CN108148570B - Preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles - Google Patents
Preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles Download PDFInfo
- Publication number
- CN108148570B CN108148570B CN201711302252.XA CN201711302252A CN108148570B CN 108148570 B CN108148570 B CN 108148570B CN 201711302252 A CN201711302252 A CN 201711302252A CN 108148570 B CN108148570 B CN 108148570B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- temperature
- nanoparticles
- heating
- room temperature
- 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.)
- Expired - Fee Related
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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0063—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres
- A61K49/0069—Preparation for luminescence or biological staining characterised by a special physical or galenical form, e.g. emulsions, microspheres the agent being in a particular physical galenical form
- A61K49/0089—Particulate, powder, adsorbate, bead, sphere
- A61K49/0091—Microparticle, microcapsule, microbubble, microsphere, microbead, i.e. having a size or diameter higher or equal to 1 micrometer
- A61K49/0093—Nanoparticle, nanocapsule, nanobubble, nanosphere, nanobead, i.e. having a size or diameter smaller than 1 micrometer, e.g. polymeric nanoparticle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
Abstract
The invention provides a preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles, wherein the composite multifunctional nanoparticles have a yolk structure, and have the characteristic of intelligent response due to double responsiveness of a shell layer; the yolk structure ensures that the yolk has sufficient storage space, thereby being expected to realize the effective load and controllable release of the anti-tumor medicament. The method comprises the following steps: 1) synthesizing homogeneous rare earth core-shell nanoparticles; 2) coating a silicon layer with the shell thickness of about 15 nm by a reverse microemulsion method; 3) preparing a dual-response shell by using photoresponse azobenzene as a cross-linking agent and N-isopropyl acrylamide as a monomer; 4) and etching the silicon layer by HF to obtain the multifunctional nanoparticles with the inner cores of the rare earth nanoparticles and the outer shells of the rare earth nanoparticles serving as double-response shell layers and the yolk structure. The multifunctional rare earth nano particle can be applied to the field of biological medicine.
Description
Technical Field
The invention relates to a preparation technology of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles, in particular to a preparation method of a special yolk structure nano carrier.
Background
With the development of smart material research, the upconversion nano luminescent material is widely researched due to unique optical properties and physical properties thereof. An Upconversion Luminescence (UCL) is an anti-stokes process, which refers to a process in which rare earth particles continuously absorb multiple low-energy long-wavelength photons and then convert the low-energy photons into high-energy short-wavelength photons. The near infrared light is used for excitation in the luminescence process, has obvious advantages compared with a high-energy light source, and has strong tissue penetrability, weak tissue background fluorescence, small damage to organisms, long luminescence time, stable luminescence frequency and stable chemical property. The light has the advantages that the light cannot be obtained by other modes, the light-responsive polymer carrier can be remotely controlled, the releasing time, the illumination direction and the irradiation area of the light-stimulated drug can be flexibly selected in vitro, and the light power can be controlled, so that the timely and proper treatment of the drug released at the focus part is realized, and the characteristic response to the external stimulation is realized to regulate and control the releasing process of the substance.
At present, the preparation method based on the up-conversion/photoresponse multifunctional nano particles is mainly to modify porous silicon dioxide through the surface of rare earth nano particles, and photoresponse elements are further grafted in the porous silicon dioxide. The porous silicon dioxide is loaded with drug molecules, and ultraviolet light excited by near infrared light enables the photoresponse element to realize the function of an optical switch, so that the diagnosis and treatment integrated research is realized. However, the loading capacity of the mesoporous channel to the drug is limited, the drug is difficult to release controllably according to the requirement, and the therapeutic effect is not good.
In view of the above, the invention provides a rare earth up-conversion nanoparticle/polyazobenzene composite yolk structure nanoparticle and a preparation method thereof, and the rare earth up-conversion nanoparticle/polyazobenzene composite yolk structure nanoparticle is prepared by a reverse emulsion method, wherein a silicon layer is used for coating rare earth nanoparticles, a shell takes photoresponse azobenzene as a cross-linking agent, N-isopropylacrylamide as a temperature-sensitive monomer, and HF selective etching is performed to obtain the yolk structure multifunctional nanoparticle with a core taking a rare earth nanoparticle shell as a double-response shell layer. The multifunctional nano particle is expected to solve the problem of integrating diagnosis and light control/temperature dual-response treatment.
Disclosure of Invention
The invention aims to overcome the defects of the existing product and provides a preparation method of light/temperature dual-response rare earth particles. After the rare earth nanoparticles are coated by the silicon layer in the inverse emulsion method, the shell takes photoresponse azobenzene as a cross-linking agent, N-isopropyl acrylamide as a temperature-sensitive monomer, and the multifunctional nanoparticles with the yolk structure and the rare earth nanoparticle shell as a double-response shell layer are prepared by HF selective etching. The multifunctional nano particle is expected to solve the problem of integrating diagnosis and light control/temperature dual-response treatment, the yolk structure is favorable for improving the utilization efficiency of the medicament, has better compatibility with organisms, does not generate chemical and physical reactions and rejection reactions with tissues, and has no toxic or side effect.
