CN110184063B - Rare earth luminescent material and preparation method and application thereof - Google Patents
Rare earth luminescent material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 13
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 30
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 30
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 9
- 238000007626 photothermal therapy Methods 0.000 claims abstract description 7
- 238000000593 microemulsion method Methods 0.000 claims abstract description 6
- 238000012634 optical imaging Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000011540 sensing material Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 239000012221 photothermal agent Substances 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 31
- 229910052786 argon Inorganic materials 0.000 description 20
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- 238000006243 chemical reaction Methods 0.000 description 6
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
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- 229910052779 Neodymium Inorganic materials 0.000 description 4
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- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 description 4
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- LOXWVAXWPZWIOO-UHFFFAOYSA-N 7-bromo-1-chloronaphthalene Chemical compound C1=C(Br)C=C2C(Cl)=CC=CC2=C1 LOXWVAXWPZWIOO-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- -1 Rare Earth ions Chemical class 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
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- 238000000295 emission spectrum Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
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- UJBPGOAZQSYXNT-UHFFFAOYSA-K trichloroerbium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Er+3] UJBPGOAZQSYXNT-UHFFFAOYSA-K 0.000 description 2
- LEYFXTUKPKKWMP-UHFFFAOYSA-K trichloroytterbium;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Yb](Cl)Cl LEYFXTUKPKKWMP-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
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- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
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- 238000004861 thermometry Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 description 1
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J5/00—Radiation pyrometry, e.g. infrared or optical thermometry
- G01J2005/0077—Imaging
Abstract
The invention discloses a rare earth luminescent material and a preparation method and application thereof. The chemical formula of the disclosed material is as follows: NaY(1‑x‑y)F4:xYb3+/yEr3+@NaY(1‑z)F4:zNd3+@SiO2@ IR780, wherein x is more than or equal to 0 and less than or equal to 20 percent, y is more than or equal to 1 percent and less than or equal to 5 percent, and y is more than or equal to 10 percent and less than or equal to 30 percent. The preparation method disclosed comprises the preparation by adopting a thermal decomposition method and a microemulsion method. The material of the invention is used for photothermal therapy materials, near infrared temperature sensing materials and optical imaging materials. The material of the invention is of a nano structure, has stronger absorption in a near infrared region, and presents characteristic emission of 500-3+、Er3+、Nd3+The infrared light source can effectively absorb the visible/near infrared emission generated by the exciting light source with 808nm and converted up/down for temperature sensing and optical imaging, and then the photothermal agent IR780 can effectively absorb the heat generated by the exciting light source with 808nm, so that the absorption of the photothermal agent on the emitted light (500-.
Description
Technical Field
The invention belongs to the technical field of inorganic nano luminescent materials in physics, and particularly relates to a composite rare earth luminescent material and a preparation method and application thereof.
Background
Rare Earth luminescent materials as a new generation fluorescent labeling material have luminescent properties incomparable with other materials, such as rich energy levels, long luminescent lifetimes, narrow emission lines, high color purity, which achieve rich luminescence from the ultraviolet to the visible to the infrared region based on the special electron arrangement of the Doped Rare Earth ions themselves (Kumar, R.; Nyk, M.; Ohulchansky, T.Y; Flask, C.A.; Pras, P.N., Combined Optical and MR Bioimaging Using ray Earth easy Earth Ion Doped NaYF4 nanocrystalline phosphors, adv.Funct.Mater, 2009, 19, 853-),
while visible and near infrared emissions show the following advantages in organisms: very low autofluorescence, high detection sensitivity and deep light penetration depth in biological tissues.
Because the inorganic material is relatively stable, the rare earth luminescent material can be used as a fluorescent marking material to greatly reduce the influence of noise, so the rare earth luminescent material can be applied to a plurality of fields, such as infrared light detection, short-wave laser, biological fluorescent marking and the like.
In recent years, rare earth luminescent materials based on near infrared light excitation have a series of advantages of reducing interference of background autofluorescence, relatively high tissue penetration capability, excellent light stability and the like, and rare earth doped nano luminescent materials are more and more widely concerned in biological tissue tumor treatment. The rare earth doped luminescent nano material excited by near infrared light is used for organism treatment, and the temperature detection and the effective photo-thermal treatment of the organism are required.
Disclosure of Invention
In view of the defects or shortcomings of the prior art, the invention aims to provide a rare earth luminescent material.
The chemical formula of the material provided by the invention is as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@ IR780 where 0<x≤20％,1％≤y≤5％,10％≤z≤30％。
The preparation method of the material comprises the following steps:
(1) preparation of NaY by thermal decomposition(1-x-y)F4:xYb3+/yEr3+；
(2) NaY prepared by the step (1)(1-x-y)F4:xYb3+/yEr3+Preparing NaY by thermal decomposition method(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+；
(3) NaY prepared by the step (2)(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Preparing NaY by microemulsion method as raw material(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780。
The invention also provides application of the material in preparing photothermal therapy materials, near-infrared temperature sensing materials and optical imaging materials.
Compared with the prior art, the invention has the following advantages:
yb provided by the invention3+、Er3+、Nd3+The doped ions have the imaging and temperature sensing functions of visible light and near infrared light simultaneously under the excitation of 808 nanometer laser through energy transfer.
Photothermal therapy (PTT) is a therapy that absorbs light energy by a light absorber and converts the light energy into heat, and kills cancer cells by the heat energy, and the effectiveness of photothermal therapy is mainly determined by the effective conversion of light into heat. Because the noble metal nano particles have special physical properties, the noble metal nano particles are widely applied to the fields of catalysis, biological diagnosis and treatment and the like. The existing inorganic photothermal agents such as Au, Ag, CuS and the like have excellent surface plasma resonance absorption effect, but the absorption range is wide, and the absorption range of the inorganic photothermal agents can be absorbed in the range of the temperature sensing emission peak so as to influence the accuracy of temperature sensing, while the photothermal agent IR780 absorption range provided by the invention can effectively avoid the up-down conversion emission of nano particles so as to improve the imaging effect and the temperature sensing accuracy.
The shell Nd of the invention3+Doping NaYF4Can be effectively excited by 808nm laser and transferred to Yb by energy transfer3+And Er3+Therefore, the visible and near-infrared characteristic emission is presented in the range of 500-. Therefore, the multifunctional nano material can realize the integrated functions of photothermal therapy, accurate temperature measurement and optical imaging.
The synthetic method is simple, the particle size of the synthesized sample is about 18 nanometers, and the sample is easy to be uniformly dispersed in the aqueous solution, so that the biological tissue compatibility is good.
Drawings
FIG. 1 shows the NaYF of this embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The process diagram synthesized by @ IR780 and the corresponding electron transmission microscope pictures in each process; (a) the column diagram is a model diagram of the synthesis procedure of this example, (b) the column diagram is a transmission electron microscope picture of the corresponding synthesis step, and (c) the column diagram is a corresponding high resolution transmission electron microscope picture.
FIGS. 2(a), (b) and (c) are NaYF of an example4:Yb3+/Er3+、NaYF4:Yb3+/Er3+@NaYF4:Nd3+、NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The XRD pattern of @ IR 780;
FIG. 3 shows the NaYF of this embodiment4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780(core-shell-IR780) visible light emission spectrum;
FIG. 4 shows the NaYF of this embodiment4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780(core-shell-IR780) near infrared light emission spectrum;
FIG. 5 shows the NaYF of this embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780 temperature sensing sensitivity curve for near infrared light;
FIG. 6 shows the near-infrared temperature sensing and thermal infrared imager of the embodiment respectively monitoring the variation of the heat generation of the sample with the laser power;
FIG. 7 is a drawing showingNaYF of this example4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780 ablative Effect on E.coli in different control groups.
Detailed description of the invention
The invention provides Yb3+、Er3+、Nd3+The chemical general formula of the tri-doped nano material is as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@ IR780 where x, y and z are each Yb3+、Er3+、Nd3+And x is 18%, y is 2%, and y is 20%.
In the present invention, "@" denotes the relationship of the core-shell structure, e.g. "NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@ IR780 "denotes" NaY (1-z) F4:zNd3+Coated NaY(1-x-y)F4:xYb3+/yEr3+”，“SiO2Coated NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+", followed by analogy.
The preparation of the multifunctional nano material adopts a thermal decomposition method and a microemulsion method for synthesis, and the basic synthesis steps can be divided into three major steps including (1) NaY(1-x-y)F4:xYb3+/yEr3+Preparing; (2) NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Preparing; (3) NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2Preparation of @ IR 780.
Wherein: NaY(1-x-y)F4:xYb3+/yEr3+The preparation of (b) can be carried out by thermal decomposition methods in the prior art. A specific preparation method comprises the following steps:
(1) weighing yttrium chloride hexahydrate, ytterbium chloride hexahydrate and erbium chloride hexahydrate in proportion, adding quantitative oleic acid and octadecylene, and mixing and reacting at an appropriate temperature under the protection of argon to obtain a solution A; wherein yttrium chloride hexahydrate can be replaced by yttrium acetate, ytterbium chloride hexahydrate can be replaced by ytterbium acetate, and erbium chloride hexahydrate can be replaced by erbium acetate;
(2) naturally cooling the solution A to room temperature under the continuous protection of argon;
(3) dissolving a proper amount of ammonium fluoride in a proper amount of methanol solution to obtain a transparent solution B, and dissolving a proper amount of sodium hydroxide in a proper amount of methanol solution to obtain a transparent solution C;
(4) dropwise adding the solution B and the solution C into the solution A at the same time, and mixing and reacting under the condition of normal temperature and argon to obtain a suspension D;
(5) heating the suspension D to a proper temperature, keeping the temperature, and continuing heating and keeping the temperature;
(6) closing argon, vacuumizing the reaction environment and continuously introducing argon;
(7) then heating and preserving heat, cooling to room temperature, closing an argon gas cylinder, and centrifugally washing the obtained solution E to obtain NaYF4:Yb3+/Er3+NaYF can be added4:Yb3+/Er3+Dispersed in cyclohexane as solution F for later use.
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+The preparation of (b) can be carried out by thermal decomposition methods in the prior art. A specific preparation method comprises the following steps:
(1) weighing yttrium chloride hexahydrate and neodymium chloride hexahydrate in proportion, adding a certain amount of oleic acid and octadecene, and mixing under the conditions of argon environment protection and proper temperature to obtain a clear solution G, wherein the yttrium chloride hexahydrate can be replaced by yttrium acetate, and the neodymium chloride hexahydrate can be replaced by neodymium acetate;
(2) based on solution G, "NaY" was carried out as described above(1-x-y)F4:xYb3+/yEr3+The preparation method comprises the steps (2) - (4) to obtain suspension H, then dropwise adding solution F, heating to a proper temperature, keeping the temperature, then normally cooling to room temperature, closing an argon gas cylinder, and centrifugally washing the obtained solution to obtain NaYF4:Yb3+/Er3+@NaYF4:Nd3+For taking out part of liquidWashing and centrifuging cyclohexane and absolute alcohol, and drying at a proper temperature for later use;
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2the preparation of @ IR780 can be synthesized by a microemulsion method in the prior art. A specific preparation method comprises the following steps:
NaYF is added4:Yb3+/Er3+@NaYF4:Nd3+Dispersing in a certain amount of absolute ethyl alcohol and deionized water solution, adding a certain amount of ammonia water, dripping a certain amount of tetraethyl orthosilicate, subsequently dripping IR780, uniformly mixing, centrifuging, washing and drying the obtained solution to obtain NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780。
The following are specific NaYF4:18％Yb3+/2％Er3+@NaYF4:20％Nd3+@SiO2The construction and preparation method of the @ IR780 multifunctional nano photothermal treatment platform are further explained for the technical scheme of the invention.
Example (b):
this example is a thermal decomposition method and a microemulsion method for preparing NaYF4:18％Yb3+/2％Er3+@NaYF4:20％Nd3+@SiO2@ IR780, the specific preparation process is as follows:
NaYF4:18％Yb3+/2％Er3+the preparation of (1):
according to molar ratio Y3+:Yb3+:Er3+YCl was weighed in a stoichiometric ratio of 0.8:0.18:0.023·6H2O(AR)0.5400g、YbCl3·6H2O(AR)0.1395g、ErCl3·6H2O (AR)0.0153g, pouring the raw materials into a reaction vessel, adding 12ml of oleic acid and 30ml of octadecane, mixing under the protection of argon and at about 160 ℃ to obtain a clear solution, and naturally cooling to room temperature under the continuous protection of argon;
weighing NH by mol ratio4F (AR)0.2963g and NaOH (AR)0.2000g are respectively dissolved in 20ml and 10ml of methanol solution to obtain transparent solutions; reacting NH4F and NaOH solution is drippedReacting the clear solution obtained in the step under the condition of argon at normal temperature to obtain suspension;
heating the suspension to about 60 ℃, then preserving heat for 20 minutes, and continuously heating to about 108 ℃ and preserving heat for 5 minutes;
closing argon, vacuumizing, continuously vacuumizing for 20 minutes, closing a vacuum pump, introducing argon, and continuously introducing air;
continuously heating to 300 ℃ and preserving heat for one hour, then normally cooling to room temperature, closing an argon gas cylinder, centrifugally washing the obtained solution to obtain a sample NaYF4:Yb3+/Er3+And dispersed in 20ml of cyclohexane for later use. Washing part of the liquid with cyclohexane and absolute alcohol for 3 times, centrifuging, drying at 70 ℃, fully grinding and testing the optical performance;
NaYF4:18％Yb3+/2％Er3+@NaYF4:20％Nd3+the preparation of (1):
according to molar ratio Y3+:Nd3+YCl was weighed in a stoichiometric ratio of 0.8:0.23·6H2O(AR)0.4854g、NdCl3·6H2O (AR)0.1435g, pouring the raw materials into a reaction vessel, adding 12ml of oleic acid and 30ml of octadecane, stirring at 160 ℃ under the protection of argon environment to obtain a clear solution, and naturally cooling to room temperature under the continuous protection of argon;
weighing NH by mol ratio4F (AR)0.2963g and NaOH (AR)0.2000g are respectively dissolved in 20ml and 10ml of methanol solution to obtain transparent solutions; reacting NH4F and NaOH solution are dripped into the clear solution, and the mixture is stirred under the condition of argon at normal temperature to obtain suspension;
NaYF dispersed in 20ml of cyclohexane is added dropwise to the suspension4:Yb3+/Er3+Then heating to 60 ℃, maintaining for 20 minutes, continuing to heat to 108 ℃ and stabilizing for 5 minutes; closing an argon gas path, vacuumizing, continuously exhausting for 20 minutes, closing a vacuum pump, introducing argon gas, and continuously introducing air;
continuously heating to 300 ℃, maintaining for one hour, then normally cooling to room temperature, closing an argon gas cylinder, and centrifugally washing the obtained solution to obtain a sample NaYF4:18％Yb3+/2％Er3+@NaYF4:20％Nd3+；
NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2Preparation of @ IR 780:
NaYF is added4:Yb3+/Er3+@NaYF4:Nd3+Dispersing in a certain amount of absolute ethyl alcohol and deionized water solution, adding a certain amount of ammonia water, dripping 200 microliters of tetraethyl orthosilicate, subsequently dripping 2 milliliters of IR780, stirring at normal temperature, centrifuging, washing and drying the obtained solution to obtain NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780。
The optical properties of the material prepared in this example were measured by the fluorescence intensity ratio thermometry technique disclosed in document [1], and the results are shown in FIG. 5. The comparison of the fluorescence intensity ratio temperature measurement technique and the thermal infrared imager temperature measurement by the method disclosed in the document [2] shows the superiority of the fluorescence intensity ratio temperature measurement technique, and the result is shown in fig. 6. The sterilization experiment disclosed in the document [3] proves that the material prepared in the example has excellent photothermal effect, and the result is shown in fig. 7.
[1]H.Suo,X.Zhao,Z.Zhang,R.Shi,Y.Wu,J.Xiang,C.Guo.Local Symmetric Distortion Boosted Photon Up-conversion and Thermometric Sensitivity in lanthanum Oxide Nanospheres.Nanoscale,2018,10,9245–9251.
[2]Suo,H.,Zhao,X.,Zhang,Z.,Guo,C.808nm Light-triggered Thermometer-Heater Up-converting Platform based on Nd3+-sensitized Yolk-shell GdOF@SiO2.ACS Appl.Mater.Interfaces 2017,9,43438-43448.
[3]Z.Zhang,H.Suo,X.Zhao,D.Sun,L.Fan,C.Guo.NIR-to-NIR Deep Penetrating Nanoplatforms Y2O3:Nd3+/Yb3+@SiO2@Cu2S towards Highly Efficient Photothermal Ablation.ACS applied materials&interfaces,2018,10,14570-14576.
FIG. 1 shows the NaYF of this embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The flow chart of the synthesis of @ IR780 and the corresponding transmission electron microscope pictures in each process illustrate the core-shell structure of the sample.
FIG. 2(a) shows the NaYF of this embodiment4:Yb3+/Er3+FIG. 1(b) shows the NaYF of this example4:Yb3+/Er3+@NaYF4:Nd3+FIG. 1(c) shows the NaYF of this example4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The XRD pattern of @ IR 780.
FIG. 3 shows the NaYF of this embodiment4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780(core-shell-IR 780). The materials of the present invention show a significant increase in visible light emission intensity.
FIG. 4 shows the NaYF of this embodiment4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780(core-shell-IR 780). The material of the invention is demonstrated to have a substantial improvement in near infrared light emission intensity.
FIG. 5 shows the NaYF of this embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780 near infrared light temperature sensing sensitivity curve.
FIG. 6 shows NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780 the heat generated in the breast tissue of a chicken with a thickness of 1mm under the excitation of 808nm laser, and the temperature change with the power was monitored by the material prepared in this example and a thermal infrared imager. It is shown that the temperature obtained with the material prepared in this example is more accurate than the temperature of the surface of the biological tissue monitored by a thermal infrared imager。
FIG. 7 shows the NaYF of this embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@ IR780 ablative Effect on E.coli in different control groups. And the comparison shows that the material of the invention generates heat under the excitation of 808nm laser, and has ablation effect on bacteria.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (5)
1. A rare earth luminescent material is characterized in that the material has a chemical formula as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@ IR780 where 0<x≤20％,1％≤y≤5％,10％≤z≤30％。
2. The method for preparing a rare earth luminescent material according to claim 1, comprising:
(1) preparation of NaY by thermal decomposition(1-x-y)F4:xYb3+/yEr3+；
(2) NaY prepared by the step (1)(1-x-y)F4:xYb3+/yEr3+Preparing NaY by thermal decomposition method(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+；
(3) NaY prepared by the step (2)(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Preparing NaY by microemulsion method as raw material(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780。
3. Use of the material of claim 1 for the preparation of a material for photothermal therapy.
4. Use of the material according to claim 1 for the preparation of a near infrared temperature sensing material.
5. Use of the material of claim 1 for the preparation of an optical imaging material.
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