CN106281327A - One class hydrophilic up-conversion and preparation method thereof - Google Patents
One class hydrophilic up-conversion and preparation method thereof Download PDFInfo
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- CN106281327A CN106281327A CN201610643798.0A CN201610643798A CN106281327A CN 106281327 A CN106281327 A CN 106281327A CN 201610643798 A CN201610643798 A CN 201610643798A CN 106281327 A CN106281327 A CN 106281327A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- C09K11/7773—Halogenides with alkali or alkaline earth metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
One class hydrophilic up-conversion and preparation method thereof, by YCl3, YbCl3Add in the container containing oleic acid and 1 octadecylene system with the mixed aqueous solution of ErCl, in container, be passed through argon, heating；Above-mentioned reaction system is cooled to room temperature, adds containing NH4The methanol solution system of F and NaOH；Two systems it is sufficiently stirred for mixing and is passed through argon, heating up；After system is cooled to room temperature, and clean particle precipitation with ethanol；Finally the particle obtained is disperseed in aqueous.Whole course of reaction is carried out in ar gas environment.This process operation is simple, and the up-conversion nanoparticle utilizing a step to obtain has the luminescent properties of good water solublity, biocompatibility and excellence.
Description
Technical field
The invention belongs to materials science field, relate generally to class hydrophilic up-conversion and preparation method thereof.
Background technology
In recent years, rare earth up-conversion luminescence nanoparticle (UCNPs) was because the mechanics of its uniqueness, electricity, magnetics, optics
Character, becomes the Main way of various fields research.It is luminous that up-conversion luminescence process is different from traditional down-conversion fluorescent, right and wrong
Linear luminescence process, the two or more low-energy photon of continuous absorption, launch the photon of a higher energy.This existing
As having run counter to Stokes' law, it is referred to as Anti-Stokes emissions.At present, the material that up-conversion luminescence efficiency is the highest is to pass through
In solid material, doping with rare-earth ions prepares.Researcher is the deepest by study up-conversion nanoparticles
Enter, it is already possible to synthesize the up-conversion luminescence nanoparticle of function admirable.UCNPs sends visible under near infrared light excites
Light, have longer light penetration depth, to biological tissue almost without damage, without advantages such as background fluorescences, for UCNPs in biomedicine
The application in field provides ideal performance basis.
But, traditional method the rare earth up-conversion luminescence nanoparticle synthesized is all hydrophobic, and to cure at biology
Field is applied, and is necessary for being converted into hydrophilic by surface modification, and whole process is numerous and diverse time-consuming.On rare earth, conversion is received
In rice corpuscles, luminous efficiency is up to lanthanide ion to Yb3+/Er3+Or Yb3+/Tm3+The NaYF of doping4Nanoparticle.Accordingly, I
Have selected Yb3+/Er3+The NaYF of doping4Nanoparticle is as object of study, it is proposed that be directly synthesized hydrophilic NaYF4 :Yb3 +, Er3+The one-step method of nanoparticle, is optimized traditional method.
Summary of the invention
Solve the technical problem that: the present invention provides class hydrophilic up-conversion and preparation method thereof, the letter of this method
Singly save time, and the particle obtained has the luminescent properties of good dispersion, water solublity and excellence.
Technical scheme: the preparation method of a class hydrophilic up-conversion, preparation process is: by YCl3, YbCl3And ErCl
Mixed aqueous solution add in the container containing oleic acid and 1-octadecylene system, described YCl3, YbCl3With the mass ratio of ErCl it is
50:10:1, the mass ratio of oleic acid and 1-octadecylene is not less than 2:5, mixed aqueous solution: oleic acid and the mass ratio of 1-octadecylene system
Example is not more than 1:10；Being passed through argon in container, heating makes temperature be not less than 90 DEG C, not higher than 120 DEG C, holds time and be not less than
30min, then it is warmed up to be not less than 140 DEG C, not higher than 300 DEG C, hold time and be not less than 30min；Above-mentioned reaction system is cooled down
To room temperature, add containing NH4The methanol solution system of F and NaOH, NH in solution system4The mass ratio of F, NaOH and methanol is 3:
2:120, reaction system with containing NH4The methanol system mass ratio of F and NaOH is not less than 3:5；It is sufficiently stirred for mixing also by two systems
It is passed through argon, is warming up to 65 DEG C and maintains 30min, then continuing at condensing unit, solution is warming up to not higher than 75 DEG C and maintains
1h, then system is warming up to be not less than 90 DEG C, finally makes solution be warming up to be not less than 300 by not higher than 110 DEG C and maintain 30min
DEG C, not higher than 350 DEG C and maintain 1h；After system is cooled to room temperature, and clean particle precipitation with ethanol；Finally will obtain
Particle disperses in aqueous.
Preferably preparation method is: by 2.42mg YCl3, 0.4mg YbCl3With 0.04mg ErCl3Mixed aqueous solution
Add in the 100mL there-necked flask containing 12mL oleic acid and the 1-octadecylene of 30mL, mixed solution is heated to 110 DEG C, maintain
After 30min, then it is warmed up to 140 DEG C of same maintenance 30min, aqueous solution evaporation is removed；Above-mentioned mixed liquor is cooled to room temperature,
Add containing 0.296g NH4The 15mL methanol solution of F and 0.2g NaOH；Insert condensing tube but non-water flowing, by solution stirring
After 30min, it is warming up to 65 DEG C and maintains 30min；It is passed through water with in backward condensing tube, solution is warming up to 69 DEG C and maintains 1h,
Reaction system is allowed to be in methanol environment；Condensing tube is extracted, makes solution be warming up to 100 DEG C and maintain 30min；Again by condensing tube
Insert water flowing, make solution be warming up to 305 DEG C and maintain 1h；After solution is cooled to room temperature, with ethanol by particle precipitation out, divide
Not Yong the ethanol purge particle three times of straight alcohol and 50wt.%, obtain the up-conversion nano material of one-step synthesis method.
The hydrophilic up-conversion that said method prepares
Beneficial effect: this method simply saves time, and the particle good dispersion obtained, pattern is homogeneous, have good water solublity,
And the luminescent properties of excellence.
Accompanying drawing explanation
Fig. 1: (A) upper conversion nano granule is reunited in chloroform, and (B) upper conversion nano granule divides in aqueous
Dissipate；
Fig. 2: upper conversion nano granule transmission electron microscope picture；
Fig. 3: under near-infrared 980nm exciting light, up-conversion nano material launches the photo of green fluorescence.
Detailed description of the invention
Embodiment 1
By YCl3(2.42mg), YbCl3(0.4mg) and ErCl3 (0.04mg) mixed aqueous solution add containing 12mL oleic acid and
In the 100mL there-necked flask of the 1-octadecylene of 30mL, mixed solution is heated to 110 DEG C, after maintaining 30min, is then warmed up to
140 DEG C of same maintenance 30min, remove aqueous solution evaporation.Above-mentioned mixed liquor is cooled to room temperature, adds containing NH4F
(0.296g) and NaOH(0.2g) 15mL methanol solution.Insert condensing tube but non-water flowing, after solution stirring 30min, heat up
To 65 DEG C and maintain 30min.It is passed through water with in backward condensing tube, solution is warming up to 69 DEG C and maintains 1h, allow at reaction system
In methanol environment.Condensing tube is extracted, makes solution be warming up to 100 DEG C and maintain 30min.Again condensing tube is inserted water flowing, make
Solution is warming up to 305 DEG C and maintains 1h.After solution is cooled to room temperature, with ethanol by particle precipitation out, straight alcohol is used respectively
Ethanol purge particle three times with 50wt.%.The up-conversion nano material of one-step synthesis method that finally will obtain, is dispersed in water-soluble
In liquid.Whole course of reaction is all carried out in ar gas environment.Characterization result is shown in accompanying drawing 1 ~ 3.
Embodiment 2
By YCl3(1.2mg), YbCl3(0.2mg) and ErCl3(0.02mg) mixed aqueous solution adds containing 8mL oleic acid and 15mL
1-octadecylene 60mL there-necked flask in, mixed solution is heated to 100 DEG C, maintains after 45min, be then warmed up to 200 DEG C
Maintain 45min equally, aqueous solution evaporation is removed.Above-mentioned mixed liquor is cooled to room temperature, adds containing NH4F(0.15g) and
NaOH(0.1g) 8mL methanol solution.Insert condensing tube but non-water flowing, after solution stirring 30min, be warming up to 65 DEG C and maintain
30min.It is passed through water with in backward condensing tube, solution is warming up to 65 DEG C and maintains 1h, allow reaction system be in methanol environment.
Condensing tube is extracted, makes solution be warming up to 100 DEG C and maintain 30min.Again condensing tube is inserted water flowing, make solution be warming up to 320
DEG C and maintain 1h.After solution is cooled to room temperature, with ethanol by particle precipitation out, respectively by straight alcohol and the second of 50 wt.%
Alcohol wash particle three times.The up-conversion nano material of one-step synthesis method that finally will obtain, dispersion is in aqueous.Whole reaction
Process is all carried out in ar gas environment.Characterization result approximates with embodiment 1.
Embodiment 3
By YCl3(2.42mg), YbCl3(0.4mg) and ErCl3(0.04mg) mixed aqueous solution add containing 12mL oleic acid and
In the 100mL there-necked flask of the 1-octadecylene of 30mL, mixed solution is heated to 115 DEG C, after maintaining 1h, is then warmed up to 260
DEG C same maintenance 1h, removes aqueous solution evaporation.Above-mentioned mixed liquor is cooled to room temperature, adds containing NH4F(0.296g) and
NaOH(0.2g) 15mL methanol solution.Insert condensing tube but non-water flowing, after solution stirring 30min, be warming up to 65 DEG C and tie up
Hold 30min.It is passed through water with in backward condensing tube, solution is warming up to 65 DEG C and maintains 1h, allow reaction system be in methanol environment
In.Condensing tube is extracted, makes solution be warming up to 100 DEG C and maintain 30min.Again condensing tube is inserted water flowing, make solution be warming up to
340 DEG C and maintain 1h.After solution is cooled to room temperature, with ethanol by particle precipitation out, respectively with straight alcohol and 50 wt.%
Ethanol purge particle three times.The up-conversion nano material of one-step synthesis method that finally will obtain, dispersion is in aqueous.Whole instead
Process is answered all to carry out in ar gas environment.Characterization result approximates with embodiment 1.
Embodiment 4
By YCl3(2mg), YbCl3(1mg) and ErCl3(0.04mg) mixed aqueous solution adds containing 10mL oleic acid and 30mL
In the 100mL there-necked flask of 1-octadecylene, mixed solution is heated to 100 DEG C, after maintaining 20min, is then warmed up to 150 DEG C together
Sample maintains 30min, aqueous solution evaporation is removed.Above-mentioned mixed liquor is cooled to room temperature, adds containing NH4And NaOH F(0.3g)
(0.24g) 15mL methanol solution.Insert condensing tube but non-water flowing, after solution stirring 30min, be warming up to 65 DEG C and maintain
30min.It is passed through water with in backward condensing tube, solution is warming up to 70 DEG C and maintains 30min, allow reaction system be in methanol environment
In.Condensing tube is extracted, makes solution be warming up to 80 DEG C and maintain 30min.Again condensing tube is inserted water flowing, make solution be warming up to
305 DEG C and maintain 1h.After solution is cooled to room temperature, with ethanol by particle precipitation out, respectively with straight alcohol and 50 wt.%
Ethanol purge particle three times.The up-conversion nano material of one-step synthesis method that finally will obtain, dispersion is in aqueous.Whole instead
Process is answered all to carry out in ar gas environment.Characterization result proves that experiment effect is the best.
Interpretation of result:
Fig. 1, up-conversion nano material dispersion in aqueous and reunite in chloroform, show by one-step synthesis method upper turn
Conversion materials is hydrophilic.
Fig. 2, transmission electron microscope picture understand up-conversion nano material pattern in approximation hexagon, mean diameter is about 28nm,
And have good dispersibility.When the pattern of rare earth upconversion nano particle is hexagonal structure, the efficiency of up-conversion luminescence is
The highest.It can thus be appreciated that the fluorescence radiation efficiency of up-conversion can be higher.
Fig. 3, up-conversion nano material is excited by near-infrared excitation light and launches the green fluorescence that light intensity is the highest.Say
Clear one-step method successfully synthesizes hydrophilic rare earth up-conversion luminescence nanoparticle, and this particle up-conversion nano material
There is the strongest up-conversion fluorescence luminous intensity.
Claims (3)
1. the preparation method of a class hydrophilic up-conversion, it is characterised in that preparation process is:
By YCl3, YbCl3Add in the container containing oleic acid and 1-octadecylene system with the mixed aqueous solution of ErCl, described YCl3,
YbCl3Being 50:10:1 with the mass ratio of ErCl, the mass ratio of oleic acid and 1-octadecylene is not less than 2:5, mixed aqueous solution: oleic acid
It is not more than 1:10 with the mass ratio of 1-octadecylene system；
Being passed through argon in container, heating makes temperature be not less than 90 DEG C, not higher than 120 DEG C, holds time not less than 30min, then
It is warmed up to be not less than 140 DEG C, not higher than 300 DEG C, holds time and be not less than 30min；
Above-mentioned reaction system is cooled to room temperature, adds containing NH4The methanol solution system of F and NaOH, NH in solution system4F、
The mass ratio of NaOH and methanol is 3:2:120, reaction system with containing NH4The methanol system mass ratio of F and NaOH is not less than 3:5；
Two systems it is sufficiently stirred for mixing and is passed through argon, be warming up to 65 DEG C and maintain 30min, then continuing at condensing unit, will
Solution is warming up to not higher than 75 DEG C and maintains 1h, then system is warming up to be not less than 90 DEG C, not higher than 110 DEG C and maintain 30min,
Solution is finally made to be warming up to be not less than 300 DEG C, not higher than 350 DEG C and maintain 1h；
After system is cooled to room temperature, and clean particle precipitation with ethanol；Finally the particle obtained is disperseed in aqueous.
The preparation method of a class hydrophilic up-conversion the most according to claim 1, it is characterised in that by 2.42mg YCl3,
0.4mg YbCl3With 0.04mg ErCl3Mixed aqueous solution add the 100mL tri-mouthfuls of the 1-octadecylene containing 12mL oleic acid and 30mL
In flask, mixed solution is heated to 110 DEG C, after maintaining 30min, is then warmed up to 140 DEG C of same maintenance 30min, by water-soluble
Liquid evaporation removes；Above-mentioned mixed liquor is cooled to room temperature, adds containing 0.296g NH4The 15mL methanol of F and 0.2g NaOH is molten
Liquid；Insert condensing tube but non-water flowing, after solution stirring 30min, be warming up to 65 DEG C and maintain 30min；With in backward condensing tube
It is passed through water, solution is warming up to 69 DEG C and maintains 1h, allow reaction system be in methanol environment；Condensing tube is extracted, makes solution
It is warming up to 100 DEG C and maintains 30min；Again condensing tube is inserted water flowing, make solution be warming up to 305 DEG C and maintain 1h；Solution is cold
But to after room temperature, with ethanol by particle precipitation out, respectively with the ethanol purge particle three times of straight alcohol and 50wt.%, one is obtained
The up-conversion nano material of footwork synthesis.
3. the hydrophilic up-conversion that method described in claim 1 or 2 prepares.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111948188A (en) * | 2020-09-23 | 2020-11-17 | 江南大学 | Method for measuring organic phosphorus |
| CN114790391A (en) * | 2022-04-14 | 2022-07-26 | 湖南科技大学 | Hydrophilic modification method of oleic acid-capped up-conversion nanoparticles based on ligand oxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111948188A (en) * | 2020-09-23 | 2020-11-17 | 江南大学 | Method for measuring organic phosphorus |
| CN114790391A (en) * | 2022-04-14 | 2022-07-26 | 湖南科技大学 | Hydrophilic modification method of oleic acid-capped up-conversion nanoparticles based on ligand oxidation |
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Application publication date: 20170104 |