CN101177610A - Method for preparing nano-grade NaYF4 up-conversion fluorescence host material under normal temperature - Google Patents
Method for preparing nano-grade NaYF4 up-conversion fluorescence host material under normal temperature Download PDFInfo
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- CN101177610A CN101177610A CNA2007101713218A CN200710171321A CN101177610A CN 101177610 A CN101177610 A CN 101177610A CN A2007101713218 A CNA2007101713218 A CN A2007101713218A CN 200710171321 A CN200710171321 A CN 200710171321A CN 101177610 A CN101177610 A CN 101177610A
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Abstract
The invention relates to a method of preparing nanometer NaYF4 up-conversion fluorescent matrix materials under the normal temperature. The preparation method comprises: under the normal temperature, yttrium salt solution is added into nonpolarity organic solvent and stirred as the surfactant water solution is added; after being fully stirred, sodium fluoride water solution is added into the reaction system; by being continuously stirred for 0.5-24 hours, the reaction completes and separates in standing, and then the products dispersing in oil phase are separated, which are dried in vacuum for 3-5 hours under 30-70 DEG C after ultrasonic washing by the mixture of acetone and deionized water, thus obtaining nanometer NaYF<4> grain. The nanometer up-conversion fluorescent matrix materials prepared by the method are characterized by even granularity, good dispersing, etc; furthermore, the minimum grain diameter can be controlled within 10mm, which can completely meet the applied requirements of the matrix materials marked by biomolecule fluorescent, has extremely high output and can establish good foundation of the output of fluorescent nanometer materials and wide application thereof in future.
Description
Technical field
The invention belongs to the upconverting fluorescent material field, particularly relate to a kind of normal temperature and prepare nano level NaYF
4The method of up-conversion fluorescence substrate material.
Background technology
Upconverting fluorescent material is that a class excites the luminescent material that can send short-wavelength light down at long wavelength light.Recently, be subjected to extensive concern with upconverting fluorescent material as the biomolecules fluorescence labeling probe.Upconverting fluorescent material (NaYF has appearred at present
4: Yb
3+/ Er
3+) in the DNA Detection Techniques, use relevant report (Chem.Commun., 2006,2557-2559); Latest report and achievement about upconverting fluorescent material constantly emerge.
With NaYF
4Be matrix, Yb, the adulterated upconverting fluorescent material of Er is find up to now most effective; As the biomolecules fluorescence labeling material, marker material itself need possess characteristics such as particle diameter is little, even particle distribution, luminous efficiency height.
Reverse micelle method is a kind of method that is widely used in nano material is synthetic, is easier to control with size, the shape of the nanoparticle of reverse micelle method preparation, and relevant research is also more; But its output is low excessively, only is applicable to the laboratory produced in small quantities, along with the expansion of up-conversion Application Areas with and the growing with each passing day of consumption, this method can not satisfy nano material and quantize the needs produced on a large scale.
Summary of the invention
The object of the present invention is to provide a kind of normal temperature to prepare nano level NaYF
4The method of up-conversion fluorescence substrate material, this method be with perchloric acid or hydrochloric acid as the yttrium oxide solvent, use anion surfactants such as nonpolar oil phase such as toluene and sodium oleate, at normal temperatures, but even, the good dispersion NaYF of high yield ground preparation size
4The up-conversion fluorescence substrate material.
A kind of normal temperature of the present invention prepares nano level NaYF
4The method of up-conversion fluorescence substrate material comprises the following steps:
(a) with rare-earth oxidation yttrium powder dissolution in acid solvent, add deionized water again, the salts solution that is made into yttrium is standby;
(b) aqueous solution of preparation anionic surface tensio-active agent is standby;
(c) preparation 0.2～0.8mol/L, pH9.0～10.0 sodium fluoride aqueous solutions are standby;
(d) it is standby to get nonpolar stronger organic solvent;
(e) under normal temperature (20 ℃-40 ℃) condition, the salts solution of the yttrium for preparing in the step (a) is added in the organic solvent that step (d) gets ready, its water, the volume ratio of oil phase is 1: 10～1: 5, the aqueous solution that adds the tensio-active agent that step (b) prepares while stirring, this moment reaction system in water, the volume ratio of oil phase is 1: 5～1: 2, after the vigorous stirring 10～60 minutes, the sodium fluoride aqueous solution for preparing in the step (c) is added reaction system, continue to stir 0.5～24 hour, the volume ratio of water oil is 1 in the reaction system at this moment: 1-2: 3, reaction was left standstill 5 minutes after finishing, and product is dispersed in the oil phase, and water is clarified relatively;
(f) isolate the product that is dispersed in the oil phase, with the mixed solution supersound washing of acetone and deionized water, 30～70 ℃ of following vacuum-drying 3～5 hours promptly gets nano level NaYF
4Particle.
Acid solvent in the described step (a) is strong acid such as perchloric acid or hydrochloric acid, and concentration is 0.1～0.5mol/L, and the pH value is 0～1;
The concentration of salt solution of described yttrium is 0.1～0.6mol/L, and the pH value is 0～5, preferred 0.1～0.4mol/L;
Described anion surfactant is AOT ([2-ethylhexyl] sodium sulfosuccinate), SDS (sodium laurylsulfonate) etc., and its concentration of aqueous solution is 0.01～0.2mol/L;
Described non-polar organic solvent is hexane, hexanaphthene or toluene;
The salts solution of described yttrium and the mol ratio of Sodium Fluoride are 1: 2～6.
Beneficial effect of the present invention:
The nano level up-conversion fluorescence substrate material that a process for preparing has characteristics such as epigranular, good dispersion, and the particle diameter minimum controllable can satisfy the requirement of biomolecules fluorescent mark substrate material on using fully below 10nm; And, to compare with traditional reverse micelle method, this preparation method's output is high, has solved the problem under yielding poorly when reverse micelle method is used for preparing nano material, for the volume production of fluorescent nano material and widespread use are from now on laid a good foundation.
Description of drawings
Fig. 1 is a main technique schema of the present invention;
Fig. 2 is the prepared NaYF of embodiment 1-3
4The X-ray diffractogram of substrate material (XRD) (a) is embodiment 1, (b) is embodiment 2, (c) is embodiment 3;
Fig. 3 is embodiment 1 prepared NaYF
4The nano NaY F of substrate material
4The transmission electron microscope picture of powder, median size are about 50 nanometers;
Fig. 4 is embodiment 2 prepared NaYF
4The nano NaY F of substrate material
4The transmission electron microscope picture of powder, median size are about 8 nanometers;
Fig. 5 is embodiment 3 prepared NaYF
4The nano NaY F of substrate material
4The transmission electron microscope picture of powder, median size are about 7 nanometers;
Fig. 6 is embodiment 4 prepared NaYF
4The nano NaY F of substrate material
4The transmission electron microscope picture of powder, median size are about 20 nanometers.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
A) take by weighing the 4.5168g yttrium oxide and be dissolved in 60ml, in the 2mol/l perchloric acid, it is fixed molten to 100ml to add deionized water, uses HClO
4Or NaOH solution is regulated the pH value to 1 of perchloric acid yttrium solution;
B) take by weighing and join the 8.7480g Sodium Fluoride and be dissolved in the 200ml deionized water, fully the dissolving back is fixed molten to 250ml;
C) it is standby to get 500ml toluene;
D) under 40 ℃ of temperature, get the perchloric acid yttrium solution for preparing in the 10ml step (a) and add in the toluene that 60ml step (c) gets ready, add the 10ml deionized water then while stirring, fully stir; Stir after 20 minutes, the sodium fluoride aqueous solution for preparing in the 20ml step (b) is added reaction system, reacted 1 hour;
E) after reaction finishes, left standstill 15 minutes, isolate oil phase then, after centrifugal 30 minutes, discard oil phase with the speed of 3900rpm;
F) with the mixed solution supersound washing product of acetone, deionized water, 60 ℃ of following vacuum-drying 5 hours.
The NaYF that it makes
4The X-ray diffractogram of substrate material is seen Fig. 2 (a), its nano NaY F
4The transmission electron microscope picture of powder is seen Fig. 3, and median size is about 50 nanometers.
Embodiment 2
A) take by weighing the 4.5168g yttrium oxide and be dissolved in the 60ml 2mol/L perchloric acid, it is fixed molten to 100ml to add deionized water, uses HClO
4Or NaOH solution is regulated the pH value to 1 of perchloric acid yttrium solution;
B) take by weighing 4.4455g AOT and be dissolved in the 80ml deionized water, fixed molten behind the ultrasonic dissolution to 100ml, promptly be mixed with 0.1mol/l AOT surfactant soln;
C) take by weighing and join the 8.7480g Sodium Fluoride and be dissolved in the 200ml deionized water, fully the dissolving back is fixed molten to 250ml;
D) it is standby to get 500ml toluene;
E) under 40 ℃ of temperature, get the perchloric acid yttrium solution for preparing in the 10ml step (a) and add in the toluene that 60ml step (d) gets ready, add the AOT aqueous solution that 10ml step (b) prepares then while stirring, fully stir; Stir after 20 minutes, the sodium fluoride aqueous solution for preparing in the 20ml step (c) is added reaction system, reacted 1 hour;
F) after reaction finishes, left standstill 15 minutes, isolate oil phase then,, discard upper strata clarification phase with the small amount of acetone breakdown of emulsion;
G) with acetone, deionized water supersound washing product, 60 ℃ of following vacuum-drying 5 hours.
The NaYF that it makes
4The X-ray diffractogram of substrate material is seen Fig. 2 (b), its nano NaY F
4The transmission electron microscope picture of powder is seen Fig. 4, and median size is about 8 nanometers.
Embodiment 3
A) take by weighing the 4.5168g yttrium oxide and be dissolved in 60ml, in the 2mol/l perchloric acid, it is fixed molten to 100ml to add deionized water, uses HClO
4Or NaOH solution is regulated the pH value to 1 of perchloric acid yttrium solution;
B) take by weighing 8.891g AOT and be dissolved in the 80ml deionized water, fixed molten behind the ultrasonic dissolution to 100ml, promptly be mixed with 0.2mol/l AOT surfactant soln;
C) take by weighing and join the 8.7480g Sodium Fluoride and be dissolved in the 200ml deionized water, fully the dissolving back is fixed molten to 250ml;
D) it is standby to get 500ml toluene;
E) under 40 ℃ of temperature, get the perchloric acid yttrium solution for preparing in the 10ml step (a) and add in the toluene that 60ml step (d) gets ready, add the AOT aqueous solution that 10ml step (b) prepares then while stirring, fully stir; Stir after 20 minutes, the sodium fluoride aqueous solution for preparing in the 20ml step (c) is added reaction system, reacted 1 hour;
F) after reaction finishes, left standstill 15 minutes, isolate oil phase then,, discard upper strata clarification phase with the small amount of acetone breakdown of emulsion;
G) with acetone, deionized water supersound washing product, 60 ℃ of following vacuum-drying 5 hours.
The NaYF that it makes
4The X-ray diffractogram of substrate material is seen Fig. 2 (c), its nano NaY F
4The transmission electron microscope picture of powder is seen Fig. 5, and median size is about 7 nanometers.
Embodiment 4
A) take by weighing the 4.5168g yttrium oxide and be dissolved in 60ml, in the 2mol/l perchloric acid, it is fixed molten to 100ml to add deionized water, uses HClO
4Or NaOH solution is regulated the pH value to 1 of perchloric acid yttrium solution;
B) take by weighing 4.4455g AOT and be dissolved in the 80ml deionized water, fixed molten behind the ultrasonic dissolution to 100ml, promptly be mixed with 0.1mol/l AOT surfactant soln;
C) take by weighing and join the 8.7480g Sodium Fluoride and be dissolved in the 200ml deionized water, fully the dissolving back is fixed molten to 250ml;
D) it is standby to get the 500ml hexane;
E) under 40 ℃ of temperature, get the perchloric acid yttrium solution for preparing in the 10ml step (a) and add in the hexane that 60ml step (d) gets ready, add the AOT aqueous solution that 10ml step (b) prepares then while stirring, fully stir; Stir after 20 minutes, the sodium fluoride aqueous solution for preparing in the 20ml step (c) is added reaction system, reacted 1 hour;
F) after reaction finishes, left standstill 15 minutes, isolate oil phase then,, discard upper strata clarification phase with the small amount of acetone breakdown of emulsion;
G) with acetone, deionized water supersound washing product, 60 ℃ of following vacuum-drying 5 hours.
The NaYF that it makes
4The nano NaY F of substrate material
4The transmission electron microscope picture of powder is seen Fig. 6, and median size is about 20 nanometers.
Claims (7)
1. a normal temperature prepares nano level NaYF
4The method of up-conversion fluorescence substrate material comprises the following steps:
(a) with rare-earth oxidation yttrium powder dissolution in acid solvent, add water again, the salts solution that is made into yttrium is standby;
(b) aqueous solution of preparation anionic surface tensio-active agent is standby;
(c) preparation 0.2～0.8mol/L, pH9.0～10.0 sodium fluoride aqueous solutions are standby;
(d) it is standby to get nonpolar stronger organic solvent;
(e) under 20 ℃ of-40 ℃ of normal temperature conditions, the salts solution of the yttrium for preparing in the step (a) is added in the organic solvent that step (d) gets ready, its water, the volume ratio of oil phase is 1: 10～1: 5, the aqueous solution that adds the tensio-active agent that step (b) prepares while stirring, this moment reaction system in water, the volume ratio of oil phase is 1: 5～1: 2, after the vigorous stirring 10～60 minutes, the sodium fluoride aqueous solution for preparing in the step (c) is added reaction system, continue to stir 0.5～24 hour, the volume ratio of water oil is 1: 1～2: 3 in the reaction system at this moment, and reaction finishes the back standing demix;
(f) isolate the product that is dispersed in the oil phase, with the mixed solution supersound washing of acetone and water, 30～70 ℃ of following vacuum-drying 3～5 hours promptly gets nano level NaYF
4Particle.
2. normal temperature according to claim 1 prepares nano level NaYF
4The method of up-conversion fluorescence substrate material is characterized in that: the acid solvent in the described step (a) is perchloric acid or hydrochloric acid, and concentration is 0.1～0.5mol/L, and the pH value is 0～1.
3. normal temperature according to claim 1 prepares nano level NaYF
4The method of up-conversion fluorescence substrate material is characterized in that: the concentration of salt solution of described yttrium is 0.1～0.6mol/L, and the pH value is 0～5.
4. normal temperature according to claim 3 prepares nano level NaYF
4The method of up-conversion fluorescence substrate material is characterized in that: the concentration of salt solution of described yttrium is 0.1～0.4mol/L.
5. normal temperature according to claim 1 prepares nano level NaYF
4The method of up-conversion fluorescence substrate material is characterized in that: described anion surfactant is AOT or SDS, and concentration of aqueous solution is 0.01～0.2mol/L.
6. normal temperature according to claim 1 prepares nano level NaYF
4The method of up-conversion fluorescence substrate material is characterized in that: described non-polar organic solvent is hexane, hexanaphthene or toluene.
7. normal temperature according to claim 1 prepares nano level NaYF
4The method of up-conversion fluorescence substrate material is characterized in that: the salts solution of described yttrium and the mol ratio of Sodium Fluoride are 1: 2～6.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289216B (en) * | 2008-06-05 | 2010-12-15 | 复旦大学 | Method for synthesizing microemulsion of water-solubility rare-earth nano material |
| CN101289217B (en) * | 2008-06-05 | 2010-12-15 | 复旦大学 | Hydro-thermal synthesis process of microemulsion of amphipathic rare-earth nano material |
| CN101504387B (en) * | 2009-03-10 | 2013-02-06 | 南京大学 | Use of rare earth fluoride nano material in MALDI-MS |
| CN104449732A (en) * | 2015-01-06 | 2015-03-25 | 东华大学 | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
| CN106430277A (en) * | 2016-09-19 | 2017-02-22 | 首都师范大学 | Water-soluble hollow rare earth nano-material and preparation method and application thereof |
| CN112897564A (en) * | 2021-02-06 | 2021-06-04 | 深圳市富诺材料有限公司 | Nano optical character material |
| CN117466251A (en) * | 2023-11-22 | 2024-01-30 | 山东科源生化有限公司 | Method for preparing yttrium perchlorate by utilizing rare earth yttrium oxide |
-
2007
- 2007-11-29 CN CNB2007101713218A patent/CN100567448C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289216B (en) * | 2008-06-05 | 2010-12-15 | 复旦大学 | Method for synthesizing microemulsion of water-solubility rare-earth nano material |
| CN101289217B (en) * | 2008-06-05 | 2010-12-15 | 复旦大学 | Hydro-thermal synthesis process of microemulsion of amphipathic rare-earth nano material |
| CN101504387B (en) * | 2009-03-10 | 2013-02-06 | 南京大学 | Use of rare earth fluoride nano material in MALDI-MS |
| CN104449732A (en) * | 2015-01-06 | 2015-03-25 | 东华大学 | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
| CN104449732B (en) * | 2015-01-06 | 2016-08-24 | 东华大学 | An a kind of utilization kind crystallization prepares KYF4: Yb3+, Er3+the method of nano material |
| CN106430277A (en) * | 2016-09-19 | 2017-02-22 | 首都师范大学 | Water-soluble hollow rare earth nano-material and preparation method and application thereof |
| CN106430277B (en) * | 2016-09-19 | 2018-06-19 | 首都师范大学 | A kind of water solubility hollow rare earth nano material and preparation method and application |
| CN112897564A (en) * | 2021-02-06 | 2021-06-04 | 深圳市富诺材料有限公司 | Nano optical character material |
| CN117466251A (en) * | 2023-11-22 | 2024-01-30 | 山东科源生化有限公司 | Method for preparing yttrium perchlorate by utilizing rare earth yttrium oxide |
| CN117466251B (en) * | 2023-11-22 | 2024-04-05 | 山东科源生化有限公司 | Method for preparing yttrium perchlorate by utilizing rare earth yttrium oxide |
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