CN101851001A - Method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly - Google Patents
Method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly Download PDFInfo
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Abstract
The invention belongs to the technical field of nanometer and super molecules, in particular to a method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly. The method mainly comprises the following steps: firstly, synthesizing oil-soluble rare-earth nanometer particles modified by adamantine carboxylic acid; then, adding beta-cyclodextrin, and converting the beta-cyclodextrin into hydrophilic rare-earth nanometer particles through the strong super molecular effect with the adamantine; and carrying out centrifugal separation for washing away excrescent beta-cyclodextrin. The method has the advantages of easy acquisition of raw materials, low cost, simple process and fast and convenient reaction, the obtained rare-earth nanometer particles have good water solubility, and can be easily connected with other molecules through the cyclodextrin, and the functionalization of the rare-earth nanometer particles is realized.
Description
Technical field
The invention belongs to nanometer and supramolecule technical field, be specifically related to a kind of method of preparing water-soluble rare-earth nanometer particles by super molecular self assembly.
Background technology
Rare earth material (also claiming rare earth nano material) with nanoscale shows unique light, electricity, magnetic property because of it has unique 4f electronic structure, makes it at biomarker and imaging side mask great application value be arranged.
Typical preparation method comprises hydrothermal method (Li Y D, Nature 2005,437,121) or pyrolysis method (Yan C H, Journal ofthe American Chemical Society 2005,127,3260) or reverse microemulsion method (Lemyre J L et al, Chemistry ofMaterials, 2005,17,3040) etc.But the rare earth nano material of these method preparations is hydrophobic, and its surface mostly is the part that the oleic oil amine contains long alkyl chain, only is soluble in non-polar organic solvent.The method of the surface modification of having reported at present is coated silica or polymer materials, though the water-soluble active group that provides can be provided, complex process, the cost height, and have influence on the particle diameter control of rare earth nanometer particle.The part oxidation style of latest developments can effectively be controlled the particle diameter of rare-earth nanometer particles, but long reaction time, and also the part of failure surface, the cost height.Therefore it is very necessary developing the nanoparticle that New Policy comes synthesizing water-solubility.
Summary of the invention
The objective of the invention is to propose a kind of simple method of preparing water-soluble rare-earth nanometer particles by super molecular self assembly fast, the water soluble nanometer particles of this method preparation is easy to further modification simultaneously.
The method of the preparing water-soluble rare-earth nanometer particles by super molecular self assembly that the present invention proposes, it mainly is the oil-soluble rare-earth nanometer particles that first synthesizing adamantane carboxylic acid is modified, add beta-cyclodextrin then and be translated into hydrophilic rare-earth nanometer particles, concrete steps are as follows:
(1) preparation of the oil soluble rare-earth nanometer particles of adamantanecarboxylic acid modification:
The oil soluble rare-earth nanometer particles that described adamantanecarboxylic acid is modified is following three classes, and its rare-earth nanometer particles composition is respectively basic metal rare earth tetrafluoride MRF
4, rare earth oxide R
2O
3And rare earth trifluoride RF
3, reaction raw materials and proportioning are as follows:
A. basic metal rare earth tetrafluoride MRF
4, raw material is 1～5mmol trifluoroacetic acid rare-earth salts R (CF
3COO)
3, 1～10mmol trifluoroacetic acid an alkali metal salt M (CF
3COO) and the adamantanecarboxylic acid sodium of 1～14mmol;
B. rare earth oxide R
2O
3, raw material is the adamantanecarboxylic acid sodium of 1～5mmol hydration acetate rare-earth salts and 1～14mmol;
C. rare earth trifluoride RF
3, raw material is 1～5mmol trifluoroacetic acid rare-earth salts R (CF
3COO)
3Adamantanecarboxylic acid sodium with 1～14mmol;
Above-mentioned reaction raw materials is scattered in the mixed solvent of 10～100ml oleyl amine and octadecylene composition, the volume ratio of oleyl amine and octadecylene is V: V=1: 20～20: 1, be warming up to 90～120 ℃, 1～2h dewaters, be warming up to 250～320 ℃ then, constant temperature 1～2h, be cooled to room temperature again, add non-polar organic solvent, ultra-sonic dispersion, 10000～14000r/min, 8～12min high speed centrifugation separates, non-polar organic solvent washing solid 1～6 time ,-30～50 ℃ of following vacuum-dryings 2～50 hours, the oil soluble rare-earth nanometer particles that needing promptly to obtain with the adamantanecarboxylic acid modification.
(2) preparation of water-soluble rare-earth nanometer particles:
The rare-earth nanometer particles that the adamantanecarboxylic acid that step 1 is made is modified is scattered in the middle of water and the alcoholic acid mixed system with the concentration of 0.1g/L～10g/L, water and alcoholic acid volume ratio are V: V=1: 5～1: 20, in this solution, add the beta-cyclodextrin of 0.1～10mg/ml or the aqueous solution of its functionalization derivative then again, wherein, nanoparticle dispersion system is 10: 1～1: 10 with the volume ratio of the beta-cyclodextrin aqueous solution, stir 0.5min～60min, centrifugation goes out rare earth nano material, with ethanol or water washing 2～5 times,-30～50 ℃ of following vacuum-dryings 2～50 hours, the title complex that promptly makes with diamantane and β～cyclodextrin was the water-solubility rare-earth nano material of part.
Trifluoroacetic acid rare-earth salts R (CF described in the present invention
3COO)
3, be one or more the mixture that comprises in the trifluoroacetate of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba).
Hydration acetate rare-earth salts described in the present invention is one or more the mixture that comprises in the hydration acetate rare-earth salts of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y).
Trifluoroacetic acid an alkali metal salt M (CF described in the present invention
3COO), be CF
3COOLi, CF
3COONa or CF
3COOK.
Non-polar organic solvent described in the present invention is hexanaphthene, normal hexane, normal heptane, chloroform or benzene.
The derivative of the functionalization beta-cyclodextrin described in the present invention is amino functional derivative, carboxyl-functional derivative or the mercapto-functionalized derivative of 2,4,6 hydroxyls.
Adamantanecarboxylic acid described in the present invention is adamantanecarboxylic acid or adamantane acetic acid.
The preparation method who pretends the water-solubility rare-earth nano material that firmly develops who passes through adamantanecarboxylic acid and beta-cyclodextrin that the present invention proposes, its advantage is that raw material is easy to get, with low cost, technology is simple, reaction is quick, simultaneously because can prepare the water-solubility rare-earth nano material that the surface has the rich functions group to introducing the functionalization group on the beta-cyclodextrin.
Description of drawings
The NaYF that Fig. 1 is hydrophobic
4The transmission electron microscope photo of rare earth nano material.
The water-soluble NaYF of Fig. 2
4The transmission electron microscope photo of rare earth nano material.
Fig. 3 water-soluble (dotted line) and hydrophobic (solid line) NaYF
4The infrared spectra of rare earth nano material.
The NaYF of Fig. 4 amino functional
4: the Yb/Er rare earth nano material, measure the absorption curve of amino density, the absorption curve of sample (solid line), the absorption curve of standard absorption reference (dotted line).
The NaYF of Fig. 5 amino functional
4: Yb/Er rare earth nano material, the curve of absorption intensity and amino density match, sample spot (hollow dots), standard reference point (solid dot).
(dotted line) that Fig. 6 is hydrophobic and water-soluble (solid line) NaYF
4: the fluorescence spectrum figure of Yb/Er rare earth nano material under the 980nm laser apparatus excites.
(dotted line) that Fig. 7 is hydrophobic and water-soluble (solid line) NaGdF
4: the fluorescence spectrum figure of Yb/Tm rare earth nano material under the 980nm laser apparatus excites.
(dotted line) that Fig. 8 is hydrophobic and water-soluble (solid line) Y
2O
3: the fluorescence spectrum figure of Ce/Tb rare earth nano material under the 254nm laser apparatus excites.
Fig. 9 Y
2O
3: the Ce/Tb rare earth nano material by with the picture of beta-cyclodextrin self-assembly phase transition.
Figure 10 Y
2O
3: the Ce/Tb rare earth nano material by with beta-cyclodextrin self-assembly phase transition after chloroform mutually (dotted line) and water (solid line) luminous intensity over time.
Embodiment
Below the present invention will be further described by specific embodiment, but the present invention is not constituted any limitation.
Embodiment 1: prepare water-soluble NaYF
4Nano particle.
With Y (CF
3COO)
32mmol adds the sodium trifluoroacetate of 4mmol and the adamantane acetic acid sodium of 7mmol, is scattered in the central (V: V=1: 7) of mixed solvent that 20ml oleyl amine and octadecylene are formed, be warming up to 110 ℃, the 1h that dewaters is warming up to 320 ℃, constant temperature 1h then, be cooled to room temperature, add hexanaphthene, ultra-sonic dispersion, 14000r/min, the 10min centrifugation, hexanaphthene washing 3 times.Vacuum-drying at room temperature 12 hours, what needing promptly to obtain is the oil soluble rare-earth nanometer particles of part with the adamantane acetic acid.The rare earth nano material that will have an adamantane acetic acid root is scattered in (V: V=1: 10) in the middle of water and the alcoholic acid mixed system with the concentration of 1g/L, the isopyknic beta-cyclodextrin aqueous solution that in solution, adds 1mg/ml then, stir 2min, centrifugation goes out rare earth nano material, wash with water 3 times, vacuum-drying at room temperature 12 hours, the title complex with diamantane and beta-cyclodextrin that needing promptly to obtain is the water-solubility rare-earth nano material of part.The pattern of particle and particle diameter adopt determination of transmission electron microscopy, and typical consequence is seen shown in Figure 1, and sample diameter is about 10～20nm, convert almost no change of later particle diameter of water soluble particle and pattern to, see Fig. 2.The infrared spectrogram of this material is seen Fig. 3, and water-soluble sample is at 1160cm
～1The absorption at place is corresponding to the asymmetric stretch shock absorbing of C-O-C on the cyclodextrin, and 1081 and 1029cm
～1The place illustrates the existence of cyclodextrin in the water-soluble sample corresponding to the flexible shock absorbing of C-O and C-C.And 1640cm
～1The place absorbs the flexible vibrations corresponding to C=O, proves the surface of adamantane acetic acid root at rare earth ion.The NaYF that makes
4Can be good at being dispersed in the water.Sodium trifluoroacetate is replaced by trifluoroacetic acid potassium or trifluoroacetic acid lithium, and other conditions are constant, can make corresponding alkali metal rare earth tetrafluoride.
Embodiment 2: prepare water-soluble NaYF
4: 20mol%Yb, 2%mol Er nano particle.
With Y (CF
3COO)
30.78mmol, Yb (CF
3COO)
30.2mmol, Er (CF
3COO)
30.02mmol, add the sodium trifluoroacetate of 2mmol and the adamantanecarboxylic acid sodium of 7mmol, be scattered in the central (V: V=2: 7) of mixed solvent that 30ml oleyl amine and octadecylene are formed, be warming up to 100 ℃, the 2h that dewaters is warming up to 330 ℃, constant temperature 1.5h then, be cooled to room temperature, add hexanaphthene, ultra-sonic dispersion, 12000r/min, the 8min centrifugation, hexanaphthene washing 2 times.Vacuum-drying at room temperature 10 hours, what needing promptly to obtain is the oil soluble rare-earth nanometer particles of part with the adamantane acetic acid.The rare earth nano material that will have an adamantane acetic acid root is scattered in (V: V=10: 1) in the middle of water and the alcoholic acid mixed system with the concentration of 0.1g/L, the isopyknic amino functional beta-cyclodextrin aqueous solution that in solution, adds 3mg/ml then, stir 5min, centrifugation goes out rare earth nano material, wash with water 2 times,-30 ℃ of following vacuum-dryings 24 hours, the title complex with diamantane and amino beta-cyclodextrin that needing promptly to obtain was the water-solubility rare-earth nano material of part.Sample is easy to be dispersed in the water, and the active group on surface is amino.When with 980nm laser during as excitaton source, present typical green glow (520～570nm) and ruddiness (650～670nm) go up switching emission, see Fig. 6, correspond respectively to
2H
11/2With
4S
3/2Arrive
4I
15/2,
4F
9/2Arrive
4I
15/2Transition.And measured amino density by the Fmocc method and seen Fig. 4 and Fig. 5, its amino density is 4.7 ± 0.8 * 10
-5Mol/g.
