CN102516995B - Method for preparing water-phase CdS quantum dots in oil phase - Google Patents
Method for preparing water-phase CdS quantum dots in oil phase Download PDFInfo
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- CN102516995B CN102516995B CN 201110373751 CN201110373751A CN102516995B CN 102516995 B CN102516995 B CN 102516995B CN 201110373751 CN201110373751 CN 201110373751 CN 201110373751 A CN201110373751 A CN 201110373751A CN 102516995 B CN102516995 B CN 102516995B
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Abstract
The invention discloses a method for preparing water-phase CdS quantum dots in an oil phase. In an oil phase system environment, a sulfur (S) precursor provided by mercapto (-SH) in 3-mercaptopropyltrimethoxysilane (MPS) molecules and a cadmium (Cd) precursor are used for generating CdS quantum dots at high temperature, and a silicon layer is coated on the surfaces of the CdS quantum dots through the hydrolysis of the silicon-oxygen chemical bonds (Si-O) in MPS molecules to obtain the quantum dots coated with a CdS@SiO2 silicon layer. Owning to the hydrophilicity of the silicon layer, the quantum dots directly have water-solubility and can be directly applied to the fields such as biological imaging labels and the like. By adopting the method for preparing the water-phase quantum dots in the oil phase, the two operating steps namely oil-phase CdS quantum dot synthesis and surface silicon layer coating which are required by the preparation of the CdS@SiO2 quantum dots, are broken, thus the quantum dots prepared in the oil phase can be directly used in bioapplication and the distance between the synthesis of quantum dots and the application can be greatly shortened.
Description
Technical field
The present invention relates to the technology of preparing of quantum dot, specifically refer to a kind of method for preparing water CdS quantum dot in oil phase.
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Background technology
Quantum dot (quantum dots, QDs) typically refer to the semiconductor nanocrystal that radius was less than or was similar to exciton bohr particle diameter, they have unique physics and chemistry and optical property, the continuous distribution such as exciting spectrum width, emission wavelength can be regulated by size and moiety, and fluorescence quantum yield is high, life-span is long, thereby in the fluorescent mark imaging, luminescent device, the fields such as photoelectric material have a wide range of applications.The method that generally prepares aqueous phase quantum point comprises direct method and indirect method, and direct method is directly synthetic in the aqueous solution, and because its temperature of reaction is lower, the general fluorescence quantum yield of the quantum dot of acquisition is on the low side, and homogeneity is also poor; Indirect method is first by synthetic oil phase quantum dot, then by the surface hydrophilicity ligand exchange or coat the method such as water-soluble silicon layer, by the oil phase quantum dot water of transduceing.Wherein on the quantum dot surface, coat nontoxic silica shell, not only can strengthen the biocompatibility of quantum dot, can also improve the stability under coenocorrelation of quantum dot, the targeting modification that the numerous chemical group of silicon ball surface is quantum dot simultaneously provides site, thereby becomes a kind of method that very popular oil phase quantum dot turns water.
But coating the method for silicon layer, common quantum dot not only need the oil phase quantum dot synthetic rapid with two operations of silicon layer coating, and the operation steps that silicon layer coats also relatively wastes time and energy, usually need the time of cost about a week, and the purification process process of strict reaction conditions and follow-up complexity has also seriously hindered its application.A. P. Alivisatos (Science, 1998,281,2013-2016; J. Phys. Chem. B, 2001,105,8861-8871) with Jackie Y. Ying (Adv. Mater., 2005,17,1620-1625) etc. at the silicon layer coated quantum dots, the oil phase quantum dot is transduced into aspect aqueous phase quantum point and has done a large amount of work, but without exception, these silicon layers coat synthetic two steps of silicon layer coating that reach of oil phase that the method for preparing aqueous phase quantum point has all experienced quantum dot without exception.
Summary of the invention
The invention solves the deficiencies in the prior art, the method for preparing aqueous phase quantum point in this oil phase, before having broken, the quantum dot surface coats two operation stepss that silicon layer need to experience, make the quantum dot prepared in oil phase can be directly towards biologic applications, distance between having shortened greatly the synthetic of quantum dot and having applied, in the oil-based system environment, the S precursor provided by the sulfydryl in the MPS molecule (SH), at high temperature generate the CdS(Cadmium Sulfide with the Cd precursor) quantum dot, hydrolysis by the silica chemical bond (Si-O) in the MPS molecule simultaneously coats silicon layer on the CdS surface, the CdS@SiO obtained
2the quantum dot that silicon layer coats, directly possess water-soluble.
Prepare the method for water CdS quantum dot in a kind of oil phase of the present invention, it comprises the steps:
1), trimethoxy mercaptopropylsilane (MPS) is added in the mixing solutions of P contained compound, amine-containing compound and octadecylene (ODE), under the condition of anhydrous and oxygen-free, use electric mantle to be heated to 260～320 ℃, the MPS precursor solution made, wherein MPS content is 0.0135～0.135 mol/L.
2) Cadmium oxide that is, 1:2 by mol ratio (CdO) and fatty acid cpds add ODE solution after mixing, jointly be heated to 230 ℃ in electric mantle, after CdO dissolves fully, be cooled to room temperature, the cadmium precursor compound that the Cd content of preparation is 0.01～0.1 mol/L.
3), the cadmium precursor fast injection is entered in the described MPS precursor solution of step 1, question response, after 3～100 minutes, cools to 100 ℃, be injected into the basic solution of 0.02～1 mL, react 1～35 minute, be cooled to room temperature, the precipitation of acquisition is the CdS with water miscible coated with silica
(CdS@SiO 2 )quantum dot.
And, in described MPS precursor solution in the MPS precursor solution P contained compound be one or both in TOPO, TOP.When being several mixing, can the arbitrary proportion configuration.
And in described MPS precursor solution, amine-containing compound is 1 ~ 3 kind in HAD, ODA, OLA, when being several mixing, can the arbitrary proportion configuration
And in described MPS precursor solution, the mass ratio of P contained compound and amine-containing compound is 1:0.1 ~ 1:99.
And in described MPS precursor solution, the mass content of ODE is 0～99%.
And described fatty acid cpds is oleic acid (OA) or stearic acid (SA).
And, the methanol solution that the described basic solution be injected into is TMAOH, its concentration is 0.1～1 g/mL, or the massfraction ammoniacal liquor that is 25 %.
And the process of preparation is all the time in single oil-based system, centre is without successive what aqueous environment.
And the MPS used in the process of preparation both, as the S precursor of synthetic CdS quantum dot, also carried out the silicon layer coating as the Si precursor to the CdS quantum dot.
In the present invention, under regulation and control high temperature, temperature and the reaction times of cadmium precursor and MPS precursors reaction, can regulate and control size and the fluorescence quantum yield of CdS quantum dot; The volume of the alkaline solution of injecting by adjusting and concentration with and subsequent the reaction times, can regulate and control the thickness of the silicon layer of coating, thereby obtain the CdS SiO of different-grain diameter size
2material, meet different application requiring.
The method of synthetic aqueous phase quantum point in relevant oil phase in the present invention, the method that coats silicon layer with traditional quantum dot surface is completely different, at first this show the MPS that uses in preparation process both as the S precursor of synthetic CdS quantum dot, also as the Si precursor that coats the CdS quantum dot, than the synthetic CdS@SiO of routine
2both need to use the S precursor substance, and needed again to use other Si precursor substance, saved reaction raw materials, and made reacting precursor be applied to greatest extent, met the demand for development of conservation-minded society; The second, in the process prepared, all the time in single oil phase environment, centre is without the environment of successive what water, and reaction conditions is simple; And employing one kettle way, only need a reactions steps, such as two step operations of the synthetic rear coated Si ball transduction water of traditional quantum dot, saved a large amount of reaction times and manpower, the quantum dot obtained directly possesses water-soluble, can directly apply to the fields such as biomarker.Therefore quantum dot preparation method shown in the present is different from the method that the synthetic rear silicon layer of traditional quantum dot coats fully, is a kind of brand-new preparation method, is also a kind of direct application oriented preparation method, can be referred to as saving type Green Chemistry preparation method.
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The accompanying drawing explanation
Fig. 1 is the method schematic diagram of preparing water-phase CdS quantum dots in oil phase of the present invention.
Fig. 2 is that the embodiment of the present invention 1 oil phase prepares product fluorescence contrast under ultraviolet lamp in the aqueous phase quantum point process, and wherein A is that oil phase CdS quantum dot, B are CdS@SiO in oil phase
2quantum dot precipitation, C are water CdS@SiO
2the fluorescence of quantum dot.
The water CdS@SiO that Fig. 3 is the embodiment of the present invention 1 preparation
2the fluorescent emission collection of illustrative plates of quantum dot.
The water CdS@SiO that Fig. 4 is the embodiment of the present invention 1 preparation
2the ultraviolet absorpting spectrum of quantum dot.
The water CdS@SiO that Fig. 5 is the embodiment of the present invention 1 preparation
2the high-resolution-ration transmission electric-lens photo of quantum dot.
The water CdS@SiO that Fig. 6 is the embodiment of the present invention 1 preparation
2the confocal fluorescent microphotograph that quantum dot and nucleus dyestuff HOECHS cell are located altogether, wherein D is water CdS SiO
2quantum dot detects the luminous situation of wave band, and E is that nucleus dyestuff HOECHS detects the luminous situation of wave band, and F is the overlapping luminous situation of D and E.
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Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Flow process can be referring to Fig. 1.
1), get 0.13 g TOPO, 0.37 g HAD, 200 μ L MPS and 9.5 mL ODE are heated to 280 ℃ after mixing under Ar gas in electric mantle, obtain the colourless MPS precursor solution of clarification.
2), get 0.0128 g CdO, 0.063 mL OA, 1 mL ODE, after mixing, under Ar gas, in electric mantle, be heated to 230 ℃ to CdO, dissolve fully after, be cooled to room temperature, obtain the colourless Cd (OA) of clarification
2precursor solution.
3), by Cd (OA)
2the precursor solution fast injection enters in the MPS solution under high temperature, and temperature of reaction is set in 285 ℃, reacts 15 minutes, is cooled to 100 ℃ in air.
4), to fast injection in above-mentioned solution, enter 500 μ L, the methanol solution of 0.4 g/mL TMAOH, react 35 minutes, removes thermal source, is cooled to room temperature.
5), by reaction soln 500 r/min low-speed centrifugal 2 minutes, acquisition be deposited in normal hexane washing after, again be dispersed in water, obtain and be dissolved in the CdS quantum dot in water.
The check of the water CdS quantum dot prepared in oil phase:
A. by product as under ultraviolet lamp, can see obvious fluorescent emission, as shown in Figure 2.
B. product is dispersed in water, detects its fluorescent emission on luminoscope, can observe obvious fluorescence emission peak, as shown in Figure 3.
C. product is dispersed in water, detects its uv-absorbing on ultraviolet-visible pectrophotometer, can observe obvious uv-absorbing, as shown in Figure 4.
D. product is dispersed in water, drips 2 in copper mesh, imaging under high-resolution-ration transmission electric-lens, can observe the structure that the silicon bag covers quantum dot, as shown in Figure 5.
E, product is dispersed in water, by with the 293T co-culture of cells after, by dying altogether with nucleus dyestuff HOECHST, under the confocal fluorescent microscope, different-waveband detects, and can observe obvious cell marking imaging, as shown in Figure 6.
Embodiment 2
Flow process can be referring to Fig. 1.
1), get 0.13 g TOPO, 1 mL TOP, 0.5mL OLA, 200 μ L MPS and 3.5 mL ODE are heated to 260 ℃ after mixing under Ar gas in electric mantle, obtain the colourless MPS precursor solution of clarification.
2), get 0.0128 g CdO, 0.0569 g SA, 10 mL ODE, after mixing, under Ar gas, in electric mantle, be heated to 230 ℃ to CdO, dissolve fully after, be cooled to room temperature, obtain the colourless Cd (SA) of clarification
2precursor solution.
3), by Cd (SA)
2the precursor solution fast injection enters in the MPS solution under high temperature, and temperature of reaction is set in 260 ℃, reacts 100 minutes, is cooled to 100 ℃ in air.
4), then to fast injection in above-mentioned solution, enter 1 mL, the ammoniacal liquor of 25 %, react 3 minutes, removes thermal source, is cooled to room temperature.
5), by reaction soln 500 r/min low-speed centrifugal 2 minutes, acquisition be deposited in normal hexane washing after, again be dispersed in water, obtain and be dissolved in the CdS quantum dot in water.
Embodiment 3
Flow process can be referring to Fig. 1.
1), get 0.13 g TOPO, 0.37 g HAD, 0.5 mL ODA, 200 μ L MPS and 9 mL ODE are heated to 320 ℃ after mixing under Ar gas in electric mantle, obtain the colourless MPS precursor solution of clarification.
2), get 0.0128 g CdO, 0.063 mL OA, 5 mL ODE, after mixing, under Ar gas, in electric mantle, be heated to 230 ℃ to CdO, dissolve fully after, be cooled to room temperature, obtain the colourless Cd (OA) of clarification
2precursor solution.
3), by Cd (OA)
2the precursor solution fast injection enters in the MPS solution under high temperature, and temperature of reaction is set in 320 ℃, reacts 3 minutes, is cooled to 100 ℃ in air.
4), then to fast injection in above-mentioned solution, enter 2 mL, the methanol solution of 0.1 g/mL TMAOH, react 10 minutes, removes thermal source, is cooled to room temperature.
5), by reaction soln 500 r/min low-speed centrifugal 2 minutes, acquisition be deposited in normal hexane washing after, again be dispersed in water, obtain and be dissolved in the CdS quantum dot in water.
Embodiment 4
Flow process is referring to Fig. 1.
1), get 1 mL TOP, 0.37 g HAD, 0.5 mL ODA, 0.5 mL OLA, 200 μ L MPS and 7.5 mL ODE are heated to 300 ℃ after mixing under Ar gas in electric mantle, obtain the colourless MPS precursor solution of clarification.
2), get 0.0128 g CdO, 0.063 mL OA, 2 mL ODE, after mixing, under Ar gas, in electric mantle, be heated to 230 ℃ to CdO, dissolve fully after, be cooled to room temperature, obtain the colourless Cd (OA) of clarification
2precursor solution.
3), by Cd (OA)
2the precursor solution fast injection enters in the MPS solution under high temperature, and temperature of reaction is set in 300 ℃, reacts 5 minutes, is cooled to 100 ℃ in air.
4), then to fast injection in above-mentioned solution, enter 200 μ L, the methanol solution of 1 g/mL TMAOH, react 1 minute, removes thermal source, is cooled to room temperature.
5), by reaction soln 500 r/min low-speed centrifugal 2 minutes, acquisition be deposited in normal hexane washing after, again be dispersed in water, obtain and be dissolved in the CdS quantum dot in water.
Claims (8)
1. the method for a preparing water-phase CdS quantum dots in oil phase, is characterized in that, it comprises the steps:
1), 3-sulfydryl propyl trimethoxy silicane (MPS) is added in the mixing solutions of P contained compound, amine-containing compound and octadecylene (ODE), under the condition of anhydrous and oxygen-free, be heated to 260～320 ℃, the MPS precursor solution made, wherein MPS content is 0.0135～0.135 mol/L;
?2), molar weight is compared for after the Cadmium oxide of 1:2 (CdO) and fatty acid cpds mixing, adding ODE solution, jointly be heated to 230 ℃, after CdO dissolves fully, be cooled to room temperature, the cadmium precursor compound that the Cd compounds content of preparation is 0.01～0.1 mol/L;
3), the cadmium precursor fast injection is entered in the described MPS precursor solution of step 1, after question response 3～100 minutes, cool to 100 ℃, be injected into the basic solution of 0.02～1 mL, react 1～35 minute, be cooled to room temperature, the precipitation of acquisition is CdS (the CdS@SiO with water miscible coated with silica
2) quantum dot.
2. prepare the method for water CdS quantum dot in oil phase according to claim 1, it is characterized in that, in the MPS precursor solution, P contained compound is one or both in trioctylphosphine oxide (TOPO), trioctylphosphine phosphorus (TOP), when being two kinds of mixing, and can the arbitrary proportion configuration.
3. prepare the method for water CdS quantum dot in oil phase according to claim 1, it is characterized in that, in the MPS precursor solution, amine-containing compound is 1 ~ 3 kind in cetylamine (HAD), stearylamine (ODA), oleyl amine (OLA), when being several mixing, and can the arbitrary proportion configuration.
4. oil phase according to claim 1 prepares the method for water CdS quantum dot, it is characterized in that, in the MPS precursor solution, the mass ratio of P contained compound and amine-containing compound is 1:0.1 ~ 1:99.
5. prepare the method for water CdS quantum dot in oil phase according to claim 1, it is characterized in that, fatty acid cpds is oleic acid (OA) or stearic acid (SA).
6. prepare the method for water CdS quantum dot in oil phase according to claim 1, it is characterized in that, the methanol solution that the basic solution be injected into is tetramethyl-aqua ammonia (TMAOH), its concentration is 0.1～1 g/mL, or the massfraction ammoniacal liquor that is 25 %.
7. prepare the method for water CdS quantum dot in oil phase according to claim 1, it is characterized in that, the process of preparation is all the time in single oil-based system, and centre is without successive what aqueous environment.
8. prepare the method for water CdS quantum dot in oil phase according to claim 1, it is characterized in that, the MPS used in the process of preparation both, as the S precursor of synthetic CdS quantum dot, also carried out the silicon layer coating as the Si precursor to the CdS quantum dot.
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