CN112920793A - Rare earth luminescent material with enhanced visible light/near-infrared two-region emission - Google Patents
Rare earth luminescent material with enhanced visible light/near-infrared two-region emission Download PDFInfo
- Publication number
- CN112920793A CN112920793A CN202110111641.4A CN202110111641A CN112920793A CN 112920793 A CN112920793 A CN 112920793A CN 202110111641 A CN202110111641 A CN 202110111641A CN 112920793 A CN112920793 A CN 112920793A
- Authority
- CN
- China
- Prior art keywords
- minutes
- nagdf
- naerf
- infrared
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 56
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 29
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 90
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 55
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 30
- 229910021266 NaErF4 Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910003317 GdCl3 Inorganic materials 0.000 claims description 16
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 10
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 10
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- -1 octadecylene Chemical group 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 abstract description 14
- 239000007850 fluorescent dye Substances 0.000 abstract description 7
- 239000002109 single walled nanotube Substances 0.000 abstract description 5
- 238000012984 biological imaging Methods 0.000 abstract description 4
- 239000002096 quantum dot Substances 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 150000003384 small molecules Chemical class 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 230000002902 bimodal effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 229920002125 Sokalan® Polymers 0.000 description 11
- 239000004584 polyacrylic acid Substances 0.000 description 11
- 206010028980 Neoplasm Diseases 0.000 description 8
- 210000003462 vein Anatomy 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 210000004204 blood vessel Anatomy 0.000 description 5
- 239000011257 shell material Substances 0.000 description 5
- 239000011162 core material Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 241000124008 Mammalia Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
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
- 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
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7772—Halogenides
- C09K11/7773—Halogenides with alkali or alkaline earth metal
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nanotechnology (AREA)
- Biomedical Technology (AREA)
- Animal Behavior & Ethology (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a rare earth luminescent material with enhanced visible light/near infrared two-region emission, which structurally comprises NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4Wherein X is 1-10, the particle size is 20-100 nm, and the compound can be used for biological imaging in visible light and near infrared regions. Compared with reported quantum dots, single-walled carbon nanotubes and organic small molecules with near-infrared two-region emission, the material has lower toxicity, narrower band gap emission, controllable size and high-efficiency near-infrared light emission. In addition, Ce is doped in the structure of the material3+Not only effectively enhance Er3+Characteristic emission in the near infrared region, andavoid Er3+And the luminescence in a visible light region is quenched, so that the material has stronger up-conversion single-band red light emission and near-infrared two-region emission at the same time. Therefore, the material has potential application value as a bimodal fluorescent probe for imaging in a visible region and a near infrared region.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a novel visible light/near infrared two-region emission enhanced rare earth luminescent material prepared based on a solvothermal method and an epitaxial growth method.
Background
In recent years, near-infrared two-zone fluorescence imaging is taken as an emerging technology to intrude into the visual field of people, provides higher signal-to-noise ratio and penetration depth, shows potential advantages in the aspects of disease detection, diagnosis, treatment and the like, and can provide direct visual guidance for medical surgery. The near-infrared two-region fluorescent probe is an ideal window for fluorescence imaging of deep tissue structures of mammals, and the imaging technology of the near-infrared two-region fluorescent probe is widely applied to scientific research and clinical tests, so that the near-infrared two-region fluorescent probe also becomes a fluorescent probe with better performance at present.
The currently studied near-infrared two-region luminescent materials mainly include: quantum dots, single-walled carbon nanotubes, organic small molecules and rare earth luminescent materials. The quantum dots have a large absorption cross section, have the advantages of near-infrared emission characteristic, high quantum efficiency and the like, and are widely applied to the fields of luminescence and display. However, most quantum dots contain toxic elements (lead or arsenic) which limit the application of such materials in the field of biomedical imaging. The single-walled nanotube is used as a direct band gap material, has strong absorption to near infrared light, and can rapidly convert light energy into heat energy so as to promote cell death. However, the morphology of the single-walled carbon nanotube is difficult to control by chemical synthesis means and mechanical processing means, and the single-walled carbon nanotube has some cytotoxicity when being used in biological experiments for a long time. Compared with other inorganic materials in the near-infrared second region, the organic micromolecules have the advantages of designable molecular structure, adjustable optical performance, good biocompatibility and the like, and are widely applied to biological imaging of the visible light and the near-infrared first region. However, the application of small organic molecules in biological imaging in the near-infrared region is limited due to the low quantum yield in aqueous environment. The rare earth luminescent material has excellent optical properties: the material has the advantages of long fluorescence lifetime, narrow emission band and the like, so that the material shows unique advantages in the aspect of biological imaging, has low toxicity in organisms and good imaging effect after surface modification, and is considered as a novel ideal fluorescent probe.
