CN111187611A - Water-soluble nano luminescent material and preparation method thereof - Google Patents

Water-soluble nano luminescent material and preparation method thereof Download PDF

Info

Publication number
CN111187611A
CN111187611A CN201911250717.0A CN201911250717A CN111187611A CN 111187611 A CN111187611 A CN 111187611A CN 201911250717 A CN201911250717 A CN 201911250717A CN 111187611 A CN111187611 A CN 111187611A
Authority
CN
China
Prior art keywords
luminescent material
nano luminescent
water
soluble
soluble nano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201911250717.0A
Other languages
Chinese (zh)
Other versions
CN111187611B (en
Inventor
范黎
王巧峰
刘文超
朱笑生
王超丽
庞翠
吴剑维
田倚
樊浩
胡锦伟
戴磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fourth Military Medical University FMMU
Original Assignee
Fourth Military Medical University FMMU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fourth Military Medical University FMMU filed Critical Fourth Military Medical University FMMU
Priority to CN201911250717.0A priority Critical patent/CN111187611B/en
Publication of CN111187611A publication Critical patent/CN111187611A/en
Application granted granted Critical
Publication of CN111187611B publication Critical patent/CN111187611B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • 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
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention discloses a water-soluble nano luminescent material and a preparation method thereof, and the preparation method specifically comprises the following steps: preparing cyclohexane solution of oil-soluble nano luminescent material; dissolving the aminoimidazole ionic liquid in a mixed solution of acetone and water to obtain an aminoimidazole ionic solution; mixing amino ionic liquid and cyclohexane solution of nano luminescent material according to the mass of the nano luminescent material: mixing amino imidazole in a mass ratio of 20: 1-2: 1; reacting for 4-24 h at room temperature, and obtaining the precipitate which is the water-soluble nano luminescent material. The water-soluble nano luminescent particles modified by the amino imidazole ionic liquid have good stability in water, and the results of spectroscopic analysis show that the water-soluble nano luminescent particles have extremely high light yield, and compared with the oil-soluble nano luminescent particles, the light yield loss is within 10 percent, thereby providing a luminescent material basis with good biocompatibility for subsequent imaging and treatment experiments.

