CN115595140A - Preparation method of DHCA (dehydroepiandrosterone) -modified upconversion luminescent nano material and method for detecting solution and cell temperature by using DHCA-modified upconversion luminescent nano material - Google Patents
Preparation method of DHCA (dehydroepiandrosterone) -modified upconversion luminescent nano material and method for detecting solution and cell temperature by using DHCA-modified upconversion luminescent nano material Download PDFInfo
- Publication number
- CN115595140A CN115595140A CN202211210457.6A CN202211210457A CN115595140A CN 115595140 A CN115595140 A CN 115595140A CN 202211210457 A CN202211210457 A CN 202211210457A CN 115595140 A CN115595140 A CN 115595140A
- Authority
- CN
- China
- Prior art keywords
- nagdf
- oleic acid
- acetate
- nano
- dhca
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 104
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LABSLXOWZIMSBL-UHFFFAOYSA-N dehydrodiooniferyl alcohol Natural products O1C=2C(OC)=CC(C=CCOC)=CC=2C(CO)C1C1=CC=C(O)C=C1 LABSLXOWZIMSBL-UHFFFAOYSA-N 0.000 title claims abstract 10
- FMGSKLZLMKYGDP-UHFFFAOYSA-N Dehydroepiandrosterone Natural products C1C(O)CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CC=C21 FMGSKLZLMKYGDP-UHFFFAOYSA-N 0.000 title abstract description 5
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 title abstract description 5
- 229960002847 prasterone Drugs 0.000 title abstract description 5
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 128
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 123
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 123
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000005642 Oleic acid Substances 0.000 claims abstract description 123
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 123
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 123
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 123
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 120
- 239000002105 nanoparticle Substances 0.000 claims abstract description 100
- 239000011258 core-shell material Substances 0.000 claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 63
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 26
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960001701 chloroform Drugs 0.000 claims abstract description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 120
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 102
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 68
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 34
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 33
- 238000003384 imaging method Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- LYQGMALGKYWNIU-UHFFFAOYSA-K gadolinium(3+);triacetate Chemical compound [Gd+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LYQGMALGKYWNIU-UHFFFAOYSA-K 0.000 claims description 24
- OSCVBYCJUSOYPN-UHFFFAOYSA-K ytterbium(3+);triacetate Chemical compound [Yb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OSCVBYCJUSOYPN-UHFFFAOYSA-K 0.000 claims description 24
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 claims description 21
- 230000005284 excitation Effects 0.000 claims description 20
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 claims description 18
- 210000004027 cell Anatomy 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- SNMVVAHJCCXTQR-UHFFFAOYSA-K thulium(3+);triacetate Chemical compound [Tm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SNMVVAHJCCXTQR-UHFFFAOYSA-K 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 9
- 239000012629 purifying agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 210000005056 cell body Anatomy 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 42
- 229960003964 deoxycholic acid Drugs 0.000 description 42
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 230000008569 process Effects 0.000 description 21
- 229910052786 argon Inorganic materials 0.000 description 18
- 239000002245 particle Substances 0.000 description 12
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000003703 image analysis method Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000009529 body temperature measurement Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004861 thermometry Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K13/00—Thermometers specially adapted for specific purposes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Optics & Photonics (AREA)
- Composite Materials (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention belongs to the technical field of up-conversion luminescent nano materials, and particularly relates to a preparation method of a DHCA (dehydroepiandrosterone) -modified up-conversion luminescent nano material and a method for detecting solution and cell temperature by using the same. The method comprises the following steps: firstly, preparing oleic acid-coated Yb, er and Tm co-doped NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano core-shell structure, nano particles are converted, and then NaGdF coated with oleic acid is used 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Dissolving the upconversion nanoparticles with the nano core-shell structure in trichloromethane, mixing the trichloromethane solution of the obtained upconversion nanoparticles with a DHCA (dehydroepiandrosterone) tetrahydrofuran solution, stirring, and centrifuging the obtained reaction product to obtain the DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
Description
Technical Field
The invention belongs to the technical field of up-conversion luminescent nano materials, and particularly relates to a preparation method of a DHCA (dehydroepiandrosterone) modified up-conversion luminescent nano material and a method for detecting solution and cell temperature by using the same.
Background
As a novel submicron thermal reading method, the luminescent nano temperature measurement attracts people's attention due to the strong temperature dependence on the nano scale, and is widely applied in the fields of biology, thermodynamics, nano medicine and the like due to the high resolution, high sensitivity and non-invasiveness. Nano thermometry can provide in vivo temperature measurements by non-contact and non-invasive luminescent bioimaging. However, absorption and scattering in complex tissues limits the signal penetration depth and causes errors due to variations in different locations in the body.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of a DHCA modified up-conversion luminescent nano material and a method for detecting the temperature of a solution and cells by the same, in order to minimize errors caused by changes of different positions in vivo and monitor the temperature in vivo, the invention prepares a different-wavelength dual-emission rate type up-conversion luminescent nano temperature sensor by doping Er and Tm in the up-conversion luminescent nano material and modifying by DHCA, wherein a rate signal is formed by the ratio of up-conversion emission intensities at the wavelength of 525nm and 812nm, the up-conversion luminescence has excellent temperature dependence due to the participation of photons in the up-conversion luminescence process, and the up-conversion luminescent nano temperature sensor is combined with an image quantitative analysis method with rapid array detection, high spatial resolution and high flux to become a proper material of a nano thermometer, and the method provides a noninvasive high-sensitivity and high-response speed cell temperature detection method for a nano temperature measurement technology.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing a DHCA-modified upconversion luminescent nanomaterial, comprising the steps of:
(1) Preparation of Yb and Er doped NaGdF coated with oleic acid 4 The up-conversion nano particles are cores, and Yb and Tm doped NaGdF is wrapped outside the cores 4 A first shell layer, andthe first shell layer is wrapped with NaYF 4 Second shell of oleic acid coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Converting nanoparticles on the nano core-shell structure;
(2) The oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Dissolving the upconversion nanoparticles with the nano core-shell structure in chloroform, mixing the obtained trichloromethane solution of the upconversion nanoparticles with a DHCA tetrahydrofuran solution, stirring, and centrifuging the obtained reaction product to obtain the DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
Preferably, the step (1) includes the steps of: 1) Comprises gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid, 1-octadecene, and NH 4 Mixing the solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain the NaGdF coated with the oleic acid and doped with the Yb and the Er 4 An upconverting nanoparticle core;
2) Oleic acid coated Yb and Er doped NaGdF 4 The up-conversion nano particle inner core cyclohexane solution and the solution contain gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid, 1-octadecene and NH 4 Mixing the mixed solution of F and NaOH, and reacting by a coprecipitation method to obtain NaGdF with an oleic acid-coated core wrapped by Yb and Tm doped 4 Converting nanoparticles on the first shell;
3) Wrapping the oleic acid-coated inner core with NaGdF doped with Yb and Tm 4 The first shell layer is converted into the nano particle cyclohexane solution and contains yttrium acetate, oleic acid, 1-octadecene and NH 4 Mixing the mixed solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain NaGdF coated with oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano core-shell structure up-conversion nanoparticles.