Disclosure of Invention
The invention aims to provide a rare earth luminescent material which has lower toxicity, narrower band gap emission, controllable size, stronger up-conversion single-band red light emission and near-infrared two-region emission.
In order to achieve the purpose, the structural composition of the rare earth luminescent material adopted by the invention is NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4Wherein X is 1-10, preferably X is 4-6; the particle size of the material is 20-100 nm.
The rare earth luminescent material with enhanced visible light/near infrared two-region emission is prepared by the following method:
1. ErCl3·6H2O、YbCl3·6H2O、TmCl3·6H2Adding O into a mixed solution of oleic acid and octadecylene with the volume ratio of 1:2.5, stirring for 60 minutes at 160 ℃ in an anhydrous oxygen-free argon protective atmosphere, then cooling the system to room temperature, adding NaOH and NH dissolved in the system4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 295-314 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF 410% Yb, 0.5% Tm rare earth luminescent material; wherein, said ErCl3·6H2O、YbCl3·6H2O、TmCl3·6H2O、NaOH、NH4The molar ratio of F is 0.895:0.1:0.005: 2.5-4: 4.
2. Mixing GdCl3·6H2O、YbCl3·6H2O、CeCl3·6H2Adding O into a mixed solution of oleic acid and octadecylene with the volume ratio of 1:2.5, stirring for 60 minutes at 160 ℃ in an anhydrous oxygen-free argon protective atmosphere, then cooling the system to room temperature, and adding the NaErF prepared in the step 1410% of Yb and 0.5% of Tm, heating to 80 ℃, vacuumizing for 20 minutes, cooling the system to room temperature, adding dissolved NaOH and NH4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 295-314 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF4:10％Yb,0.5％Tm@NaGdF 420% of Yb and X% of Ce rare earth luminescent material; wherein, the NaErF4:10％Yb,0.5％Tm、GdCl3·6H2O、YbCl3·6H2O、CeCl3·6H2O、NaOH、NH4The molar ratio of F is 1 (0.4-Y):0.1: Y:1.25:2, Y is 0.01-0.1, preferably Y is 0.04-0.06.
3. Mixing GdCl3·6H2Adding O into a mixed solution of oleic acid and octadecylene with the volume ratio of 1:2.5, stirring for 60 minutes at 160 ℃ in an anhydrous oxygen-free argon protective atmosphere, then cooling the system to room temperature, and adding NaErF prepared in the step 24:10％Yb,0.5％Tm@NaGdF 420% of Yb and X% of Ce, heating to 80 ℃, vacuumizing for 20 minutes, cooling the system to room temperature, adding dissolved NaOH and NH4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 295-314 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4A rare earth luminescent material; wherein, the NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce、GdCl3·6H2O、NaOH、NH4The molar ratio of F is 1:0.4:1: 1.6.
The invention has the following beneficial effects:
1. the invention adopts NaErF410% Yb and 0.5% Tm as crystal nucleus to construct NaErF with core-shell structure4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4Rare earth luminescent material, wherein NaErF410% Yb, 0.5% Tm as a core material is capable of producing single band red emission. In addition, the first shell layer is doped with Ce3+Not only can effectively enhance Er3+Characteristic emission in the near infrared region (about 1550nm) and effective avoidance of Er3+Quenching of luminescence in the visible region, and finally NaGdF4The construction of the inert shell layer is beneficial to improving the overall luminous intensity of the material. The rare earth luminescent material prepared by the invention can be used for the imaging of organism visible light and near infrared, and the material is expected to become an ideal fluorescent probe in the biomedical imaging field due to the advantages of high light stability, narrow band gap emission, long fluorescence life, good biocompatibility, deep tissue penetration depth and the like.
2. The invention utilizes NaErF4As a substrate, NaErF is prepared by adopting a solvothermal method and an epitaxial growth method4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4The rare earth luminescent material has simple and controllable preparation process and uniform particle size distribution of the obtained material. Experimental results show that the material has good biocompatibility and low toxicity after being subjected to polyacrylic acid surface modification, can realize whole body vascular imaging after being injected into a mouse body through a tail vein, and is enriched to a tumor part under the EPR effect so as to realize tumor part imaging.
