CN112080278A - Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof - Google Patents
Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 51
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 43
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 34
- 229940049964 oleate Drugs 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- -1 rare earth chloride Chemical class 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000005642 Oleic acid Substances 0.000 claims abstract description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 9
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- 238000000034 method Methods 0.000 claims abstract description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 56
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 53
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- 239000000243 solution Substances 0.000 claims description 43
- 229910052691 Erbium Inorganic materials 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052689 Holmium Inorganic materials 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 25
- 150000002910 rare earth metals Chemical class 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 20
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 20
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000004020 luminiscence type Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
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- 239000012153 distilled water Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- HZMBANJECWHRGE-GNOQXXQHSA-K cerium(3+);(z)-octadec-9-enoate Chemical compound [Ce+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HZMBANJECWHRGE-GNOQXXQHSA-K 0.000 claims description 8
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 8
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 8
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 8
- 239000003937 drug carrier Substances 0.000 claims description 6
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 5
- 150000001805 chlorine compounds Chemical class 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
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- 239000000843 powder Substances 0.000 claims description 5
- 238000012984 biological imaging Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
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- 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
-
- 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
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- 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
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
Abstract
The invention discloses an up/down conversion dual-mode luminescent nanocrystal and a preparation method and application thereof, and belongs to the technical field of nanocrystal materials; the nanocrystalline takes rare earth chloride as a precursor, and under the joint participation of sodium hydroxide and ammonium fluoride, monodisperse rare earth fluoride nanoparticles with small particle size are prepared as a core; and (3) coating the shell layer rare earth fluoride nanocrystalline by using an epitaxial growth method, taking oleic acid and octadecene as a mixed solvent, and taking the combined action of a rare earth oleate precursor and sodium fluoride in a high-temperature solvent. The method has the advantages of simple synthetic route operation, uniform particle size distribution of products and high purity, and the nano-crystal is endowed with stronger red and near-infrared two-region fluorescence by doping different rare earth elements and controlling the sizes of a core and a shell in a core-shell structure, the near-infrared fluorescence can be used as a potential optical imaging contrast agent, and the prepared nano-crystal can be used as a nano-energy converter for light trigger treatment by red light emission.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a sunflower-shaped dual-mode up/down conversion luminescence nanocrystal with red light (an emission peak is about 650nm) and near infrared (an emission peak is about 1520nm) and a preparation method and application thereof.
Background
Upconversion luminescence is an anti-Stokes process, which refers to a luminescence phenomenon capable of absorbing two or more long wavelength photons and emitting one short wavelength photon. The substrate of the rare earth up-conversion luminescent material mainly comprises oxide, fluoride, oxyfluoride, sulfur-containing compound, halide and the like, wherein the rare earth fluoride has the characteristics of low phonon energy, less radiationless transition, high doping concentration of elements and the like, and is an ideal substrate for up-conversion luminescence, so the rare earth up-conversion luminescent material has wide application prospect in the field of luminescent materials. Currently, the most widely studied up-conversion luminescent materials are rare earth doped nanocrystals using Er, Tm or Ho as an activator.
Near-infrared excited rare-earth upconversion luminescence nanotechnology has attracted extensive research interest in upconversion light-triggered therapy and the like due to its unique luminescence mechanism and excellent luminescence property. The rare earth up-conversion nanocrystal has deeper tissue penetration depth, lower autofluorescence and excellent photobleaching resistance when applied to light trigger treatment, so the rare earth up-conversion nanocrystal is relatively suitable for being used as a 'photon converter' in deep biological tissues. However, for up-conversion fluorescence imaging, there still exist problems of high absorption and scattering by biological tissues due to up-converted short wavelength photons. In addition, the simultaneous use of up-conversion fluorescence for light-triggered therapy and optical imaging has the problem of uncontrollable energy distribution or insufficient energy supply. Therefore, in order to obtain higher optical imaging signal-to-noise ratio, the development of rare earth nanocrystals with excellent near infrared (700-. Currently, a subject group reports that Yb/Ce/Er or Ce/Er co-doped nanocrystals are used for near-infrared two-region biosensing or imaging related researches, however, high doping of Ce inevitably brings about matrix lattice defects, and further causes reduction of luminous intensity.
In the field of anticancer, rare earth upconversion fluorescence mediated light-triggered therapy remains a current research hotspot. For rare earth luminescent nanocrystals, only the near infrared down-conversion fluorescence property has limitations. In order to realize the expanded application of the rare earth luminescent nanocrystal in biological diagnosis and other related fields, the rare earth luminescent nanocrystal has important significance for giving up-conversion and down-conversion near-infrared dual-mode fluorescence performance. And a new nanocrystal with up-conversion and down-conversion dual-mode luminescence properties is sought as a potential anticancer diagnosis and treatment nano platform, and further research and exploration are still needed.
In conclusion, no report has been made on the scheme or route for preparing the high-performance rare earth fluoride nanocrystal which takes near-infrared light as an excitation light source and has strong up-conversion red light and down-conversion near-infrared two-region dual-mode fluorescence.
Disclosure of Invention
The invention aims to provide an up/down conversion dual-mode luminescence nanocrystal and a preparation method and application thereof, wherein the nanocrystal is sunflower-shaped and can emit light in an infrared region (an emission peak is about 650nm) and a near infrared region (an emission peak is about 1520nm), so that the problems in the prior art are solved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an up/down conversion dual-mode luminescent nanocrystal, which has the chemical expression as follows: NaGdF4:Yb,Ce,Ho,Er
@NaGdF4Yb, Ce; where @ denotes a package.
A preparation method of up/down conversion dual-mode luminescent nanocrystals comprises the following steps:
s1, respectively synthesizing chlorides of rare earth metal elements gadolinium, ytterbium, cerium, erbium and holmium;
s2, respectively synthesizing oleate containing rare earth metal elements of gadolinium, ytterbium, cerium, erbium and holmium;
s3, preparing NaGdF by adopting high-temperature solvothermal method454% of Yb/20% of Ce/1% of Ho/2% of Er core nano-crystal: according to the weight percentage of the substances, 23% of gadolinium chloride, 54% of ytterbium chloride, 20% of cerium chloride, 1% of holmium chloride and 2% of erbium chloride are respectively weighed and placed in a reaction container, and then the mixture is added into the reaction container according to the volume ratio of 2: 5 oleic acid and octadecene; heating the reaction solution to 100-110 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device until no bubbles are generated, introducing nitrogen for 10-20 min, heating the reaction solution to 160-180 ℃, keeping the temperature for 30-60 min, and naturally cooling to obtain a solution A;
slowly adding 10-15 mL of methanol solution in which 2-4 times of sodium hydroxide and 3-6 times of ammonium fluoride of the rare earth chloride precursor are dissolved into the solution A and continuously stirring for 30-45 min; heating the reaction system to 100-120 ℃ under the stirring and vacuumizing states, closing a vacuum device until no bubbles are generated, introducing nitrogen for 10-20 min, heating to 240-260 ℃, keeping for 40-50 min, and naturally cooling to room temperature; carrying out centrifugal washing on ethanol and cyclohexane to obtain nano particles, and storing the nano particles in cyclohexane liquid;
s4, preparation by coating method
NaGdF4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF420% Yb/30% Ce: the sum of the amounts of the substances is equal to that in the step S3, the amount fractions of the substances are respectively 50% gadolinium oleate, 20% ytterbium oleate and 30% cerium oleate, sodium fluoride in an amount which is 4-6 times that of the rare earth oleate substance and the cyclohexane solution for storing the nanoparticles in the step S3 are mixed, and then the mixture is added with the solvent with the volume ratio of 1: 1 oleic acid and octadecene; heating to 110-120 ℃ under the stirring and vacuumizing states, closing a vacuum device and introducing nitrogen when no bubbles are generatedKeeping for 0.5-1 h, then heating to 300-320 ℃, reacting for 1-1.5 h, and then naturally cooling to room temperature; after centrifugal washing by ethanol and cyclohexane, NaGdF is obtained4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF4:20％Yb/30％Ce。