Preferably, the step 1) includes the steps of: mixing a mixed solution containing gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid and 1-octadecene, heating to 150-180 ℃, and keeping for 40-60min; cooling to 50-55 deg.C, adding NH respectively 4 F methanol solution and NaOH methanol solution at 50-55 deg.CKeeping for 30-40min, heating to 100-120 deg.C, and keeping for 20-40min; then introducing inert gas under the vacuum condition, heating to 280-320 ℃, keeping for 50-80min, centrifuging the reaction product after the reaction is finished, and dissolving and washing the obtained solid part to obtain the oleic acid-coated Yb and Er doped NaGdF 4 An upconversion nanoparticle core.
Preferably, the gadolinium acetate, erbium acetate, ytterbium acetate, NH 4 The molar ratio of the F to the NaOH is 45-55:1:44-54:300-360: 20-30.
Preferably, the ratio of the molar amount of erbium acetate to the volume of oleic acid is 1mmol:900-1100mL; the dosage ratio of the molar weight of erbium acetate to the volume of the 1-octadecene is 1mmol:1400-1600mL.
Preferably, the NH 4 The concentration of the methanol solution F is 0.30-0.50mmol/L; the concentration of the NaOH methanol solution is 0.90-1.10mmol/L.
Preferably, the step 2) includes the steps of: mixing mixed solution containing gadolinium acetate, ytterbium acetate, thulium acetate, oleic acid and 1-octadecene, heating to 150-180 deg.C, and maintaining for 40-60min; cooling to 50-55 deg.C, adding NH 4 Yb and Er doped NaGdF coated with F methanol solution, naOH methanol solution and oleic acid 4 Up-converting the cyclohexane solution of the inner core of the nanoparticle, keeping the temperature at 50-55 ℃ for 30-40min, and then heating to 100-120 ℃ for 20-40min; then introducing inert gas under the vacuum condition, heating to 280-320 ℃, keeping for 50-80min, centrifuging the reaction product after the reaction is finished, dissolving and washing the obtained solid part to obtain the NaGdF with the oleic acid-coated kernel and the Yb and Tm doped outside the kernel 4 The nanoparticles are converted on the first shell.
Preferably gadolinium acetate, ytterbium acetate, thulium acetate, NH 4 The molar ratio of the F to the NaOH is 45-55:44-54:1:300-360: 20-30.
Preferably, the ratio of the molar amount of the thulium acetate to the volume of the oleic acid is 1mmol:900-1100mL; the dosage ratio of the molar weight of the thulium acetate to the volume of the 1-octadecene is 1mmol:1400-1600mL.
Preferably, the NH is 4 The concentration of the methanol solution F is 0.30-0.50mmol/L; the concentration of the NaOH methanol solution is 0.90-1.10mmol/L.
The oleic acid-coated Yb and Er doped NaGdF 4 The concentration of the cyclohexane solution in the up-conversion nano particle inner core is 30-50mg/mL.
Preferably, the step 3) includes the steps of: mixing the mixed solution containing yttrium acetate, oleic acid and 1-octadecene, heating to 150-180 deg.C, and maintaining for 40-60min; cooling to 50-55 deg.C, adding NH respectively 4 The kernel coated by the F methanol solution, the NaOH methanol solution and the oleic acid is wrapped by the Yb and Tm doped NaGdF 4 Converting nano-particle cyclohexane solution on the first shell layer, keeping at 50-55 deg.C for 30-40min, and heating to 100-120 deg.C for 20-40min; then introducing inert gas under the vacuum condition, heating to 280-320 ℃, keeping the temperature for 50-80min, centrifuging the reaction product after the reaction is finished, and dissolving and washing the obtained solid part to obtain the NaGdF coated with the oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nanoparticles on the nano core-shell structure.
Preferably, yttrium acetate, NH 4 The molar ratio of the dosage of F to the dosage of NaOH is 1:3.0-3.6:0.20-0.30.
Preferably, the ratio of the molar amount of the yttrium acetate to the volume of the oleic acid is 1mmol:7.0-8.0mL; the dosage ratio of the molar weight of the yttrium acetate to the volume of the 1-octadecene is 1mmol:17.0-18.0mL.
Preferably, the NH is 4 The concentration of the methanol solution F is 0.30-0.50mmol/L; the concentration of the NaOH methanol solution is 0.90-1.10mmol/L.
Preferably, the oleic acid-coated inner core is coated with Yb and Tm doped NaGdF 4 The concentration of the converted nano particle cyclohexane solution on the first shell is 30-50mg/mL.
Preferably, in step (2), the oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The dosage ratio of the weight of the conversion nano particles on the nano core-shell structure to the volume of the trichloromethane is1mg：0.05-0.20mL。
Preferably, the oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The weight ratio of the dosage of the upconversion nanoparticles to DHCA on the nano core-shell structure is 1:2-3.
Preferably, the concentration of the DHCA tetrahydrofuran solution is 0.01-0.03g/mL.
Preferably, in the step (2), the stirring conditions include: the stirring temperature is 45-47 ℃; the stirring time is 12-13h, and the stirring speed is 300-700rpm/min.
Preferably, in step (2), the reagents used in the centrifugation include a precipitant and a purifying agent, and the ratio of the weight of the reaction product to the volume of the precipitant is 1mg:0.020-0.030mL, wherein the volume ratio of the dosage of the precipitator to the dosage of the purifying agent is 1:2-5; more preferably, the precipitant is ethanol and the purifying agent is N, N-dimethylformamide.
The second aspect of the invention provides DHCA modified NaGdF prepared by the method 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature of the aqueous solution by using the nano core-shell structure material comprises the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the water solution of the nano core-shell structure material at a constant temperature of 25-70 ℃, and imaging by using a fluorescence spectrometer under 980nm laser excitation to obtain the luminous intensity I at the wavelength of 525nm and 812nm 525 And I 812 Is shown in formula (1), R of formula (1) 2 ＝0.99，
Ln(I 525 /I 812 ) = -2.28819-0.31825 × (1/T) formula (1).
Preferably, the time of the constant temperature condition is more than or equal to 10min. More preferably, the amount of the organic solvent is, the time of the constant temperature condition is 10-15min.
Preferably, the DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The concentration of the nano core-shell structure material aqueous solution is 1-1.25mg/mL.
In a third aspect of the invention there is providedThe DHCA-modified NaGdF prepared by the method of the invention 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A method for detecting the temperature of an aqueous solution by using a nano core-shell structure material comprises the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nano core-shell structure material water solution at a constant temperature of 30-60 ℃, and imaging by using a total internal reflection imaging platform under 980nm laser excitation to obtain a linear relation between the ratio of luminous intensity at the wavelength of 525nm to that at the wavelength of 812nm and the temperature, wherein the linear relation is shown as a formula (2), and R of the formula (2) 2 ＝0.99，
Ln(I 525 /I 812 ) =3.06815-2.07908 × (1/T) formula (2).
The fourth aspect of the invention provides DHCA modified NaGdF prepared by the method of the invention 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature in the living cell body by using the nano core-shell structure material comprises the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the water solution of the nano core-shell structure material and cells at a constant temperature of 31-43 ℃ for 12-14h, and imaging by utilizing a total internal reflection imaging platform under the excitation of 980nm laser to obtain a linear relation between the ratio of luminous intensity at the wavelength of 525nm and 812nm and the temperature, wherein the linear relation is shown as a formula (3), and R of the formula (3) 2 ＝0.99，
Ln(I 525 /I 812 ) =15.23783-4.80306 × (1/T) formula (3).
Through the technical scheme, the preparation method of the DHCA modified up-conversion luminescent nano material and the method for detecting the temperature of the solution and the cells have the following beneficial effects that:
(1) In the present invention, DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The up-conversion luminescent nano material has the advantages of high resolution and high sensitivity in temperature detection, so that the up-conversion luminescent nano material can be used for detecting the temperature change in living cells;
(2) The preparation method is simple and easy to operate, and the method for quantitatively detecting the temperature by the image has high response speed and high sensitivity;
(3) The up-conversion luminescence has excellent temperature dependence due to the participation of photons in the up-conversion luminescence process, and is made into a suitable material of the nano thermometer by combining a rapid array detection and high-spatial resolution and high-flux image quantitative analysis method.
Drawings
FIG. 1 shows oleic acid-coated NaGdF of example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A fluorescence intensity curve graph of the conversion nanoparticles on the nano core-shell structure;
FIG. 2A is the oleic acid-coated Yb and Er doped NaGdF of example 1 4 Up-converting a transmission electron micrograph of the nanoparticle core;
FIG. 2B shows the Yb and Tm doped NaGdF coated outside the oleic acid coated core in example 1 4 Converting a transmission electron microscope image of the nano particles on the first shell layer;
FIG. 2C is the oleic acid-coated NaGdF of example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Transmission electron microscopy images of the converted nanoparticles on the nano core-shell structure;
FIG. 3 shows oleic acid-coated NaGdF of example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 An elemental analysis diagram of the converted nanoparticles on the nano core-shell structure;
FIG. 4 shows oleic acid-coated NaGdF of example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano core-shell structure up-conversion nano particle and DHCA modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 An infrared spectrogram of the nano core-shell structure material;
FIG. 5A shows DHCA-modified NaGdF prepared by the method of the present invention in example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature of the aqueous solution of the nano core-shell structure material in a fluorescence spectrometer obtains fluorescence intensity curve graphs at different temperatures;
FIG. 5B shows DHCA-modified NaGdF prepared by the method of the present invention in example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A linear relation graph of fluorescence intensity to temperature is obtained by a method for detecting the temperature of an aqueous solution in a fluorescence spectrometer by using the nano core-shell structure material;
FIG. 6 shows DHCA-modified NaGdF prepared by the method of the present invention in example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The fluorescence intensity curve diagrams at different temperatures are obtained by a method for detecting the temperature of an aqueous solution in a total internal reflection imaging platform by using the nano core-shell structure material;
FIG. 7A shows DHCA-modified NaGdF prepared by the method of the present invention in example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A method for detecting the temperature in a living cell by using the nano core-shell structure material is used for obtaining cell luminous intensity histograms at different temperatures;
FIG. 7B shows DHCA-modified NaGdF prepared by the method of the present invention in example 1 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A method for detecting the temperature in a living cell by using the nano core-shell structure material is used for obtaining a linear relation graph of cell luminous intensity at different temperatures;
fig. 8 is a schematic diagram of energy levels for detecting temperature changes according to the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The inventor discovers through research that the NaGdF modified by DHCA and prepared by the method of the invention 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The upconversion nanoparticles have thermal quenching effects at different temperatures, and as shown in fig. 8, the detection principle of the material for the temperature is as follows: when the temperature is increased from 25 ℃ to 70 ℃, under excitation of 980nm, DHCA-UCNPs emit green emission (centered at 525 nm) and emission centered at 812nm, which are respectively attributed to Er 3+ 4S3/2 transition and Tm of 3+ The emission intensity of both the 525nm and 812nm peaks decreased due to thermal quenching effect, but the ratio of the 525nm and 812nm emission peaks increased in a boltzmann distribution. Based on this principle, the inventors have completed the present invention.
The invention provides a preparation method of a DHCA modified up-conversion luminescent nano material, which comprises the following steps:
(1) Preparation of Yb and Er doped NaGdF coated with oleic acid 4 The up-conversion nano particles are cores, and Yb and Tm doped NaGdF is wrapped outside the cores 4 A first shell layer, and the outside of the first shell layer is wrapped with NaYF 4 Oleic acid-coated NaGdF of second shell 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Converting nanoparticles on the nano core-shell structure;
(2) Coating the oleic acid with NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Dissolving the upconversion nanoparticles with the nano core-shell structure in chloroform, mixing the obtained trichloromethane solution of the upconversion nanoparticles with a DHCA tetrahydrofuran solution, stirring, and centrifuging the obtained reaction product to obtain the DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
In a particular embodiment of the process of the present invention, in step (1), the oleic acid-coated Yb and Er-doped NaGdF is formed by coating a substrate with a solution of an acid and a solvent 4 The inner core of the up-conversion nano particle and the NaGdF doped with Yb and Tm are wrapped outside the inner core coated with the oleic acid 4 On the first shellThe conversion nano particle and the first shell layer are wrapped with NaYF 4 Oleic acid-coated NaGdF of second shell 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The converted nanoparticles on the nano core-shell structure are all in a uniform hexagonal phase.
In a particular embodiment of the process of the invention, in step (2), the oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The nano core-shell structure up-conversion nano particles undergo ligand exchange reaction, DHCA and NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Ligand exchange is carried out on oleic acid ligands on the surfaces of the conversion nanoparticles on the nano core-shell structure, and finally the DHCA modified NaGdF is obtained 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
In the method of the present invention, in a specific embodiment, the step (1) comprises the steps of:
1) Comprises gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid, 1-octadecene, and NH 4 Mixing the solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain the NaGdF coated with the oleic acid and doped with the Yb and the Er 4 Up-converting the nanoparticle core;
2) NaGdF coated by oleic acid and doped with Yb and Er 4 The up-conversion nano particle inner core cyclohexane solution and the solution contain gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid, 1-octadecene and NH 4 Mixing the mixed solution of F and NaOH, and reacting by a coprecipitation method to obtain NaGdF with an oleic acid-coated core wrapped by Yb and Tm doped 4 Converting nanoparticles on the first shell;
3) Wrapping the oleic acid-coated inner core with NaGdF doped with Yb and Tm 4 The first shell layer is converted into nano particle cyclohexane solution and contains yttrium acetate, oleic acid, 1-octadecene and NH 4 Mixing the mixed solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain NaGdF coated with oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nano particles on the nano core-shell structure.
In the method of the present invention, the step 1) includesThe method comprises the following steps: mixing the mixed solution containing gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid and 1-octadecene, heating to 150-180 deg.C, and maintaining for 40-60min, wherein in specific embodiment, the mixed solution can be heated to 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C or 180 deg.C, and maintained for 40min, 45min, 50min, 55min or 60min; then cooling to 50-55 deg.C, in specific embodiments, for example, to 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C or 55 deg.C, and then adding NH respectively 4 F methanol solution and NaOH methanol solution, keeping at 50-55 deg.C for 30-40min, in specific embodiment, keeping at 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C or 55 deg.C for 30min, 35min or 40min, then heating to 100-120 deg.C for 20-40min, in specific embodiment, heating to 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C or 120 deg.C for 20min, 25min, 30min, 35min or 40min; then introducing inert gas under the vacuum condition, raising the temperature to 280-320 ℃ and keeping the temperature for 50-80min, in a specific embodiment, for example, raising the temperature to 280 ℃, 290 ℃, 300 ℃, 310 ℃ or 320 ℃ and keeping the temperature for 50min, 55min, 60min, 65min, 70min, 75min or 80min, centrifuging the reaction product after the reaction is finished, dissolving and washing the obtained solid part to obtain the NaGdF coated with the Yb and the Er and doped with the oleic acid 4 An upconversion nanoparticle core.
In a preferred embodiment of the method of the present invention, the gadolinium acetate, erbium acetate, ytterbium acetate, NH 4 The molar ratio of the F to the NaOH is 45-55:1:44-54:300-360:20-30, for example 45:1:44:300: 20. 48:1:47:320: 25. 50:1:49:330: 25. 53:1:52:350:30 or 55:1:54: 360:30.
in a preferred embodiment of the process of the present invention, the ratio of the molar amount of erbium acetate to the volume of oleic acid is 1mmol:900-1100mL, for example 1mmol:900mL, 1mmol:950mL, 1mmol: 1000mL, 1mmol:1050mL or 1mmol:1100mL.
In the process of the present invention, in a preferred embodiment, the ratio of the molar amount of erbium acetate to the volume of 1-octadecene is 1mmol:1400-1600mL, for example 1mmol:1400mL, 1mmol:1450mL, 1mmol:1500mL, 1mmol:1550mL or 1mmol:1600mL.
In the process of the invention, in a preferred embodiment, the NH 4 The concentration of the solution of F in methanol is 0.30 to 0.50mmol/L, for example 0.30mmol/L, 0.35mmol/L, 0.40mmol/L, 0.45mmol/L or 0.50mmol/L; the concentration of the NaOH in methanol is 0.90 to 1.10mmol/L, for example 0.90mmol/L, 0.95mmol/L, 1.00mmol/L or 1.10mmol/L.
In the method of the present invention, the step 2) includes the steps of: mixing the mixed solution containing gadolinium acetate, ytterbium acetate, thulium acetate, oleic acid and 1-octadecene, heating to 150-180 deg.C, and maintaining for 40-60min, wherein in specific embodiment, the mixed solution can be heated to 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C or 180 deg.C, and maintained for 40min, 45min, 50min, 55min or 60min; then cooling to 50-55 deg.C, in specific embodiments, for example, to 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C or 55 deg.C, and then adding NH respectively 4 Yb and Er doped NaGdF coated with F methanol solution, naOH methanol solution and oleic acid 4 The subsequent steps of up-converting the cyclohexane solution of the nanoparticle inner core are the same as the step 1), and are not repeated here, so that the NaGdF doped with Yb and Tm is wrapped outside the oleic acid coated inner core 4 The nanoparticles are converted in the first shell.
In a preferred embodiment of the method of the invention, gadolinium acetate, ytterbium acetate, thulium acetate, NH 4 The molar ratio of the F to the NaOH is 45-55:44-54:1:300-360:20-30, for example 45:44:1:300: 20. 48:47:1:320: 25. 50:49:1:330: 25. 53:52:1:350:30 or 55:54:1: 360:30.
in the method of the present invention, in a preferred embodiment, the ratio of the molar amount of thulium acetate to the volume of oleic acid is 1mmol:900-1100mL, for example 1mmol:900mL, 1mmol:950mL, 1mmol: 1000mL, 1mmol:1050mL or 1mmol:1100mL.
In the method of the present invention, in a preferred embodiment, the ratio of the molar amount of thulium acetate to the volume of 1-octadecene is 1mmol:1400-1600mL, for example 1mmol:1400mL, 1mmol:1450mL, 1mmol:1500mL, 1mmol:1550mL or 1mmol:1600mL.
In the process of the invention, in a preferred embodiment, the NH is 4 The concentration of the solution of F in methanol is 0.30 to 0.50mmol/L, for example 0.30mmol/L, 0.35mmol/L, 0.40mmol/L, 0.45mmol/L or 0.50mmol/L; the concentration of the NaOH in methanol is 0.90 to 1.10mmol/L, for example 0.90mmol/L, 0.95mmol/L, 1.00mmol/L or 1.10mmol/L.
In a preferred embodiment of the process of the present invention, the oleic acid-coated Yb and Er doped NaGdF is 4 The concentration of the solution of upconverting nanoparticle inner core cyclohexane is 30-50mg/mL, for example 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL or 50mg/mL.
In the method of the present invention, the step 3) includes the steps of: mixing the mixed solution containing yttrium acetate, oleic acid and 1-octadiene, heating to 150-180 deg.C, and maintaining for 40-60min, wherein in specific embodiment, the temperature can be raised to 150 deg.C, 155 deg.C, 160 deg.C, 165 deg.C, 170 deg.C, 175 deg.C or 180 deg.C, and maintained for 40min, 45min, 50min, 55min or 60min; the temperature is reduced to 50-55 deg.C, and in specific embodiments, the temperature can be reduced to 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C or 55 deg.C, and NH can be added 4 The methanol solution of F, the methanol solution of NaOH and the kernel coated by oleic acid are wrapped by NaGdF doped with Yb and Tm 4 The nano-particle cyclohexane solution is converted on the first shell layer, the subsequent steps are the same as the step 1), and the subsequent steps are not repeated here, so that the NaGdF coated by the oleic acid is obtained 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nanoparticles on the nano core-shell structure.
In the method of the present invention, in a preferred embodiment, yttrium acetate, NH 4 The molar ratio of the dosage of F to the dosage of NaOH is 1:3.0-3.6:0.20 to 0.30, for example 1:3.0:0.20, 1:3.2:0.23, 1:3.3:0.25, 1:3.5: 0.28 or 1:3.6:0.30.
in the method of the present invention, in a preferred embodiment, the ratio of the molar amount of the yttrium acetate to the volume of the oleic acid is 1mmol:7.0-8.0mL, for example 1mmol:7.0mL, 1mmol:7.2mL, 1mmol:7.4mL, 1mmol:7.6mL, 1mmol:7.8mL or 1mmol:8.0mL.
In the method of the present invention, in a preferred embodiment, the ratio of the molar amount of yttrium acetate to the volume of 1-octadecene is 1mmol:17.0-18.0mL, for example 1mmol:17.2mL, 1mmol:17.4mL, 1mmol: 17.6mL, 1mmol:17.8mL or 1mmol:18.0mL.
In the process of the invention, in a preferred embodiment, the NH is 4 The concentration of the solution of F in methanol is 0.30 to 0.50mmol/L, for example 0.30mmol/L, 0.35mmol/L, 0.40mmol/L, 0.45mmol/L or 0.50mmol/L; the concentration of the NaOH in methanol is 0.90 to 1.10mmol/L, for example 0.90mmol/L, 0.95mmol/L, 1.00mmol/L or 1.10mmol/L.
In a preferred embodiment of the method of the present invention, the oleic acid-coated inner core is coated with Yb and Tm doped NaGdF 4 The concentration of the cyclohexane solution of the converted nanoparticles on the first shell is 30-50mg/mL, for example 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL or 50mg/mL.
In a particular embodiment of the process of the invention, in step (2), the oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The dosage ratio of the weight of the conversion nano particles on the nano core-shell structure to the volume of the trichloromethane is 1mg:0.05-0.20mL, for example, 1mg:0.05mL, 1mg:0.08mL, 1mg:0.10mL, 1mg:0.15mL, 1mg:0.18mL or 1mg:0.20mL.
In a particular embodiment of the process of the invention, in step (2), the oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The weight ratio of the dosage of the conversion nanoparticles to DHCA on the nano core-shell structure is 1:2-3, for example, 1:2. 1:2.5 or 1:3.
in a particular embodiment of the method according to the invention, in step (2), the concentration of the DHCA tetrahydrofuran solution is 0.01-0.03g/mL, for example 0.01g/mL, 0.02g/mL or 0.03g/mL.
In the method of the present invention, in a specific embodiment, in the step (2), the stirring conditions include: the stirring temperature is 45-47 deg.C, such as 45 deg.C, 46 deg.C or 47 deg.C; the stirring time is 12-13h, for example 12h or 13h, and the stirring speed is 300-700rpm/min, for example 300rpm/min, 400rpm/min, 500rpm/min, 600rpm/min or 700rpm/min.
In the method of the present invention, in a specific embodiment, in the step (2), the reagents used for the centrifugation include a precipitant and a purifying agent. In a preferred embodiment, the ratio of the weight of the reaction product to the volume of the precipitant is 1mg:0.020-0.030mL, for example 1mg:0.020mL, 1mg:0.022mL, 1mg:0.024mL, 1mg:0.026mL, 1mg:0.028mL or 1mg:0.030mL. In a more preferred embodiment, the volume ratio of the amount of said precipitant to said purifying agent is 1:2-5, for example 1:2. 1:3. 1:4 or 1:5. in a still further preferred embodiment, the precipitant is ethanol and the purifying agent is N, N-dimethylformamide.
In the method, when the DHCA modified NaGdF4: yb, er @ NaGdF4: yb, tm @ NaYF4 nano core-shell structure material is used for detecting the temperature in an aqueous solution or a living cell body, the incubation temperatures are set to be different, so that the temperature of the nano particles is changed, and the linear relation between the luminous intensity and the temperature in a specific temperature range is realized.
The second aspect of the invention provides DHCA modified NaGdF prepared by the method 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A method for detecting the temperature of an aqueous solution by using a nano core-shell structure material comprises the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the water solution of the core-shell structure nano-material at a constant temperature of 25-70 deg.C, such as 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C or 70 deg.C, and measuring the temperature at 25-70 deg.C under 980nm laser excitation by fluorescence spectrometerDHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Luminous intensity I of nano core-shell structure material water solution at the wavelength of 525nm and 812nm 525 And I 812 Calculating a linear relationship between the emitted light intensity and the temperature according to the Boltzmann equation, wherein the linear relationship is represented by the formula (1), and R in the formula (1) 2 ＝0.99，
Ln(I 525 /I 812 ) = -2.28819-0.31825 × (1/T) formula (1).
In a preferred embodiment of the method of the present invention, the time of the constant temperature condition is not less than 10min. More preferably, the time of the constant temperature condition is 10-15min, such as 10min, 11min, 12min, 13min, 14min or 15min.
In a preferred embodiment of the method of the invention, the DHCA-modified NaGdF is 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The concentration of the aqueous solution of the nano core-shell structure material is 1-1.25mg/mL, for example, 1mg/mL, 1.05mg/mL, 1.10mg/mL, 1.15mg/mL, 1.20mg/mL or 1.25mg/mL.
The third aspect of the invention provides DHCA modified NaGdF prepared by the method 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature of the aqueous solution by using the nano core-shell structure material comprises the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nano core-shell structure material aqueous solution under a constant temperature condition of 30-60 ℃, in a specific embodiment, for example, the constant temperature condition can be 30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃ or 60 ℃, using a total internal reflection imaging platform to image under excitation of 980nm laser, deriving the luminous intensity by an image quantitative analysis method through a formula photon number = (ADU-offset). Times.gain/QE, deriving the luminous intensity of a single particle through a software ImageJ, and drawing a linear relation according to a change relation between a ratio of the luminous intensity at wavelengths of 525nm and 812nm and the temperature, wherein the linear relation is shown as a formula (2), and R of the formula (2) 2 ＝0.99，
Ln(I 525 /I 812 ) =3.06815-2.07908 × (1/T) formula (2).
In the method, the total internal reflection imaging platform is a combined instrument and comprises an IX-83 electric inverted fluorescence microscope, a CellTIRF total reflection imaging system and a Prime 95B scientific grade sCMOS camera.
In the method of the present invention, in the formula of photon number = (ADU-offset) × gain/QE, ADU (Analog Digital Unit) is a Digital signal, that is, a light emission intensity; offset is an offset value of the factory specifications of the camera, and is 100ADU; gain is 2e - (ii)/ADU; QE is the Quantum Efficiency (Quantum Efficiency) from a wavelength range look at the camera workbook.
The fourth aspect of the invention provides DHCA modified NaGdF prepared by the method of the invention 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature in the living cell body by using the nano core-shell structure material comprises the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The nano core-shell structure material aqueous solution and the cells are placed at a constant temperature of 31-43 ℃ for 12-14h, in a specific embodiment, for example, the nano core-shell structure material aqueous solution and the cells can be placed at a constant temperature of 31-43 ℃ for 12h, 13h or 14h, then an all internal reflection imaging platform is used for imaging under 980nm laser excitation, the luminous intensity is derived from the formula photon number = (ADU-offset). Times gain/QE through an image quantitative analysis method, the luminous intensity of a single particle is derived through software ImageJ, and a linear relation is drawn according to the change relation between the ratio of the luminous intensity at the wavelength of 525nm and the wavelength of 812nm and the temperature, wherein the linear relation is shown as a formula (3), and R of the formula (3) 2 ＝0.99，
Ln(I 525 /I 812 ) =15.23783-4.80306 × (1/T) formula (3).
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
And (3) reagent sources: in the present invention, the deoxycholic acid (DHCA) is purchased from shanghai alatin reagent, ltd.
Description of the test methods:
in the present invention, the fluorescence intensity measuring instrument is an F-4600 fluorometer, and the manufacturer of the instrument is Hitachi, japan;
in the invention, the transmission electron microscope image test method comprises the following steps: prepare the up-conversion nano-particle cyclohexane solution (concentration is 0.8 mg/mL), take about 8 μ L of solution from it to drop on the clean copper net, dry the copper net for standby. And then sending the copper mesh into a transmission electron microscope for shooting to obtain a transmission electron microscope picture. The test instrument is a HT-7700 transmission electron microscope, and the manufacturer of the instrument is Hitachi, japan;
in the invention, the element analysis test method comprises the steps of adhering a conductive adhesive tape on a sample table, drying the upconversion nanoparticles by about 10 mg) for standby, and uniformly coating about 1mg of upconversion nanoparticle solid powder on the conductive adhesive tape. And then, the sample stage is sent to a scanning electron microscope for shooting to obtain an element analysis spectrogram. The test instrument is an S-8100 scanning electron microscope, and the manufacturer of the instrument is Hitachi, japan;
in the present invention, the infrared spectrum testing instrument is IRPrestige-21 infrared spectrometer, and the manufacturer of the instrument is Shimadzu corporation, japan.
Example 1
1. The preparation process of the DHCA modified up-conversion luminescent nano material comprises the following steps:
(1) Oleic acid coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Process for preparing upconversion nanoparticles with nano core-shell structure
1) At room temperature, 0.2mmol of gadolinium acetate, 0.004mmol of erbium acetate, 0.196mmol of ytterbium acetate, 4mL of oleic acid and 6mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, the mixture is heated to 150 ℃ in an oil bath and kept for 40min, and then after the mixture is cooled to 50 ℃, 3.3mL of NH with the concentration of 0.4mol/L is added respectively 4 Keeping the methanol solution F and the 0.1mL,1mol/L NaOH methanol solution at 50 ℃ for 30min, continuously heating to 110 ℃ and keeping for 30min, connecting the flask to a double-row pipe provided with an argon bottle, keeping the solution under vacuum, switching a cock position to introduce argon, raising the temperature of the flask to 300 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove the supernatant, and ultrasonically dissolving and precipitating the obtained solid part by using cyclohexanePrecipitating, washing with absolute ethyl alcohol for three times to obtain oleic acid-coated NaGdF doped with Yb and Er 4 An upconverting nanoparticle core;
2) At room temperature, 0.2mmol of gadolinium acetate, 0.196mmol of ytterbium acetate, 0.004mmol of thulium acetate, 4mL of oleic acid and 6mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, the mixture is heated to 150 ℃ by oil bath and kept for 40min, then after the temperature is reduced to 50 ℃, 1mL of NaGdF doped with Yb and Er and coated with 40mg/mL of oleic acid are respectively added 4 Cyclohexane solution of upconversion nano particle inner core, 3.3mL,0.4mol/L NH 4 Keeping the methanol solution and 0.1mL,1mol/L NaOH methanol solution at 50 ℃ for 30min, continuously heating to 110 ℃ and keeping for 30min, connecting the flask to a double-row pipe with an argon bottle, keeping the solution under vacuum, switching a cock position to introduce argon, raising the temperature of the flask to 300 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove supernatant, ultrasonically dissolving and precipitating the obtained solid part by cyclohexane, washing three times by absolute ethyl alcohol to obtain NaGdF with Yb and Tm doped outside the oleic acid coated inner core 4 Converting nanoparticles on the first shell;
3) At room temperature, 0.4mmol of yttrium acetate, 3mL of oleic acid and 7mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, the two-neck flask is heated in an oil bath to 150 ℃ and kept for 40min, then the two-neck flask is cooled to 50 ℃ and then is respectively added with 1mL of NaGdF with Yb and Tm doped outside an inner core coated with 40mg/mL of oleic acid 4 The first shell layer is converted into nano-particle cyclohexane solution, 3.3mL of NH with the concentration of 0.4mol/L 4 Keeping the methanol solution F and the 0.1mL,1mol/L NaOH methanol solution at 50 ℃ for 30min, continuously heating to 110 ℃ and keeping for 30min, connecting the flask to a double-row pipe with an argon bottle, keeping the solution under vacuum, switching a cock position to introduce argon, raising the temperature of the flask to 300 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove the supernatant, ultrasonically dissolving the obtained solid part by cyclohexane for precipitation, washing the solid part by absolute ethyl alcohol for three times to obtain the NaGdF coated by oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nanoparticles on the nano core-shell structure.
(2) DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Preparation process of nano core-shell structure material
0.01g of oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Dissolving the up-conversion nano particles with the nano core-shell structure in 1mL of trichloromethane, mixing the obtained up-conversion nano particle trichloromethane solution with 5mL of DHCA tetrahydrofuran solution of 0.02g/mL, stirring at 45 ℃ for 12h at the stirring speed of 500rpm/min, and then centrifugally separating the DHCA-modified NaGdF from the obtained reaction product according to ethanol and N, N-dimethylformamide of 1:3 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
2. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature of the aqueous solution by the nano core-shell structure material comprises the following steps:
1.25mg/mL of DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Respectively placing the nano core-shell structure material aqueous solution at the constant temperature of 25 ℃,30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃ and 70 ℃ for 10min, and then respectively measuring the DHCA modified NaGdF prepared by the invention at the temperature of 25-70 ℃ by adopting a fluorescence spectrometer under the excitation of 980nm laser 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Luminous intensity I of nano core-shell structure material aqueous solution at the wavelength of 525nm and 812nm 525 And I 812 Calculating a linear relationship between the emitted light intensity and the temperature according to the Boltzmann equation, wherein the linear relationship is represented by the formula (1), and R in the formula (1) 2 ＝0.99， Ln(I 525 /I 812 ) = -2.28819-0.31825 × (1/T) formula (1). The results are shown in FIGS. 5A and 5B.
3. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature of the aqueous solution by the nano core-shell structure material comprises the following steps:
1.25mg/mL of DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano core-shell junctionRespectively placing the aqueous solution of the construction material under the constant temperature conditions of 30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃ and 60 ℃ for 10min, imaging under 980nm laser excitation on a total internal reflection imaging platform, deriving the luminous intensity by the formula photon number = (ADU-offset) x gain/QE according to the quantitative image analysis method, deriving the luminous intensity of a single particle by software ImageJ, and drawing a linear relation according to the change relation between the ratio of the luminous intensity at the wavelength of 525nm and 812nm and the temperature, wherein the linear relation is shown as a formula (2), and R of the formula (2) 2 ＝0.99，
Ln(I 525 /I 812 ) =3.06815-2.07908 × (1/T) formula (2). The results are shown in FIG. 6.
4. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature in the living cell body by the nano core-shell structure material is as follows:
1.25mg/mL DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nano core-shell structure material aqueous solution and the HeLa cell under constant temperature conditions of 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 41 ℃ and 43 ℃ for 12h respectively, on a total internal reflection imaging platform, then imaging under 980nm laser excitation, deriving luminous intensity by a formula of photon number = (ADU-offset) x gain/QE through an image quantitative analysis method, deriving the luminous intensity of a single particle through software ImageJ, and drawing a linear relation according to the change relation between the ratio of the luminous intensity at the wavelength of 525nm and 812nm and the temperature, wherein the linear relation is shown as a formula (3), and R of the formula (3) 2 ＝0.99， Ln(I 525 /I 812 ) =15.23783-4.80306 × (1/T) formula (3). The results are shown in FIG. 7A, 7B.
As can be seen from the graph of wavelength and luminous intensity of FIG. 1, under the excitation of 980nm laser, naGdF coated with oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The upconversion nano particles generate upconversion emission at 525nm, 550nm, 665nm and 812nm respectively, and the upconversion emission peaks at 525nm, 550nm and 665nm are attributed to Er element 2 H 11/2 → 4 I 15/2 、 4 S 3/2 → 4 I 15/2 And 4 F 9/2 → 4 I 15/2 is detected. The peak appears at 808nm, which is attributed to the Tm element 3 H 4 → 3 H 6 And (4) transition.
As can be seen from fig. 2, as the number of shells coating the core layer increases, the particle size gradually increases, as shown in the transmission electron microscope diagram of fig. 2, the inset is the particle size distribution of the nanoparticles, the particle size of the nanoparticles increases from about 21nm to about 30nm, and finally the final particle size of the core-shell type nanoparticles is about 35 nm.
Example 2
1. The preparation process of the DHCA modified up-conversion luminescent nano material comprises the following steps:
(1) Oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Process for preparing upconversion nanoparticles with nano core-shell structure
1) At room temperature, 0.18mmol of gadolinium acetate, 0.004mmol of erbium acetate, 0.176mmol of ytterbium acetate, 3.6mL of oleic acid and 5.6mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, heated to 160 ℃ by oil bath heating and kept for 50min, and then cooled to 55 ℃, and respectively added with 2.4mL of 0.50mol/L NH 4 Keeping a methanol solution and a 0.13mL/L NaOH methanol solution at 55 ℃ for 30min, continuously heating to 110 ℃ and keeping for 30min, connecting the flask to a double-row pipe provided with an argon bottle, switching the position of a cock to introduce argon while keeping the solution in vacuum, raising the temperature of the flask to 290 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove supernatant, ultrasonically dissolving and precipitating the obtained solid part by using cyclohexane, washing with absolute ethyl alcohol for three times to obtain the NaGdF coated with the Yb and the Er, wherein the Yb and the Er are doped, and the NaGdF is coated with oleic acid 4 An upconverting nanoparticle core;
2) At room temperature, 0.18mmol of gadolinium acetate, 0.176mmol of ytterbium acetate, 0.004mmol of thulium acetate, 3.6mL of oleic acid and 5.6mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, the temperature is raised to 160 ℃ by oil bath heating and kept for 50min, then after the temperature is lowered to 55 ℃, 1mL,50mg/mL of oleic acid coated NaGdF doped with Yb and Er are respectively added 4 Cyclohexane solution of upconversion nanoparticle cores, 2.4mL, 0.50mol/ml-NH of L 4 Keeping a methanol solution and a 0.13 mL/L0.90 mol/L NaOH methanol solution at 55 ℃ for 30min, continuously heating to 110 ℃ and keeping for 30min, connecting the flask to a double-row pipe with an argon bottle, switching a cock position to introduce argon gas while keeping the solution in vacuum, raising the temperature of the flask to 290 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging a reaction product after the reaction is finished to remove a supernatant, ultrasonically dissolving and precipitating the obtained solid part by using cyclohexane, washing three times by using absolute ethyl alcohol to obtain NaGdF with an oleic acid-coated inner core coated with Yb and Tm doped outside the inner core 4 Converting nanoparticles on the first shell;
3) At room temperature, 0.375mmol of yttrium acetate, 3mL of oleic acid and 6.75mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, the mixture is heated in an oil bath to 160 ℃ and kept for 50min, then the mixture is cooled to 55 ℃, and 1mL of NaGdF with Yb and Tm doped outside an inner core coated with 50mg/mL of oleic acid is respectively added 4 Cyclohexane solution of the converted nanoparticles on the first shell, 2.625mL,0.50mol/L NH 4 Keeping the methanol solution and 0.083mL,0.90mol/L NaOH methanol solution at 55 ℃ for 30min, continuously heating to 110 ℃ and keeping for 30min, connecting the flask to a double-row pipe with an argon bottle, switching the position of a cock to introduce argon while keeping the solution in vacuum, raising the temperature of the flask to 290 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove the supernatant, ultrasonically dissolving the obtained solid part by using cyclohexane for precipitation, washing the solid part by using absolute ethyl alcohol for three times to obtain the NaGdF coated with oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nanoparticles on the nano core-shell structure.