Drawings
FIG. 1 is NaErF prepared in example 14:10％Yb,0.5％Tm、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce@NaGdF4NaErF prepared in comparative example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb@NaGdF4And NaErF prepared in comparative example 24:10％Yb,0.5％Tm,5％Ce@NaGdF4XRD pattern of 20% Yb.
FIG. 2 is NaErF prepared in example 14Transmission electron micrograph of 10% Yb, 0.5% Tm.
FIG. 3 is NaErF prepared in example 14:10％Yb,0.5％Tm@NaGdF 420% Yb and 5% Ce.
FIG. 4 is NaErF prepared in example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce@NaGdF4Transmission electron micrograph (D).
FIG. 5 is NaErF prepared in comparative example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb@NaGdF4Transmission electron micrograph (D).
FIG. 6 is NaErF prepared in comparative example 24:10％Yb,0.5％Tm,5％Ce@NaGdF4Transmission electron microscopy of 20% Yb.
FIG. 7 is NaErF prepared in example 14:10％Yb,0.5％Tm、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce@NaGdF4And NaErF prepared in comparative example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb@NaGdF4The near infrared two-region emission spectrogram.
FIG. 8 shows NaErF prepared in examples 1 to 54:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,1％Ce、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,3％Ce、NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,7％Ce、NaErF4:10％Yb,0.5％Tm@NaGdF 420% Yb and 10% Ce.
FIG. 9 is NaErF prepared in example 14:10％Yb,0.5％Tm@NaGdF 420% Yb, 5% Ce and NaErF prepared in comparative example 24:10％Yb,5％Ce,0.5％Tm@NaGdF4Emission spectrum in the visible region of 20% Yb.
FIG. 10 is NaErF prepared according to example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb@NaGdF4And (3) carrying out surface modification on polyacrylic acid, injecting the polyacrylic acid into a mouse body through a tail vein, and then carrying out a blood vessel imaging graph in a near infrared region II.
FIG. 11 NaErF prepared in example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce@NaGdF4And (3) carrying out surface modification on polyacrylic acid, injecting the polyacrylic acid into a mouse body through a tail vein, and then carrying out a blood vessel imaging graph in a near infrared region II.
FIG. 12 NaErF prepared in comparative example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb@NaGdF4And (3) carrying out surface modification on polyacrylic acid, injecting the polyacrylic acid into a mouse body through a tail vein, and then carrying out tumor imaging in a near-infrared region II.
FIG. 13 NaErF prepared in example 14:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce@NaGdF4And (3) carrying out surface modification on polyacrylic acid, injecting the polyacrylic acid into a mouse body through a tail vein, and then carrying out tumor imaging in a near-infrared region II.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. 0.3415g (0.895mmol) ErCl3·6H2O、0.0387g(0.1mmol)YbCl3·6H2O、0.0019g(0.005mmol)TmCl3And 6mL of oleic acid and 15mL of octadecene were added to a 100mL three-necked flask, and stirred at 160 ℃ for 60 minutes under a water-free, oxygen-free, argon-protected atmosphere to form a uniform, transparent, pale pink liquid. The system was then cooled to room temperature and 0.1g (2.5mmol) NaOH and 0.1482g (4mmol) NH dissolved were added4Stirring 10mL of methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 300 ℃, keeping the temperature for 60 minutes, cooling the system temperature to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF 410% Yb, 0.5% Tm rare earth luminescent material (core material).
2. 0.1394g (0.375mmol) GdCl3·6H2O、0.0388g(0.1mmol)YbCl3·6H2O、0.0089g(0.025mmol)CeCl3·6H2Adding O, 6mL of oleic acid and 15mL of octadecene into a 100mL three-neck flask, and stirring for 60 minutes at 160 ℃ under the atmosphere of anhydrous oxygen-free argon protection to form a uniform transparent solution which is slightly yellowish; then the system is mixedCooling to room temperature, adding NaErF prepared in step 1410% Yb, 0.5% Tm and heating to 80 ℃ and evacuating for 20 minutes, cooling the system to room temperature and adding a solution of 0.05g (1.25mmol) NaOH and 0.0741g (2mmol) NH4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 300 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF4:10％Yb,0.5％Tm@NaGdF 420% Yb, 5% Ce rare earth luminescent material (core/shell material).
