CN110184063A - A kind of rare earth luminescent material and the preparation method and application thereof - Google Patents
A kind of rare earth luminescent material and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110184063A CN110184063A CN201910463186.7A CN201910463186A CN110184063A CN 110184063 A CN110184063 A CN 110184063A CN 201910463186 A CN201910463186 A CN 201910463186A CN 110184063 A CN110184063 A CN 110184063A
- Authority
- CN
- China
- Prior art keywords
- nay
- nayf
- nanometers
- xyb
- yer
- 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 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 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 10
- 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 15
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 238000007626 photothermal therapy Methods 0.000 claims abstract description 8
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 8
- 238000000593 microemulsion method Methods 0.000 claims abstract description 5
- 239000011540 sensing material Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 25
- 229910052786 argon Inorganic materials 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical class [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 6
- 229910052691 Erbium Inorganic materials 0.000 description 5
- 229910052769 Ytterbium Inorganic materials 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 238000002679 ablation Methods 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-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
- 238000010792 warming Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- -1 compound rare earth Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical class [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910009523 YCl3 Inorganic materials 0.000 description 2
- DUSUCKWNBGMKRV-UHFFFAOYSA-N acetic acid;yttrium Chemical group [Y].CC(O)=O DUSUCKWNBGMKRV-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ISEXWJYBJMXWCC-UHFFFAOYSA-N erbium;hydrate Chemical compound O.[Er] ISEXWJYBJMXWCC-UHFFFAOYSA-N 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000001215 fluorescent labelling Methods 0.000 description 2
- 238000003384 imaging method Methods 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
- 210000002429 large intestine Anatomy 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004861 thermometry Methods 0.000 description 2
- 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
- 241000272201 Columbiformes Species 0.000 description 1
- 229910017544 NdCl3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- WFNBSLYTFHMPBY-UHFFFAOYSA-N acetic acid;erbium Chemical group [Er].CC(O)=O WFNBSLYTFHMPBY-UHFFFAOYSA-N 0.000 description 1
- MIJKIIBNAPRONL-UHFFFAOYSA-N acetic acid;neodymium Chemical group [Nd].CC(O)=O MIJKIIBNAPRONL-UHFFFAOYSA-N 0.000 description 1
- SSLZBJYDOYVVCG-UHFFFAOYSA-N acetic acid;ytterbium Chemical group [Yb].CC(O)=O SSLZBJYDOYVVCG-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Organic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epidemiology (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of rare earth luminescent materials and the preparation method and application thereof.Disclosed materials chemistry formula are as follows: NaY(1‑x‑y)F4:xYb3+/yEr3+@NaY(1‑z)F4:zNd3+@SiO2@IR780, wherein 0≤x≤20%, 1%≤y≤5%, 10%≤y≤30%.Disclosed preparation method includes being prepared using thermal decomposition method and microemulsion method.Material of the invention is used for photo-thermal therapy material, near-infrared temperature sensing material and optical imagery material.Material of the invention is in nanostructure, has stronger absorption in the near infrared region, and show 500-1350 nanometers of characteristic emission, wherein rare earth ion Yb3+、Er3+、Nd3+808 nanometers of excitation light source can effectively be absorbed and generate the visible/near infrared transmitting of up/down conversion for temperature sensing and optical imagery, secondly the excitation light source that light thermit powder IR780 can effectively absorb 808 nanometers generates heat, light thermit powder is avoided to improve the accuracy of its temperature sensing to the absorption of the transmitting light (500-580 nanometers, 900-1350 nanometers) for temperature sensitive range.
Description
Technical field
The invention belongs to the inorganic nano luminescent material technical fields in physics, and in particular to a kind of compound rare earth
Luminescent material and the preparation method and application thereof.
Background technique
The characteristics of luminescence that rare earth luminescent material has other materials incomparable as fluorescence labeling material of new generation, example
Such as energy level abundant, longer luminescent lifetime, narrow emission lines, high colour purity, the rare earth ion based on doping itself are special
Electronic configuration and obtain from ultraviolet to visible (Kumar, the R. abundant of shining to infrared light district again；Nyk, M.；
Ohulchanskyy,T.Y；Flask, C.A.；Pras, P.N., Combined Optical and MR Bioimaging
Using Rare Earth Ion Doped NaYF4 Nanocrystals.Adv.Funct.Mater, 2009,19,853-
859.),
And visible and near infrared emission shows following advantage in organism: having in biological tissues low-down spontaneous
The light penetration depth of fluorescence, high detection sensitivity and depth.
Since inorganic material is more stable, it can be greatly lowered and be made an uproar as fluorescence labeling material using rare earth luminescent material
The influence of sound, therefore rare earth luminescent material can be applied to many fields, such as infrared light detecting, short-wave laser and bioluminescence mark
The fields such as note.
In recent years, there is the interference, relatively for reducing background auto-fluorescence based on the light activated rare earth luminescent material of near-infrared
A series of advantages such as high tissue penetration and excellent photostability, rear-earth-doped nano luminescent material is in biological tissue
More and more extensive concern is obtained in oncotherapy.Using the light activated rear-earth-doped Illuminant nanometer material of near-infrared for biology
Body treatment not only needs to carry out temperature detection to organism also to carry out effective photo-thermal therapy to it.
Summary of the invention
For the defects or inadequacies for existing technologies, the purpose of the present invention is to provide a kind of rare earth luminescent materials.
Its chemical formula of material provided by the present invention are as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@
SiO2@IR780, wherein 0≤x≤20%, 1%≤y≤5%, 10%≤y≤30%.
The preparation method of material of the present invention includes:
(1) NaY is prepared using thermal decomposition method(1-x-y)F4:xYb3+/yEr3+；
(2) NaY prepared with step (1)(1-x-y)F4:xYb3+/yEr3+NaY is prepared using thermal decomposition method for raw material(1-x-y)
F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+；
(3) NaY prepared with step (2)(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Micro emulsion is used for raw material
Liquid method prepares NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780。
Present invention simultaneously provides can above-mentioned material be used to prepare photo-thermal therapy material, near-infrared temperature sensing material and light
Learn the application of image forming material.
Compared with prior art, the invention has the following advantages that
Yb provided by the invention3+、Er3+、Nd3+Doped ions are made under the excitation of 808 nanometer lasers by energy transmission
Have the function of the imaging and temperature sensing of visible light and near infrared light simultaneously.
Photo-thermal therapy (PTT) is to absorb luminous energy by light absorber and convert light energy into heat, kills cancer using thermal energy
For cell to achieve the purpose that treatment, the validity of photo-thermal therapy depends mainly on effective conversion that light turns heat.Due to noble metal
Nano particle has special physical property, they are widely used in the fields such as catalysis and biological diagnosis and treatment.Existing Au, Ag,
The inorganic light thermit powder such as CuS has excellent surface plasmon absorption effect, but absorption region is wider, while can absorb
The accuracy of temperature sensing is influenced for the range of temperature sensing emission peak, and light thermit powder IR780 provided by the invention inhales
The switching emission up and down of nanoparticle can be avoided effectively to improve imaging effect and temperature sensing accuracy by receiving range.
Shell Nd of the invention3+Adulterate NaYF4It can effectively be excited by 808 nanometers of laser, be transmitted by energy transmission
To Yb3+And Er3+, to show visible and near-infrared characteristic emission within the scope of 500-1350nm, for temperature sensing and
Optical imagery, the excitation light source that secondly light thermit powder IR780 can effectively absorb 808 nanometers generate heat, avoid light thermit powder to being used for
The absorption of the transmitting light (500-580 nanometers, 900-1350 nanometers) of temperature sensitive range is to improve the accurate of its temperature sensing
Degree.Therefore, which may be implemented the integrated function of photo-thermal therapy, accurate thermometric and optical imagery.
Synthetic method of the present invention is simple, and the sample particle diameter of synthesis is about 18 nanometers, is easy to be dispersed in aqueous solution, from
And there is good biological tissue's compatibility.
Detailed description of the invention
Fig. 1 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The flow chart of@IR780 synthesis and each mistake
Corresponding transmission electron microscope(TEM) picture in journey；(a) column figure is the illustraton of model of the embodiment synthesis flow, and it is corresponding for (b) arranging figure
The transmission electron microscope(TEM) picture of synthesis step, (c) arranging figure is corresponding high resolution transmission electron microscope photo.
Fig. 2 (a), (b) and (c) are respectively the NaYF of embodiment4:Yb3+/Er3+、NaYF4:Yb3+/Er3+@NaYF4:Nd3+、
NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The XRD spectrum of@IR780；
Fig. 3 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-
shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The VISIBLE LIGHT EMISSION map of@IR780 (core-shell-IR780)；
Fig. 4 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-
shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The near infrared light of@IR780 (core-shell-IR780) emits figure
Spectrum；
Fig. 5 is embodiment NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The temperature sensing of@IR780 near infrared light is sensitive
It writes music line；
Fig. 6 is to monitor sample heat production respectively with laser power with the near-infrared temperature sensing and thermal infrared imager of embodiment
Situation of change；
Fig. 7 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780 is in different control groups to large intestine
The ablation of bacillus.
Specific implementation method
The present invention provides Yb3+、Er3+、Nd3+The chemical general formula of the nano material of three doping are as follows: NaY(1-x-y)F4:xYb3+/
yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780, wherein x, y, z is respectively Yb3+、Er3+、Nd3+Mole percent doping,
And x=18%, y=2%, y=20%.
"@" indicates the relationship of core-shell structure, such as " NaY in the present invention(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:
zNd3+@SiO2@IR780 " indicates " NaY (1-z) F4:zNd3+Coat NaY(1-x-y)F4:xYb3+/yEr3+", " SiO2Cladding
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+", behind and so on.
The preparation of multi-functional nanometer material of the present invention is synthesized using thermal decomposition method and microemulsion method, and basic synthesis step can divide
For three big steps, including (1) NaY(1-x-y)F4:xYb3+/yEr3+Preparation；(2)NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)
F4:zNd3+Preparation；(3)NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2The preparation of@IR780.
Wherein: NaY(1-x-y)F4:xYb3+/yEr3+Preparation thermolysis process in the prior art preparation can be used.It is a kind of
It is specific the preparation method is as follows:
(1) it is dilute that six water yttrium chlorides, six water ytterbium chlorides, six water erbium chlorides, the quantitative oleic acid of addition and 18 are weighed in proportion,
Solution A is obtained after hybrid reaction under ar gas environment protection preference temperature；Wherein six water yttrium chlorides can use acetic acid yttrium substitution, six water
Ytterbium chloride can be replaced with acetic acid ytterbium, six water erbium chlorides can be replaced with acetic acid erbium；
(2) by solution A under argon gas sustainable protection Temperature fall to room temperature；
(3) appropriate ammonium fluoride is dissolved in proper amount of methanol solution and obtains clear solution B, appropriate sodium hydroxide is dissolved in appropriate first
Clear solution C is obtained in alcoholic solution；
(4) solution B and C are added drop-wise in solution A dropwise simultaneously, hybrid reaction obtains suspension D under the conditions of room temperature argon gas；
(5) after suspension D being warming up to suitable temperature heat preservation, continue heating and heat preservation；
(6) argon gas is closed, is continually fed into argon gas after vacuumizing to reaction environment；
(7) it is then cooled to room temperature after heating and heat preservation, closes argon gas gas cylinder, after obtained solution E centrifuge washing
NaYF4:Yb3+/Er3+, can be by NaYF4:Yb3+/Er3+It is scattered in hexamethylene as solution F, for future use.