Preferably, the chlorides of the rare earth metal elements gadolinium, ytterbium, cerium, erbium and holmium synthesized in step S1 are specifically:
at room temperature, taking 10-30 mmol of rare earth oxide and 60-180 mmol of concentrated hydrochloric acid, uniformly mixing in a container, slowly heating the mixed solution to 80-90 ℃ while stirring, adding 10-30 mL of distilled water, continuously reacting for 0.5-1 h, cooling and filtering the obtained solution to obtain a clear transparent solution, continuously heating at 80-90 ℃ until chloride crystals are separated out on the surface of the solution, transferring to a 60-70 ℃ oven, and drying to obtain solid powder which is the chloride of the corresponding metal element;
preferably, the specific steps of respectively synthesizing oleates containing the rare earth metal elements gadolinium, ytterbium, cerium, erbium and holmium in step S2 are as follows:
adding 10-30 mmol of corresponding rare earth chloride, 30-90 mmol of sodium oleate, 30-50 mL of distilled water, 40-70 mL of ethanol and 70-110 mL of n-hexane into a container, heating the mixed solution to 70 ℃ under stirring, continuously reacting for 4 hours, and stopping heating; cooling to room temperature, pouring the mixed solution into a separating funnel for separation, washing, taking the upper layer liquid, drying in a water bath at the temperature of 80 ℃, and placing at room temperature until a solid waxy substance is obtained, wherein the solid waxy substance is an oleate precursor containing corresponding metal elements;
preferably, the NaGdF is prepared4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF420% Yb/30% Ce in cyclohexane liquid.
The invention also aims to apply the prepared up/down conversion dual-mode luminescence nanocrystal to a biological imaging probe or a drug carrier.
The invention has the beneficial effects that:
the invention discloses an up/down conversion dual-mode luminescent nanocrystal and a preparation method and application thereof, and a high-temperature solvothermal method and an epitaxial growth method are adopted to prepare a NaGdF4 Yb, Ce, Ho, Er @ NaGdF4 Yb and Ce core-shell structure nanocrystal. The preparation method has four characteristics:
1. the preparation method of the material comprises a two-step high-temperature solvothermal method, is simple and easy to implement, and the generated nanocrystals have good dispersibility and uniform particle size distribution.
2. When rare earth ions gadolinium and ytterbium are doped into the inner core, the doping of gadolinium is favorable for obtaining the core nano-crystal with a hexagonal phase, and the hexagonal phase is favorable for realizing stronger fluorescence emission;
3. the core is doped with low-content holmium, so that the down-conversion near-infrared luminescence is not obviously influenced, meanwhile, three cross relaxation processes between cerium and holmium endow the nanocrystalline with an up-conversion red light emission function, and the coating of the shell layer is favorable for improving the up-conversion luminescence intensity of the nanocrystalline;
4. when the core with smaller size is doped with rare earth ion erbium and the shell with thicker size is doped with rare earth ion cerium, because of the unique energy level matching between cerium and erbium, after ytterbium transfers energy to erbium, the cross relaxation effect occurs between erbium and cerium, and the small size of the core is very favorable for improving the occurrence probability of the cross relaxation, thereby leading the photons on the red light level and the green light level of erbium to be sharply reduced and the photons on the near infrared two-region light level to be rapidly accumulated; the doping concentration of erbium ions in the core is 2%, the doping concentration of ytterbium ions is 20% of the traditional doping concentration, and the doping of ytterbium in the shell layer greatly improves the absorption capacity of the nanocrystalline on near-infrared excitation photons; the luminous intensity of the near-infrared two regions of erbium is increased and then decreased along with the increase of the doping concentration of cerium ions of the shell layer, and when the doping concentration of cerium is 30%, the near-infrared two regions emit strongest light, which is 11.7 times higher than that of the core-shell structure nanocrystalline undoped with Ce.
The preparation method has the advantages of simple and easy operation of the synthetic route, uniform particle size distribution, high product purity and environmental protection, and can endow the nanocrystalline with stronger red and near-infrared two-region fluorescence by doping different rare earth elements and controlling the sizes of the core and the shell in the core-shell structure, the near-infrared fluorescence can be used as a potential optical imaging contrast agent, and the prepared nanocrystalline can be used as a nano energy converter for light trigger treatment by red light emission. Therefore, the nanocrystalline can be used as a potential diagnosis and treatment integrated nano platform.
Drawings
FIG. 1 is a transmission electron microscope photograph of a core nanocrystal prepared by the high temperature solvothermal method of step (3) in example 1;
FIG. 2 is a TEM image of core-shell nanocrystals prepared by continuous coating in step (4) of example 1;
FIG. 3 shows the X-ray diffraction pattern and hexagonal phase NaGdF of the core-shell structure nanocrystal prepared in example 14The standard card of (1);
FIG. 4 is a spectrum of a 980nm laser excited core-shell structure nanocrystal with visible conversion and near infrared down-conversion emission spectra.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The chemical expression of the up/down conversion dual-mode luminescent nanocrystal provided by the invention is NaGdF4:Yb,Ce,Ho,Er@NaGdF4Yb, Ce; wherein @ represents the package, and the content of each metal can be adjusted according to actual requirements in actual preparation production. Several examples are given below for the preparation of NaGdF4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF4:20％Yb/30％Ce。
Example 1
(1) Respectively synthesizing gadolinium chloride, ytterbium chloride, cerium chloride, holmium chloride and erbium chloride: at room temperature, uniformly mixing 20mmol of corresponding metal oxide and 60mmol of concentrated hydrochloric acid in a container, slowly heating the mixed solution to 80 ℃ on a constant-temperature heating magnetic stirrer under magnetic stirring, adding 10mL of distilled water, continuously reacting for 0.5h, cooling and filtering the obtained solution to obtain a clear transparent solution, continuously heating at 80 ℃ until chloride crystals are separated out on the surface of the solution, transferring the solution to a 60 ℃ oven, and drying to obtain solid powder which is the chloride of the corresponding metal element;
(2) respectively synthesizing gadolinium oleate, ytterbium oleate and cerium oleate: adding 20mmol of corresponding metal chloride, 60mmol of sodium oleate, 30mL of distilled water, 40mL of ethanol and 70mL of n-hexane into a container, heating the mixed solution to 70 ℃ under magnetic stirring in a constant-temperature heating magnetic stirrer, reacting for 4 hours, stopping heating and cooling to room temperature, pouring the mixed solution into a separating funnel, washing with distilled water for three times, taking the upper layer liquid, drying in a water bath at 80 ℃, standing at room temperature for three days, and obtaining a solid waxy substance which is an oleate precursor containing rare earth elements;
(3) preparation of NaGdF by high-temperature solvothermal method454 percent of Yb/20 percent of Ce/2 percent of Ho/0.5 percent of Er core nanocrystalline. Weighing 0.0615g of gadolinium chloride, 0.1519g of ytterbium chloride, 0.0559g of cerium chloride, 0.0055g of holmium chloride and 0.0014g of erbium chloride into a three-neck flask, and adding 6mL of oleic acid and 15mL of octadecene; heating to 110 deg.C under stirring and vacuum-pumping state, stopping vacuum device, introducing nitrogen for 10min, heating to 160 deg.C, maintaining for 30min, and naturally cooling to room temperature; slowly adding 10mL of methanol solution dissolved with 0.1g of sodium hydroxide and 0.1482g of ammonium fluoride into the solution and continuously stirring for 30 min; heating the reaction system to 120 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device, introducing nitrogen for 10min when no bubbles are generated, then heating to 250 ℃ for 45min, naturally cooling to room temperature, washing with ethanol and cyclohexane for three times, and storing the prepared nanoparticles in cyclohexane liquid;
(4) preparation of NaGdF by coating method4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF420% Yb/30% Ce. Adding the cyclohexane solution in the previous step into a 100mL three-necked bottle; meanwhile, 0.5008g of gadolinium oleate, 0.2035g of ytterbium oleate, 0.2954g of cerium oleate and 0.21g of sodium fluoride are weighed into a three-neck flask, and 15mL of oleic acid and 15mL of octadecene are added; heating to 120 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device when no bubbles are generated, introducing nitrogen for 20min, heating to 300 ℃, reacting for 1h, and naturally cooling to room temperature; after three washes with ethanol and cyclohexane, the prepared nanoparticles were stored in cyclohexane liquid.