Description

Water-soluble nano luminescent material and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and relates to a water-soluble nano luminescent material, a preparation method and application thereof.
Background
Due to its excellent new luminescence energy and its wide application in the fields of chemical sensors, biomarkers and medical imaging, nano luminescent materials are becoming an important branch of new functional materials. The nano luminescent material is a luminescent material with the particles of the matrix being 1-100 nm.
The light conversion efficiency of the nano luminescent material in an organic solvent is high, but the nano luminescent material in an aqueous solution has great attenuation, so that the light yield of a water-soluble luminescent center is obviously lower than that of an oil-soluble luminescent center under the excitation of the same X-ray dosage. In the field of biomarkers, an organic solvent cannot be used to directly contact with the body, so the solubility of the nano luminescent centers in an aqueous solution must be enhanced in order to be better applied to the body.
At present, various methods for water-soluble modification of nano luminescent materials exist, for example, silicon is used as a water-soluble shell, which greatly improves the solubility of a nano luminescent center in water, but obviously reduces the light yield of nano luminescent particles, so that the biological application of the nano luminescent particles is limited. Therefore, how to better perform water-soluble modification on the nano luminescence center and maintain the light conversion efficiency to a greater extent becomes the focus of research.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for modifying the hydrophilicity of a nano luminescent material, which solves the problems that the light yield of nano luminescent particles is obviously reduced and the biological application of the nano luminescent particles is limited by the existing water-soluble modification mode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a water-soluble nano luminescent material comprises the following steps:
coating oleic acid or oil ammonia on the surface of the nano luminescent particles to form an oil-soluble nano luminescent material, and adding the oil-soluble nano luminescent material into a cyclohexane solution to form a cyclohexane solution of the nano luminescent material;
dissolving aminoimidazole in a mixed solution of acetone and water to obtain an aminoimidazole ion solution;
mixing the aminoimidazole ion solution with a cyclohexane solution of the nano luminescent material according to the mass of the nano luminescent material: mixing amino imidazole in a mass ratio of 20: 1-2: 1; reacting for 4-24 h at room temperature, and obtaining the precipitate which is the water-soluble nano luminescent material.
Specifically, the nano luminescent material is a lanthanum fluoride nano luminescent material.
Specifically, the acetone and the water are mixed according to the volume ratio of 2: 1.
Specifically, the concentration of the nano luminescent material in the cyclohexane solution of the nano luminescent material is 1-10 mg/mL, and the concentration of the amino ionic liquid is 1 ug/mL-1 mg/mL.
The invention also discloses the water-soluble nano luminescent material obtained by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the nano luminescent particles are modified by the amino imidazole ionic liquid, the obtained water-soluble nano luminescent material has good stability in water, and the spectroscopic analysis result shows that the water-soluble nano luminescent particles keep extremely high light yield, and compared with the oil-soluble nano luminescent particles, the light yield loss is within 10 percent, so that a luminescent material base with good biocompatibility is provided for subsequent imaging and treatment experiments.
Drawings
FIG. 1 is NaGdF in example 14A spectrum comparison graph before and after the 15 percent Tb nano luminescent material is modified by the amino imidazole ionic liquid;
FIG. 2 is example 2NaLuF4A spectrum comparison graph before and after the 15 percent Tb nano luminescent material is modified by the amino imidazole ionic liquid;
FIG. 3 is NaGdF in comparative example 14A spectrum comparison graph before and after the 15% Tb nano luminescent material is modified by PEG;
FIG. 4 is NaLuF in comparative example 24A spectrum comparison chart before and after the 15% Tb nano luminescent material is modified by PEG.
FIG. 5 is NaGdF415% Tb-IL1-MC540 water-soluble nano luminescent particles (1mg/mL) under different X-ray doses;
FIG. 6 shows NaGdF at different concentrations4A luminous intensity chart of 15% Tb-IL1-MC540 water-soluble nano luminous particles under the X-ray dose of 1.0 Gy;
FIG. 7 is NaLuF415% Tb-IL1-MC540 water-soluble nano luminescent particles (1mg/mL) under different X-ray doses;
FIG. 8 shows different concentrations of NaLuF 415% Tb-IL1-MC540 water-soluble nano luminescent particles under the X-ray dose of 0.1 Gy.
Detailed Description
The invention discloses a preparation method of a water-soluble nano luminescent material, which comprises the following steps:
step 1: the method comprises the following steps of coating oleic acid or oil ammonia on the surface of a nano luminescent material to form an oil-soluble nano luminescent material, and adding the oil-soluble nano luminescent material into a cyclohexane solution to form a cyclohexane solution of the oil-soluble nano luminescent material, wherein the concentration of the nano luminescent material in the cyclohexane solution of the nano luminescent material is preferably 1-10 mg/mL; in the inventionThe nano-luminescent material is a lanthanum fluoride nano-luminescent material, such as NaGdF listed in the following examples415% of Tb or NaLuF4:15％Tb。
Dissolving the aminoimidazole ionic liquid in a mixed solution of acetone and water to obtain an aminoimidazole ionic solution; according to the invention, preferably, the acetone and the water are mixed according to the volume ratio of 2: 1; preferably, the concentration of the amino ionic liquid is 1 ug/mL-1 mg/mL.
The aminoimidazole ionic liquid (hereinafter referred to as "IL 1") used in the invention can be purchased from the market, and has the structure:
Figure RE-GDA0002421404390000041
step 2: mixing the aminoimidazole ionic liquid with a cyclohexane solution of the nano luminescent material according to the mass of the nano luminescent material: mixing amino imidazole in a mass ratio of 20: 1-2: 1; reacting for 4-24 h at room temperature, and obtaining the precipitate which is the water-soluble nano luminescent material.
The aminoimidazole ions are attached to the surface of the nano luminescent particles to form the water-soluble nano luminescent material. The nano luminescent material is coupled with a photosensitizer MC540, and a constructed coupling system has high singlet oxygen generation amount excited by low dose, thereby providing a material basis for realizing low-dose X-ray excitation photodynamic therapy.
In the invention, the surface of the oil-soluble nano luminescent material is coated with oleic acid, is a negative charge carboxyl surface, can react with the positive charge of an imidazole ring of ionic liquid, and coats the ionic liquid on the surface of the nano luminescent material through electrostatic interaction to endow the nano luminescent material with water solubility. Meanwhile, in an aqueous solution, positive charges generated by protonation of amino groups can also perform electrostatic interaction with oleic acid carboxyl negative ions, so that the ionic liquid and the nano luminescent material are combined more tightly. The selected amino imidazole ionic liquid has small molecular weight, is tightly combined with the nano luminescent material, and forms a small hydration layer, so the method has great protection effect on the light yield of the nano luminescent material.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1
Step 1, to oil-soluble NaGdF 415% Tb nano luminescent material is fixed to 10mL, 0.5mL is taken out and dried and weighed by a differential method, and the concentration of the nano luminescent material in the whole solution is calculated by taking mg/mL as a unit. Preparing 10mg/mL nano luminescent material cyclohexane solution;
the amino ionic liquid adopted in this example is an aminoimidazole ionic solution, and the amino ionic liquid IL1 is weighed and dissolved in acetone: water in a 2:1 volume ratio solution, a 1mg/mL IL1 solution was prepared.
Step 2, mixing the IL1 solution and the cyclohexane solution (10mg/mL) of the nano luminescent material in a volume ratio of 1: 2 (namely the mass ratio of the nano luminescent material to the aminoimidazole is 20: 1), and stirring for 16 hours at room temperature by magnetic force. After completion of the reaction, the mixture was centrifuged at 12000rpm for 20 minutes), and the supernatant was discarded. Dispersing the precipitate in 4mL of water, and washing for three times to obtain the water-soluble nano luminescent particles.
The spectrum of the water-soluble nano luminescent particle prepared in this example is shown in fig. 1. The nanoparticle concentration was 1mg/mL, and the X-ray irradiation dose was 80keV, 0.5 mA.
The water-soluble nano luminescent particles obtained in the embodiment are coupled with a photosensitizer MC540 to construct NaGdF4FIG. 5 shows the results of examining the singlet oxygen generation rate by the fluorescent intensity of SOSG-EP using the SOSG method under different X-ray excitation conditions, i.e., at different coupling system concentrations, using 15% Tb-IL1-MC540 coupled system.
Example 2
This example differs from example 1 in that: the nano luminescent material is NaLuF4:15％Tb。
The spectrum of the water-soluble nano luminescent particle prepared in this example is shown in fig. 2.
The water-soluble nano luminescent particles obtained in the embodiment are coupled with a photosensitizer MC540 to construct NaLuF 415% Tb-IL1-MC540 coupled system, under different X-ray excitation conditions, i.e. different concentrations of coupled system are expressed as SThe OSG method was conducted to examine the singlet oxygen generation rate based on the fluorescence intensity of SOSG-EP. The results are shown in FIG. 2.
Example 3
The difference between this example and example 1 is: the mass ratio of the nano luminescent material to the aminoimidazole is 2: 1. The water-soluble nano luminescent particles prepared in the embodiment are coupled with a photosensitizer MC540 to construct NaGdF4The singlet oxygen generation rate was examined by the SOSG method using 15% Tb-IL1-MC540 coupled system under different X-ray excitation conditions, i.e., different concentrations of coupled system, based on the fluorescence intensity of SOSG-EP, and the results were found to be slightly lower than that of example 1, but still higher than that of the conventional modification method.
Comparative example 1
The comparative example adopts a PEG water-soluble modification method to modify the nano luminescent particles, and the specific method comprises the following steps:
step 1, to oil-soluble NaGdF 415 percent Tb nano luminescent material is subjected to constant volume to 5mL, 0.3mL is taken out and dried and weighed by a differential method, and the concentration of the nano luminescent material in the whole solution is calculated by taking mg/mL as a unit;
step 2, completely drying the solvent, adding about 5mL of Dichloromethane (DCM), and adding stirring magnetons;
step 3, according to the nanometer luminescent material and PEG-NH2Weighing PEG according to the mass ratio of 1:6, and dissolving the PEG in about 5ml of EDCM;
step 4, introducing argon gas above the liquid level of the solution in the step 2 and the solution in the step 3 for 1min respectively to remove air in the container;
step 5, quickly pouring the solution in the step 3 into the solution in the step 2, and then introducing argon below the liquid level for 5min to remove air in the solution; rapidly sealing the container, and stirring at 200rpm for 48 h;
step 6, drying the solution, adding 6mL of deionized water, centrifuging at 12000rpm for 30min, removing the supernatant, and dissolving the precipitate in 10mL of deionized water to obtain PEG-modified NaGdF4:15％Tb。
The spectrum of the water-soluble nano-sized luminescent particles prepared in this comparative example is shown in fig. 3.
Comparative example 2
Book pairThe ratio differs from comparative example 1 in that: the nano luminescent material is NaLuF4:15％Tb。
The spectrum of the water-soluble nano-sized luminescent particles prepared in this comparative example is shown in fig. 4.
By combining examples 1-2 and comparative examples 1-2, it is found that, with the PEG water-soluble modification method as a reference, as shown in fig. 1, the light yield of the water-soluble nano luminescent particles prepared by using the aminoimidazole ionic liquid as the water-soluble modification ligand is significantly improved compared with PEG modification.
As shown in FIG. 5, the nano luminescent material modified by the amino imidazole ionic liquid is coupled with a photosensitizer MC540, and the constructed coupling system has high singlet oxygen generation amount excited by low dose, thereby providing a material basis for realizing low-dose X-ray excitation photodynamic therapy.

