CN100500276C - Water phase transferring method of water insoluble nucleus-shell nanometer crystal - Google Patents
Water phase transferring method of water insoluble nucleus-shell nanometer crystal Download PDFInfo
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- CN100500276C CN100500276C CNB2004100112111A CN200410011211A CN100500276C CN 100500276 C CN100500276 C CN 100500276C CN B2004100112111 A CNB2004100112111 A CN B2004100112111A CN 200410011211 A CN200410011211 A CN 200410011211A CN 100500276 C CN100500276 C CN 100500276C
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Abstract
The present invention relates to a water-phase transfer method of non-water solubility core-shell nanometer crystal, which belongs to the nanometer technical field. The process for synthesizing CdSe/ZThe way exchanging water belongs to the nano technique field. The synthesize process of CdSe/ZnSe is: mix and heat satiric acid ge, TOPO and HAD, add the TOP solution of Se, cool to 200 DEG C in 90 senSe nanometer crystal comprises the steps that cadmium stearate, TOPO and HDA are mixed, are warmed and then are filled with a TOP solution with excessive Se for cooling to 200 DEG C within 40 to 90 sconds, then CdSe is made, then add the solution of satiric acid Zn--methyl benzene. The way' step is mixing, scatter to film, water round oil made; scatter to film is heating the mixing material, bloweconds so as to be made into CdSe nanometer crystal; then, a zinc stearate-toluene solution is directly filled in the system. The water-phase transfer method comprises the steps that water solubility nitrogen spirit. The craft of the invention is simple, and the product has the living creature compatibility and high round rate, good stability, high efficiency of lightening. micell for covering CdSe/ZnSe quantum dots is made by the processes of material mixture, dispersive film formation, the formation of oil-in-water microemulsion and polycondensation reaction; a siloxane surface active agent is C18H37-N<+>(Me)2CH2CH2CH2-Si(OMe)3Cl<->; the dispersive film formation comprises the steps that water bath and warming are carried out to mixed materials, and simultaneously, nitrogen gas is blown to distill chloroform which is evenly swung for film formation. The present invention has simple technology, and a product has the advantages of biocompatibility, high covering rate, good stability and high luminous efficiency.
Description
Technical field
The invention belongs to nano material and field of nanometer technology, relate to biotechnology, be to adopt one kettle way will be used for the nanocrystalline ZnSe of using of the CdSe surface coating that fluorescence immunoassay detects specifically, it is nanocrystalline to be prepared into water-insoluble CdSe/ZnSe nuclear-shell, adopt into embrane method again, by the coating of silicon surface active agent, the phase transfer method that polycondensation forms a kind of water miscible micella.
Background technology
Quantum dot is called semiconductor nano again, is a kind of stabilized nano crystal grain of being made up of II-VI family and III-V family element.That research is more at present is CdS, CdSe, CdTe, ZnS etc.In recent years, semiconductor-quantum-point more and more is subject to people's attention owing to its unique character.
The most promising application of quantum dot is as fluorescence probe in living things system, luminous marker as living things system is compared with traditional organic dyestuff fluorescence probe, quantum dot has significant dimensional effect, it absorbs bandwidth, emission peak is narrow, the nano semiconductor material of single kind just can rely on change in size to produce an emission wavelength label family different, that color is clearly demarcated, and this is that dye molecule can't be realized at all.The fluorescence lifetime of general quantum dot approximately is 20 times of organic dyestuff, and lasting stability can allow the researcher observe cell and tissue for more time, and carries out the modifying interface connection without difficulty.The benefit of quantum dot maximum is that abundant color is arranged.Use the nanocrystal of different sizes (having different color) to come the different biomolecule of mark, use single light source just can make the different particles can be by immediately monitoring.The special optical property of quantum dot makes it in researchs such as biochemistry, molecular biology, cell biology, genomics, proteomics, drug screening, interaction of biomacromolecules great application prospect be arranged.
The prior art close with the present invention can be referring to the paper of Nano Lett.Vol.2 No.11 2002 P1299-1302 publication, and exercise question is Luminescent CdSe Quantum Dot Doped Stabilized Micelles.The water transfer method of the CdSe nanocrystalline (quantum dot) that paper is introduced is: in order to prepare quantum dot-doped micella, 1mlCdSe is mixed with the chloroform that contains surfactant, this mixture is dropwise joined in the 10ml water, stir at 750C temperature lower magnetic force, chloroform is removed in distillation, and ultimate density is that 15mM forms to guarantee micella, and the CdSe quantum dot is encased in hydrophobic region and forms micella, the pH value of micella is transferred to 9, and the hydrolysis of Si end group forms SiO
2Layer is at micellar surface.The paper text does not relate to the nanocrystalline preparation method of CdSe, but has provided the article of the nanocrystalline preparation method of CdSe in list of references, that is, and and list of references 6 " Qu, L.; Peng, X.J.Am.Chem.Soc.2002,124 (9), 2049 ".With the predecessor of CdO and stearic acid reaction as Cd, the trioctylphosphine phosphorus solution of Se powder is the predecessor of Se.Synthetic CdSe nuclear is nanocrystalline in trioctylphosphine oxide/hexadecylamine (TOPO/HAD) mixed solvent.
The water-soluble quantum dot doping micella that background technology is made, use be that the CdSe that coats through broad-band gap is not nanocrystalline; Dripping CdSe when making water-soluble micella mixes with the chloroform-water mixed system that contains surfactant, therefore before forming micella CdSe nanocrystalline just with the water effect, be easy to cause destruction to part, promptly in the process of experience part displacement, destroy the surface texture of quantum dot, reduced quantum dot productive rate and stability.
Summary of the invention
The technical problem to be solved in the present invention is, for overcoming disadvantages of background technology, increase the stability of fluorescence quantum, adopt the synthetic CdSe/ZnSe nuclear-shell of one kettle way nanocrystalline, adopt into embrane method and realize that water shifts, reach that technology is simple, mild condition, stability height, purpose that productive rate is high.
The present invention is under the high-temperature anhydrous oxygen free condition, with organic ligand as reaction environment, the CdSe/ZnSe nucleocapsid structure semiconductor nano of synthetic high fluorescent characteristic selects for use an a kind of end to have the surfactant of siloxane group again, utilizes hydrophobic effect to form micella, quantum dot is coated on the inside, and then carry out surperficial silanol polycondensation, form a kind of stable, colourless, the water-soluble micella of modified surface, size is in 100～200 nanometers.
In order to improve CdSe stability, reduce its blemish, improve fluorescence quantum yield, adopt at CdSe superficial growth ZnSe shell.Detailed process is as follows.
The synthetic CdSe/ZnSe nucleocapsid structure semiconductor nano process of the present invention is: at first CdO is mixed with stearic acid and stir and heating, generate cadmium stearate, cool the temperature to room temperature again, trioctylphosphine oxide (TOPO) and hexadecylamine (HDA) are joined in the above-mentioned reaction vessel, mix and be warmed up to 300～320 ℃, inject trioctylphosphine phosphorus (TOP) solution of Se in reaction vessel, and be cooled to 180～220 ℃ in 40～90 second time, it is nanocrystalline to make CdSe; The mol ratio of Se and CdO is 3:1～10:1.After the nanocrystalline growth of CdSe is finished, directly in system, inject zinc stearate-toluene solution, make CdSe/ZnSe nuclear shell structured nano-crystalline substance.
Zinc stearate makes the shell growth temperature drop to 180-220 ℃ as extraordinary zinc source.Owing to have excessive Se in the system, and be adsorbed on the CdSe surface, after zinc stearate injects, the Zn ion will directly combine formation, and to have the ZnSe shell structurre be the fat-soluble CdSe fluorescence nano of CdSe/ZnSe-TOPO with Se, ZnSe layer has suppressed radiationless emission, has improved the fluorescence efficiency of CdSe crystal.
After adding zinc stearate-toluene solution,, can carry out annealing in process in order to reduce nanocrystalline lattice defect.Annealed 0.5～1.5 hour down at 100～150 ℃.
Be the purpose that realizes that water of the present invention shifts, obtain the fluorescent material of Bc, fat-soluble fluorescence nano need be transferred to water by organic facies.The present invention considers the phase transfer problem from three aspects, at first, synthesize and stablize the higher CdSe/ZnSe shell of quantum yield-layer structure nano crystalline substance more as fluorescence labeling material, secondly, phase transition behavior can not deface part, if part is destroyed, perhaps is substituted so stability and luminosity and all can be affected.At last, used phase transfer material should be that stability is high, absorptivity is low, can not cause that fluorescent quenching, surface are modified easily, eco-friendly material.
Silicone surfactant can be realized phase transfer to the coating of fluorescence nano, and makes it have Bc.The luminosity of water-soluble micella is by nanocrystalline character decision.The present invention utilizes surfactant to form micella, forms oil-in-water microemulsion, embeds quantum dot, and heating steams chloroform then, adds ammoniacal liquor and carries out polycondensation reaction, forms the water-soluble micella that coats the CdSe/ZnSe quantum dot.
The concrete grammar step is as follows:
, ammoniacal liquor nanocrystalline (can working concentration be 25% ammoniacal liquor) and silicone surfactant C with CdSe/ZnSe
18H
37-N
+(Me)
2CH
2CH
2CH
2-Si (OMe)
3Cl
-(DTPAC, available from Fluka) be raw material, with chloroform (can be analytically pure chloroform) and high purity water is solvent, makes the water-soluble micella that coats the CdSe/ZnSe quantum dot through batch mixing, dispersion film forming, the formation of oil-in-water microemulsion, polycondensation reaction technical process.
Said batch mixing is to be dissolved in the chloroform solvent concentration 0.5～3mg/ml with CdSe/ZnSe is nanocrystalline.Silicone surfactant DTPAC is dissolved in the chloroform solvent concentration 20～100mg/ml.Both are blended in-rise.Press mass ratio, silicone surfactant DTPAC/ quantum dot is 10～50.
Said dispersion film forming is to add behind the chloroformic solution mixing of batch mixing in the container, and water-bath is heated to 60～70 ℃ of while nitrogen blowing, steams chloroform, shakes up film forming.
The oil-in-water microemulsion of said formation is, adds the high purity water ultrasonic dissolution of 5～50 times of chloroformic solution volumes in preparing the container of film, keeps temperature to steam the residue chloroform for 60～70 ℃, forms water oil-packaging type micro-emulsion liquid.
Said polycondensation reaction is that by every milligram of DTPAC adding ammoniacal liquor 0.2～1 microlitre, normal temperature reaction down after 8～24 hours filters product, obtains the compound water-soluble micella of stable fluorescence.
When disperseing film forming, can in container, add filler to increase to membrane area, said filler can be ballotini or little porcelain bead.The thickness of film forming is preferably less than 20 microns.
The preparation of CdSe/ZnSe quantum dot of the present invention owing to adopt one kettle way to do the zinc source with zinc stearate, not only makes technology simple, mild condition, and ZnSe layer effectively suppressed radiationless emission, improved the quantum yield of CdSe crystal, improved the photochemical stability of fluorescent marker.The water transfer method is by the method that silicon surface active agent coats, polycondensation forms a kind of water-soluble micella, makes product have Bc, clad ratio height, productive rate height; Owing to add nitrogen protection in the film forming, can prevent CdSe/ZnSe quantum dot and part oxidation; Since destroy seldom to part, so stability is high, the luminous efficiency height.
The specific embodiment
Embodiment 1 prepares the nanocrystalline of CdSe/ZnSe nucleocapsid structure
Choose 99.9% CdO:0.0128g, Se powder: 0.079g, stearic acid: 0.015g.Between 140-150 ℃, CdO and stearic acid react in reaction vessel and generate cadmium stearate, again reactor is reduced to room temperature, and in the condition downhill reaction container of room temperature, add 2gTOPO, 2gHDA, temperature with reaction vessel rises to 310 ℃ then, inject TOP-Se under this temperature in system, Se is excessive, Se and CdO mol ratio 10: 1.Cooling rapidly was cooled to 200 ℃ after injecting in 40～90 seconds.Different temperature fall times can obtain the nanocrystalline of different size, have promptly obtained size nanocrystalline from 3～6 nanometers, and the fluorescence color of crystal promptly gradually becomes red from green along with the lengthening red shift gradually of time.On the nanocrystalline basis of the CdSe of synthetic required size, in system, directly inject the zinc stearate toluene solution, Se excessive on Zn and the CdSe surface combines generation CdSe/ZnSe nucleocapsid structure.
Se and CdO mol ratio also can be 4: 1 or 7: 1, and different ratios is just influential slightly to the speed of CdSe growth.Mol ratio is easy to the control to the reaction that generates CdSe nuclear more greatly.TOPO and HDA mol ratio can be 1: 1 or 1: 2.TOP-Se concentration is 0.01～0.04g/ml.TOPO and Se ratio are 20: 1～50: 1.
Excessive Se is used when forming the ZnSe shell,, directly injects the zinc stearate toluene solution that is, and-pot generates the CdSe/ZnSe nucleocapsid structure.
Injecting zinc stearate-toluene solution, the Zn consumption can be selected routine in molar ratio Zn: CdO=0.7: 1～15: 1, the size of ratio influences quantum yield, ratio quantum yield height greatly then in this scope, at aforementioned proportion scope ZnSe shell at 0.5～4 layer.Shell is many again will to influence luminous efficiency.
In a word, different Se and CdO mol ratio, Zn: the CdO mol ratio all can make particle diameter different, coat the nanocrystalline of the different CdSe/ZnSe nucleocapsid structure of thickness.
The nanocrystalline water-soluble micella of embodiment 2 preparation composite fluorescences
At first, the 2mgCdSe/ZnSe quantum dot is dissolved in the 1ml chloroform, as raw material.Getting silicone surfactant DTPAC40mg is dissolved in the 1ml chloroform solvent.Nitrogen flushing in the chloroformic solution adding container of raw material and DTPAC is heated to 60～70 ℃, steam unnecessary chloroform, shake up film forming.Get 10 milliliters of high purity waters and be heated to 70 ℃, steam unnecessary chloroform, form water oil-packaging type micro-emulsion liquid.
Formed water oil-packaging type micro-emulsion liquid is the silicone surfactant hydrolysis, hydrophilic silicon hydroxyl outside, the alkyl of long-chain is inside.
At last, add 20 microlitre ammoniacal liquor, normal temperature reacted 12 hours down, the silicone surfactant polycondensation, and the surface forms network structure by silicon oxygen bond.The silicon hydroxyl forms the compound water-soluble micella of a kind of stable fluorescence outside.Product is filtered, remove the material that is not coated in the micella, obtain the compound water-soluble micella of stable fluorescence.
The nanocrystalline water-soluble micella of embodiment 3 preparation composite fluorescences
On the basis of embodiment 2, as long as the chloroform solvent concentration of silicone surfactant DTPAC is in 5～20mg scope, adding high purity water is 5～50 times of chloroform volumes, can both make the compound water-soluble micella of stable fluorescence by the technical process of embodiment 2.
In the polycondensation reaction, add ammoniacal liquor 0.2～1 microlitre by every milligram of DTPAC, normal temperature reacted 8～24 hours down, all can realize making the effect of the compound water-soluble micella of stable fluorescence.
Claims (2)
1, the nanocrystalline water transfer method of a kind of water-insoluble nuclear-shell has synthetic CdSe/ZnSe nucleocapsid structure semiconductor nano process and preparation to coat the water-soluble micella process of CdSe/ZnSe quantum dot;
Described synthetic CdSe/ZnSe nucleocapsid structure semiconductor nano process is:
At first CdO is mixed with stearic acid and stir and heating, generate cadmium stearate, cool the temperature to room temperature again, trioctylphosphine oxide and hexadecylamine are joined in the above-mentioned reaction vessel, mix and be warmed up to 300～320 ℃, inject the trioctylphosphine phosphorus solution of Se in reaction vessel, and be cooled to 180～220 ℃ in 40～90 second time, it is nanocrystalline to make CdSe; The mol ratio of Se and CdO is 3:1～10:1; After the nanocrystalline growth of CdSe is finished, directly in system, inject zinc stearate-toluene solution, make CdSe/ZnSe nucleocapsid structure semiconductor nano;
The water-soluble micella process that described preparation coats the CdSe/ZnSe quantum dot is:
With CdSe/ZnSe nucleocapsid structure semiconductor nano, ammoniacal liquor and silicone surfactant C
18H
37-N
+(Me)
2CH
2CH
2CH
2-Si (OMe)
3Cl
-Being raw material, is solvent with chloroform and high purity water, makes the water-soluble micella that coats the CdSe/ZnSe quantum dot through batch mixing, dispersion film forming, the formation of oil-in-water microemulsion, polycondensation reaction technical process;
Said batch mixing is CdSe/ZnSe nucleocapsid structure semiconductor nano to be dissolved in the chloroform solvent concentration 0.5～3mg/ml; Silicone surfactant is dissolved in the chloroform solvent concentration 20～100mg/ml; Both mix; Press mass ratio, silicone surfactant/quantum dot is 10～50;
Said dispersion film forming is to add behind the chloroformic solution mixing of batch mixing in the container, and water-bath is heated to 60～70 ℃ of while nitrogen blowing, steams chloroform, shakes up film forming;
The oil-in-water microemulsion of said formation is, adds the high purity water ultrasonic dissolution of 5～50 times of chloroformic solution volumes in preparing the container of film, keeps temperature to steam the residue chloroform for 60～70 ℃, forms water oil-packaging type micro-emulsion liquid;
Said polycondensation reaction is that by every milligram of silicone surfactant adding ammoniacal liquor 0.2～1 microlitre, normal temperature reaction down after 8～24 hours filters product, obtains the compound water-soluble micella of stable fluorescence.
According to the nanocrystalline water transfer method of the described water-insoluble nuclear-shell of claim 1, it is characterized in that 2, said injection zinc stearate-toluene solution, Zn consumption example in molar ratio are Zn: CdO=0.7: 1～15: 1.
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| CN1328351C (en) * | 2005-09-23 | 2007-07-25 | 上海大学 | Method for preparing II-VI family fluorescent mark semiconductor quantum point MX |
| ES2684372T3 (en) * | 2013-11-22 | 2018-10-02 | Dsm Ip Assets B.V. | Process for preparing an anti-reflective coating composition and a porous coating therefrom |
| CN106175542A (en) * | 2016-07-08 | 2016-12-07 | 浙江优全护理用品科技有限公司 | A kind of water can break up wet tissue of type natural degradation and preparation method thereof |
| CN111909682B (en) * | 2019-05-10 | 2024-04-19 | 苏州星烁纳米科技有限公司 | Preparation method of quantum dot with core-shell structure and product prepared by same |
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Non-Patent Citations (7)
| Title |
|---|
| CdSe/CdS核/壳型纳米晶的光谱特性. 刘舒曼.光谱学与光谱分析，第22卷第6期. 2002 |
| CdSe/CdS核/壳型纳米晶的光谱特性. 刘舒曼.光谱学与光谱分析，第22卷第6期. 2002 * |
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