Embodiment 3: prepare water-soluble NaGdF
4: 20mol%Yb, 1%mol Tm nano particle.
With Gd (CF
3COO)
33.18mmol, Yb (CF
3COO)
30.8mmol, Tm (CF
3COO)
30.04mmol, add the sodium trifluoroacetate of 10mmol and the adamantane acetic acid sodium of 14mmol, be scattered in the central (V: V=7: 1) of mixed solvent that 40ml oleyl amine and octadecylene are formed, be warming up to 80 ℃, the 1.5h that dewaters is warming up to 310 ℃, constant temperature 1h then, be cooled to room temperature, add hexanaphthene, ultra-sonic dispersion, 13000r/min, the 10min centrifugation, hexanaphthene washing 3 times.Vacuum-drying at room temperature 12 hours, what needing promptly to obtain is the oil soluble rare-earth nanometer particles of part with the adamantane acetic acid.The rare earth nano material that will have an adamantane acetic acid root is scattered in (V: V=1: 10) in the middle of water and the alcoholic acid mixed system with the concentration of 5g/L, the isopyknic carboxyl-functional beta-cyclodextrin aqueous solution that in solution, adds 5mg/ml then, stir 60min, centrifugation goes out rare earth nano material, wash with water 3 times, vacuum-drying at room temperature 12 hours, the title complex with diamantane and beta-cyclodextrin that needing promptly to obtain is the water-solubility rare-earth nano material of part.Surface active groups is a carboxyl.Under the exciting of 980nm laser apparatus, this material presents 4 emission bands and sees Fig. 7 in water, be respectively two bluenesss emission band (440～500nm) corresponding to
1D
2Arrive
3F
4,
1G
4Arrive
3H
6Transition; Red color development band a little less than in the of one (635～665nm) corresponding with
1G
4Arrive
3F
4Transition; Extremely strong near infrared emission band (755～840nm) corresponding to
3H
4Arrive
3H
6Transition.
Embodiment 4: prepare water-soluble Y
2O
3: 15mol%Ce, 5mol%Tb nano particle.
Yttium acetate 1.6mmol is closed in water intaking, hydration cerous acetate 0.3mmol and hydration acetate terbium 0.1mmol, the adamantane acetic acid sodium of adding 8mmol, (V: V=6: 1), be warming up to 110 ℃, 1h dewaters in the middle of being scattered in the mixed solvent that 20ml oleyl amine and octadecylene form, be warming up to 320 ℃ then, constant temperature 1h is cooled to room temperature, adds hexanaphthene, ultra-sonic dispersion, 14000r/min, 10min centrifugation, hexanaphthene washing 3 times.Vacuum-drying at room temperature 12 hours, what needing promptly to obtain is the oil soluble rare-earth nanometer particles of part with the adamantane acetic acid.The rare earth nano material that will have an adamantane acetic acid root is scattered in (V: V=1: 10) in the middle of water and the alcoholic acid mixed system with the concentration of 1g/L, the mercapto-functionalized beta-cyclodextrin aqueous solution that in solution, adds the two volumes of 1mg/ml then, stir 10min, centrifugation goes out rare earth nano material, wash with water 3 times, vacuum-drying at room temperature 12 hours, the title complex with diamantane and beta-cyclodextrin that needing promptly to obtain is the water-solubility rare-earth nano material of part.Active group is a sulfydryl.When with the 254nm UV-light as excitaton source, its spectrum has represented Tb
3+The typical emission peak of ionic is seen Fig. 8, they between 450～650nm, corresponding to
5D
4Arrive
7F
J(J=6-3).And measured the oil soluble particle by with beta-cyclodextrin by seeing Fig. 9 and Figure 10 over time with the luminous situation of water mutually at chloroform after the role of phase transfer, within 20 seconds, have 95% nano material to transfer to water approximately.
Embodiment 5: prepare water-soluble LaF
3: the 10mol%Eu nano particle.
Get trifluoroacetic acid lanthanum 1.8mmol, trifluoroacetic acid europium 0.2mmol, the adamantane acetic acid sodium of adding 14mmol, (V: V=1: 7), be warming up to 110 ℃, 1h dewaters in the middle of being scattered in the mixed solvent that 20ml oleyl amine and octadecylene form, be warming up to 320 ℃ then, constant temperature 1h is cooled to room temperature, adds hexanaphthene, ultra-sonic dispersion, 14000r/min, 10min centrifugation, hexanaphthene washing 3 times.40 ℃ of following vacuum-dryings 5 hours, what needing promptly to obtain was the oil soluble rare-earth nanometer particles of part with the adamantane acetic acid.The rare earth nano material that will have an adamantane acetic acid root is scattered in (V: V=1: 10) in the middle of water and the alcoholic acid mixed system with the concentration of 10g/L, the long-pending beta-cyclodextrin aqueous solution of decaploid that in solution, adds 1mg/ml then, stir 15min, centrifugation goes out rare earth nano material, wash with water 3 times, vacuum-drying at room temperature 12 hours, the title complex with diamantane and beta-cyclodextrin that needing promptly to obtain is the water-solubility rare-earth nano material of part.
Claims (5)
1. the method for a preparing water-soluble rare-earth nanometer particles by super molecular self assembly, it is characterized in that it being the oil-soluble rare-earth nanometer particles that first synthesizing adamantane carboxylic acid is modified, add beta-cyclodextrin then and be translated into hydrophilic rare-earth nanometer particles, concrete steps are as follows:
(1) preparation of the oil soluble rare-earth nanometer particles of adamantanecarboxylic acid modification:
The oil soluble rare-earth nanometer particles that described adamantanecarboxylic acid is modified is following three classes, and its rare-earth nanometer particles composition is respectively basic metal rare earth tetrafluoride MRF
4, rare earth oxide R
2O
3And rare earth trifluoride RF
3, reaction raw materials and proportioning are as follows respectively:
A. basic metal rare earth tetrafluoride MRF
4, its raw material is 1～5mmol trifluoroacetic acid rare-earth salts R (CF
3COO)
3, 1～10mmol trifluoroacetic acid an alkali metal salt M (CF
3COO) and the adamantanecarboxylic acid sodium of 1～14mmol;
B. rare earth oxide R
2O
3, its raw material is the adamantanecarboxylic acid sodium of 1～5mmol hydration acetate rare-earth salts and 1～14mmol;
C. rare earth trifluoride RF
3, its raw material is 1～5mmol trifluoroacetic acid rare-earth salts R (CF
3COO)
3Adamantanecarboxylic acid sodium with 1～14mmol;
Above-mentioned reaction raw materials is scattered in the mixed solvent of 10～100ml oleyl amine and octadecylene composition, the volume ratio of oleyl amine and octadecylene is V: V=1: 20～20: 1, system is warming up to 90～120 ℃, 1～2h dewaters, be warming up to 250～320 ℃ then, constant temperature 1～2h, after being cooled to room temperature, add non-polar organic solvent, ultra-sonic dispersion, centrifugation is washed solid 1～6 time with non-polar organic solvent again,-30～50 ℃ of following vacuum-dryings 2～50 hours, the oil soluble rare-earth nanometer particles that needing promptly to obtain with the adamantanecarboxylic acid modification;
(2) preparation of water-soluble rare-earth nanometer particles:
The rare-earth nanometer particles that the adamantanecarboxylic acid that step 1 is made is modified is scattered in the middle of water and the alcoholic acid mixed system with the concentration of 0.1g/L～10g/L, water and alcoholic acid volume ratio are V: V=1: 5～1: 20, in this solution, add the beta-cyclodextrin of 0.1～10mg/ml or the aqueous solution of its functionalization derivative then again, wherein, nanoparticle dispersion system is 10: 1～1: 10 with the volume ratio of the beta-cyclodextrin aqueous solution, stir 0.5min～60min, centrifugation goes out rare earth nano material, with ethanol or water washing 2～5 times,-30～50 ℃ of following vacuum-dryings 2～50 hours, promptly making with the title complex of diamantane and beta-cyclodextrin was the water-soluble rare-earth nanometer particles material of part;
Wherein,
Described trifluoroacetic acid an alkali metal salt M (CF
3COO) be CF
3COOLi, CF
3COONa or CF
3COOK;
Described adamantanecarboxylic acid is adamantanecarboxylic acid or adamantane acetic acid.
2. the method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly according to claim 1 is characterized in that described trifluoroacetic acid rare-earth salts R (CF
3COO)
3, be one or more the mixture that comprises in the trifluoroacetate of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc), yttrium (Y), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).
3. the method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly according to claim 1, it is characterized in that described hydration acetate rare-earth salts, is one or more the mixture that comprises in the hydration acetate rare-earth salts of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), scandium (Sc) and yttrium (Y).
4. the method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly according to claim 1 is characterized in that described non-polar organic solvent is hexanaphthene, normal hexane, normal heptane, chloroform or benzene.
5. the method for preparing water-soluble rare-earth nanometer particles by super molecular self assembly according to claim 1, the derivative that it is characterized in that described functionalization beta-cyclodextrin is amino functional derivative, carboxyl-functional derivative or the mercapto-functionalized derivative of 2,4,6 hydroxyls.
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|---|---|---|---|---|
| CN105462338A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Alpha-cyclodextrin and gold complex as well as application of alpha-cyclodextrin and gold complex in microcontact printing technology |
| CN111071991A (en) * | 2020-01-03 | 2020-04-28 | 大连民族大学 | Environment-friendly fluoride nano-material large-scale preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544372A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Production method of self-assemble rare earth nanometer membrane on glass substrate surface |
| WO2006073416A1 (en) * | 2004-03-30 | 2006-07-13 | University Of Florida Research Foundation, Inc. | Rare earth oxide nanocrystals and methods of forming |
| US20070092423A1 (en) * | 2005-10-08 | 2007-04-26 | Taeg-Hwan Hyeon | Process for producing cerium oxide nanocrystals |
| CN101121543A (en) * | 2007-08-02 | 2008-02-13 | 复旦大学 | Process for preparing water-soluble rare earth nano material |
| CN101289216A (en) * | 2008-06-05 | 2008-10-22 | 复旦大学 | Method for synthesizing microemulsion of water-solubility rare-earth nano material |
-
2010
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544372A (en) * | 2003-11-27 | 2004-11-10 | 上海交通大学 | Production method of self-assemble rare earth nanometer membrane on glass substrate surface |
| WO2006073416A1 (en) * | 2004-03-30 | 2006-07-13 | University Of Florida Research Foundation, Inc. | Rare earth oxide nanocrystals and methods of forming |
| US20070092423A1 (en) * | 2005-10-08 | 2007-04-26 | Taeg-Hwan Hyeon | Process for producing cerium oxide nanocrystals |
| CN101121543A (en) * | 2007-08-02 | 2008-02-13 | 复旦大学 | Process for preparing water-soluble rare earth nano material |
| CN101289216A (en) * | 2008-06-05 | 2008-10-22 | 复旦大学 | Method for synthesizing microemulsion of water-solubility rare-earth nano material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105462338A (en) * | 2015-12-28 | 2016-04-06 | 广西师范学院 | Alpha-cyclodextrin and gold complex as well as application of alpha-cyclodextrin and gold complex in microcontact printing technology |
| CN111071991A (en) * | 2020-01-03 | 2020-04-28 | 大连民族大学 | Environment-friendly fluoride nano-material large-scale preparation method |
| CN111071991B (en) * | 2020-01-03 | 2021-07-20 | 大连民族大学 | Environment-friendly fluoride nano-material large-scale preparation method |
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