3. 0.1487g (0.4mmol) GdCl3·6H2O, 6mL of oleic acid and 15mL of octadecene are added into a 100mL three-neck flask, stirred for 60 minutes at 160 ℃ under the atmosphere of anhydrous oxygen-free argon protection, then the system is cooled to room temperature, and NaErF prepared in the step 2 is added4:10％Yb,0.5％Tm@NaGdF 420% Yb, 5% Ce and heating to 80 ℃ and evacuating for 20 minutes, then cooling the system to room temperature and adding a solution of 0.04g (1mmol) NaOH and 0.0593g (1.6mmol) NH4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 300 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,5％Ce@NaGdF4Rare earth luminescent materials (core/shell materials).
Comparative example 1
In step 2 of example 1, GdCl3·6H2The amount of O used was 0.1487g, no CeCl was added3·6H2O, other procedure the same as example 1, NaErF was obtained4:10％Yb,0.5％Tm@NaGdF4:20％Yb@NaGdF4A rare earth luminescent material.
Comparative example 2
In step 1 of example 1, ErCl3·6H2The amount of O was 0.3225g, and 0.0177g of CeCl was added3·6H2O, step 2, GdCl3·6H2The amount of O0.1487g, without addition of CeCl3·6H2O, without the operation of the step 3, NaErF is prepared4:10％Yb,5％Ce,0.5％Tm@NaGdF 420% of Yb rare earth luminescent material.
Example 2
In step 2 of example 2, GdCl3·6H2The amount of O used was 0.1468g, CeCl3·6H2The amount of O used was 0.0018g, and the other steps were the same as in example 1 to obtain NaErF4:10％Yb,0.5％Tm@NaGdF 420% of Yb and 1% of Ce rare earth luminescent material.
Example 3
In step 2 of example 3, GdCl3·6H2The amount of O used was 0.1431g, CeCl3·6H2Using 0.0053g of O, NaErF was obtained in the same manner as in example 14:10％Yb,0.5％Tm@NaGdF 420% of Yb and 3% of Ce rare earth luminescent material.
Example 4
In step 2 of example 4, GdCl3·6H2The amount of O used was 0.1357g, CeCl3·6H2The amount of O used was 0.0124g, and the other steps were the same as in example 1 to obtain NaErF4:10％Yb,0.5％Tm@NaGdF 420% of Yb and 7% of Ce rare earth luminescent material.
Example 5
In step 2 of example 5, GdCl3·6H2The amount of O used was 0.1301g, CeCl3·6H2The amount of O used was 0.0178g, and the other steps were the same as in example 1 to obtain NaErF4:10％Yb,0.5％Tm@NaGdF 420% of Yb and 10% of Ce rare earth luminescent material.
The inventor adopts an X-ray diffractometer, a transmission electron microscope, a fluorescence spectrometer and a near-infrared two-zone fluorescence living body imager to perform material characterization on samples obtained in examples 1-5, comparative example 1 and comparative example 2, and the results are shown in figures 1-13.
As can be seen from FIG. 1, the crystallinity of the materials obtained in example 1, comparative example 1 and comparative example 2 is good, being pure hexagonal phase NaErF in comparison with standard card4And (3) no other impurity diffraction peaks appear in the material. FIG. 2EThe characterization results of 6 show that the materials obtained in example 1, comparative example 1 and comparative example 2 have uniform morphology and good dispersibility. FIG. 7 shows that Ce is added to the reaction solution under otherwise identical conditions3+The doping of (a) makes the luminescent material of example 1 have a stronger near infrared two-region emission than comparative example 1. The characterization results of FIG. 8 show that, under otherwise identical conditions, Ce is present3+When the doping amount is 5%, the material obtains optimal near-infrared two-region emission. FIG. 9 shows that Ce is added to the reaction solution under otherwise identical conditions3+The doping in the shell structure makes the luminescent material of example 1 have stronger visible region emission than comparative example 2. FIG. 11 is a graph of the near-infrared image of blood vessels of a mouse treated with polyacrylic acid and injected via tail vein into the body for 3 minutes in example 1, in which the blood vessels of the mouse are clearly visible, the image signal is strong, the noise signal is weak, and in the same case, the resolution of the image of the blood vessels of the mouse in example 1 is low (FIG. 10). FIG. 13 is a diagram showing the image of the tumor site in the near-infrared region of the luminescent material of example 1 after being modified with polyacrylic acid and injected into the mouse body via the tail vein for 3 hours, where the mark is the tumor site. From the figure, the imaging signal of the tumor site of example 1 is obvious and the signal-to-noise ratio is high, while the imaging effect of the tumor site of the mouse of comparative example 1 is fuzzy and the signal is weak (fig. 12).
Claims (4)
1. A rare earth luminescent material with enhanced visible light/near infrared two-region emission is characterized in that: the structural composition of the material is NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4Wherein X is 1 to 10, and the particle size is 20 to 100 nm.
2. The visible/near-infrared two-region emission enhanced rare earth luminescent material according to claim 1, characterized in that: x is 4-6.
3. The visible/near-infrared two-region emission enhanced rare earth luminescent material according to claim 1 or 2, characterized in that the material is prepared by the following method:
(1) ErCl3·6H2O、YbCl3·6H2O、TmCl3·6H2Adding O into a mixed solution of oleic acid and octadecylene with the volume ratio of 1:2.5, stirring for 60 minutes at 160 ℃ in an anhydrous oxygen-free argon protective atmosphere, then cooling the system to room temperature, adding NaOH and NH dissolved in the system4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 295-314 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF410% Yb, 0.5% Tm rare earth luminescent material; wherein, said ErCl3·6H2O、YbCl3·6H2O、TmCl3·6H2O、NaOH、NH4The molar ratio of F is 0.895:0.1:0.005: 2.5-4: 4;
(2) mixing GdCl3·6H2O、YbCl3·6H2O、CeCl3·6H2Adding O into a mixed solution of oleic acid and octadecylene with the volume ratio of 1:2.5, stirring for 60 minutes at 160 ℃ in an anhydrous oxygen-free argon protective atmosphere, cooling the system to room temperature, and adding NaErF prepared in the step (1)410% of Yb and 0.5% of Tm, heating to 80 ℃, vacuumizing for 20 minutes, cooling the system to room temperature, adding dissolved NaOH and NH4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 295-314 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF4:10％Yb,0.5％Tm@NaGdF420% of Yb and X% of Ce rare earth luminescent material; wherein, the NaErF4:10％Yb,0.5％Tm、GdCl3·6H2O、YbCl3·6H2O、CeCl3·6H2O、NaOH、NH4The molar ratio of F is 1 (0.4-Y) to 0.1: Y:1.25:2, and Y is 0.01-0.1;
(3) mixing GdCl3·6H2Adding O into a mixed solution of oleic acid and octadecylene with the volume ratio of 1:2.5, stirring for 60 minutes at 160 ℃ in an anhydrous oxygen-free argon protective atmosphere, and cooling the systemCooling to room temperature, adding NaErF prepared in step (2)4:10％Yb,0.5％Tm@NaGdF420% of Yb and X% of Ce, heating to 80 ℃, vacuumizing for 20 minutes, cooling the system to room temperature, adding dissolved NaOH and NH4Stirring the methanol solution of F at normal temperature for 60 minutes, heating to 55-60 ℃, continuously stirring for 60 minutes to remove the methanol, heating to 110-120 ℃, vacuumizing for 20 minutes, finally heating to 295-314 ℃, keeping the temperature for 60 minutes, cooling the system to room temperature after the reaction is finished, and centrifugally washing with absolute ethyl alcohol to obtain NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce@NaGdF4A rare earth luminescent material; wherein, the NaErF4:10％Yb,0.5％Tm@NaGdF4:20％Yb,X％Ce、GdCl3·6H2O、NaOH、NH4The molar ratio of F is 1:0.4:1: 1.6.
4. The visible/near-infrared two-region emission enhanced rare earth luminescent material according to claim 3, wherein: in the step (2), Y is 0.04-0.06.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110111641.4A CN112920793B (en) | 2021-01-27 | 2021-01-27 | Rare earth luminescent material with enhanced visible light/near-infrared two-region emission |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110111641.4A CN112920793B (en) | 2021-01-27 | 2021-01-27 | Rare earth luminescent material with enhanced visible light/near-infrared two-region emission |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112920793A true CN112920793A (en) | 2021-06-08 |
| CN112920793B CN112920793B (en) | 2022-05-31 |
Family
ID=76167047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110111641.4A Expired - Fee Related CN112920793B (en) | 2021-01-27 | 2021-01-27 | Rare earth luminescent material with enhanced visible light/near-infrared two-region emission |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112920793B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891743A (en) * | 2023-07-11 | 2023-10-17 | 广州大学 | Up-conversion nano material with strong near infrared light emission and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009138120A (en) * | 2007-12-07 | 2009-06-25 | Konica Minolta Medical & Graphic Inc | Near infrared ray-emitting fluorophor, biological substance-labeling agent using the same |
| CN107739603A (en) * | 2017-10-23 | 2018-02-27 | 合肥工业大学 | Conversion nano particle and preparation method thereof on a kind of red green luminescence rare earth of exciting light regulation and control |
| CN112011338A (en) * | 2020-09-11 | 2020-12-01 | 陕西师范大学 | Method for improving near-infrared emission intensity of up-conversion material |
-
2021
- 2021-01-27 CN CN202110111641.4A patent/CN112920793B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009138120A (en) * | 2007-12-07 | 2009-06-25 | Konica Minolta Medical & Graphic Inc | Near infrared ray-emitting fluorophor, biological substance-labeling agent using the same |
| CN107739603A (en) * | 2017-10-23 | 2018-02-27 | 合肥工业大学 | Conversion nano particle and preparation method thereof on a kind of red green luminescence rare earth of exciting light regulation and control |
| CN112011338A (en) * | 2020-09-11 | 2020-12-01 | 陕西师范大学 | Method for improving near-infrared emission intensity of up-conversion material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891743A (en) * | 2023-07-11 | 2023-10-17 | 广州大学 | Up-conversion nano material with strong near infrared light emission and preparation method thereof |
| CN116891743B (en) * | 2023-07-11 | 2024-06-07 | 广州大学 | Up-conversion nano material with strong near infrared light emission and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112920793B (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Near-infrared in vivo bioimaging using a molecular upconversion probe | |
| Zhang et al. | Hydrogen bonding boosted the persistent room temperature phosphorescence of pure organic compounds for multiple applications | |
| Wang et al. | Enhanced upconversion luminescence and single-band red emission of NaErF4 nanocrystals via Mn2+ doping | |
| CN112480925B (en) | Near-infrared two-region luminous long-afterglow nanoprobe based on X-ray excitation, preparation method and application thereof in living body imaging analysis | |
| CN110878207A (en) | Up-conversion nanometer optical switch material and preparation method thereof | |
| CN108559511B (en) | Rare earth doped up-conversion nanocrystalline luminescent material and preparation method thereof | |
| CN105694888B (en) | A kind of Mg2+Adulterate NaREF4Upconverting fluorescent material and preparation method thereof | |
| KR101441485B1 (en) | Green-emitting upconversion nanophosphor and synthesis method thereof | |
| Li et al. | Facile microemulsion route to coat carbonized glucose on upconversion nanocrystals as high luminescence and biocompatible cell-imaging probes | |
| CN110452682B (en) | Method for preparing rare earth doped fluoride nanocrystalline on large scale by one-pot method | |
| CN112940726B (en) | Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof | |
| EP4086324A1 (en) | In vivo degradable upconversion nanomaterial, and preparation method therefor and use thereof | |
| CN112920793B (en) | Rare earth luminescent material with enhanced visible light/near-infrared two-region emission | |
| CN110408377B (en) | Rare earth doped NaCeF4Near-infrared fluorescent nano probe and preparation method and biological application thereof | |
| CN109180715B (en) | Boron-dipyrromethene derivative, nanoparticle, preparation method and application | |
| CN112011338B (en) | Method for improving near-infrared emission intensity of up-conversion material | |
| Rao et al. | Sub-10 nm BaLaF 5: Mn/Yb/Er nanoprobes for dual-modal synergistic in vivo upconversion luminescence and X-ray bioimaging | |
| Ma et al. | Coumarin derivative dye sensitized NaYGdF4: Yb, Er nanoparticles with enhanced NIR II luminescence for bio-vascular imaging | |
| CN112940711A (en) | Biodegradable up-conversion core-shell nanocrystal, preparation method and application thereof | |
| CN115895641A (en) | Short-wave infrared fluorescence emission rare earth nano material and preparation method thereof | |
| CN109913979A (en) | A kind of holmium double doped miscellaneous Jiao Lvshi phase nanofiber preparation method and applications of rare earth ytterbium | |
| CN108743978A (en) | A kind of gold@gadolinium polymerization of olefin using catalyst polymer nanocomposites and its preparation method and application | |
| CN109722247A (en) | A kind of doping Fe3+The NaYF of ion4:Yb3+,Er3+The preparation method of upconversion fluorescence nano material | |
| CN113088288A (en) | Rare earth fluorescent material with high quantum yield and preparation method thereof | |
| CN110016344B (en) | Flower cluster-shaped rare earth up-conversion core-shell nano luminescent material and preparation method 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: 20220531 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |