.1M of peroxide, under inert atmosphere, adds 2.2 * 10
-6The mol silver nitrate solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in BR solution, successively with 3.3 * 10 near the pH6.5 of physiological condition
-6Mol GSH, 1.1 * 10
-6Mol Na
2SeO
3, 1.1 * 10
-6Mol codehydrogenase (NADPH) and NADPH-GSSG reductase (GR) are (by every mole of substrate Na
2SeO
3Add 7U) in the BR solution of the pH6.5 of 4mL, mix.
3, quantum dot generates
After the solution of step (1) is warming up to 80 ℃, the solution in the step (2) of prepared fresh is added in (1) fast,, be cooled to room temperature, can obtain required Ag at 80 ℃ of reaction 15min
2The Se quantum dot.
At fixing [Ag-Al]
+With-Se
+The condition of solubility product under, only change [Ag-Al] in the above-mentioned steps
+With-Se
+Mol ratio, can obtain the Ag of different emission
2The Se quantum dot is realized Ag
2The control of the size of Se quantum dot.
Instance 3 Ag
2The preparation of Se quantum dot:
This example is with Ag
2Preparing method of the present invention is explained in the preparation of Se quantum dot.
1, [Ag-Al]
+Preparation
With 5.5 * 10
-6Mol L-L-Ala (L-Al) is dissolved in the NaOH solution of 6mL except that the 0.1M of peroxide, under inert atmosphere, adds 5.5 * 10
-6The mol silver nitrate solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in BR solution, successively with 5.5 * 10 near the pH8.5 of physiological condition
-6Mol GSH, 1.1 * 10
-6Mol Na
2SeO
3, 1.1 * 10
-6Mol codehydrogenase (NADPH) and NADPH-GSSG reductase (GR) are (by every mole of substrate Na
2SeO
3Add 10U) in the BR solution of the pH8.5 of 4mL, mix.
3, quantum dot generates
After the solution of step (1) is warming up to 95 ℃, the solution in the step (2) of prepared fresh is added in (1) fast,, be cooled to room temperature, can obtain required Ag at 95 ℃ of reaction 10min
2The Se quantum dot.
At fixing [Ag-Al]
+With-Se
+The condition of solubility product under, only change [Ag-Al] in the above-mentioned steps
+With-Se
+Mol ratio, can obtain the Ag of different emission
2The Se quantum dot is realized Ag
2The control of the size of Se quantum dot.
Claims (8)
1. controlledly synthesis near infrared Ag
2The method of Se nanocrystal, the method comprising the steps of:
1) [Ag-Al]
+Preparation: under inert atmosphere, silver nitrate solution is joined in the L-L-Ala solution of prepared fresh, solution A;
2)-Se
+Preparation: under inert atmosphere, with gsh, Na
2SeO
3, codehydrogenase and NADPH-GSSG reductase mix in the BR of pH6.5 ~ 8.5 solution, solution B;
3) solution A is warming up to 80-95 ℃, the solution B of prepared fresh is joined in the solution A, 80-95 ℃ of reaction 10-15min is cooled to room temperature, promptly obtains nanocrystal;
Wherein step 3) is through regulating blended [Ag-Al]
+With-Se
+Mol ratio, the fluorescent emission wavelength region and the size of regulating nanocrystal.
2. the method for claim 1 is characterized in that, the mol ratio of Silver Nitrate and L-L-Ala is 1:1 ~ 1:2 in the said step 1).
3. according to claim 1 or claim 2 method is characterized in that said step 2) in gsh, Na
2SeO
3With the mol ratio of codehydrogenase be 3:1:1 ~ 5:1:1.
4. according to claim 1 or claim 2 method is characterized in that said step 2) in NADPH-GSSG reductase add 7 ~ 10U according to every mole of substrate.
5. according to claim 1 or claim 2 method is characterized in that said step 2) in gsh, Na
2SeO
3, codehydrogenase and NADPH-GSSG reductase mix in the BR of pH7.5 solution.
6. according to claim 1 or claim 2 method is characterized in that the temperature of reaction of said step 3) is 90 ℃, and the reaction times is 10min.
7. according to claim 1 or claim 2 method is characterized in that wherein step 3) is at fixing [Ag-Al]
+With-Se
+The condition of solubility product under, through regulating blended [Ag-Al]
+With-Se
+Mol ratio, the fluorescent emission wavelength region and the size of regulating nanocrystal.
8. according to claim 1 or claim 2 method is characterized in that wherein solution A and solution B are according to [Ag-Al]
+With-Se
+Mol ratio 7:1 ~ 3:1 mix.
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|---|---|---|---|
| CN201110385651.3A CN102517339B (en) | 2011-11-29 | 2011-11-29 | Method for controllably synthesizing near-infrared Ag2Se nano crystal |
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|---|---|---|---|
| CN201110385651.3A CN102517339B (en) | 2011-11-29 | 2011-11-29 | Method for controllably synthesizing near-infrared Ag2Se nano crystal |
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|---|---|
| CN102517339A true CN102517339A (en) | 2012-06-27 |
| CN102517339B CN102517339B (en) | 2014-07-16 |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734767A (en) * | 2019-11-15 | 2020-01-31 | 武汉大学 | method for preparing size-controllable organic phase silver selenide quantum dots |
| WO2021029389A1 (en) * | 2019-08-15 | 2021-02-18 | Ｎｓマテリアルズ株式会社 | Quantum dots and production method therefor |
| CN112430463A (en) * | 2020-11-11 | 2021-03-02 | 武汉大学 | Biosynthesis and purification method of silver selenide quantum dots |
| CN116333725A (en) * | 2023-03-23 | 2023-06-27 | 南开大学 | Method for regulating and controlling luminous property of quantum dot by surface ligand |
-
2011
- 2011-11-29 CN CN201110385651.3A patent/CN102517339B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| BYRON GATES ET AL.,: "Single-Crystalline Nanowires of Ag2Se Can Be Synthesized by Templating against Nanowires of Trigonal Se", 《J.AM.CHEM.SOC.》 * |
| YI-PING GU ET AL.,: "Ultrasmall Near-Infrared Ag2Se Quantum Dots with Tunable Ag2Se Quantum Dots with Tunable Fluorescence for in Vivo Imaging", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021029389A1 (en) * | 2019-08-15 | 2021-02-18 | Ｎｓマテリアルズ株式会社 | Quantum dots and production method therefor |
| CN110734767A (en) * | 2019-11-15 | 2020-01-31 | 武汉大学 | method for preparing size-controllable organic phase silver selenide quantum dots |
| CN110734767B (en) * | 2019-11-15 | 2022-04-22 | 武汉大学 | Method for preparing size-controllable organic phase silver selenide quantum dots |
| CN112430463A (en) * | 2020-11-11 | 2021-03-02 | 武汉大学 | Biosynthesis and purification method of silver selenide quantum dots |
| CN112430463B (en) * | 2020-11-11 | 2022-03-04 | 武汉大学 | Biosynthesis and purification method of silver selenide quantum dots |
| CN116333725A (en) * | 2023-03-23 | 2023-06-27 | 南开大学 | Method for regulating and controlling luminous property of quantum dot by surface ligand |
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| Publication number | Publication date |
|---|---|
| CN102517339B (en) | 2014-07-16 |
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