In order to achieve the above-mentioned objects,the technical scheme adopted by the invention is as follows: a preparation method of rare earth fluoride/polyazobenzene/N-isopropyl acrylamide composite multifunctional nanoparticles is characterized in that the composite nanoparticles are yolk structures, the inner core is homogeneous core-shell rare earth nanoparticles, and the chemical formula of the composite nanoparticles is as follows: NaYF4:Tm3+,Yb3+,Tm3+/NaYF4The outer shell is a PNIPAM shell layer (PAZO-NIPAM @ UCNPs) taking BMAAB as a cross-linking agent, and the size of the inner core is 40 nm; the shell thickness is 60nm, and the preparation method comprises the following steps:
(1)20％Yb3+/0.5％Tm3+preparation of upconversion nanoparticles: mixing 1-Octadecene (ODE), Oleic Acid (OA), and yttrium chloride (YCl)3) Aqueous solution, ytterbium chloride (YbCl)3) Aqueous solution and thulium chloride (TmCl)3) Uniformly mixing the aqueous solution, heating to 110-120 ℃ under nitrogen flow, removing water and oxygen in the system, heating to 140-160 ℃, keeping the temperature for 45-55 min, cooling, adding a sodium hydroxide methanol solution and an ammonium fluoride methanol solution, and stirring at room temperature for 1-2 h; heating to 100-150 ℃ to remove methanol and water, then heating to 290-300 ℃, keeping the temperature for 60-90 min, cooling to room temperature, adding 10mL of ethanol to precipitate a product, centrifuging the mixed solution at 5000-10000 r/min for 10-20 min, washing with ethanol for three times, and dispersing the product in chloroform for later use.
(2) The specific operation of homogeneous inert shell coating comprises the following steps: mixing 1-octadecene, oleic acid and yttrium chloride YCl3Adding the aqueous solution into a four-neck flask; heating to 110-120 ℃ in an oxygen-free environment, keeping the temperature for 4-5 min, heating to 140-160 ℃, keeping the temperature for 50-60 min, and cooling to room temperature; adding the NaYF prepared in the step (1)4:20％Yb3+/0.5％Tm3+Up-converting the nanoparticles, stirring for 1-2 h at room temperature, heating to 80-90 ℃, preserving heat for 3-6 min, and then cooling to room temperature; adding a sodium hydroxide methanol solution and an ammonium fluoride methanol solution, and stirring for 1-2 h; heating to 100-150 ℃, preserving heat for 3-4 min, then heating to 290-300 ℃, preserving heat for 60-90 min, cooling to room temperature, and then adding ethanol to precipitate a product; centrifuging the mixed solution for 10-20 min at 5000-10000 r/min, and washing with ethanolAfter 3 times, the product was taken up in cyclohexane until use.
(3)SiO2Preparation of @ UCNPs core-shell structure particles: adding a surfactant CO-520, cyclohexane and the converted nanoparticle cyclohexane solution in the step (2) into a three-neck flask, and stirring for 10-30 min; adding ammonia water (wt 30%), sealing and ultrasonic treating for 20-30 min; adding tetraethoxysilane, and stirring at room temperature for 20-30h at the rotating speed of 500-800 r/min; then adding an MPS silane coupling agent, and stirring for 20-30 h; adding acetone to demulsify, and centrifuging to obtain product (UCNPs @ SiO)2) And washing the mixture for 2-4 times by using an ethanol solution.
(4)PAZO-NIPAM@SiO2Preparation of @ UCNPs three-layer nano-particles: vinylated UCNPs @ SiO2Dispersing microspheres in acetonitrile by ultrasonic for 20-30 min, then sequentially adding a BMAAB cross-linking agent, an NIPAM temperature-sensitive monomer, a DVB auxiliary cross-linking agent and an AIBN initiator (3 wt% of the total amount of the monomers), installing an oil-water separator and a reflux condenser tube, replacing 4-5 times with nitrogen to remove air in a reaction container, connecting a nitrogen bag, heating the temperature from room temperature to 80-100 ℃ within 30min, keeping the temperature for 12-20 min, heating to 100-120 ℃, evaporating a reaction solvent for half within 3.5h (including heating time), stopping the reaction, adding p-diphenol into the reaction solution, cooling the solution to room temperature, filtering to obtain a product, and washing with ethanol until a centrifugal supernatant is colorless.
(5) Preparing PAZO-NIPAM @ UCNPs yolk structure nanoparticles: dispersing the core-shell structure microspheres obtained in the step (4) in absolute ethyl alcohol, adding hydrofluoric acid, stirring for 20-30h, centrifuging, adding absolute ethyl alcohol until supernatant is colorless, and drying the obtained product in a vacuum drying oven at 30-60 ℃ to constant weight to obtain PAZO-NIPAM @ SiO2@ UCNPs composite nanoparticles.
Preferably, in the preparation method of the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle, in the step (1), the addition amounts of 1-octadecene and oleic acid are 10mL to 20mL, 5mL to 10mL, 0.2mol/L yttrium chloride aqueous solution, 0.2mol/L ytterbium chloride aqueous solution and 0.2mol/L thulium chloride aqueous solution are 1mL to 5mL, 1mL to 4mL, 10 μ L to 30 μ L, the amounts of 0.5mol/L sodium hydroxide methanol solution and 0.5mol/L ammonium fluoride methanol are 3mL to 6mL and 5mL to 10mL, the amount of ethanol precipitation product is 5mL to 20mL, and the amount of chloroform is 5mL to 20mL, respectively.
Preferably, in the preparation method of the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle, in the step (2), the addition amounts of 1-octadecene and oleic acid are 10mL to 20mL, 5mL to 10mL, the addition amount of 0.2mol/L yttrium chloride aqueous solution is 1mL to 5mL, the amounts of sodium hydroxide methanol solution and ammonium fluoride methanol are 3mL to 6mL,5mL to 10mL, the amount of ethanol precipitation product is 5mL to 20mL, and the amount of cyclohexane is 5mL to 20mL, respectively.
Preferably, in the preparation method of the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle, in the step (3), the addition amounts of the surfactant CO-520, the cyclohexane and the up-conversion nanoparticle cyclohexane solution are 1mL to 3mL, 10mL to 15mL and 5mL to 10mL, the addition amount of ammonia water (30 wt.%) is 0.1mL to 0.3mL, the use amount of ethyl orthosilicate is 0.1mL to 0.2mL, and the use amount of the MPS silane coupling agent is 1mL to 3mL, respectively.
Preferably, the preparation method of the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle comprises the step (4) vinylating UCNPs @ SiO2The volume ratio of microspheres dispersed in acetonitrile is 1: 2, the dosages of the BMAAB cross-linking agent, the PAA p H responsive monomer, the DVB auxiliary cross-linking agent and the AIBN initiator are respectively 20mg to 40mg, 80mg to 100mg, 30 muL to 50 muL and 1mg to 5 mg; the consumption of the polymerization inhibitor hydroquinone is 1 mg-2 mg.
The preparation method of the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nano particle comprises the step (5), wherein the use amounts of the absolute ethyl alcohol and the hydrofluoric acid are respectively 1-5 mL and 3-6 mL.
Preferably, the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle is a light-control and heat-sensitive dual-response material, and simultaneously realizes development detection and in-vivo release of a medicament.
Compared with the prior art, the invention has the beneficial effects that:
1. the up-conversion luminescent material can exactly convert near infrared light into visible light and ultraviolet light, wherein the ultraviolet light can be used for stimulation of the material, and the visible light can be used for development imaging to trace a drug carrier in real time, so that the problem of separation of medical diagnosis and treatment can be well solved by combining the two materials.
2. The synthesis method is novel, rare earth up-conversion nanoparticles which are regular in shape, uniform in particle size, high in crystallinity and high in luminous efficiency and have high quality and luminous performance meeting requirements are successfully synthesized by adopting an Ostwald curing method, the surface defects of the particles are few, a layer of oleic acid molecules is connected to the surface of the rare earth up-conversion nanoparticles, the solubility of the rare earth up-conversion nanoparticles in a nonpolar solvent is greatly improved, the stability of the rare earth up-conversion nanoparticles in water is improved by modifying and modifying the surface of the rare earth up-conversion nanoparticles, a silica shell layer is added to the non-hydrophilic surface of UCNPs by using a reverse microemulsion method, and the UCNPs are specifically modified by using a silane coupling agent to enable the particles to have carbon-carbon double bonds, so that SiO with2@ UCNPs core-shell structure nanoparticles.
3. The PAZO-NIPAM @ SiO is successfully prepared by a distillation precipitation polymerization method mainly through a physical addition method by taking BMAAB as a cross-linking agent, ethylene silicon dioxide as a template and NIPAM as a temperature-sensitive functional monomer2The @ UCNPs three-layer core-shell structure microsphere is prepared by selectively etching away a silicon dioxide core by using HF (hydrogen fluoride) to obtain the PAZO-NIPAM @ UCNPs temperature/light double-response rare earth nanoparticles with a yolk structure. The whole operation has strong practicability and reasonable cost, and can well meet the requirement of batch production.
4. The hollow part of the yolk structure of the nanoparticle with the PAZO-NIPAM @ UCNPs composite yolk structure consists of a PAZO-NIPAM polymer shell layer and a SiO (silicon dioxide) intermediate of rare earth nanoparticle UCNPs2The etching results in the yolk structure providing the necessary space for loading the drug.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) analysis photograph of rare earth upconversion nanoparticles according to a first embodiment of the present invention.
FIG. 2 is an infrared spectroscopy (FTIR) analysis of rare earth upconverting nanoparticles according to a first embodiment of the present invention.
Fig. 3 is a Transmission Electron Microscope (TEM) analysis diagram of the rare earth upconversion luminescent material/polyazobenzene composite nanoparticle according to the first embodiment of the present invention.
Detailed Description
For a better understanding of the present invention, the contents of the present invention will be further explained below with reference to the drawings and examples, but the contents of the present invention are not limited to the following examples.
Example 1
A preparation method of rare earth fluoride/polyazobenzene/N-isopropyl acrylamide composite multifunctional nanoparticles is characterized in that the composite nanoparticles are yolk structures, the inner core is homogeneous core-shell rare earth nanoparticles, and the chemical formula of the composite nanoparticles is as follows: NaYF4:Tm3+,Yb3+,Tm3+/NaYF4The outer shell is a PNIPAM shell layer (PAZO-NIPAM @ UCNPs) taking BMAAB as a cross-linking agent, and the size of the inner core is 40 nm; the shell thickness is 60nm, and the preparation method comprises the following steps:
(1)20％Yb3+/0.5％Tm3+preparation of upconversion nanoparticles: 15mL of 1-Octadecene (ODE), 7mL of Oleic Acid (OA), 3.975mL of yttrium chloride (YCl)3) Aqueous solution (0.2mol/L), 1mL ytterbium chloride (YbCl)3) Aqueous solution (0.2mol/L) and 25. mu.L of thulium chloride (TmCl)3) Mixing the aqueous solutions (0.1mol/L), heating to 120 ℃ under nitrogen flow, removing water and oxygen in the system, heating to 150 ℃, keeping the temperature for 50min, cooling, adding 5mL of sodium hydroxide methanol solution (0.5mol/L) and 8mL of ammonium fluoride methanol solution (0.5mol/L), and stirring at room temperature for 1 h; heating to 130 ℃ to remove methanol and water, then heating to 300 ℃, keeping the temperature for 80min, cooling to room temperature, adding 10mL of ethanol to precipitate a product, centrifuging the mixed solution for 10min at 5000-10000 r/min, washing for 3 times by using ethanol, and dispersing the product in 10mL of chloroform for later use.
(2) The specific operation of homogeneous inert shell coating comprises the following steps: 15mL of 1-octadecene, 7mL of oleic acid and 5mL of yttrium chloride YCl3Adding the aqueous solution (0.2mol/L) into a 100mL four-neck flask; heating to 120 deg.C in oxygen-free environment for 5min, and heating toKeeping the temperature at 150 ℃ for 50min, and cooling to room temperature; adding the NaYF prepared in the step (1)4:20％Yb3+/0.5％Tm3+Up-converting the nanoparticles, stirring for 1h at room temperature, heating to 85 ℃, preserving heat for 4min, and then cooling to room temperature; adding 5mL of sodium hydroxide methanol solution and 8mL of ammonium fluoride methanol solution, and stirring for 1 h; heating to 120 ℃, preserving heat for 4min, then heating to 300 ℃, preserving heat for 90min, cooling to room temperature, and then adding 12.5mL of ethanol to precipitate a product; the mixed solution is centrifuged for 10min at 8000 rpm, and the product is washed with ethanol three times and then placed in 10mL cyclohexane for later use.
(3)SiO2Preparation of @ UCNPs core-shell structure particles: adding 2mL of surfactant CO-520, 12mL of cyclohexane and 8mL of up-conversion nanoparticle cyclohexane solution into a 100mL three-neck flask, and stirring for 10 min; adding 0.16mL of ammonia water (wt 30%), sealing and performing ultrasonic treatment for 20 min; adding 0.12mL of tetraethoxysilane, and stirring at room temperature for 24 hours at the rotating speed of 600 revolutions per minute; then 2mL of MPS silane coupling agent is added and stirred for 24 h; adding acetone to demulsify, and centrifuging to obtain product (UCNPs @ SiO)2) And washed 3 times with ethanol solution.
(4)PAZO-NIPAM@SiO2Preparation of @ UCNPs three-layer nano-particles: 30mg of vinylated UCNPs @ SiO2Dispersing microspheres in 50mL of acetonitrile by ultrasonic wave for 30min, then sequentially adding 30mg of BMAAB crosslinking agent, 85mg of NIPAM temperature-sensitive monomer, 40 mu L of DVB auxiliary crosslinking agent and 3mg of AIBN initiator (3 wt% of the total amount of the monomers), installing an oil-water separator and a reflux condenser tube, removing air in a reaction container by nitrogen replacement for 4 times, connecting a nitrogen bag, heating the temperature from room temperature to 90 ℃ within 30min, keeping the temperature for 15min, heating to 110 ℃, stopping the reaction after the reaction solvent is distilled out for half within 3.5h (including heating time), adding 1.5mg of p-diphenol into the reaction solution, cooling the solution to room temperature, filtering to obtain a product, washing with ethanol until the supernatant of centrifugation is colorless.
(5) Preparing PAZO-NIPAM @ UCNPs yolk structure nanoparticles: dispersing the core-shell structure microspheres obtained in the step (4) in 2mL of absolute ethyl alcohol, adding 5mL of hydrofluoric acid, stirring for 24h, centrifuging, adding absolute ethyl alcohol until supernatant is colorless, and drying the obtained product in a vacuum drying oven at 50 ℃ to constant weight to obtain PAZO-NIPAM@SiO2@ UCNPs composite nanoparticles.
Example 2
(1)20％Yb3+/0.5％Tm3+Preparation of upconversion nanoparticles: 10mL of 1-Octadecene (ODE), 5mL of Oleic Acid (OA), 1mL of yttrium chloride (YCl)3) Aqueous solution (0.2mol/L), 1mL ytterbium chloride (YbCl)3) Aqueous solution (0.2mol/L) and 10. mu.L of thulium chloride (TmCl)3) Mixing the aqueous solutions (0.1mol/L), heating to 110 ℃ under nitrogen flow, removing water and oxygen in the system, heating to 140 ℃, keeping the temperature for 45min, cooling, adding 5mL of sodium hydroxide methanol solution (0.5mol/L) and 8mL of ammonium fluoride methanol solution (0.5mol/L), and stirring at room temperature for 1 h; heating to 100 ℃ to remove methanol and water, then heating to 290 ℃, keeping the temperature for 60min, cooling to room temperature, adding 7mL of ethanol to precipitate a product, centrifuging the mixed solution at 5000 r/min for 10min, washing with ethanol for 3 times, and dispersing the product in 10mL of chloroform for later use.
(2) The specific operation of homogeneous inert shell coating comprises the following steps: 10mL of 1-octadecene, 5mL of oleic acid and 1mL of yttrium chloride YCl3Adding the aqueous solution (0.2mol/L) into a 100mL four-neck flask; heating to 110 deg.C in oxygen-free environment for 4min, heating to 150 deg.C, maintaining the temperature for 50min, and cooling to room temperature; adding the NaYF prepared in the step (1)4:20％Yb3+/0.5％Tm3+Up-converting the nanoparticles, stirring for 1h at room temperature, heating to 80 ℃, preserving heat for 4min, and then cooling to room temperature; adding 3mL of sodium hydroxide methanol solution and 5mL of ammonium fluoride methanol solution, and stirring for 1 h; heating to 100 ℃, preserving heat for 4min, then heating to 290 ℃, preserving heat for 60min, cooling to room temperature, and then adding 5mL of ethanol to precipitate a product; the mixed solution is centrifuged for 10min at 5000 r/min, and after washing with ethanol three times, the product is placed in 10mL cyclohexane for later use.
(3)SiO2Preparation of @ UCNPs core-shell structure particles: adding 1mL of surfactant CO-520, 10mL of cyclohexane and 6mL of up-conversion nanoparticle cyclohexane solution into a 100mL three-neck flask, and stirring for 10 min; adding 0.16mL of ammonia water (wt 30%), sealing and performing ultrasonic treatment for 20 min; adding 0.12mL of tetraethoxysilane, and stirring at room temperature for 20 hours at the rotating speed of 500 revolutions per minute; then adding 1mL of MPS silane coupling agent, and stirring for 20 h; adding intoDemulsifying with acetone, and centrifuging to obtain product (UCNPs @ SiO)2) And washed 3 times with ethanol solution.
(4)PAZO-NIPAM@SiO2Preparation of @ UCNPs three-layer nano-particles: 30mg of vinylated UCNPs @ SiO2Dispersing microspheres in 50mL of acetonitrile by ultrasonic wave for 20min, then sequentially adding 20mg of BMAAB crosslinking agent, 80mg of NIPAM temperature-sensitive monomer, 30 mu L of DVB auxiliary crosslinking agent and 2mg of AIBN initiator (3 wt% of the total amount of the monomers), installing an oil-water separator and a reflux condenser tube, replacing 4 times with nitrogen to remove air in a reaction container, connecting a nitrogen bag, heating the temperature from room temperature to 80 ℃ within 30min, keeping the temperature for 12min, then heating to 100 ℃, evaporating half of a reaction solvent within 3.5h (including heating time), stopping the reaction, adding 1mg of p-diphenol into the reaction solution, cooling the solution to room temperature, filtering to obtain a product, and washing with ethanol until a centrifugal supernatant is colorless.
(5) Preparing PAZO-NIPAM @ UCNPs yolk structure nanoparticles: dispersing the core-shell structure microspheres obtained in the step (4) in 2mL of absolute ethyl alcohol, adding 3mL of hydrofluoric acid, stirring for 20h, centrifuging, adding absolute ethyl alcohol until supernatant is colorless, and drying the obtained product in a vacuum drying oven at 30 ℃ to constant weight to obtain PAZO-NIPAM @ SiO2@ UCNPs composite nanoparticles.
Example 3
(1)20％Yb3+/0.5％Tm3+Preparation of upconversion nanoparticles: 20mL of 1-Octadecene (ODE), 10mL of Oleic Acid (OA), 5mL of yttrium chloride (YCl)3) Aqueous solution (0.2mol/L), 4mL ytterbium chloride (YbCl)3) Aqueous solution (0.2mol/L) and 30. mu.L of thulium chloride (TmCl)3) Mixing the aqueous solutions (0.1mol/L), heating to 120 ℃ under nitrogen flow, removing water and oxygen in the system, heating to 160 ℃, keeping the temperature for 55min, cooling, adding 7mL of sodium hydroxide methanol solution (0.5mol/L) and 10mL of ammonium fluoride methanol solution (0.5mol/L), and stirring at room temperature for 2 h; heating to 150 ℃ to remove methanol and water, then heating to 300 ℃, keeping the temperature for 90min, cooling to room temperature, adding 13mL of ethanol to precipitate a product, centrifuging the mixed solution at 10000 r/min for 20min, washing with ethanol for 3 times, and dispersing the product in 15mL of chloroform for later use.
(2) Homogeneous inertiaSpecific operation of sex shell coating: 20mL of 1-octadecene, 8mL of oleic acid and 6mL of yttrium chloride YCl3Adding the aqueous solution (0.2mol/L) into a 100mL four-neck flask; heating to 120 deg.C in oxygen-free environment for 5min, heating to 160 deg.C, maintaining the temperature for 60min, and cooling to room temperature; adding the NaYF prepared in the step (1)4:20％Yb3+/0.5％Tm3+Converting the nanoparticles, stirring for 2h at room temperature, heating to 90 ℃, keeping the temperature for 5min, and then cooling to room temperature; adding 6mL of sodium hydroxide methanol solution and 10mL of ammonium fluoride methanol solution, and stirring for 2 h; heating to 150 ℃, preserving heat for 4min, then heating to 300 ℃, preserving heat for 90min, cooling to room temperature, and then adding 20mL of ethanol to precipitate a product; and centrifuging the mixed solution at 10000 rpm for 20min, washing the mixed solution with ethanol for three times, and then putting the product in 10mL of cyclohexane for later use.
(3)SiO2Preparation of @ UCNPs core-shell structure particles: adding 1mL of surfactant CO-520, 14mL of cyclohexane and 10mL of up-conversion nanoparticle cyclohexane solution into a 100mL three-neck flask, and stirring for 15 min; adding 0.20mL of ammonia water (wt 30%), sealing and performing ultrasonic treatment for 30 min; adding 0.15mL of tetraethoxysilane, and stirring at room temperature for 30h at the rotating speed of 800 revolutions per minute; then adding 1.2mL of MPS silane coupling agent, and stirring for 30 h; adding acetone to demulsify, and centrifuging to obtain product (UCNPs @ SiO)2) And washed 3 times with ethanol solution.
(4)PAZO-NIPAM@SiO2Preparation of @ UCNPs three-layer nano-particles: 30mg of vinylated UCNPs @ SiO2Dispersing microspheres in 55mL of acetonitrile by ultrasonic wave for 30min, then adding 40mg of BMAAB crosslinking agent, 100mg of NIPAM temperature-sensitive monomer, 50 mu of LDVB auxiliary crosslinking agent and 4.1mg of AIBN initiator (3 wt% of the total amount of the monomers) according to the above, installing an oil-water separator and a reflux condenser tube, replacing with nitrogen for 5 times to remove air in a reaction container, connecting a nitrogen bag, heating the temperature from room temperature to 100 ℃ within 30min, keeping the temperature for 20min, then heating the temperature to 120 ℃, stopping the reaction after evaporating half of the reaction solvent within 3.5h (including heating time), adding 2mg of p-diphenol into the reaction solution, cooling the solution to room temperature, filtering to obtain a product, washing with ethanol until the supernatant is colorless.
(5) Preparing PAZO-NIPAM @ UCNPs yolk structure nanoparticles: subjecting the core of step (4)Dispersing the shell structure microspheres in 5mL of absolute ethyl alcohol, adding 6mL of hydrofluoric acid, stirring for 30h, centrifuging, adding absolute ethyl alcohol until supernatant is colorless, and drying the obtained product in a vacuum drying oven at 60 ℃ to constant weight to obtain PAZO-NIPAM @ SiO2@ UCNPs composite nanoparticles.
We performed performance tests on the prepared samples and the like as follows:
test one, Transmission Electron Microscope (TEM) analysis: 3-5 mL of UCNPs particles obtained in the preparation step of the upconversion nanoparticles in example 1 were dispersed in chloroform, and after adjusting to a suitable concentration, a drop was placed on a copper mesh, and after allowing the solvent to evaporate freely, the particle shape was observed, and the results are shown in FIG. 1.
FIGS. 1(a), (b) are transmission diagrams of core structure upconversion nanoparticles (core UCNPs) and core-shell structure upconversion nanoparticles (core-s hell UCNPs), respectively, subjected to performance tests. As can be seen from a transmission electron microscope image, the UCNPs crystal prepared by the experiment shows an obvious elliptical shape, the particle size is uniform, and the nano particles are uniformly dispersed in a chloroform solvent. Fig. 1(a) shows UCNPs particles having a core structure, in which a layer of oleic acid structure is successfully coated on the surface of the particles, and the oleic acid surface layer makes the particles well dispersed in a non-polar solvent, so that the volatilization of the organic solvent makes the nanoparticles form an array structure with regular and ordered arrangement by means of van der waals force between molecules, and the array structure is coated on a copper mesh. The particle size of the particles was calculated to be 25.7. + -. 1.8nm by Image J measurement. Fig. 1(b) shows UCNPs having a core-shell structure, and the particles form an ordered structural arrangement on a copper mesh due to the presence of an oleic acid layer on the surface. The coating of a shell layer without other ions enables the particle growth degree to be further improved, the shape to be more regular and the shape to be spherical. The small amount of particles in the transmission electron microscope is caused by the crystal phase nucleation of the particles in the experimental process, and the particle size of the particles is 29.7 +/-1.5 nm through Image J measurement and detection. According to the morphology of the particles in fig. 1(a) and (b), it can be judged that the outer surface of the up-conversion nanoparticle as the core structure has been successfully coated with a shell-free layer, the shell structure of the outer layer has no rare earth ions, is inert, and has a shell thickness of about 4 nm.
Experiment two, rare earth up-conversion nanoInfrared spectroscopic analysis of the particles: taking 1-2 g of the sample prepared in the example 1, drying, grinding and uniformly mixing the sample with spectrum-level potassium bromide, and tabletting, wherein the resolution of an instrument is 4cm-1And 16 scans, the results are shown in figure 2.
Infrared analysis shows that a layer of oleic acid molecules exists on the surface of UCNPs particles, so that particles which cannot be dissolved in a nonpolar solvent originally can be uniformly dispersed in nonpolar chloroform, because long carbon chains of oleic acid can help the particles to be uniformly separated in a nonpolar environment and can well prevent the particles from aggregating. 3442cm-1An infrared absorption peak is formed, and analysis shows that the infrared absorption peak belongs to stretching vibration of hydroxyl in oleic acid molecules on the outer layer of the nano particles; while oleic acid molecule is-C H2The stretching vibration of-corresponds to 2923cm in the spectrum-1And 2852cm-1Two strong infrared spectrum absorption peaks; at 1554cm-1The absorption peak at (A) is the oscillation peak of the carboxylate group.
And thirdly, dispersing a small amount (about 3-5 mL) of rare earth up-conversion luminescent material/polyazobenzene composite nanoparticles (UCNPs) in chloroform, adjusting the concentration to be proper, dripping a drop of the UCNPs on a copper net, and observing after the solvent is freely volatilized, wherein the result is shown in figure 3.
The composite nanoparticles prepared in example 1 were structurally characterized by a transmission electron microscope, and the results are shown in fig. 3(a), where SiO is2The @ UCNPs particles are elliptical, have moderate particle size and are SiO2The thickness of the shell layer is uniform and moderate, and is about 10 nm. Followed by the UCNPs @ SiO2The PAZO-NIPAM @ SiO is obtained by distillation precipitation based on particles2The @ UCNPs nano particle is shown in figure 3(b), the coating layer of the particle is uniform and regular, a core-shell structure with a clear structure can be obviously seen under a projection electron microscope, the dispersion among the particles is better, excessive adhesion does not occur, the dispersion is good mainly because the concentration of microspheres in a solution is low, the dispersion is better, the adhesion among particles is not obvious, the dispersion is good, after a silica shell is removed by HF (hydrogen fluoride), the hollow structure area of the core-shell structure after etching is large, the dispersion of the nano particle is good, the thickness of the silica shell is enough, after a hard core is etched, the polymer shell structure is stable, and high up-conversion efficiency can be realizedAnd (4) rate.
The above examples illustrate the present invention in detail. It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and that various changes, modifications, additions, deletions, and substitutions which may be made by those skilled in the art within the spirit of the present invention are also within the scope of the present invention.
Claims (6)
1. A preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles is characterized by comprising the following steps: the composite nano particle is of a yolk structure, the inner core is homogeneous core-shell rare earth nano particle, and the chemical formula is as follows: NaYF4: Yb3+, Tm3+/ NaYF4The outer shell is a PNIPAM shell layer taking BMAAB as a cross-linking agent, and the preparation method comprises the following steps:
（1）20%Yb3+/0.5%Tm3+preparation of upconversion nanoparticles: uniformly mixing 1-octadecene, oleic acid, a yttrium chloride aqueous solution, a ytterbium chloride aqueous solution and a thulium chloride aqueous solution, heating to 110-120 ℃ under nitrogen flow, removing water and oxygen in a system, heating to 140-160 ℃, keeping the temperature for 45-55 min, removing a heating jacket, naturally cooling to room temperature, adding a sodium hydroxide methanol solution and an ammonium fluoride methanol solution, and stirring at room temperature for 1-2 h; heating to 100-150 ℃ to remove methanol and water, then heating to 290-300 ℃, keeping the temperature for 60-90 min, cooling to room temperature, adding ethanol into a reaction flask to precipitate a product, centrifuging and washing with ethanol, wherein the centrifugation rate is 5000-10000 r/min, the centrifugation time is 10-20 min, and the product is dispersed in chloroform for later use;
(2) the specific operation of homogeneous inert shell coating comprises the following steps: adding 1-octadecene, oleic acid and yttrium chloride aqueous solution into a four-neck flask; heating to 110-120 ℃ in an oxygen-free environment, keeping the temperature for 4-5 min, heating to 140-160 ℃, keeping the temperature for 50-60 min, removing the electric heating jacket, and naturally cooling to room temperature; adding the NaYF prepared in the step (1)4:20%Yb3+/0.5%Tm3+Up-converting the nanoparticles, stirring for 1-2 h at room temperature, heating to 80-90 ℃, keeping the temperature for 3-6 min,then cooling to room temperature; adding a sodium hydroxide methanol solution and an ammonium fluoride methanol solution, and stirring for 1-2 h; heating to 100-150 ℃, keeping the temperature for 3-4 min, heating to 290-300 ℃, keeping the temperature for 60-90 min, cooling to room temperature, adding an ethanol precipitate product into a reaction flask, centrifuging, washing the product with ethanol, centrifuging at the speed of 5000-10000 r/min for 10-20 min, and dispersing the product in cyclohexane for later use;
（3）SiO2preparation of @ UCNPs core-shell structure particles: adding a surfactant CO-520, cyclohexane and the up-conversion nano particle cyclohexane solution obtained in the step (2) into a three-neck flask, and stirring for 10-30 min; adding ammonia water, sealing and then carrying out ultrasonic treatment for 20-30 min; adding tetraethoxysilane, and stirring at room temperature for 20-30h at the rotating speed of 500-800 r/min; then adding an MPS silane coupling agent, and stirring for 20-30 h; adding acetone to demulsify, and centrifuging to obtain a product UCNPs @ SiO2Washing with an ethanol solution for 2-4 times;
（4）PAZO~NIPAM @ SiO2preparation of @ UCNPs three-layer nano-particles: vinylated UCNPs @ SiO2Dispersing microspheres in acetonitrile by ultrasonic for 20-30 min, then sequentially adding a BMAAB cross-linking agent, an NIPAM temperature-sensitive monomer, a DVB auxiliary cross-linking agent and an AIBN initiator, installing an oil-water separator and a reflux condenser tube, replacing 4-5 times with nitrogen to remove air in a reaction container, connecting a nitrogen bag, raising the temperature from room temperature to 80-100 ℃ within 30min, keeping the temperature for 12-20 min, raising the temperature to 100-120 ℃, evaporating half of a reaction solvent within 1-3.5 h, stopping reaction, adding p-diphenol into the reaction solution, cooling the solution to room temperature, filtering to obtain a product, washing with ethanol until a centrifugal supernatant is colorless;
(5) preparing PAZO-NIPAM @ UCNPs yolk structure nanoparticles: dispersing the core-shell structure microspheres obtained in the step (4) in absolute ethyl alcohol, adding hydrofluoric acid, stirring for 20-30h, centrifuging, using the absolute ethyl alcohol until supernatant liquid is colorless, and drying the obtained product in a vacuum drying oven at 30-60 ℃ to constant weight to obtain PAZO-NIPAM @ UCNPs yolk structure nanoparticles.
2. The method for preparing the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle according to claim 1, wherein the method comprises the following steps: in the step (1), the addition amounts of 1-octadecene and oleic acid are respectively 10 mL-20 mL,5 mL-10 mL, the addition amounts of 0.2mol/L yttrium chloride aqueous solution, 0.2mol/L ytterbium chloride aqueous solution and 0.1mol/L thulium chloride aqueous solution are 1 mL-5 mL, 1 mL-4 mL, 10 mu L-30 mu L, the usage amounts of 0.5mol/L sodium hydroxide methanol solution and ammonium fluoride methanol are 3 mL-6 mL,5 mL-10 mL, the usage amount of ethanol precipitation products is 5 mL-20 mL, and the usage amount of chloroform is 5 mL-20 mL.
3. The method for preparing the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle according to claim 1, wherein the method comprises the following steps: the adding amount of the 1-octadecene and the oleic acid in the step (2) is 10-20 mL and 5-10 mL respectively; the adding amount of 0.2mol/L yttrium chloride aqueous solution is 1-5 mL, the dosage of sodium hydroxide methanol solution and ammonium fluoride methanol is 3-6 mL and 5-10 mL, the dosage of ethanol precipitation product is 5-20 mL, and the dosage of cyclohexane is 5-20 mL.
4. The method for preparing the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle according to claim 1, wherein the method comprises the following steps: in the step (3), the addition amounts of the surfactant CO-520, the cyclohexane and the up-conversion nano particle cyclohexane solution in the step (2) are respectively 1 mL-3 mL, 10 mL-15 mL and 5 mL-10 mL, the addition amount of ammonia water is 0.1 mL-0.3 mL, the use amount of ethyl orthosilicate is 0.1 mL-0.2 mL, and the use amount of the MPS silane coupling agent is 1 mL-3 mL.
5. The method for preparing the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle according to claim 1, wherein the method comprises the following steps: the dosage of the BMAAB cross-linking agent, the NIPAM temperature-sensitive monomer, the DVB auxiliary cross-linking agent and the AIBN initiator in the step (4) is respectively 20-40 mg, 80-100 mg, 30-50 muL and 1-5 mg; the consumption of the polymerization inhibitor hydroquinone is 1 mg-2 mg.
6. The method for preparing the rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticle according to claim 1, wherein the method comprises the following steps: the consumption of the absolute ethyl alcohol and the consumption of the hydrofluoric acid in the step (5) are respectively 1 mL-5 mL and 3 mL-6 mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711302252.XA CN108148570B (en) | 2017-12-10 | 2017-12-10 | Preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711302252.XA CN108148570B (en) | 2017-12-10 | 2017-12-10 | Preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108148570A CN108148570A (en) | 2018-06-12 |
| CN108148570B true CN108148570B (en) | 2020-04-17 |
Family
ID=62466902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711302252.XA Expired - Fee Related CN108148570B (en) | 2017-12-10 | 2017-12-10 | Preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108148570B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171820B (en) * | 2019-12-23 | 2021-12-21 | 华南师范大学 | Etching method of rare earth fluoride up-conversion nanocrystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251005A (en) * | 2015-11-17 | 2016-01-20 | 天津大学 | Novel light-dependent control living cell dyeing method based on up-conversion and application |
| CN106075437A (en) * | 2016-06-12 | 2016-11-09 | 哈尔滨工业大学 | A kind of near infrared light excites the preparation method of the nuclear shell structure drug carrier of monitoring release in real time |
-
2017
- 2017-12-10 CN CN201711302252.XA patent/CN108148570B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251005A (en) * | 2015-11-17 | 2016-01-20 | 天津大学 | Novel light-dependent control living cell dyeing method based on up-conversion and application |
| CN106075437A (en) * | 2016-06-12 | 2016-11-09 | 哈尔滨工业大学 | A kind of near infrared light excites the preparation method of the nuclear shell structure drug carrier of monitoring release in real time |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108148570A (en) | 2018-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108192590B (en) | Preparation method of polyazobenzene multifunctional nanoparticles based on rare earth up-conversion material | |
| CN104017581B (en) | Photothermal deformation nano material and preparations and applicatio method thereof | |
| CN112080278B (en) | Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof | |
| CN109762562A (en) | A kind of CsPbX3@TiO2Nano material and its preparation method and application | |
| US11407941B2 (en) | Fluorescent nanomaterial and preparation method and applications thereof | |
| Li et al. | Facile microemulsion route to coat carbonized glucose on upconversion nanocrystals as high luminescence and biocompatible cell-imaging probes | |
| CN104449662B (en) | A kind of surface modification method of oil-soluble upconversion fluorescence nano material | |
| CN107098940B (en) | A kind of hollow tannic acid potassium nanoparticle of granatohedron and preparation method thereof | |
| CN111334296A (en) | Ultrathin SiO2Encapsulated NaYF4Method for synthesizing Yb, Er composite nano particle | |
| CN103540310A (en) | Surface direct mesoporous modification method used for multi-morphology rear earth-doped up-conversion luminescent nanocrystallines | |
| WO2023041005A1 (en) | Virus-like hollow oxide loaded near-infrared two-b region excited rare earth nanocrystal, preparation method therefor and application thereof | |
| CN108148570B (en) | Preparation method of rare earth fluoride/polyazobenzene/N-isopropylacrylamide composite multifunctional nanoparticles | |
| CN107418554A (en) | A kind of gold nanorods and upper conversion nano crystalline substance composite nano materials and preparation method thereof | |
| CN105664955B (en) | A kind of preparation method of the metal co-doped carbon quantum dot of copper zinc | |
| CN107376955B (en) | Photocatalytic antibacterial material and preparation method thereof | |
| CN100515556C (en) | Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application | |
| CN109970896B (en) | Method for constructing temperature-sensitive carbon nanotube composite material based on carbon dot modification | |
| CN105602566B (en) | A kind of rear-earth-doped NaGdF4Upper conversion nano crystalline substance and preparation method thereof | |
| CN110317606B (en) | Method for preparing carbon dots by using bromoacetonitrile and imidazole compounds and product | |
| CN103074066B (en) | Preparation method of multifunctional mesoporous directly-cladded fluorescence nano-bioprobe | |
| Giang et al. | Preparation and characterization of yttrium hydroxide and oxide doped with rare earth ions (Eu3+, Tb3+) nano one-dimensional | |
| CN106798922A (en) | A kind of mesoporous silicon oxide coated carbon nano-tube composite material difunctional with magnetic, up-conversion luminescence and preparation method thereof | |
| CN106867006A (en) | A kind of silicomolybdic acid is nanocrystalline/preparation method of composite membrane of polyvinyl alcohol | |
| CN111303863A (en) | Up-conversion luminescent nanoparticle and preparation method and application thereof | |
| CN111139065A (en) | Bio-based luminescent nano material and preparation method and application thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200417 Termination date: 20211210 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |