CN102942933B - In-water-phase monodisperse sodium yttrium tetrafluoride multi-color luminescent nanoparticle and preparation method thereof - Google Patents

In-water-phase monodisperse sodium yttrium tetrafluoride multi-color luminescent nanoparticle and preparation method thereof Download PDF

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CN102942933B
CN102942933B CN201210507270.2A CN201210507270A CN102942933B CN 102942933 B CN102942933 B CN 102942933B CN 201210507270 A CN201210507270 A CN 201210507270A CN 102942933 B CN102942933 B CN 102942933B
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汪乐余
李�浩
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Beijing University of Chemical Technology
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Abstract

The invention discloses an in-water-phase monodisperse sodium yttrium tetrafluoride ytterbium-and-erbium-doped multi-color upconversion luminescent nanoparticle and a preparation method thereof, belonging to the field of multifunctional application-oriented inorganic advanced nano materials. According to the method, a product is synthesized in one step through a hydrothermal method, and a sodium yttrium tetrafluoride nanoparticle capable of emitting light of different colors can be obtained by regulating the amount of NaF; and the particle which is uniform in size and is in morphology of cubic phases or hexagonal phases can be obtained through simple condition change. The sodium yttrium tetrafluoride multi-color luminescent nanoparticle can stably exist in water for long time, has excellent biocompatibility and can be directly used in hydrophilic systems of biosensors, cell imaging, magnetic resonance imaging, disease diagnosis and treatment and the like. The cost of raw materials is low, less pollution is caused to the environment, and the method is simple, so that the sodium yttrium tetrafluoride multi-color luminescent nanoparticle has wide application prospects in the field of biology and the fields such as thin-film materials, luminescent devices, anti-counterfeiting materials and the like. It is worth mentioning that the material has been successfully used in the field of cell imaging.

Description

Single multicolor luminous nano particle of tetrafluoro yttrium sodium and preparation method thereof that disperses in a kind of water
Technical field
The invention belongs to the inorganic advanced nano material fabricating technology of multifunctional application type field, particularly single tetrafluoro yttrium sodium doping ytterbium erbium polychrome up-conversion luminescence nano particle and preparation method thereof that disperses in a kind of water.Can realize at biomedicine field, thin-film material, luminescent device, directly apply in the fields such as anti-fake material.
Technical background
Rare earth up-conversion luminescent material refers to that, under long wavelength light excites, sustainable emission wavelength is than the light of excitation wave length.Rear-earth-doped up-conversion luminescence nano material is low owing to having exciting light energy, emmission spectrum is narrow, and Stokes displacement is large, and chemical stability is good, luminous intensity is high and stable, and emission wavelength can obtain paying close attention to widely by controlling the high-performances such as its composition regulates and toxicity is low.In addition, near-infrared laser can be avoided interference and the scattered light phenomenon of biological sample autofluorescence as its excitation light source, to biological tissue's not damaged almost, light penetration depth is darker, thereby reduction detection background, improve signal to noise ratio, these features make them as fluorescent marker, in biomacromolecule analysis and clinical medicine detection field, have extraordinary application prospect.
In recent years, report synthetic about rare earth up-conversion and application was increasing, (Ostrowski A D, Chan E M, Gargas D J, Katz E M, Han G, Schuck P J, Milliron D J, Cohen B E.ACS Nano.2012,6,2686-2692; Wang F, Liu X G, J.Am.Chem.Soc.2008,130,5642-5643); and the people's that the research of applying about this kind of material also obtains extensive concern, (Liu J L, Liu Y, Liu Q, Li C Y; Sun L N, Li F Y.J.Am.Chem.Soc.2011,133,15276-15279; Li L L, Zhang R B, Yin L L, Zheng K Z, Qin W P, Selvin PR, Lu Y.Angew.Chem.-Int.Edit.2012,51,6121-6125), well-known, in the application process of up-conversion nano material, except possessing monodispersity, granular size homogeneous, also should there is good biocompatibility, this just requires material stable existence in water.The comparatively ripe preparation method of present condition is the nano particle that preparation has hydrophobic grouping, and then phase inversion, obtains being connected to the product of hydrophilic radical, and this process is very complicated and can cause gathering and the fluorescent weakening of particle.Therefore, the up-conversion luminescent material of stable existence and then directly apply to biological field and the thin-film material such as Clinics and Practices, nuclear magnetic resonance of cell imaging, disease in one-step synthesis water, other field such as luminescent device has great importance.
Summary of the invention
The present invention aims to provide and a kind ofly can directly apply, single tetrafluoro yttrium sodium doping ytterbium erbium polychrome up-conversion luminescence nano particle that disperses of stable existence in water.The diameter of tetrafluoro yttrium natrium nanocrystalline prepared by the method is about 110nm, is single crystal particle and distributes.
In described water, single preparation method one of the multicolor luminous nano particle of tetrafluoro yttrium sodium that disperses is:
A. Y (the NO that compound concentration is 0.40-0.50mol/L respectively 3) 3, Yb (NO 3) 3, Er (NO 3) 3rare earths salt; Compound concentration is the HCl solution of 1-2mol/L; Compound concentration is the NaF solution of 1-2mol/L;
B. in reactor, add 10-20ml dehydrated alcohol, 5-15mL ethylene glycol, magnetic agitation is even to solution;
C. continue to add the Y (NO of 1.70-2.10ml in reactor 3) 3yb (the NO of rare earths salt, 200-250 μ l 3) 3er (the NO of rare earths salt, 100-125 μ l 3) 3rare earths salt, stirs 10-35 minute;
D. in reactor, add 3.5-5mLNaF solution again, stir;
E. in the most backward solution, add 0.5-1.0mLHCl solution, magnetic agitation 10-35 minute;
F. reactor is reacted to 24-72h at 185-195 ℃, after naturally cooling, use deionized water centrifuge washing, remove solvent in product, with 4-6ml deionized water, disperse product, obtain single multicolor luminous nano particle of tetrafluoro yttrium sodium that disperses in water.
In described water, single preparation method two of the multicolor luminous nano particle of tetrafluoro yttrium sodium that disperses is: in the step b of method one, add 0.05-1.0g polyacrylic acid in reactor, polyacrylic acid molecular weight is 1790-1810 simultaneously; Remaining reaction condition is identical with method one.
The product that NaF add-on described in method one obtains while being 4.32-4.35mmol glows.
The product green light that NaF add-on described in method one obtains while being 5.50-6.50mmol.
When the NaF add-on described in method two is 3.50-4.50mmol, the product obtaining is Emission in Cubic.
When the NaF add-on described in method two is 5.50-6.50mmol, the product obtaining is six side's phases.
Beneficial effect of the present invention: the present invention adopts hydrothermal method, one-step synthesis goes out the multicolor luminous nano particle of tetrafluoro yttrium sodium of good water solubility, single dispersion, macroscopic strong up-conversion luminescence performance.The present invention is by regulating NaF consumption can obtain sending the tetrafluoro yttrium sodium nano particle of different colours light.And by simple condition, changing the particle that can obtain uniform Emission in Cubic or six side's phase patterns, diameter is about as 110nm, is monocrystalline and distributes.The multicolor luminous nano particle of tetrafluoro yttrium sodium that the present invention prepares is due to the coated extremely strong polyacrylic acid polymer of wetting ability, can be for a long time in water stable existence, biocompatibility fabulous, can realize directly application in hydrophilic system such as biosensor, cell imaging, nuclear magnetic resonance and medical diagnosis on disease and treatment etc.Due to aqueous solvent and coating material polyacrylic acid cheap, environmental pollution is little, process is simple, no matter is at biological field or at thin-film material, luminescent device, the fields such as anti-fake material all have very wide application prospect.It is worth mentioning that, this material has successfully been realized the application in cell imaging field.
Accompanying drawing explanation
Fig. 1 is the XRD figure of monodispersed Emission in Cubic tetrafluoro yttrium sodium luminous nano granule in the water of embodiment 1 preparation;
Fig. 2 is the TEM photo of monodispersed Emission in Cubic tetrafluoro yttrium sodium luminous nano granule in the water of embodiment 1 preparation;
Fig. 3 is fluorescence spectrum figure and the photo in kind of monodispersed Emission in Cubic tetrafluoro yttrium sodium luminous nano granule in the water of embodiment 1 preparation;
Fig. 4 is the XRD figure of monodispersed six side's phase tetrafluoro yttrium sodium luminous nano granules in the water of embodiment 2 preparation;
Fig. 5 is the TEM photo of monodispersed six side's phase tetrafluoro yttrium sodium luminous nano granules in the water of embodiment 2 preparation;
Fig. 6 is fluorescence spectrum figure and the photo in kind of monodispersed six side's phase tetrafluoro yttrium sodium luminous nano granules in the water of embodiment 2 preparation;
Fig. 7 is the two-photon Laser Scanning Confocal Microscope HeLa cell fluorescence image of monodispersed six side's phase tetrafluoro yttrium sodium luminous nano granules in the water of embodiment 2 preparation;
Fig. 8 is the XRD figure of monodispersed tetrafluoro yttrium sodium red light-emitting nano particle in the water of embodiment 3 preparation;
Fig. 9 is the TEM photo of monodispersed tetrafluoro yttrium sodium red light-emitting nano particle in the water of embodiment 3 preparation;
Figure 10 is fluorescence spectrum figure and the photo in kind of monodispersed tetrafluoro yttrium sodium red light-emitting nano particle in the water of embodiment 3 preparation;
Figure 11 is the XRD figure of monodispersed tetrafluoro yttrium sodium green luminescence nano particle in the water of embodiment 4 preparation;
Figure 12 is the TEM photo of monodispersed tetrafluoro yttrium sodium green luminescence nano particle in the water of embodiment 4 preparation;
Figure 13 is fluorescence spectrum figure and the photo in kind of monodispersed tetrafluoro yttrium sodium green luminescence nano particle in the water of embodiment 4 preparation.
Embodiment
Embodiment 1:
1. the Y(NO that compound concentration is 0.50mol/L respectively 3) 3, Yb(NO 3) 3, Er(NO 3) 3rare earths salt; Compound concentration is the HCl solution of 1mol/L; Compound concentration is the NaF solution of 1mol/L;
2. in reactor, add successively 0.1g polyacrylic acid, 15ml dehydrated alcohol, 10mL ethylene glycol, magnetic agitation is even to solution;
3. continue to add the Y(NO of 1.7ml in reactor 3) 3the Yb(NO of rare earths salt, 200 μ l 3) 3the Er(NO of rare earths salt, 100 μ l 3) 3rare earths salt, stirs 10 minutes;
4. in reactor, add 4mLNaF solution again, slowly drip, stir;
5. in the most backward solution, add 600 μ lHCl solution, magnetic agitation 10 minutes;
6. reactor is reacted to 72h at 190 ℃, after naturally cooling, use deionized water centrifuge washing, remove solvent in product, with 4ml deionized water, disperse product, obtain monodispersed Emission in Cubic tetrafluoro yttrium sodium luminous nano granule in water, structure is the coated NaYF4:Yb of polyacrylic acid 3+/ Er 3+nano particle.
Embodiment 2:
1. the Y(NO that compound concentration is 0.50mol/L respectively 3) 3, Yb(NO 3) 3, Er(NO 3) 3rare earths salt; Compound concentration is the HCl solution of 1mol/L; Compound concentration is the NaF solution of 1mol/L;
2. in reactor, add successively 0.1g polyacrylic acid, 15ml dehydrated alcohol, 10mL ethylene glycol, magnetic agitation is even to solution;
3. continue to add the Y(NO of 1.7ml in reactor 3) 3the Yb(NO of rare earths salt, 200 μ l 3) 3the Er(NO of rare earths salt, 100 μ l 3) 3rare earths salt, stirs 10 minutes;
4. in reactor, add 6mLNaF solution again, slowly drip, stir;
5. in the most backward solution, add 600 μ lHCl solution, magnetic agitation 10 minutes;
6. reactor is reacted to 72h at 190 ℃, after naturally cooling, use deionized water centrifuge washing, remove solvent in product, with 4ml deionized water, disperse product, obtain monodispersed six side's phase tetrafluoro yttrium sodium luminous nano granules in water, structure is the coated NaYF of polyacrylic acid 4: Yb 3+/ Er 3+nano particle.
Embodiment 3:
1. the Y(NO that compound concentration is 0.50mol/L respectively 3) 3, Yb(NO 3) 3, Er(NO 3) 3rare earths salt; Compound concentration is the HCl solution of 1mol/L; Compound concentration is the NaF solution of 1mol/L;
2. in reactor, add successively 15ml dehydrated alcohol, 10mL ethylene glycol, magnetic agitation is even to solution;
3. continue to add the Y(NO of 1.7ml in reactor 3) 3the Yb(NO of rare earths salt, 200 μ l 3) 3the Er(NO of rare earths salt, 100 μ l 3) 3rare earths salt, stirs 10 minutes;
4. in reactor, add 4.35mLNaF solution again, slowly drip, stir;
5. in the most backward solution, add 600 μ lHCl solution, magnetic agitation 10 minutes;
6. reactor is reacted to 24h at 190 ℃, use deionized water centrifuge washing after naturally cooling, remove solvent in product, with 4ml deionized water, disperse product, obtain monodispersed tetrafluoro yttrium sodium red light-emitting nano particle in water, structure is NaYF 4: Yb 3+/ Er 3+nano particle.
Embodiment 4:
1. the Y(NO that compound concentration is 0.50mol/L respectively 3) 3, Yb(NO 3) 3, Er(NO 3) 3rare earths salt; Compound concentration is the HCl solution of 1mol/L; Compound concentration is the NaF solution of 1mol/L;
2. in reactor, add successively 15ml dehydrated alcohol, 10mL ethylene glycol, magnetic agitation is even to solution;
3. continue to add the Y(NO of 1.7ml in reactor 3) 3the Yb(NO of rare earths salt, 200 μ l 3) 3the Er(NO of rare earths salt, 100 μ l 3) 3rare earths salt, stirs 10 minutes;
4. in reactor, add 6mLNaF solution again, slowly drip, stir;
5. in the most backward solution, add 600 μ l HCl solution, magnetic agitation 10 minutes;
6. reactor is reacted to 24h at 190 ℃, use deionized water centrifuge washing after naturally cooling, remove solvent in product, with 4ml deionized water, disperse product, obtain monodispersed tetrafluoro yttrium sodium green luminescence nano particle in water, structure is NaYF 4: Yb 3+/ Er 3+nano particle.

Claims (1)

1. a single preparation method who disperses the multicolor luminous nano particle of tetrafluoro yttrium sodium in water, is characterized in that, its concrete preparation process is as follows:
A. Y (the NO that compound concentration is 0.40-0.50mol/L respectively 3) 3, Yb (NO 3) 3, Er (NO 3) 3rare earths salt; Compound concentration is the HCl solution of 1-2mol/L; Compound concentration is the NaF solution of 1-2mol/L;
B. in reactor, add 10-20ml dehydrated alcohol, 5-15mL ethylene glycol, magnetic agitation is even to solution;
C. continue to add the Y (NO of 1.70-2.10ml in reactor 3) 3yb (the NO of rare earths salt, 200-250 μ L 3) 3er (the NO of rare earths salt, 100-125 μ L 3) 3rare earths salt, stirs 10-35 minute;
D. in reactor, add NaF solution again, stir;
E. in the most backward solution, add 0.5-1.0mLHCl solution, magnetic agitation 10-35 minute;
F. reactor is reacted to 24-72h at 185-195 ℃, after naturally cooling, use deionized water centrifuge washing, remove solvent in product, with 4-6ml deionized water, disperse product, obtain single multicolor luminous nano particle of tetrafluoro yttrium sodium that disperses in water;
The product that described NaF add-on obtains while being 4.32-4.35mmol glows;
The product green light that described NaF add-on obtains while being 5.50-6.50mmol.
CN201210507270.2A 2012-11-30 2012-11-30 In-water-phase monodisperse sodium yttrium tetrafluoride multi-color luminescent nanoparticle and preparation method thereof Expired - Fee Related CN102942933B (en)

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