CN102241968A - Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase - Google Patents
Method for implementing transfer of up-conversion nanocrystals from oil phase to aqueous phase Download PDFInfo
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- CN102241968A CN102241968A CN2011101758785A CN201110175878A CN102241968A CN 102241968 A CN102241968 A CN 102241968A CN 2011101758785 A CN2011101758785 A CN 2011101758785A CN 201110175878 A CN201110175878 A CN 201110175878A CN 102241968 A CN102241968 A CN 102241968A
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Abstract
The invention belongs to the technical field of functional inorganic nanocrystal surface modification, and relates to a method for transferring oil-soluble up-conversion nanocrystals to an aqueous phase so as to improve the biocompatibility of the up-conversion nanocrystals. The method comprises the following steps of: dissolving 0.02 to 0.2g of small molecular surfactant in 10 to 20ml of water in a room temperature open system; and adding 1 to 4 ml of up-conversion nanocrystal solution prepared by dissolving up-conversion nanocrystals in a low boiling point organic solvent, and heating to the temperature of between 55 and 80DEG C to volatilize the organic solvent so as to obtain the water-soluble up-conversion nanocrystals. By lyophobic-lyophobic interaction of the small molecular surfactant and ligands on the surfaces of the up-conversion nanocrystals, stable coating layers are formed, and the hydrophobicity of the surfaces of the nanocrystals is changed to hydrophilcity. The method is easy and convenient to implement; different surfactants can be introduced according to requirements; a problem that the up-conversion nanocrystals are hardly transferred from the oil phase to the aqueous phase is solved; and the method provides a reaction platform for coupling the up-conversion nanocrystals with biomolecules and other materials.
Description
Technical field
The invention belongs to functional inorganic nano-crystal process for modifying surface field, be specifically related to a kind of with the nanocrystalline universal method of transferring to water of oil soluble up-conversion, thereby increase the nanocrystalline bio-compatibility of up-conversion.
Background technology
The nanocrystalline optical property of up-conversion with uniqueness, can absorb two or more energy photons, inspire a high-energy photons, therefore become a focus of novel material research, be used in many fundamental researchs field, for example solid statelaser, light emitting devices, bioprobe, biological test, low density infrared imaging etc.But the up-conversion nanocrystal surface that prior art for preparing goes out is coated by the hydrophobic alkyl chain, can only be dispersed in the non-polar solvents such as toluene, trichloromethane, realizes the compatibility of further application, raising and the other materials of this type of material, need carry out surface modification.Especially up-conversion is nanocrystalline when being applied in the organism near infrared imaging, can not damage organism, receives increasing concern in life science.But organism generally all is hydrophilic, and is incompatible with the dewatering nano crystalline substance, has only the nanocrystalline surface hydrophilic modification that carries out, and transfers to water from oil phase, just can be implemented in the application on the life science.Previous methods is to carry out modification with high polymer, need control pH, temperature, time etc. under the nitrogen protection condition, the method complexity, and also the reaction conditions of every kind of method is all inequality, lacks universality.Seek the bottleneck that universal method is this field always.
In order to address this problem, we use various small molecules tensio-active agents to the nanocrystalline surface hydrophilic modification that carries out of up-conversion.This method generally is applicable to positively charged ion, negatively charged ion and nonionic surface active agent, can give abundant function of surface simultaneously very simply with the nanocrystalline water of transferring to.The raw material that uses all is commercial direct purchase, is a kind of suitable industrial to the nanocrystalline effective ways that carry out the surface hydrophilic processing of up-conversion.
Summary of the invention
Purpose of the present invention just provides a kind of method easy and simple to handle, blanket, with the nanocrystalline water of transferring to of oil soluble up-conversion, promptly directly add the small molecules tensio-active agent, obtain the different surfaces function by use different sorts tensio-active agent under identical jump condition: make the surface positively charged, negative charge or neutrality are further reacted such as polypyrrole such as silicon-dioxide or organism with inorganics
This method is directly used various small molecules tensio-active agents, and the hydrophobic-hydrophobic interaction by between they and the up-conversion nanocrystal surface part forms stable coating layer, realizes nanocrystal surface change from hydrophobic to hydrophilic.Should method is simple, can introduce the different sorts tensio-active agent as required, solved that up-conversion is nanocrystalline transfers to the difficult point of water from oil phase, for the coupling with biomolecules and other materials provides the reaction platform.
The raw material that the present invention uses all is commercial direct purchase, do not need further processing, directly mix according to a certain percentage and get final product, has good experimental repeatability, having kept the nanocrystalline luminescent properties of up-conversion simultaneously, is a kind of suitable industrial to the nanocrystalline effective ways that carry out the surface hydrophilic processing of up-conversion.
Specifically, step of the present invention is as follows:
In the unlimited system of room temperature, small molecules tensio-active agent 0.02～0.2g is dissolved in 10ml～20ml water, add the up-conversion nanocrystal solution 1～4ml that is dissolved in the low boiling point organic solvent again, up-conversion nanocrystalline with the mol ratio small molecules dosage of surfactant be 1: 5～15, be heated to 55～80 degree and make the organic solvent volatilization, thereby it is nanocrystalline to obtain water-soluble up-conversion.
Up-conversion described in the aforesaid method is nanocrystalline can be NaYF
4(Yb, Er), NaYF
4(Yb, Tm), NaYF
4(Yb, Ho), NaGdF
4(Yb, Er), YF
3(Yb, Er), LaF
3(Yb, Tm), NdF
3(Yb, Tm), GdF
3(Yb, Er), EuF
3(Yb, Er) etc.; Low boiling point organic solvent is trichloromethane, methylene dichloride, toluene, normal hexane, hexanaphthene etc.; The small molecules tensio-active agent is aniorfic surfactant such as sodium lauryl sulphate (SDS), Sodium dodecylbenzene sulfonate (SDBS), nine-sodium oleate, sodium stearate, cationic surfactants such as cetyl trimethylammonium bromide (CTAB), Trimethyllaurylammonium bromide (DTAB), two-octadecyl dimethyl brometo de amonio also can be Triton X-100 nonionic surface active agent such as (Triton x-100).
Description of drawings
Fig. 1 (a): the nanocrystalline NaYF of up-conversion
4(18%Yb, luminescent spectrum 2%Er);
Fig. 1 (b): trichloromethane phase NaYF
4(18%Yb, transmission electron microscope photo 2%Er);
Fig. 1 (c): forward water NaYF to SDS
4(18%Yb, transmission electron microscope photo 2%Er);
Fig. 1 (d): water NaYF
4(18%Yb, 2%Er) outside coats the transmission photo of polypyrrole;
Fig. 2: forward water NaYF to CTAB
4(18%Yb, transmission electron microscope photo 2%Er);
Fig. 3: forward water NaYF to DTAB
4(18%Yb, transmission electron microscope photo 2%Er);
Fig. 4: forward water NaYF to Triton x-100
4(18%Yb, transmission electron microscope photo 2%Er);
Fig. 5 (a): the nanocrystalline NaYF of up-conversion
4(18%Yb, luminescent spectrum 2%Tm);
Fig. 5 (b): toluene phase NaYF
4(18%Yb, transmission electron microscope photo 2%Tm);
Fig. 5 (c): toluene is mutually nanocrystalline to forward water NaYF to SDS
4(18%Yb, transmission electron microscope photo 2%Tm);
Fig. 6: normal hexane is mutually nanocrystalline to forward water NaYF to CTAB
4(18%Yb, transmission electron microscope photo 2%Tm);
Fig. 7: hexanaphthene is mutually nanocrystalline to forward water NaYF to DTAB
4(18%Yb, transmission electron microscope photo 2%Tm);
Fig. 8: methylene dichloride is mutually nanocrystalline to forward water NaYF to Triton x-100
4(18%Yb, transmission electron microscope photo 2%Tm);
Embodiment
The present invention is further elaborated below in conjunction with embodiment, rather than will limit the invention with this.
Embodiment 1
Add 0.04g aniorfic surfactant SDS in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration then is 1.9 * 10
-2The NaYF of mol/L
4The chloroform soln of (mole number 18%Yb, 2%Er); Be heated to 70 degrees centigrade and make the trichloromethane volatilization, cool to room temperature obtains water white water NaYF
4(mole number 18%Yb, 2%Er) solution.Shown in Fig. 1 (a), provided the nanocrystalline luminescent spectrum of up-conversion, proved nanocrystalline character with up-conversion; Fig. 1 (b) provided trichloromethane mutually in nanocrystalline transmission electron microscope photo, nanocrystalline as seen from the figure size is even, and is dispersed fine; Fig. 1 (c) has provided the nanocrystalline transmission electron microscope photo of aqueous phase, and we can see not gathering of particle, and are dispersed fine, have proved that the nanocrystalline of oil phase successfully forwarded to water; Utilize SDS electronegative and pyrroles's amino with positive electricity interact, around nanocrystalline, coated one deck shell, Fig. 1 (d) has provided further the transmission photo to water is nanocrystalline after carrying out that surface biological is compatible and modify with polypyrrole, further proved the nanocrystalline water that has been transferred to of oil phase, utilized the electric charge on surface to interact with the pyrroles.
Embodiment 2
Add 0.04g cats product CTAB in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Er) chloroform soln; Be heated to 70 degrees centigrade and make the trichloromethane volatilization, cool to room temperature obtains water white water NaYF
4(mole number 18%Yb, 2%Er) solution.Shown in Fig. 1 (b), provided trichloromethane mutually in nanocrystalline transmission electron microscope photo, Fig. 2 has provided the nanocrystalline transmission electron microscope photo of aqueous phase, we can see that particle do not assemble, dispersed fine, proved that the nanocrystalline of oil phase successfully forwarded to water.
Embodiment 3
Add 0.04g cats product DTAB in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Er) chloroform soln; Be heated to 70 degrees centigrade and make the trichloromethane volatilization, cool to room temperature obtains water white water NaYF4 (mole number 18%Yb, 2%Er) solution.Shown in Fig. 1 (b), provided trichloromethane mutually in nanocrystalline transmission electron microscope photo, Fig. 3 has provided the nanocrystalline transmission electron microscope photo of aqueous phase, we can see that particle do not assemble, dispersed fine, proved that the nanocrystalline of oil phase successfully forwarded to water.
Add 0.04g nonionic surface active agent Triton x-100 in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Er) chloroform soln; Be heated to 70 degrees centigrade and make the trichloromethane volatilization, cool to room temperature obtains water white water NaYF4 (mole number 18%Yb, 2%Er) solution.Shown in Fig. 1 (b), provided trichloromethane mutually in nanocrystalline transmission electron microscope photo, Fig. 4 has provided the nanocrystalline transmission electron microscope photo of aqueous phase, we can see that particle do not assemble, dispersed fine, proved that the nanocrystalline of oil phase successfully forwarded to water.
Embodiment 5
Add 0.04g anion surfactant SDS in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Tm) toluene solution; Be heated to 55 degrees centigrade and make the toluene volatilization, cool to room temperature obtains water white water NaYF
4(mole number 18%Yb, 2%Tm) solution.Shown in Fig. 5 (a), provided the nanocrystalline luminescent spectrum of up-conversion, proved nanocrystalline character with up-conversion; Fig. 5 (b) provided toluene mutually in nanocrystalline transmission electron microscope photo, nanocrystalline as seen from the figure size is even, and is dispersed fine; Fig. 5 (c) has provided the nanocrystalline transmission electron microscope photo of aqueous phase, and we can see not gathering of particle, and are dispersed fine, have proved that the nanocrystalline of oil phase successfully forwarded to water.
Embodiment 6
Add 0.04g cats product CTAB in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Tm) hexane solution; Be heated to 65 degrees centigrade and make the normal hexane volatilization, cool to room temperature obtains water white water NaYF
4(mole number 18%Yb, 2%Tm) solution.Shown in Fig. 5 (a), provided normal hexane mutually in nanocrystalline transmission electron microscope photo, Fig. 6 has provided the nanocrystalline transmission electron microscope photo of aqueous phase, we can see that particle do not assemble, and are dispersed fine, have proved that the nanocrystalline of oil phase successfully forwarded to water.
Embodiment 7
Add 0.04g cats product DTAB in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Tm) cyclohexane solution; Be heated to 75 degrees centigrade and make the hexanaphthene volatilization, cool to room temperature obtains water white water NaYF
4(mole number 18%Yb, 2%Tm) solution.Shown in Fig. 5 (a), provided hexanaphthene mutually in nanocrystalline transmission electron microscope photo, Fig. 7 has provided the nanocrystalline transmission electron microscope photo of aqueous phase, we can see that particle do not assemble, and are dispersed fine, have proved that the nanocrystalline of oil phase successfully forwarded to water.
Embodiment 8
Add 0.04g nonionic surface active agent Triton x-100 in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The NaYF of mol/L
4(mole number 18%Yb, 2%Tm) dichloromethane solution; Be heated to 80 degrees centigrade and make the methylene dichloride volatilization, cool to room temperature obtains water white water NaYF
4(mole number 18%Yb, 2%Tm) solution.Shown in Fig. 5 (a), provided methylene dichloride mutually in nanocrystalline transmission electron microscope photo, Fig. 8 has provided the nanocrystalline transmission electron microscope photo of aqueous phase, we can see that particle do not assemble, dispersed fine, proved that the nanocrystalline of oil phase successfully forwarded to water.
Embodiment 9
Add 0.04g aniorfic surfactant SDS in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The YF of mol/L
3(mole number 18%Yb, 2%Tm) chloroform soln; Be heated to 70 degrees centigrade and make the trichloromethane volatilization, cool to room temperature obtains water white water YF
3(mole number 18%Yb, 2%Tm) solution.Particle also is not assemble, and is dispersed fine.
Embodiment 10
Add 0.04g nonionic surface active agent Triton x-100 in 10ml water, stir the back dissolving and obtain colourless transparent solution, adding 2ml concentration is 1.9 * 10
-2The LaF of mol/L
3(mole number 18%Yb, 2%Er) toluene solution; Be heated to 60 degrees centigrade and make the toluene volatilization, cool to room temperature obtains water white water LaF
3(mole number 18%Yb, 2%Er) solution.Particle also is not assemble, and is dispersed fine.
Claims (4)
1. realize the nanocrystalline method that from the oil phase to the water, shifts of up-conversion for one kind, it is characterized in that: in the unlimited system of room temperature, small molecules tensio-active agent 0.02～0.2g is dissolved in 10ml～20ml water, add the up-conversion nanocrystal solution 1～4ml that is dissolved in the low boiling point organic solvent again, up-conversion nanocrystalline with the mol ratio small molecules dosage of surfactant be 1: 5～15, be heated to 55～80 degree and make the organic solvent volatilization, thereby it is nanocrystalline to obtain water-soluble up-conversion.
2. a kind of nanocrystalline method that shifts from the oil phase to the water of up-conversion that realizes as claimed in claim 1 is characterized in that: the nanocrystalline NaYF of being of up-conversion
4(Yb, Er), NaYF
4(Yb, Tm), NaYF
4(Yb, Ho), NaGdF
4(Yb, Er), YF
3(Yb, Er), LaF
3(Yb, Tm), NdF
3(Yb, Tm), GdF
3(Yb, Er) or EuF
3(Yb, Er).
3. a kind of nanocrystalline method that shifts from the oil phase to the water of up-conversion that realizes as claimed in claim 1, it is characterized in that: low boiling point organic solvent is trichloromethane, methylene dichloride, toluene, normal hexane or hexanaphthene.
4. a kind of nanocrystalline method that shifts from the oil phase to the water of up-conversion that realizes as claimed in claim 1, it is characterized in that: the small molecules tensio-active agent is sodium lauryl sulphate SDS, Sodium dodecylbenzene sulfonate SDBS, nine-sodium oleate, sodium stearate, cetyl trimethylammonium bromide CTAB, Trimethyllaurylammonium bromide DTAB, two-octadecyl dimethyl brometo de amonio or Triton X-100 Triton x-100.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127744A (en) * | 2011-11-28 | 2013-06-05 | 中国科学院金属研究所 | Method for transferring nano-particles from oil phase into aqueous phase |
| CN103374346A (en) * | 2012-04-13 | 2013-10-30 | 中国科学院高能物理研究所 | Method for improving water solubility of nanomaterial through surface modification and nanomaterial modified by method |
| CN106085432A (en) * | 2016-06-07 | 2016-11-09 | 中国科学院合肥物质科学研究院 | Organic-inorganic hybrid nanometer powder body of praseodymium doped lanthanum fluoride and its production and use |
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| WO2008048190A1 (en) * | 2006-10-17 | 2008-04-24 | National University Of Singapore | Upconversion fluorescent nano-structured material and uses thereof |
| CN101735816A (en) * | 2009-12-14 | 2010-06-16 | 孙家跃 | Dual mode luminous rare earth doped cerium fluoride nano crystal, preparation method and surface modification method thereof |
| CN101948694A (en) * | 2010-09-08 | 2011-01-19 | 吉林大学 | Rare earth upconversion nano crystal/silver difunctional composite nano material, preparation method thereof and application thereof in cancer detection and treatment |
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2011
- 2011-06-28 CN CN2011101758785A patent/CN102241968A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008048190A1 (en) * | 2006-10-17 | 2008-04-24 | National University Of Singapore | Upconversion fluorescent nano-structured material and uses thereof |
| CN101735816A (en) * | 2009-12-14 | 2010-06-16 | 孙家跃 | Dual mode luminous rare earth doped cerium fluoride nano crystal, preparation method and surface modification method thereof |
| CN101948694A (en) * | 2010-09-08 | 2011-01-19 | 吉林大学 | Rare earth upconversion nano crystal/silver difunctional composite nano material, preparation method thereof and application thereof in cancer detection and treatment |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127744A (en) * | 2011-11-28 | 2013-06-05 | 中国科学院金属研究所 | Method for transferring nano-particles from oil phase into aqueous phase |
| CN103127744B (en) * | 2011-11-28 | 2014-12-10 | 中国科学院金属研究所 | Method for transferring nano-particles from oil phase into aqueous phase |
| CN103374346A (en) * | 2012-04-13 | 2013-10-30 | 中国科学院高能物理研究所 | Method for improving water solubility of nanomaterial through surface modification and nanomaterial modified by method |
| CN106085432A (en) * | 2016-06-07 | 2016-11-09 | 中国科学院合肥物质科学研究院 | Organic-inorganic hybrid nanometer powder body of praseodymium doped lanthanum fluoride and its production and use |
| CN106085432B (en) * | 2016-06-07 | 2018-04-20 | 中国科学院合肥物质科学研究院 | Organic-inorganic hybrid nanometer powder of praseodymium doped lanthanum fluoride and its preparation method and application |
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