Claims (5)

1. A preparation method of a water-soluble nano luminescent material is characterized by comprising the following steps:
coating oleic acid or oil ammonia on the surface of the nano luminescent particles to form an oil-soluble nano luminescent material, and adding the oil-soluble nano luminescent material into a cyclohexane solution to form a cyclohexane solution of the nano luminescent material;
dissolving aminoimidazole in a mixed solution of acetone and water to obtain an aminoimidazole ion solution;
mixing the aminoimidazole ion solution with a cyclohexane solution of the nano luminescent material according to the mass of the nano luminescent material: mixing amino imidazole in a mass ratio of 20: 1-2: 1; reacting for 4-24 h at room temperature, and obtaining the precipitate which is the water-soluble nano luminescent material.
2. The method of claim 1, wherein the electroluminescent nanoparticles are lanthanum fluoride electroluminescent nanoparticles.
3. The method of claim 1, wherein the acetone and water are mixed in a volume ratio of 2: 1.
4. The method for preparing the water-soluble nano luminescent material according to claim 1, wherein the concentration of the nano luminescent material in the cyclohexane solution of the nano luminescent material is 1-10 mg/mL, and the concentration of the amino ionic liquid is 1 ug/mL-1 mg/mL.
5. A water-soluble nano luminescent material obtained by the preparation method as claimed in any one of claims 1 to 4.
CN201911250717.0A 2019-12-09 2019-12-09 Water-soluble nano luminescent material and preparation method thereof Active CN111187611B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911250717.0A CN111187611B (en) 2019-12-09 2019-12-09 Water-soluble nano luminescent material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911250717.0A CN111187611B (en) 2019-12-09 2019-12-09 Water-soluble nano luminescent material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111187611A true CN111187611A (en) 2020-05-22
CN111187611B CN111187611B (en) 2023-07-28

Family

ID=70703203

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911250717.0A Active CN111187611B (en) 2019-12-09 2019-12-09 Water-soluble nano luminescent material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111187611B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080245186A1 (en) * 2005-05-13 2008-10-09 University Of Rochester Synthesis of nano-materials in ionic liquids
CN101471166A (en) * 2007-12-28 2009-07-01 中国科学院兰州化学物理研究所 Method for modifying magnetic nano particle by functionalized ionic liquid
CN103923638A (en) * 2014-04-21 2014-07-16 河北工业大学 Water-soluble high-efficiency rare-earth luminescent material and preparation method thereof
CN105776306A (en) * 2016-02-02 2016-07-20 合肥工业大学 Surface modification method of sub-10 nanometer NaGdF4 nanocrystalline and application of method to nuclear magnetic resonance
CN106281307A (en) * 2016-07-18 2017-01-04 天津泰达环保有限公司 A kind of flexible chitosan light-emitting film containing rare earth and preparation method thereof
CN108580923A (en) * 2018-04-16 2018-09-28 中国科学院兰州化学物理研究所 A kind of method that glyoxaline cation modification carbon quantum dot auxiliary prepares nanogold

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080245186A1 (en) * 2005-05-13 2008-10-09 University Of Rochester Synthesis of nano-materials in ionic liquids
CN101471166A (en) * 2007-12-28 2009-07-01 中国科学院兰州化学物理研究所 Method for modifying magnetic nano particle by functionalized ionic liquid
CN103923638A (en) * 2014-04-21 2014-07-16 河北工业大学 Water-soluble high-efficiency rare-earth luminescent material and preparation method thereof
CN105776306A (en) * 2016-02-02 2016-07-20 合肥工业大学 Surface modification method of sub-10 nanometer NaGdF4 nanocrystalline and application of method to nuclear magnetic resonance
CN106281307A (en) * 2016-07-18 2017-01-04 天津泰达环保有限公司 A kind of flexible chitosan light-emitting film containing rare earth and preparation method thereof
CN108580923A (en) * 2018-04-16 2018-09-28 中国科学院兰州化学物理研究所 A kind of method that glyoxaline cation modification carbon quantum dot auxiliary prepares nanogold

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
乔海霞: "巯基功能化离子液体对CdSe量子点稳定性影响的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Also Published As

Publication number Publication date
CN111187611B (en) 2023-07-28

Similar Documents

Publication Publication Date Title
CN105903016B (en) A kind of preparation method of the nuclear shell structure drug carrier of the near infrared light excitation light-operated drug release of supermolecule valve
Jain et al. Synthesis and characterization of (3-Aminopropyl) trimethoxy-silane (APTMS) functionalized Gd2O3: Eu3+ red phosphor with enhanced quantum yield
CN107158378B (en) Copper-manganese sulfide protein composite nanoparticle for photothermal effect and preparation method thereof
CN111253931B (en) Up-conversion core-shell-based covalent organic framework material, and preparation method and application thereof
CN108456518A (en) A kind of rare-earth nanometer particles of intense red fluorescence and preparation method thereof and the application in cell imaging
CN106318375A (en) Preparing method of reinforced gold nanoparticle cluster fluorescence system based on surface plasma
CN114806544A (en) Luminescent nanoparticle based on activated alkyne click reaction and preparation method thereof
CN114276808B (en) Near-infrared two-region luminescence enhanced rare earth nanomaterial, preparation method thereof and biological imaging application thereof
CN109498807B (en) Up-conversion nanoparticle oxygen-independent photodynamic diagnosis and treatment probe and preparation method thereof
CN105602566B (en) A kind of rear-earth-doped NaGdF4Upper conversion nano crystalline substance and preparation method thereof
WO2015156385A1 (en) Carbon nanohorn for encapsulating and carrying boron compound on outer wall, and method for producing carbon nanohorn
CN111187611A (en) Water-soluble nano luminescent material and preparation method thereof
CN110559438B (en) Photothermal and photodynamic diagnosis and treatment integrated reagent guided by nuclear magnetic resonance imaging and preparation method thereof
CN101962532B (en) Method for synthesizing polyacrylic acid (PAA)-coated rare earth fluoride functionalized nanomaterial by in-situ polymerization
CN110373179A (en) Upper conversion light power targeted nano tumour cell probe and its preparation method and application
CN102127443B (en) Preparation method of rare earth fluoride-PVP core-shell material
CN112933247B (en) Preparation method of solvent-induced self-assembled gold nanoparticle material
CN105778902A (en) Preparation method of rare earth hollow nanocrystal
CN113105882B (en) CsPbI for improving stability3Nanocrystalline composite material and preparation method thereof
CN110946999B (en) Diagnosis and treatment integrated nano platform, preparation method and application thereof
CN109321233B (en) Quantum dot low-density lipoprotein nano composite probe and preparation method and application thereof
CN113201344A (en) Rare earth doped near-infrared luminescent hydrogel and preparation method and application thereof
Wang et al. A strategy for prompt phase transfer of upconverting nanoparticles through surface oleate-mediated supramolecular assembly of amino-β-cyclodextrin
CN103211767B (en) Preparation method of multifunctional eccentric mesoporous silicon dioxide core-shell nano particles
JP2012188362A (en) Metal nanorod complex and method of manufacturing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant