CN104109531A - Core-shell structure rare earth light-emitting nano material and preparation method - Google Patents
Core-shell structure rare earth light-emitting nano material and preparation method Download PDFInfo
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Abstract
The invention provides a core-shell structure rare earth light-emitting nano material and a preparation method. The rare earth light-emitting material is fluoride complex salt with a core-shell structure of one layer or multiple shell layers. The core layer is a rear earth fluoride complex salt with lightly-doped rare earth ions, the shell layer is alkaline earth metal fluoride which is doped or not doped with the rare earth ions, the average particle size is less than 15nm, and light emitting of the enhanced rare earth ions of the core-layer nano material serving as the raw material. The core-shell structure light-emitting nano material preparation method is simple, convenient and universal. Through reaction of a core-layer precursor and a shell-layer precursor in a solution, the core-shell structure with doped rare earth ions is prepared, the entire size of the particle is continuously controllable through adjusting the thickness of the shell layer, and in the meanwhile, the layer number of the shell can be controlled so as to enable the particle to be provided with multi-color light emitting or multi-channel detection features.
Description
Technical field
The invention belongs to nano material and inorganic synthesis technical field, be specifically related to rare earth luminous nano material of a kind of nucleocapsid structure and preparation method thereof.
Background technology
Nano material is the research field of enlivening very much in recent years.The fast development of nanotechnology and the Application and Development of nano material, making the mankind fundamentally solve environment, resource and life problem becomes possibility.Rare earth nano material has a wide range of applications, and in the fields such as electronics, optics, magnetics, chemistry and biology, shows good application prospect.Rare earth luminous nano material has the plurality of advantages such as transmitting is narrow, life-span length, anti-light bleaching, is having important using value aspect biological fluorescent labelling and fluorescence imaging.
Rare earth fluorine double salt is the important rare earth nano luminous host material of a class, can utilize hydrothermal method or high temperature thermal decomposition method etc. to prepare.Rare earth fluorine double salt can two kinds of phases exist, and is respectively cube (α-) mutually and six sides (β-) phase.Typical Emission in Cubic rare earth fluorine double salt nano particle has less size (general <10nm), but its crystallization degree is generally lower, surface imperfection degree is high, thereby makes Emission in Cubic particle have lower luminous efficiency, is unfavorable for the application such as biological fluorescent labelling.And typical six side's phase rare earth fluorine double salt nano particles have higher luminosity, but its larger size (general >20nm) has limited its practical application in organism.In addition,, because up-conversion luminescence nano particle Rare Earth Ion is directly exposed to particle surface, rare earth ion release in vivo has also formed the genotoxic potential to human body.
Summary of the invention
In order to make rare earth fluorine double salt material meet the requirement of the actual application such as biological fluorescent labelling, need one badly and have small size and high brightness concurrently, and can suppress the rare earth up-conversion luminescence nano material that rare earth ion discharges.The object of the present invention is to provide a kind of rare earth luminous nano material of nucleocapsid structure with small size, high brightness and preparation method thereof.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of rare earth luminous nano material, comprises stratum nucleare, and the shell of one deck parcel stratum nucleare at least, and wherein said stratum nucleare is for containing rare earth element and alkali-metal rare earth fluorine double salt nano particle, and described shell is alkaline-earth metal fluoride.
Further, rare earth luminous nano material as above, described alkaline-earth metal fluoride adulterates on a small quantity or the rare earth element ion that undopes.
Further, rare earth luminous nano material as above, described rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium; Described basic metal is selected from lithium, sodium or potassium; Described alkaline-earth metal is selected from magnesium, calcium, strontium or barium.
Further, rare earth luminous nano material as above, the number of plies of described shell is 1～5 layer, the composition of each shell is identical or different.
Further, rare earth luminous nano material as above, in described shell, the molar weight of alkaline-earth metal fluoride is 0.5～40 times of described stratum nucleare middle-weight rare earths fluorochemical double salt.
Further, rare earth luminous nano material as above, the volumetric molar concentration of the rare earth element ion in described stratum nucleare or shell is 0%～50%.
Further, rare earth luminous nano material as above, the particle median size of described shell is below 15nm.
A preparation method for rare earth luminous nano material, concrete technical scheme is:
Will be containing rare earth element and alkali-metal rare earth fluorine double salt nanoparticulate dispersed in organic solvent, evenly mix with appropriate alkaline-earth metal fluoride presoma, at 140～330 DEG C, react 5min～24h, by reaction product centrifugation, adopt organic solvent washing dry, obtain rare earth luminous nano material.
Further, preparation method as above, proceed one or many following steps: obtained rare earth luminous nano material is evenly mixed with appropriate alkaline-earth metal fluoride presoma or alkaline earth/rare earth fluorine presoma, at 140～330 DEG C, react 5min～24h, by reaction product centrifugation, adopt organic solvent washing dry, obtaining shell increases one or more layers rare earth luminous nano material.
Further, preparation method as above, described containing rare earth element and alkali-metal rare earth fluorine double salt nano particle, prepare by following method: utilize one or more inorganic salt that contain rare earth element or organic acid salt and one or more alkali-metal inorganic salt or organic acid salts, wherein have at least a kind of inorganic salt or organic acid salt to contain fluorine element, in solvent, at 140～330 DEG C, keep 5min～24h that building-up reactions occurs, by reaction product centrifugation and adopt organic solvent washing dry, obtain rare earth ion doped rare earth fluorine double salt nano particle.
Further, preparation method as above, contains rare earth element or alkali-metal inorganic salt or organic acid salt and comprises nitrate, fluorochemical, muriate, acetate, trifluoroacetate.
Further, preparation method as above, the solvent of building-up reactions is selected from one or more in water, ethanol, toluene, ethylene glycol, glycol ether, glycerol, tetradecy lamine, cetylamine, stearylamine, oleyl amine, TETRADECONIC ACID, Palmiticacid, stearic acid, oleic acid, octadecylene.
Further, preparation method as above, the organic solvent of washing use is selected from one or more in hexanaphthene, normal hexane, methyl alcohol, ethanol, chloroform, methylene dichloride, acetone, benzene, toluene.
The beneficial effect that the present invention reaches is as follows:
(1) a kind of rare earth luminous nano material with nucleocapsid structure provided by the present invention, can observe be compared to raw material stratum nucleare nanostructure strengthen rare earth luminescence; Comprise the VISIBLE LIGHT EMISSION (containing quantum-cutting) of ultraviolet/visible light under exciting, near infrared light transmitting under ultraviolet/visible light excites, and visible ray and the near infrared light transmitting (up-conversion luminescence of near infrared light under exciting, comprise biphotonic process and multiphoton process, and non-up-conversion luminescence) enhancing.
(2) a kind of rare earth luminous nano material with nucleocapsid structure provided by the present invention, in the time that its outermost layer shell undopes rare earth ion or doping low (<5%), can suppress the release of rare earth ion in vivo or in other aqueous environments, can be applicable to the field such as biomarker and bio-imaging.
(3) preparation method of a kind of rare earth luminous nano material with nucleocapsid structure provided by the present invention is easy, general, can utilize multiple synthetic method to prepare required nano particle; According to concrete condition and needs, can select different types of presoma and solvent.
(4) preparation method of a kind of rare earth luminous nano material with nucleocapsid structure provided by the present invention, by changing the charging capacity of shell presoma, can regulate continuously the thickness of shell, thereby make particle overall dimensions controlled continuously.
(5) preparation method of a kind of rare earth luminous nano material with nucleocapsid structure provided by the present invention, by introducing polystep reaction, individual layer or the multilayer of growing continuously of can growing forms identical or different shell, thereby makes particle possess the multicolor luminous or detectable characteristic of hyperchannel.
Brief description of the drawings
The rare earth luminous nano particle α-NaGdF of Fig. 1
4: Yb, Er@CaF
2: the transmission electron microscope photo of Er.
The rare earth luminous nano particle α-NaGdF of Fig. 2
4: Yb, Er and α-NaGdF
4: Yb, Er@CaF
2: the up-conversion luminescence spectrum of Er.
The rare earth luminous nano particle α-NaYF of Fig. 3
4: Nd@CaF
2transmission electron microscope photo.
The rare earth luminous nano particle α-NaYF of Fig. 4
4: Nd and α-NaYF
4: Nd@CaF
2near-infrared luminescence;
The rare earth luminous nano particle NaYF of Fig. 5
4: Yb, Tm@SrF
2transmission electron microscope photo.
The rare earth luminous nano particle NaYF of Fig. 6
4: Yb, Tm@SrF
2up-conversion luminescence spectrum.
The rare earth luminous nano particle KYF of Fig. 7
4: Yb, Ho@CaF
2@NaLuF
4angle of elevation annular dark scanning transmission electron photomicrograph.
The rare earth luminous nano particle KYF of Fig. 8
4: Yb, Ho@CaF
2@NaLuF
4up-conversion luminescence spectrum.
The rare earth luminous nano particle NaLaF of Fig. 9
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb@CaF
2: the angle of elevation annular dark scanning transmission electron photomicrograph of Dy.
The rare earth luminous nano particle NaLaF of Figure 10
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb@CaF
2: the up-conversion luminescence spectrum of Dy.
Embodiment
Below by specific embodiment, the invention will be further described, but the present invention is not constituted any limitation.
Embodiment 1:
As shown in Figure 1, for thering is the rare earth luminous nano particle NaGdF of nucleocapsid structure
4: Yb, Er@CaF
2: the transmission electron microscope photo of Er, in figure, can find out that this particle median size is about 10～15nm.The interior illustration (amplifying 7.5 times) of Fig. 1 has shown the angle of elevation annular dark picture of this particle, and wherein brighter interior layer segment is NaGdF
4: Yb, Er, darker outer layer segment is CaF
2: Er.
This has the rare earth luminous nano particle NaGdF of nucleocapsid structure
4: Yb, Er@CaF
2: the preparation method of Er is as follows:
(1) by 0.78mmol Y (CF
3cOO)
3, 0.20mmol Yb (CF
3cOO)
3, 0.02mmolEr (CF
3cOO)
3, 1.00mmol CF
3cOONa is dispersed in the solvent of 10mmol oleyl amine, 10mmol oleic acid and 20mmol1-octadecylene composition and mixes vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 280 DEG C and keep again 1h.After naturally cooling, add acetone centrifugation, after disperseing with hexanaphthene, use washing with alcohol 3 times, dry, can obtain Emission in Cubic NaGdF
4: Yb, Er luminous nano granule.
(2) NaGdF step (1) being obtained
4: Yb, Er luminous nano granule is scattered in the mixture of 20mmol oleic acid and 20mmol1-octadecylene, adds 0.98mmol Ca (CF
3cOO)
2with 0.02mmolEr (CF
3cOO)
3, mix vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 310 DEG C and keep again 1h.After naturally cooling, add ethanol, centrifugation, uses washing with alcohol 3 times, dry, can obtain NaGdF
4: Yb, Er@CaF
2: Er luminous nano granule.
This material can be dispersed in non-polar organic solvent well.Its up-conversion luminescence spectrum is as Fig. 2.Under the exciting of 980nm laser apparatus, this material presents typical green glow (520-570nm) and the upper switching emission of ruddiness (650-670nm) in toluene.Its Up-conversion Intensity is with the NaGdF of concentration
4: Yb, Er nano particle has obvious enhancing.Peak intensity with 540nm and 650nm two place's emission peaks calculates, and intensification factor has reached 300 times of left and right.
Embodiment 2:
As shown in Figure 3, for thering is the rare earth luminous nano particle KYF of nucleocapsid structure
4: the transmission electron microscope photo of Nd@CaF, in figure, can find out that this particle median size is about 10～15nm.
This has the rare earth luminous nano particle KYF of nucleocapsid structure
4: the preparation method of Nd@CaF is as follows:
(1) by 0.95mmol Y (CF
3cOO)
3, 0.05mmol Nd (CH
3cOO)
3, 1.00mmolCF
3cOOK is dispersed in the solvent of 10mmol oleyl amine, 10mmol oleic acid and 20mmol1-octadecylene composition and mixes vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 330 DEG C and keep again 1h.After naturally cooling, add ethanol, centrifugation, after again disperseing with toluene, with chloroform washing 3 times, dry, can obtain KYF
4: Nd luminous nano granule.
(2) KYF step (1) being obtained
4: Nd luminous nano granule is scattered in the mixture of 20mmol oleic acid and 20mmol1-octadecylene, adds 8.00mmol Ca (CF
3cOO)
2, mix vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 300 DEG C and keep again 10min.After naturally cooling, add ethanol, centrifugation, uses washing with alcohol 3 times, dry, can obtain KYF
4: Nd@CaF
2luminous nano granule.
This material can be dispersed in non-polar organic solvent well.It is scattered in up-conversion luminescence spectrum after normal hexane as Fig. 4.Under 576nm (visible ray) excites, this material presents typical near infrared (1020-1120nm and 1280-1400nm) transmitting in normal hexane.Its near infrared luminous intensity is with the KYF of concentration
4: Nd nano particle has obvious enhancing.The emission peak intensity of the contrast Nd of 1064nm place, can observe 4 times of above near-infrared luminous enhancings.
Embodiment 3:
1.4g NaOH is dissolved in to 20g deionized water, after stirring and dissolving, adds 10g ethylene glycol, 10g glycol ether and 50mmol oleic acid.Stir 30min, obtain a colourless solution.The NaF solution 15mL that adds 1.0mol/L under stirring, mixes.Dropwise add the Y (NO of 0.5mol/L
3)
3yb (the NO of aqueous solution 5.9mL, 0.5mol/L
3)
3tm (the NO of aqueous solution 4.0mL and 0.1mol/L
3)
3aqueous solution 0.5mL, obtains a white suspension liquid under vigorous stirring.This suspension liquid is proceeded in 100mL polytetrafluoroethylliner liner, supplement deionized water to about 80mL, at 220 DEG C, react 24h, obtain NaYF
4: Yb, Tm nano particle.Centrifugation goes out product, is a white solid, adds by 1.4g NaOH, 20g deionized water, 50mmol oleic acid and 20g ethanol and mixes in the colourless solution obtaining, and adds the NaF solution 15mL of 1.0mol/L under stirring, mixes.Dropwise add the Sr (NO of 0.5mol/L
3)
2aqueous solution 20.0mL, obtains a white suspension liquid under vigorous stirring.This suspension liquid is proceeded in 100mL polytetrafluoroethylliner liner, supplement deionized water to about 80mL, at 220 DEG C, react 6h, centrifugation, the white solid powder obtaining is NaYF
4: Yb, Tm@SrF
2luminous nano granule.Its transmission electron micrograph is shown in Fig. 5.Its up-conversion luminescence spectrum is as Fig. 6.Under the exciting of 980nm laser apparatus, the pressed powder of this material presents the upper switching emission of typical blue light (450-500nm).
Embodiment 4:
As shown in Figure 7, for thering is the rare earth luminous nano particle KYF of nucleocapsid structure
4: Yb, Ho@CaF
2@NaLuF
4angle of elevation annular dark scanning transmission electron photomicrograph, in figure, can find out, this particle median size is about 10～15nm.This particle tool nucleocapsid structure that haves three layers, wherein each particle inner side is divided into KYF compared with highlights
4: Yb, Ho, centre is CaF compared with dark-part
2, outside is divided into NaLuF compared with highlights
4.As shown in Figure 8, contrast Ho, in the emission peak intensity of 550nm and 650nm, can observe the enhancing of 300 times of left and right to its up-conversion luminescence spectrum.
This has the rare earth luminous nano particle KYF of nucleocapsid structure
4: Yb, Ho@CaF
2@NaLuF
4preparation method as follows:
(1) by 0.78mmol Y (CF
3cOO)
3, 0.20mmol Yb (CF
3cOO)
3, 0.02mmolHo (CF
3cOO)
3, 1.00mmol CF
3cOOK is dispersed in the solvent of 5mmol stearylamine, 5mmol cetylamine, 10mmol stearic acid and 20mmol 1-octadecylene composition and mixes, vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 280 DEG C and keep again 1h.After naturally cooling, add ethanol, centrifugation, uses washing with alcohol 3 times, dry, can obtain Emission in Cubic KYF
4: Yb, Ho luminous nano granule.
(2) KYF step (1) being obtained
4: Yb, Ho luminous nano granule is scattered in the mixture of 20mmol oleic acid and 20mmol1-octadecylene, adds 4.00mmol Ca (CF
3cOO)
2mix vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 310 DEG C and keep again 0.5h.After naturally cooling, add methyl alcohol, centrifugation, uses methanol wash 3 times, dry, can obtain KYF
4: Yb, Ho@CaF
2luminous nano granule.
(3) KYF step (2) being obtained
4: Yb, Er@CaF
2luminous nano granule is scattered in the mixture of 20mmol oleic acid and 20mmol1-octadecylene again, adds 2.00mmol Lu (CF
3cOO)
3, 2.00mmolCF
3cOONa mixes, vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 310 DEG C and keep again 0.5h.After naturally cooling, add ethanol, centrifugation, uses washing with alcohol 3 times, dry, can obtain KYF
4: Yb, Er@CaF
2@NaLuF
4luminous nano granule.
Embodiment 5:
As shown in Figure 9, for thering is the rare earth luminous nano particle NaLaF of nucleocapsid structure
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb@CaF
2: the angle of elevation annular dark scanning transmission electron photomicrograph of Dy, in figure, can find out, this particle median size is about 20nm.This particle has 4 layers of nucleocapsid structure, and wherein each particle is divided into NaLaF compared with highlights in inner side
4: Yb, Tm, inferior internal layer is CaF compared with dark-part
2: Gd, then outside is divided into NaGdF compared with highlights
4: Tb, outermost layer is CaF compared with dark-part
2: Dy.Its up-conversion luminescence spectrum as shown in Figure 8, contrasts NaLaF
4: Yb, Tm, Tb, Dy nano particle, in the transmitting at 475nm place, can be observed the enhancing of 5 times of left and right.
This has the rare earth luminous nano particle NaLaF of nucleocapsid structure
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb@CaF
2: the preparation method of Dy is as follows:
(1) by 0.60mmol La (CF
3cOO)
3, 0.39mmol Yb (CF
3cOO)
3, 0.01mmolTm (CF
3cOO)
3, 1.00mmol CF
3cOONa is dispersed in the solvent of 10mmol oleyl amine, 10mmol Palmiticacid and 20mmol 1-octadecylene composition and mixes vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 310 DEG C and keep again 1h.After naturally cooling, add ethanol, centrifugation, after again disperseing with toluene, with washed with dichloromethane 3 times, dry, can obtain NaLaF
4: Yb, Tm luminous nano granule.
(2) NaLaF step (1) being obtained
4: Yb, Tm luminous nano granule is scattered in the mixture of 20mmol oleic acid and 20mmol 1-octadecylene, adds 7.20mmol Ca (CF
3cOO)
2with 0.80mmolGd (CF
3cOO)
3, mix vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 300 DEG C and keep again 40min.After naturally cooling, add ethanol, centrifugation, uses washing with acetone 3 times, dry, can obtain NaLaF
4: Yb, Tm@CaF
2: Gd luminous nano granule.
(3) NaLaF step (2) being obtained
4: Yb, Tm@CaF
2: Gd luminous nano granule is scattered in the mixture of 40mmol oleic acid and 40mmol1-octadecylene, adds 19mmol Gd (CF
3cOO)
3with 1mmol Tb (CF
3cOO)
3, mix vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 310 DEG C and keep again 30min.After naturally cooling, add ethanol, centrifugation, uses washing with acetone 3 times, dry, can obtain NaLaF
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb luminous nano granule.
(4) NaLaF step (3) being obtained
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb luminous nano granule is scattered in the mixture of 40mmol oleic acid and 40mmol1-octadecylene, adds 36mmolCa (CF
3cOO)
2with 4mmol Dy (CF
3cOO)
3, mix vaccum dewatering, oxygen at 100 DEG C.Under nitrogen atmosphere, be heated to 310 DEG C and keep again 30min.After naturally cooling, add ethanol, centrifugation, uses washing with acetone 3 times, dry, can obtain NaLaF
4: Yb, Tm@CaF
2: Gd@NaGdF
4: Tb@CaF
2: Dy luminous nano granule.
Claims (12)
1. a rare earth luminous nano material, comprises stratum nucleare, and the shell of one deck parcel stratum nucleare at least, and wherein said stratum nucleare is for containing rare earth element and alkali-metal rare earth fluorine double salt nano particle, and described shell is alkaline-earth metal fluoride.
2. rare earth luminous nano material as claimed in claim 1, is characterized in that, described alkaline-earth metal fluoride adulterates on a small quantity or the rare earth element ion that undopes.
3. rare earth luminous nano material as claimed in claim 2, is characterized in that, the volumetric molar concentration of the rare earth element ion in described stratum nucleare or shell is 0%～50%.
4. rare earth luminous nano material as claimed in claim 1, is characterized in that, described rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium; Described basic metal is selected from lithium, sodium or potassium; Described alkaline-earth metal is selected from magnesium, calcium, strontium or barium.
5. rare earth luminous nano material as claimed in claim 1, is characterized in that, the number of plies of described shell is 1～5 layer, and the composition of each shell is identical or different.
6. rare earth luminous nano material as claimed in claim 1, is characterized in that, in described shell, the molar weight of alkaline-earth metal fluoride is 0.5～40 times of described stratum nucleare middle-weight rare earths fluorochemical double salt.
7. a preparation method for rare earth luminous nano material, comprising:
Will be containing rare earth element and alkali-metal rare earth fluorine double salt nanoparticulate dispersed in organic solvent, evenly mix with appropriate alkaline-earth metal fluoride presoma, at 140～330 DEG C, react 5min～24h, by reaction product centrifugation, adopt organic solvent washing dry, obtain rare earth luminous nano material.
8. preparation method as claimed in claim 7, it is characterized in that, also comprise and proceed one or many following steps: obtained rare earth luminous nano material is evenly mixed with appropriate alkaline-earth metal fluoride presoma or alkaline earth/rare earth fluorine presoma, at 140～330 DEG C, react 5min～24h, by reaction product centrifugation, adopt organic solvent washing dry, obtaining shell increases one or more layers rare earth luminous nano material.
9. preparation method as claimed in claim 7, it is characterized in that, described containing rare earth element and alkali-metal rare earth fluorine double salt nano particle, prepare by following method: utilize one or more inorganic salt that contain rare earth element or organic acid salt and one or more alkali-metal inorganic salt or organic acid salts, wherein have at least a kind of inorganic salt or organic acid salt to contain fluorine element, in solvent, at 140～330 DEG C, keep 5min～24h that building-up reactions occurs, by reaction product centrifugation and adopt organic solvent washing dry, obtain rare earth ion doped rare earth fluorine double salt nano particle.
10. preparation method as claimed in claim 9, is characterized in that, described in contain rare earth element or alkali-metal inorganic salt or organic acid salt and comprise nitrate, fluorochemical, muriate, acetate, trifluoroacetate.
11. preparation methods as claimed in claim 9, it is characterized in that, the solvent of building-up reactions is selected from one or more in water, ethanol, toluene, ethylene glycol, glycol ether, glycerol, tetradecy lamine, cetylamine, stearylamine, oleyl amine, TETRADECONIC ACID, Palmiticacid, stearic acid, oleic acid, octadecylene.
12. preparation methods as described in as arbitrary in claim 7-11, is characterized in that, the organic solvent of washing use is selected from one or more in hexanaphthene, normal hexane, methyl alcohol, ethanol, chloroform, methylene dichloride, acetone, benzene, toluene.
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| CN108445219A (en) * | 2018-03-16 | 2018-08-24 | 南京微测生物科技有限公司 | A kind of preparation method and application of high performance time resolved fluorometric microballoon |
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| CN113292988A (en) * | 2021-05-27 | 2021-08-24 | 深圳先进技术研究院 | Rare earth core-shell nano material and preparation method thereof |
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| WO2022261967A1 (en) * | 2021-06-18 | 2022-12-22 | 深圳先进技术研究院 | Rare earth core-shell nanomaterial and preparation method therefor |
| CN116285988A (en) * | 2023-03-28 | 2023-06-23 | 中国科学院长春应用化学研究所 | Rare earth-framework nucleic acid nanocomposite and preparation method and application thereof |
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| CN107831151A (en) * | 2017-10-25 | 2018-03-23 | 首都师范大学 | Application of the rare-earth fluorescent nano material of molybdenum base heteropoly acid modification in glutathione detection |
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| CN108445219A (en) * | 2018-03-16 | 2018-08-24 | 南京微测生物科技有限公司 | A kind of preparation method and application of high performance time resolved fluorometric microballoon |
| CN111040764A (en) * | 2019-12-11 | 2020-04-21 | 昆明理工大学 | Fluoride high-brightness X-ray scintillator and preparation method thereof |
| CN113292988A (en) * | 2021-05-27 | 2021-08-24 | 深圳先进技术研究院 | Rare earth core-shell nano material and preparation method thereof |
| WO2022261967A1 (en) * | 2021-06-18 | 2022-12-22 | 深圳先进技术研究院 | Rare earth core-shell nanomaterial and preparation method therefor |
| CN113549446A (en) * | 2021-07-09 | 2021-10-26 | 上海大学 | Neodymium-sensitized rare earth luminescent multilayer core-shell structure material, and preparation method and application thereof |
| CN116285988A (en) * | 2023-03-28 | 2023-06-23 | 中国科学院长春应用化学研究所 | Rare earth-framework nucleic acid nanocomposite and preparation method and application thereof |
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