Example 2
(1) Respectively synthesizing gadolinium chloride, ytterbium chloride, cerium chloride, holmium chloride and erbium chloride: at room temperature, uniformly mixing 30mmol of corresponding metal oxide and 180mmol of concentrated hydrochloric acid in a container, slowly heating the mixed solution to 90 ℃ under magnetic stirring on a constant-temperature heating magnetic stirrer, adding 30mL of distilled water, continuously reacting for 1h, cooling and filtering the obtained solution to obtain a clear and transparent solution, continuously heating at 90 ℃ until chloride crystals are separated out on the surface of the solution, transferring the solution to a 70 ℃ oven, and drying to obtain solid powder which is the chloride of the corresponding metal element;
(2) respectively synthesizing gadolinium oleate, ytterbium oleate and cerium oleate: adding 30mmol of corresponding metal chloride, 90mmol of sodium oleate, 50mL of distilled water, 60mL of ethanol and 90mL of n-hexane into a container, heating the mixed solution to 70 ℃ under magnetic stirring in a constant-temperature heating magnetic stirrer, reacting for 4 hours, stopping heating and cooling to room temperature, pouring the mixed solution into a separating funnel, washing with distilled water for three times, taking the upper layer liquid, drying in a water bath at 80 ℃, standing at room temperature for three days, and obtaining a solid waxy substance which is an oleate precursor containing rare earth elements;
(3) preparation of NaGdF by high-temperature solvothermal method454 percent of Yb/20 percent of Ce/2 percent of Ho/0.5 percent of Er core nanocrystalline. Weighing 0.0615g of gadolinium chloride, 0.1519g of ytterbium chloride, 0.0559g of cerium chloride, 0.0055g of holmium chloride and 0.0014g of erbium chloride into a three-neck flask, and adding 6mL of oleic acid and 15mL of octadecene; heating to 100 deg.C under stirring and vacuum-pumping, stopping vacuum device, introducing nitrogen for 20min, heating to 180 deg.C for 45min, and naturally cooling to room temperature; slowly adding 15mL of methanol solution dissolved with 0.1g of sodium hydroxide and 0.1482g of ammonium fluoride into the solution and continuously stirring for 45 min; heating the reaction system to 110 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device, introducing nitrogen for 20min when no bubbles are generated, then heating to 240 ℃ for 50min, naturally cooling to room temperature, washing with ethanol and cyclohexane for three times, and storing the prepared nanoparticles in cyclohexane liquid;
(4) preparation of NaGdF by coating method4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF 420% Yb/30% Ce. Adding the cyclohexane solution in the previous step into a 100mL three-necked bottle; meanwhile, 0.5008g of gadolinium oleate, 0.2035g of ytterbium oleate, 0.2954g of cerium oleate and 0.21g of sodium fluoride are weighed into a three-neck flask, and 15mL of oleic acid and 15mL of octadecene are added; heating to 110 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device when no bubbles are generated, introducing nitrogen for 30min, heating to 310 ℃, reacting for 1.5h, and naturally cooling to room temperature; after three washes with ethanol and cyclohexane, the prepared nanoparticles were stored in cyclohexane liquid.
Example 3
(1) Respectively synthesizing gadolinium chloride, ytterbium chloride, cerium chloride, holmium chloride and erbium chloride: at room temperature, taking 10mmol of corresponding metal oxide and 90mmol of concentrated hydrochloric acid, uniformly mixing in a container, slowly heating the mixed solution to 85 ℃ on a constant-temperature heating magnetic stirrer under magnetic stirring, adding 20mL of distilled water, continuously reacting for 0.8h, cooling and filtering the obtained solution to obtain a clear transparent solution, continuously heating at 85 ℃ until chloride crystals are separated out on the surface of the solution, transferring to a 65 ℃ oven, and drying to obtain solid powder which is the chloride of the corresponding metal element;
(2) respectively synthesizing gadolinium oleate, ytterbium oleate and cerium oleate: adding 10mmol of corresponding metal chloride, 30mmol of sodium oleate, 40mL of distilled water, 70mL of ethanol and 110mL of n-hexane into a container, heating the mixed solution to 70 ℃ under magnetic stirring in a constant-temperature heating magnetic stirrer, reacting for 4 hours, stopping heating and cooling to room temperature, pouring the mixed solution into a separating funnel, washing with distilled water for three times, taking the upper layer liquid, drying in a water bath at 80 ℃, standing at room temperature for three days, and obtaining a solid waxy substance which is an oleate precursor containing rare earth elements;
(3) preparation of NaGdF by high-temperature solvothermal method454 percent of Yb/20 percent of Ce/2 percent of Ho/0.5 percent of Er core nanocrystalline. Weighing 0.0615g of gadolinium chloride, 0.1519g of ytterbium chloride, 0.0559g of cerium chloride, 0.0055g of holmium chloride and 0.0014g of erbium chloride into a three-neck flask, and adding 6mL of oleic acid and 15mL of octadecene; heating to 105 deg.C under stirring and vacuum-pumping, turning off vacuum device, and introducing nitrogen gasKeeping for 15min, then heating to 170 ℃ and keeping for 60min, and then naturally cooling to room temperature; slowly adding 12mL of methanol solution dissolved with 0.1g of sodium hydroxide and 0.1482g of ammonium fluoride into the solution and continuing stirring for 40 min; heating the reaction system to 100 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device, introducing nitrogen for keeping for 15min when no bubbles are generated, then heating to 260 ℃ for keeping for 40min, then naturally cooling to room temperature, washing with ethanol and cyclohexane for three times, and storing the prepared nanoparticles in cyclohexane liquid;
(4) preparation of NaGdF by coating method4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF 420% Yb/30% Ce. Adding the cyclohexane solution in the previous step into a 100mL three-necked bottle; meanwhile, 0.5008g of gadolinium oleate, 0.2035g of ytterbium oleate, 0.2954g of cerium oleate and 0.21g of sodium fluoride are weighed into a three-neck flask, and 15mL of oleic acid and 15mL of octadecene are added; heating to 110 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device until no bubbles are generated, introducing nitrogen for 60min, heating to 320 ℃, reacting for 1.2h, and naturally cooling to room temperature; after three washes with ethanol and cyclohexane, the prepared nanocrystalline particles were stored in cyclohexane liquid.
The product prepared in example 1 was selected for morphological characterization, the picture of the core nanocrystal projection electron microscope prepared in the third step is shown in fig. 1, and the characterization result of the core-shell structure nanocrystal obtained in the fourth step is shown in fig. 1
The preparation methods described in the above three examples have four characteristics: the preparation method for generating the material comprises a two-step high-temperature solvothermal method, is simple and feasible, and the generated nanocrystals have good dispersibility and uniform particle size distribution. Secondly, when rare earth ions gadolinium and ytterbium are doped into the inner core, the doping of gadolinium is favorable for obtaining the core nanocrystal with the hexagonal phase, and the hexagonal phase is favorable for realizing stronger fluorescence emission; and thirdly, low-content holmium is doped in the core, so that the down-conversion near-infrared luminescence is not obviously influenced, meanwhile, three cross relaxation processes between cerium and holmium endow the nanocrystalline with an up-conversion red light emission function, and the coating of the shell layer is favorable for improving the up-conversion luminescence intensity of the nanocrystalline. Fourthly, when the core with smaller size is doped with rare earth ion erbium and the shell with thicker size is doped with rare earth ion cerium, because of unique energy level matching between cerium and erbium, after ytterbium transfers energy to erbium, cross relaxation effect occurs between erbium and cerium, the small size of the core is very favorable for improving the occurrence probability of the cross relaxation, and further, photons on the red light level and the green light level of erbium are sharply reduced and photons on the near infrared two-region light level are rapidly accumulated; the doping concentration of erbium ions in the core is 2%, the doping concentration of ytterbium ions is 20% of the traditional doping concentration, and the doping of ytterbium in the shell layer greatly improves the absorption capacity of the nanocrystalline on near-infrared excitation photons; the luminous intensity of the near-infrared two regions of erbium is increased and then decreased along with the increase of the doping concentration of cerium ions of the shell layer, and when the doping concentration of cerium is 30%, the near-infrared two regions emit strongest light, which is 11.7 times higher than that of the core-shell structure nanocrystalline undoped with Ce.
The nanocrystalline obtained in the embodiment can be used for preparing a drug carrier, such as a mesoporous nano-drug carrier, and the preparation method comprises the following steps:
mixing the nanocrystals prepared at any of examples 1-3 with cetyltrimethylammonium bromide and deionized water, and stirring to obtain a transparent and clear solution; adding ethanol and sodium hydroxide solution; heating the mixture to 70-75 ℃ under a stirring state, dropwise adding ethyl orthosilicate, and continuing the reaction process for 10-15 min; repeatedly washing with ethanol, adding ethanol and ammonium nitrate, heating to 60 ℃, keeping for 2-3 h, and centrifugally separating with ethanol to obtain a product, namely the drug carrier coated with the mesoporous silica, wherein the specific chemical expression is as follows:
NaGdF4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF4:20％Yb/30％Ce@mSiO2。
by adopting the technical scheme disclosed by the invention, the following beneficial effects are obtained:
the synthesis route provided by the invention has the advantages of simple and easy operation, uniform particle size distribution, high product purity and environmental protection, and the strong red and near-infrared two-region fluorescence of the nanocrystalline is given by doping different rare earth elements and controlling the sizes of the core and the shell in the core-shell structure, the near-infrared fluorescence can be used as a potential optical imaging contrast agent, and the prepared nanocrystalline can be used as a nano energy converter for light trigger treatment by red light emission. Therefore, the nanocrystalline can be used in the fields of biological imaging probes or drug carriers and the like, and can be used as a potential diagnosis and treatment integrated nano platform.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements should also be considered within the scope of the present invention.
Claims (6)
1. An up/down conversion dual-mode luminescent nanocrystal is characterized by comprising the following chemical expression:
NaGdF4:Yb,Ce,Ho,Er@NaGdF4yb, Ce; where @ denotes a package.
2. A preparation method of up/down conversion dual-mode luminescent nanocrystals is characterized by comprising the following steps:
s1, respectively synthesizing chlorides of rare earth metal elements gadolinium, ytterbium, cerium, erbium and holmium;
s2, respectively synthesizing oleate containing rare earth metal elements of gadolinium, ytterbium, cerium, erbium and holmium;
s3, preparing NaGdF by adopting high-temperature solvothermal method454% of Yb/20% of Ce/1% of Ho/2% of Er core nano-crystal: according to the weight percentage of the substances, 23% of gadolinium chloride, 54% of ytterbium chloride, 20% of cerium chloride, 1% of holmium chloride and 2% of erbium chloride are respectively weighed and placed in a reaction container, and then the mixture is added into the reaction container according to the volume ratio of 2: 5 oleic acid and octadecene; heating the reaction solution to 100-110 ℃ under the conditions of stirring and vacuumizing, closing a vacuum device until no bubbles are generated, introducing nitrogen for 10-20 min, heating the reaction solution to 160-180 ℃, keeping the temperature for 30-60 min, and naturally cooling to obtain a solution A;
slowly adding 10-15 mL of methanol solution in which 2-4 times of sodium hydroxide and 3-6 times of ammonium fluoride of the rare earth chloride precursor are dissolved into the solution A and continuously stirring for 30-45 min; heating the reaction system to 100-120 ℃ under the stirring and vacuumizing states, closing a vacuum device until no bubbles are generated, introducing nitrogen for 10-20 min, heating to 240-260 ℃, keeping for 40-50 min, and naturally cooling to room temperature; carrying out centrifugal washing on ethanol and cyclohexane to obtain nano particles, and storing the nano particles in cyclohexane liquid;
s4, preparation by coating method
NaGdF4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF420% Yb/30% Ce: the sum of the amounts of the substances is equal to that in the step S3, the amount fractions of the substances are respectively 50% gadolinium oleate, 20% ytterbium oleate and 30% cerium oleate, sodium fluoride in an amount which is 4-6 times that of the rare earth oleate substance and the cyclohexane solution for storing the nanoparticles in the step S3 are mixed, and then the mixture is added with the solvent with the volume ratio of 1: 1 oleic acid and octadecene; heating to 110-120 ℃ under the stirring and vacuumizing states, closing a vacuum device after no bubbles are generated, introducing nitrogen for 0.5-1 h, heating to 300-320 ℃, reacting for 1-1.5 h, and naturally cooling to room temperature; after centrifugal washing by ethanol and cyclohexane, NaGdF is obtained4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF4:20％Yb/30％Ce。
3. The preparation method according to claim 2, wherein the chlorides of the respective rare earth metal elements gadolinium, ytterbium, cerium, erbium and holmium synthesized in step S1 are specifically:
at room temperature, 10-30 mmol of rare earth oxide and 60-180 mmol of concentrated hydrochloric acid are uniformly mixed in a container, the mixed solution is slowly heated to 80-90 ℃ under stirring, 10-30 mL of distilled water is added and the reaction is continued for 0.5-1 h, the obtained solution is cooled and filtered to obtain a clear transparent solution, the solution is continuously heated at 80-90 ℃ until chloride crystals are separated out on the surface of the solution, the solution is transferred to a 60-70 ℃ oven for drying, and the obtained solid powder is chloride of corresponding metal elements.
4. The method according to claim 2, wherein the step S2 of synthesizing oleates containing rare earth metal elements gadolinium, ytterbium, cerium, erbium and holmium respectively comprises the following steps:
adding 10-30 mmol of corresponding rare earth chloride, 30-90 mmol of sodium oleate, 30-50 mL of distilled water, 40-70 mL of ethanol and 70-110 mL of n-hexane into a container, heating the mixed solution to 70 ℃ under stirring, continuously reacting for 4 hours, and stopping heating; and cooling to room temperature, pouring the mixed solution into a separating funnel for separation, washing, taking the upper layer liquid, drying in a water bath at the temperature of 80 ℃, and placing at room temperature until a solid waxy substance is obtained, wherein the solid waxy substance is an oleate precursor containing corresponding metal elements.
5. The method of claim 2, wherein the NaGdF is prepared4:54％Yb/20％Ce/2％Ho/0.5％Er@NaGdF420% Yb/30% Ce in cyclohexane liquid.
6. Use of the up/down conversion dual-mode luminescence nanocrystal prepared by the preparation method of any one of claims 2-5 in a biological imaging probe or a drug carrier.
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