CN101871127B - Size-controllable synthesis method for MSe (M equal to Cd, Pb) nanocrystals - Google Patents
Size-controllable synthesis method for MSe (M equal to Cd, Pb) nanocrystals Download PDFInfo
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- CN101871127B CN101871127B CN201010192141XA CN201010192141A CN101871127B CN 101871127 B CN101871127 B CN 101871127B CN 201010192141X A CN201010192141X A CN 201010192141XA CN 201010192141 A CN201010192141 A CN 201010192141A CN 101871127 B CN101871127 B CN 101871127B
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Abstract
The invention discloses a size-controllable synthesis method for MSe (M equal to Cd, Pb) nanocrystals. By regulating the pH value of a system, the method simulates the optimal conditions of the reduction process of catalyzing sodium selenite (Na2SeO3) in vivo with glutathione reductase and coenzyme II outside cells to obtain low-valent Se, the low-valent Se reacts with glutathione-coordinated M2 plus ([M-(GS)2]2 plus) under the inert atmosphere, and thereby MSe (M equal to Cd, Pb) nanocrystals with good monodispersity, uniform grain size and fluorescence are obtained under the aqueous-phase condition. The method can control the size of the product by regulating the proportion between the Se precursor and the M precursor. The method is simple, and can repetitively prepare a large quantity of MSe (M equal to Cd, Pb) nanocrystals, moreover, because flammable, explosive and toxic metal organic compound is not used, safety is high, and the method can be widely applied to the field of chemical and material science.
Description
Technical field
The present invention relates to a kind ofly come controlledly synthesis MSe through the regulation and control biochemical reaction (M=Cd, the Pb) preparation method of nanocrystal belong to biological, chemistry and material science.
Background technology
In recent years, II-VI family quantum dot obtains widespread use at biomedical sectors such as detection, separation, diagnosis, spike, imagings.When how under green gentle condition, obtaining nano material, the pattern and the performance of nano material controlled well is the focus that this field receives much concern.The quantum dot that common practical application needs has all adopted extremely dangerous and expensive organometallics raw material or complicacy, unmanageable working method usually among the preparation method.
Steigerwald had reported the (CH with Cd in 1989
3)
2(TMS)
2(TMS is a trimethyl silyl to E; E=S, Se Te) is mixed with the method for CdE in different solvents, and the process of taking off alkyl silicon has been experienced in reaction.After this, Murray [43] reported and a kind ofly prepared the method for high quality, single (± 5%) II-VI of dispersion QDs with organometallic reagent cracking in oxidation tri-n-octyl phosphine (TOPO) solvent of heat, wherein primary study CdSe QDs synthetic., because Cd (CH
3)
2, Zn (CH
3)
2Deng metallorganics severe toxicity, unstable, explosive, therefore, it is extremely dangerous to make raw material with them, and the appointed condition that needs is harsh.
After this, Peng etc. has reported (the CH with CdO replaced C d
3)
2, adopt hexyl phosphonic acids (HPA) or tetradecyl phosphonic acids (TDPA)/TOPO two component solvent to synthesize the method for II-VI type QDs.Experimental result shows, makes cadmium precursor with CdO, single jar of synthetic high quality nanoparticle repeatedly, and like CdSe, CdTe, CdS etc.And; Because the relative advantages of higher stability of Cd-HPA/TDPA mixture adopts this method, after initial nucleogenesis can be postponed hundred seconds reciprocal; This just makes it that some significant advantage is arranged in actually operating: for example injection temperature can reduce, the synthetic good reproducibility; Initial nucleogenesis can prolong; And CdO is spontaneous combustion neither, also is difficult for blast, therefore, can use reaction raw materials in large quantities, and this just makes plant-scale possibility that becomes.
Another kind of method in metallic compound/element organism route is that the precursor that utilizes single metal-E key (E=S, Se etc.) to exist is made reactant.Trindade and O ' Brien send out, thermolysis [CdE in TOP
2CNR1R
2]
2, particularly the asymmetric basic substituent of air-stable can carry out the preparation of II-VI type QDs effectively., still,,, need the multistep synthesis program so will obtain the product quantum dot because precursor all needs oneself synthetic, cumbersome.
The controllability that how to realize nano material 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, the characteristic of control material indiscriminately ad. as one wishes just, thus obtain various desirable material.The more thermodynamic (al) method that is to use of research is the crystallisation process that classical crystallization theory comes control material at present.This classical crystallization theory model based on the Gibbs-Thompson formula is extensively quoted by lot of documents, but increasing people finds that the crystallization theory of this classics and actual result have some bigger discrepancy, at nanoscale more so.Therefore, be necessary to seek the method that is more suitable for and solve this difficult problem.
Organism and biological intravital various efficient single-minded biochemical reactions then are the good platform that realizes the biological labled material controllability.Biochemical reaction is meant the chemical reaction relevant with vital movement that relates to biomolecules.In various biochemical reaction processes, cellular constituent and biomolecules are all followed the principle that instructs the reaction of belongings materialization, and biochemical reaction process and vital movement that biomolecules is participated in finally can be explained with these principles of chemistry.Therefore can be directed against the biochemical reaction characteristics; According to designing by different principles such as the thermodynamics of reaction path that a plurality of biochemical reaction constituted or path and related reaction, kinetics; Thereby autotelic it is regulated and controls; Even a plurality of differential responses approach are regulated and control, realize reaction desired, that can not take place originally, thereby reach control properties of materials.
In the method for above-mentioned various metallic compound/element organism route, though can use CdO, Cd (Ac)
2Prepare high-quality bare quantum spot in mineral compound, but the preparation of common employed II-VI family quantum dot still to be used Cd (CH basically
3)
2, Zn (CH
3)
2Make raw material Deng organometallic compound; And all need comparatively harsh reaction conditions; If so can these methods be improved; Select raw material cheap, stable in properties, 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 MSe (M=Cd, Pb) method of nanocrystal of under green gentle condition, synthesizing to controllable size.
The inventive method is through regulation and control organism glutathion inside reductase enzyme and coenzyme II catalysis Sodium Selenite (Na
2SeO
3) the reduction process biochemical reaction comes controlledly synthesis MSe (M=Cd, Pb) nanocrystal.Concrete steps are following:
1) [M (SG)
2]
2+Preparation: under inert atmosphere, with Cadmium chloride fine powder (CdCl
2) or plumbic acetate (Pb (Ac)
2) solution joins in gsh (GSH) solution of prepared fresh, solution A;
2)-Se
+Preparation: under inert atmosphere, with GSH, Na
2SeO
3, coenzyme II (NADPH) and NADPH-GSSG reductase (GR) mix in the BR of pH6.8-7.6 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 [M (SG)
2]
2+With-Se
+Mol ratio, the size of regulating nanocrystal.Especially at fixing [M (SG)
2]
2+(M=Cd is Pb) with-Se
+The condition of solubility product under, through regulating blended [M (SG)
2]
2+With-Se
+Mol ratio, can obtain the nanocrystal of specific size.Preferably, solution A and solution B can be according to [M (SG)
2]
2+With-Se
+Mol ratio 1: 1～5 mix.
Wherein, the mol ratio of Cadmium chloride fine powder or plumbic acetate and gsh reaction is 1: 2 in the step 1), when actually operating, can add according to mol ratio 1: 2～3.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 coenzyme II mol ratio be 4: 1: 4.NADPH-GSSG reductase adds 10U according to every mole of substrate.
Preferred steps 2) gsh, Na in
2SeO
3, coenzyme II and NADPH-GSSG reductase mixes in the BR of pH7.2 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 the (CH as Cd
3)
2, Zn (CH
3), virose organometallic compound or organic reagent such as TOPO; 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 nanocrystalline transmission electron microscope photo of the prepared CdSe of the present invention.
The X-ray diffractogram of the CdSe quantum dot of Fig. 2, the present invention's preparation.
Uv absorption spectra of the CdSe quantum dot of Fig. 3, the present invention's preparation (figure A) and fluorescence emission spectrogram (figure B).
The PbSe nano cubic of the different-grain diameter size of Fig. 4, the present invention's preparation.A) [Pb (SG)
2]
2+:-Se
+=1: 1; Particle size is: long: 26.95 ± 0.39nm, and wide: 24.8 ± 0.29nm; B) [Pb (SG)
2]
2+:-Se
+=1: 2.5, particle size is: long: 21.47 ± 0.32nm, and wide: 19.4 ± 0.3nm; C) [Pb (SG)
2]
2+:-Se
+=1: 5, particle size is: long: 13.71 ± 0.21nm, and wide: 12.43 ± 0.23nm.
The X-ray diffractogram of the PbSe nano cubic of Fig. 5, the present invention's preparation.
The X-ray energy spectrum figure of the PbSe nano cubic of Fig. 6, the present invention's preparation.
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.
The preparation of instance 1CdSe quantum dot:
This example is explained preparation method of the present invention with the preparation of CdSe quantum dot.
1, [Cd (SG)
2]
2+Preparation
With 5.5 * 10
-5Mol gsh (GSH) is dissolved in the NaOH solution of 11mL except that the 0.1M of peroxide, under inert atmosphere, adds 2.2 * 10
-5Mol Cadmium chloride fine powder (CdCl
2) solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in BR solution, successively with 8.8 * 10 near the pH7.2 of physiological condition
-5Mol GSH, 2.2 * 10
-5Mol Na
2SeO
3, 8.8 * 10
-5Mol coenzyme II (NADPH) and NADPH-GSSG reductase (GR) mix in the BR of the pH7.2 of 3mL solution.
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 CdSe quantum dot at 90 ℃ of reaction 30min.
At fixing [Cd (SG)
2]
2+With-Se
+The condition of solubility product under, only change [Cd (SG) in the above-mentioned steps
2]
2+With-Se
+Mol ratio (mol ratio was respectively 1: 1; 1: 2.5; 1: 5), can obtain the CdSe quantum dot (Fig. 3) of different emission, realize control to the size of CdSe quantum dot.
The preparation of instance 2PbSe nano cubic:
1, [Pb (SG)
2]
2+Preparation:
With 5.5 * 10
-6Mol gsh (GSH) is dissolved in the NaOH solution of 11mL except that the 0.1M of peroxide, under inert atmosphere, adds 2.2 * 10
-6Mol plumbic acetate (Pb (Ac)
2) solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in BR solution, successively with 8.8 * 10 near the pH7.2 of physiological condition
-6Mol GSH, 2.2 * 10
-6Mol Na
2SeO
3, 8.8 * 10
-6Mol coenzyme II (NADPH) and NADPH-GSSG reductase (GR) mix in the BR of the pH7.2 of 3mL solution.
3, crystal 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 PbSe nano cubic at 90 ℃ of reaction 10min.
At fixing [Pb (SG)
2]
2+With-Se
+The condition of solubility product under, only change [Pb (SG) in the above-mentioned steps
2]
2+With-Se
+Mol ratio (mol ratio was respectively 1: 1; 1: 2.5; 1: 5), can obtain different big or small PbSe nano cubics (Fig. 4), realize control to PbSe nano cubic size.
The preparation of instance 3PbSe nano cubic:
1, [Pb (SG)
2]
2+Preparation:
With 5.5 * 10
-6Mol gsh (GSH) is dissolved in the NaOH solution of 11mL except that the 0.1M of peroxide, under inert atmosphere, adds 2.2 * 10
-6Mol plumbic acetate (Pb (Ac)
2) solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in BR solution, successively with 8.8 * 10 near the pH6.8 of physiological condition
-6Mol GSH, 2.2 * 10
-6Mol Na
2SeO
3, 8.8 * 10
-6Mol coenzyme II (NADPH) and NADPH-GSSG reductase (GR) (adding 10U by every mole of substrate) mix in the BR solution of the pH6.8 of 3mL.
3, crystal 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 PbSe nano cubic at 80 ℃ of reaction 15min.
At fixing [Pb (SG)
2]
2+With-Se
+The condition of solubility product under, only change [Pb (SG) in the above-mentioned steps
2]
2+With-Se
+Mol ratio (mol ratio was respectively 1: 1; 1: 2.5; 1: 5), can obtain different big or small PbSe nano cubics, realize control to PbSe nano cubic size.
The preparation of instance 4PbSe nano cubic:
1, [Pb (SG)
2]
2+Preparation:
With 4.4 * 10
-6Mol gsh (GSH) is dissolved in the NaOH solution of 11mL except that the 0.1M of peroxide, under inert atmosphere, adds 2.2 * 10
-6Mol plumbic acetate (Pb (Ac)
2) solution.
2 ,-Se
+Preparation:
Under room temperature and inert atmosphere, in the BR of pH7.6 solution, successively with 8.8 * 10
-6Mol GSH, 2.2 * 10
-6Mol Na
2SeO
3, 8.8 * 10
-6Mol coenzyme II (NADPH) and NADPH-GSSG reductase (GR) (adding 10U by every mole of substrate) mix in the BR solution of the pH7.6 of 3mL.
3, crystal 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, promptly obtain required PbSe nano cubic at 95 ℃ of reaction 10min.
At fixing [Pb (SG)
2]
2+With-Se
+The condition of solubility product under, only change [Pb (SG) in the above-mentioned steps
2]
2+With-Se
+Mol ratio (mol ratio was respectively 1: 1; 1: 2.5; 1: 5), can obtain different big or small PbSe nano cubics, realize control to PbSe nano cubic size.
Claims (5)
1. the method for the synthetic MSe nanocrystal of a controllable size, said M is Cd or Pb, the method comprising the steps of:
1) [M (SG)
2]
2+Preparation: under inert atmosphere, Cadmium chloride fine powder or plumbic acetate solution are joined in the glutathione solution of prepared fresh, solution A;
2)-Se
+Preparation: under inert atmosphere, with gsh, Na
2SeO
3, coenzyme II and NADPH-GSSG reductase in the BR of pH6.8～7.6 solution, mix 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 [M (SG)
2]
2+With-Se
+Mol ratio, the size of regulating nanocrystal;
Wherein, the mol ratio of Cadmium chloride fine powder or plumbic acetate and gsh is 1: 2～3 in the said step 1);
Wherein, gsh, Na said step 2)
2SeO
3With coenzyme II mol ratio be 4: 1: 4, said step 2) in NADPH-GSSG reductase add 10U according to every mole of substrate;
Wherein said coenzyme II be NADPH, said BR solution is Britton-Robinson buffered soln.
2. the method for claim 1 is characterized in that, said step 2) in gsh, Na
2SeO
3, coenzyme II and NADPH-GSSG reductase mixes in the BR of pH7.2 solution.
3. 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.
4. according to claim 1 or claim 2 method is characterized in that wherein step 3) is at fixing [M (SG)
2]
2+With-Se
+The condition of solubility product under, through regulating blended [M (SG)
2]
2+With-Se
+Mol ratio, the size of regulating nanocrystal.
5. according to claim 1 or claim 2 method is characterized in that wherein solution A and solution B are according to [M (SG)
2]
2+With-Se
+Mol ratio 1: 1～5 mix.
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| CN102108540B (en) * | 2010-12-27 | 2012-07-25 | 中国科学院长春光学精密机械与物理研究所 | Method for synthesizing mono-dispersed multicomponent compound nanocrystals |
| CN103215042B (en) * | 2013-04-12 | 2015-07-01 | 浙江师范大学 | Method for preparing CdSe quantum dots by water phase via one-pot method |
Citations (6)
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|---|---|---|---|---|
| US6379635B2 (en) * | 1995-09-15 | 2002-04-30 | Imperial College Of Science, Technology & Medicine | Process for preparing a nanocrystalline material |
| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
| CN1524782A (en) * | 2003-09-17 | 2004-09-01 | 中国科学院长春应用化学研究所 | Manufacturing method of cadmium selenide and cadmium telluride nanometer rod |
| CN1792773A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing aqueous phase lead selenide nano material |
| CN101108725A (en) * | 2007-07-05 | 2008-01-23 | 复旦大学 | Method of manufacturing cadmium selenide nano thread |
| CN101580233A (en) * | 2009-06-12 | 2009-11-18 | 清华大学 | Method for synthesizing CdSe nanosphere |
-
2010
- 2010-05-31 CN CN201010192141XA patent/CN101871127B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6379635B2 (en) * | 1995-09-15 | 2002-04-30 | Imperial College Of Science, Technology & Medicine | Process for preparing a nanocrystalline material |
| CN1403379A (en) * | 2002-10-10 | 2003-03-19 | 武汉大学 | Prepn of CdSe/CdS or CdSe/ZnS core-shell quantum dot |
| CN1524782A (en) * | 2003-09-17 | 2004-09-01 | 中国科学院长春应用化学研究所 | Manufacturing method of cadmium selenide and cadmium telluride nanometer rod |
| CN1792773A (en) * | 2005-12-28 | 2006-06-28 | 中国科学院长春应用化学研究所 | Process for preparing aqueous phase lead selenide nano material |
| CN101108725A (en) * | 2007-07-05 | 2008-01-23 | 复旦大学 | Method of manufacturing cadmium selenide nano thread |
| CN101580233A (en) * | 2009-06-12 | 2009-11-18 | 清华大学 | Method for synthesizing CdSe nanosphere |
Non-Patent Citations (1)
| Title |
|---|
| LI Li等.Synthesis and optical property of PbSe nanocubes via a facile organic solvent route.《Journal of university of science and technology of China》.2008,第38卷(第6期),639-643. * |
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