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Preparation thermal decomposition side in the prior art can be used
Method preparation.It is a kind of specific the preparation method is as follows:
(1) it weighs six water yttrium chlorides, neodymium chloride six hydrate in proportion, quantitative oleic acid and 18 dilute is added, is protected in ar gas environment
It is mixed to get clear solution G under shield, appropriate temperature conditions, wherein six water yttrium chlorides can be replaced with acetic acid yttrium, neodymium chloride six hydrate
It can be replaced with acetic acid neodymium；
(2) it is based on solution G, implements " NaY according to the above method(1-x-y)F4:xYb3+/yEr3+Preparation method " step (2)-
(4) it operates, obtains suspension H, solution F is then added dropwise, be warming up to suitable temperature heat preservation, be then normally cooled to room temperature, close
Argon gas gas cylinder is NaYF after obtained solution centrifuge washing4:Yb3+/Er3+@NaYF4:Nd3+, desirable partially liq hexamethylene
It is dried for standby under preference temperature after alkane and absolute alcohol washing centrifugation；
NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2The preparation of@IR780 can be used in the prior art
Microemulsion method synthesis.It is a kind of specific the preparation method is as follows:
By NaYF4:Yb3+/Er3+@NaYF4:Nd3+It is scattered in quantitative dehydrated alcohol and deionized water solution, is added quantitative
Ammonium hydroxide instills quantitative tetraethyl orthosilicate, and subsequent instillation IR780 is mixed, and resulting solution is dried to obtain into centrifuge washing is crossed
NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780。
It is specific NaYF below4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+@SiO2@IR780 multifunctional nano light
The building and preparation method thereof of heat cure platform, to be further explained explanation to technical solution of the present invention.
Embodiment:
The embodiment is that thermal decomposition method and microemulsion method prepare NaYF4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+@
SiO2@IR780, specific preparation process are as follows:
NaYF4: 18%Yb3+/ 2%Er3+Preparation:
Y in molar ratio3+:Yb3+:Er3+The stoichiometric ratio of=0.8:0.18:0.02 weighs YCl3·6H2O(AR)
0.5400g、YbCl3·6H2O(AR)0.1395g、ErCl3·6H2O (AR) 0.0153g, raw material is poured into reaction vessel and is added
12ml oleic acid and 30ml 18 are dilute, are mixed to get clear solution under the conditions of argon gas protection and 160 DEG C or so, persistently protect in argon gas
Lower Temperature fall is protected to room temperature；
NH is weighed in molar ratio4F (AR) 0.2963g, NaOH (AR) 0.2000g is dissolved in 20ml and 10ml methanol solution respectively
In obtain clear solution；By NH4F and NaOH solution instill in clear solution obtained by above-mentioned steps, react under the conditions of room temperature argon gas
Obtain suspension；
Suspension is warming up to 60 DEG C or so rear heat preservations 20 minutes, 108 DEG C or so is continuously heating to and keeps the temperature 5 minutes；
It closes argon gas, vacuumize, vacuum pump is closed in lasting pumping after twenty minutes, leads to argon gas, Continuous aeration；
It is continuously heating to 300 DEG C and keeps the temperature one hour, be then normally cooled to room temperature, close argon gas gas cylinder, it is obtained molten
Sample NaYF is obtained after liquid centrifuge washing4:Yb3+/Er3+, it is scattered in spare in 20ml hexamethylene.Take partially liq hexamethylene and
Absolute alcohol washs 70 DEG C of drying after 3 centrifugations, is fully ground and tests its optical property；
NaYF4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+Preparation:
Y in molar ratio3+:Nd3+The stoichiometric ratio of=0.8:0.2 weighs YCl3·6H2O(AR)0.4854g、NdCl3·
6H2O (AR) 0.1435g, by raw material pour into reaction vessels be added 12ml oleic acid and 30ml 18 it is dilute, ar gas environment protection under
160 DEG C stir to get clear solution, and Temperature fall is to room temperature under argon gas sustainable protection；
NH is weighed in molar ratio4F (AR) 0.2963g, NaOH (AR) 0.2000g is dissolved in 20ml and 10ml methanol solution respectively
In obtain clear solution；By NH4F and NaOH solution instill in clear solution, stir to get suspension under the conditions of room temperature argon gas；
The NaYF being scattered in 20ml hexamethylene is added dropwise in suspension4:Yb3+/Er3+, it is warming up to 60 DEG C later, maintains 20
Minute, it is continuously heating to 108 DEG C and stablizes 5 minutes；Argon gas gas circuit to be closed, is vacuumized, vacuum pump is closed in lasting pumping after twenty minutes,
Logical argon gas, Continuous aeration；
300 degrees Celsius are continuously heating to, maintains one hour, is then normally cooled to room temperature, closes argon gas gas cylinder, it is acquired
Solution centrifuge washing after obtain sample NaYF4: 18%Yb3+/ 2%Er3+@NaYF4: 20%Nd3+；
NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The preparation of@IR780:
By NaYF4:Yb3+/Er3+@NaYF4:Nd3+It is scattered in quantitative dehydrated alcohol and deionized water solution, is added quantitative
Ammonium hydroxide, instills 200 microlitres of tetraethyl orthosilicates, 2 milliliters of IR780 of subsequent instillation, stirring at normal temperature, and resulting solution is washed into centrifugation is crossed
It washs drying and obtains NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780。
Optical property is carried out to material prepared by the embodiment, using fluorescence intensity ratio thermometric skill disclosed in document [1]
Art obtains the relation curve of its sensitivity and temperature, as a result as shown in Figure 5.It is strong using the comparison fluorescence of method disclosed in document [2]
The superiority than thermometry and the comparative illustration fluorescence intensity ratio thermometry of thermal infrared imager thermometric is spent, as a result such as Fig. 6 institute
Show.With superior photo-thermal effect, as a result material prepared by the embodiment is demonstrated using sterilization experiment disclosed in document [3]
As shown in Figure 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 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The flow chart of@IR780 synthesis and each mistake
Corresponding transmission electron microscope(TEM) picture, illustrates the core-shell structure of sample in journey.
Fig. 2 (a) is the NaYF of the embodiment4:Yb3+/Er3+XRD spectrum, Fig. 1 (b) be the embodiment NaYF4:Yb3+/
Er3+@NaYF4:Nd3+XRD spectrum, Fig. 1 (c) be the embodiment NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780's
XRD spectrum.
Fig. 3 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-
shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The VISIBLE LIGHT EMISSION map of@IR780 (core-shell-IR780).
Illustrate that material of the invention is greatly improved in VISIBLE LIGHT EMISSION intensity.
Fig. 4 is embodiment NaYF4:Yb3+/Er3+(core),NaYF4:Yb3+/Er3+@NaYF4:Nd3+(core-
shell),NaYF4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The near infrared light of@IR780 (core-shell-IR780) emits figure
Spectrum.Illustrate that material of the invention is greatly improved near infrared light emissive porwer.
Fig. 5 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2The near infrared light temperature sensing spirit of@IR780
Acuity curve.
Fig. 6 is the NaYF of the case study on implementation4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780 swashs 808 nanometer lasers
It gives, the heat generated in the pigeon breast meat tissue with a thickness of 1mm, and the material made from the embodiment and thermal infrared imager point
The case where other monitoring temperature is with changed power.Illustrate the obtained temperature of the material as made from the embodiment compared to infrared heat
As the biological tissue surface temperature that instrument monitors is more accurate.
Fig. 7 is the NaYF of the embodiment4:Yb3+/Er3+@NaYF4:Nd3+@SiO2@IR780 is in different control groups to large intestine
The ablation of bacillus.And heat is produced under the excitation of 808nm laser by comparative illustration material of the present invention, to bacterium
It has arrived ablation.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (5)
1. a kind of rare earth luminescent material, which is characterized in that its chemical formula of the material are as follows: NaY(1-x-y)F4:xYb3+/yEr3+@NaY
(1-z)F4:zNd3+@SiO2@IR780, wherein 0≤x≤20%, 1%≤y≤5%, 10%≤y≤30%.
2. the preparation method of rare earth luminescent material described in claim 1, which is characterized in that method includes:
(1) NaY is prepared using thermal decomposition method(1-x-y)F4:xYb3+/yEr3+；
(2) NaY prepared with step (1)(1-x-y)F4:xYb3+/yEr3+NaY is prepared using thermal decomposition method for raw material(1-x-y)F4:
xYb3+/yEr3+@NaY(1-z)F4:zNd3+；
(3) NaY prepared with step (2)(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+Microemulsion method is used for raw material
Prepare NaY(1-x-y)F4:xYb3+/yEr3+@NaY(1-z)F4:zNd3+@SiO2@IR780。
3. the application that material described in claim 1 is used to prepare photo-thermal therapy material.
4. the application that material described in claim 1 is used to prepare near-infrared temperature sensing material.
5. the application that material described in claim 1 is used to prepare optical imagery material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910463186.7A CN110184063B (en) | 2019-05-30 | 2019-05-30 | Rare earth luminescent material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910463186.7A CN110184063B (en) | 2019-05-30 | 2019-05-30 | Rare earth luminescent material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110184063A true CN110184063A (en) | 2019-08-30 |
| CN110184063B CN110184063B (en) | 2021-09-07 |
Family
ID=67718968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910463186.7A Active CN110184063B (en) | 2019-05-30 | 2019-05-30 | Rare earth luminescent material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110184063B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891742A (en) * | 2023-06-07 | 2023-10-17 | 西安邮电大学 | Rare earth luminescent material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017581A (en) * | 2014-06-18 | 2014-09-03 | 东南大学 | Photothermal conversion nanometer material as well as preparation method and application method thereof |
| CN104804741A (en) * | 2015-03-31 | 2015-07-29 | 复旦大学 | Single-emission up-conversion nano fluorescent probe and synthetic method thereof |
| CN105505374A (en) * | 2016-02-01 | 2016-04-20 | 东南大学 | Up-conversion luminescence composite material based on dye sensitization and preparation method of up-conversion luminescence composite material |
| CN105664158A (en) * | 2016-01-07 | 2016-06-15 | 复旦大学 | Photoluminescence-photothermal nano composite structural material and preparation method and application thereof |
| CN107523289A (en) * | 2017-09-05 | 2017-12-29 | 哈尔滨工程大学 | A kind of dye sensitization rare earth up-conversion and preparation method thereof |
| CN108079297A (en) * | 2018-01-16 | 2018-05-29 | 复旦大学 | A kind of application of up-conversion luminescence-thermochemotherapy composite Nano probe and preparation method thereof and therapeutic alliance Programmed control |
| CN108165270A (en) * | 2018-02-06 | 2018-06-15 | 长春工业大学 | A kind of nanometer of golden shell coats upper conversion nano crystalline substance sandwich and preparation method thereof |
-
2019
- 2019-05-30 CN CN201910463186.7A patent/CN110184063B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017581A (en) * | 2014-06-18 | 2014-09-03 | 东南大学 | Photothermal conversion nanometer material as well as preparation method and application method thereof |
| CN104804741A (en) * | 2015-03-31 | 2015-07-29 | 复旦大学 | Single-emission up-conversion nano fluorescent probe and synthetic method thereof |
| CN105664158A (en) * | 2016-01-07 | 2016-06-15 | 复旦大学 | Photoluminescence-photothermal nano composite structural material and preparation method and application thereof |
| CN105505374A (en) * | 2016-02-01 | 2016-04-20 | 东南大学 | Up-conversion luminescence composite material based on dye sensitization and preparation method of up-conversion luminescence composite material |
| CN107523289A (en) * | 2017-09-05 | 2017-12-29 | 哈尔滨工程大学 | A kind of dye sensitization rare earth up-conversion and preparation method thereof |
| CN108079297A (en) * | 2018-01-16 | 2018-05-29 | 复旦大学 | A kind of application of up-conversion luminescence-thermochemotherapy composite Nano probe and preparation method thereof and therapeutic alliance Programmed control |
| CN108165270A (en) * | 2018-02-06 | 2018-06-15 | 长春工业大学 | A kind of nanometer of golden shell coats upper conversion nano crystalline substance sandwich and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHAN, GUOBIN等: "Upconverting Organic Dye Doped Core-Shell Nano-Composites for Dual-Modality NIR Imaging and Photo-Thermal Therapy", 《THERANOSTICS》 * |
| 陈川: "基于稀土上转换纳米材料的荧光探针研究", 《厦门大学博士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116891742A (en) * | 2023-06-07 | 2023-10-17 | 西安邮电大学 | Rare earth luminescent material and preparation method and application thereof |
| CN116891742B (en) * | 2023-06-07 | 2024-05-17 | 西安邮电大学 | Rare earth luminescent material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110184063B (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mahalingam et al. | Bright white upconversion emission from Tm3+/Yb3+/Er3+-doped Lu3Ga5O12 nanocrystals | |
| Yu et al. | Luminescent properties of LaPO4: Eu nanoparticles and nanowires | |
| CN104017581B (en) | Photothermal deformation nano material and preparations and applicatio method thereof | |
| Song et al. | Gd 2 O 2 S: Yb, Er submicrospheres with multicolor upconversion fluorescence | |
| Zhao et al. | Design of infrared-emitting rare earth doped nanoparticles and nanostructured composites | |
| CN103450875A (en) | 800-nanometer continuous laser excited rare earth upconversion nanoparticles (UCNPs), and preparation method and application thereof | |
| CN105623663B (en) | A kind of red up-conversion luminescence nano-carrier and preparation method | |
| CN104083777B (en) | Upper conversion composite nano materials and preparation method thereof, application | |
| CN103623852A (en) | Upconversion nanocrystalline/titanium dioxide composite nanomaterial and preparation method thereof | |
| CN106350057B (en) | Preparation method of fluorescent nano hybrid particles | |
| CN112940726B (en) | Blue-violet and near-infrared two-region dual-mode luminescent nanocrystal and preparation method thereof | |
| CN112080278B (en) | Up/down conversion dual-mode luminescent nanocrystal and preparation method and application thereof | |
| CN113817469B (en) | Ultra-bright monochromatic up-conversion nano probe for excitation/emission in biological window and preparation method and application thereof | |
| CN107722967B (en) | A method of red fluorescence emits in enhancing ytterbium/holmium/cerium codope fluorine lutetium natrium nanocrystalline body | |
| Jain et al. | Rare-earth-doped Y3Al5O12 (YAG) nanophosphors: synthesis, surface functionalization, and applications in thermoluminescence dosimetry and nanomedicine | |
| CN106634988B (en) | Nanocrystalline material for fluorescence temperature probe | |
| Kang et al. | Enhanced upconversion luminescence intensity of core–shell NaYF4 nanocrystals guided by morphological control | |
| CN103468266A (en) | Preparation method of water-soluble upconversion fluorescence nano material | |
| CN107794043A (en) | Rear-earth-doped upper conversion@silica nanometer compound bars and preparation method thereof | |
| CN105602566B (en) | A kind of rear-earth-doped NaGdF4Upper conversion nano crystalline substance and preparation method thereof | |
| Gao et al. | Synthesis of Yb 3+, Ho 3+ and Tm 3+ co-doped β-NaYF 4 nanoparticles by sol–gel method and the multi-color upconversion luminescence properties | |
| CN110184063A (en) | A kind of rare earth luminescent material and the preparation method and application thereof | |
| CN109735325A (en) | A kind of composite material using quantum dot enhancing up-conversion luminescence | |
| CN103897696A (en) | Cr-doped nano near infrared long-persistence material and preparation method thereof | |
| CN103666474B (en) | Ruddiness/near infrared light double-color up-conversion luminescence nanomaterial 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 |