(2) DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Preparation process of nano core-shell structure material
0.01g of oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Dissolving the nano core-shell structure in 2mL of trichloromethane, mixing the obtained up-conversion nano particle trichloromethane solution with 1mL of DHCA tetrahydrofuran solution of 0.03g/mL, stirring at 46 ℃ for 13h and at 500rpm/miN, stirring, and then mixing the obtained reaction product according to the proportion that ethanol and N, N-dimethylformamide are 1:4 centrifugal separation of DHCA modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
2. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature of the aqueous solution by the nano core-shell structure material comprises the following steps:
1mg/mL of DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Respectively placing the nanometer core-shell structure material aqueous solution at constant temperature of 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C and 70 deg.C for 15min, and respectively measuring DHCA modified NaGdF at 25-70 deg.C under 980nm laser excitation by fluorescence spectrometer 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Luminous intensity I of nano core-shell structure material aqueous solution at the wavelength of 525nm and 812nm 525 And I 812 Calculating a linear relationship Ln (I) of the emitted light intensity and the temperature according to the Boltzmann equation 525 /I 812 )＝-2.28819-0.31825×(1/T)，R 2 ＝0.99。
3. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature of the aqueous solution by the nano core-shell structure material comprises the following steps:
1mg/mL of DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nanometer core-shell structure material aqueous solution at constant temperature of 30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃ and 60 ℃ for 15min respectively, imaging under 980nm laser excitation on a total internal reflection imaging platform, deriving luminous intensity by a formula photon number = (ADU-offset) x gain/QE according to an image quantitative analysis method, deriving the luminous intensity of a single particle by software ImageJ, and drawing a linear relation Ln (I) according to the change relation between the ratio of luminous intensity at the wavelength of 525nm and 812nm and the temperature 525 /I 812 )＝3.06815-2.07908×(1/T)，R 2 ＝0.99。
4. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature in the living cell body by the nano core-shell structure material comprises the following steps:
1mg/mL DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nano core-shell structure material aqueous solution and the HeLa cell in constant temperature conditions of 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 41 ℃ and 43 ℃ for 13h respectively, imaging on a total internal reflection imaging platform under the excitation of 980nm laser, deriving the luminous intensity by the formula photon number = (ADU-offset). Times.gain/QE according to the quantitative image analysis method, deriving the luminous intensity of a single particle by software ImageJ, and drawing a linear relationship Ln (I) according to the change relationship between the ratio of the luminous intensity at the wavelength of 525nm and the wavelength of 812nm and the temperature 525 /I 812 )＝15.23783-4.80306×(1/T)，R 2 ＝0.99。
Example 3
1. The preparation process of the DHCA modified up-conversion luminescent nano material comprises the following steps:
(1) Oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Process for preparing upconversion nanoparticles with nano core-shell structure
1) At room temperature, 0.33mmol of gadolinium acetate, 0.006mmol of erbium acetate, 0.324mmol of ytterbium acetate, 6.6mL of oleic acid and 9.6mL of 1-octadecene are mixed and placed in a 50mL two-necked flask, heated to 180 ℃ in an oil bath and kept for 60min, and then cooled to 50 ℃, 4.32mL of 0.50mol/L NH is added respectively 4 Keeping a methanol solution and a 0.164mL methanol solution of 1.10mol/L NaOH at 50 ℃ for 40min, continuously heating to 120 ℃ and keeping for 30min, connecting the flask to a double-row pipe provided with an argon bottle, switching the position of a cock to introduce argon while keeping the solution in vacuum, raising the temperature of the flask to 320 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove supernatant, ultrasonically dissolving and precipitating the obtained solid part by using cyclohexane, washing three times by using absolute ethyl alcohol to obtain the NaGdF coated with Yb and Er doped with oleic acid, wherein the NaGdF is coated by oleic acid 4 An upconverting nanoparticle core;
2) At the room temperature, the reaction kettle is used for heating, mixing 0.003mmol of gadolinium acetate, 0.324mmol of ytterbium acetate, 0.006mmol of thulium acetate, 6.6mL of oleic acid and 9.6mL of 1-eighteenMixing alkene, placing in a 50mL two-neck flask, heating to 180 deg.C in oil bath, maintaining for 60min, cooling to 50 deg.C, adding 2mL,30mg/mL oleic acid coated Yb and Er doped NaGdF 4 Cyclohexane solution of upconversion nanoparticle inner core, 4.32mL,0.50mol/L NH 4 Keeping a methanol solution and a 0.164mL methanol solution of NaOH of 1.10mol/L at 50 ℃ for 40min, continuously heating to 120 ℃ and keeping for 30min, connecting the flask to a double-row pipe provided with an argon bottle, switching the position of a cock to introduce argon gas while keeping the solution in vacuum, raising the temperature of the flask to 320 ℃ and keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished to remove supernatant, ultrasonically dissolving and precipitating the obtained solid part by using cyclohexane, washing three times by using absolute ethyl alcohol to obtain NaGdF with an oleic acid-coated inner core wrapped by Yb and Tm doped outside the inner core 4 Converting nanoparticles on the first shell;
3) At room temperature, 0.75mmol of yttrium acetate, 6mL of oleic acid and 12.7mL of 1-octadecene are mixed and placed in a 50mL two-neck flask, the mixture is heated to 180 ℃ in an oil bath and kept for 60min, then the mixture is cooled to 50 ℃, and then 2mL of NaGdF with Yb and Tm doped outside an inner core coated with 30mg/mL of oleic acid and 2mL of NaGdF with Yb and Tm doped outside the inner core are respectively added 4 Cyclohexane solution of conversion nanoparticles on the first shell, 4.5mL,0.50mol/L NH 4 Keeping the F methanol solution and 0.136mL,1.10mol/L NaOH methanol solution at 50 ℃ for 40min, continuously heating to 120 ℃ and keeping for 30min, connecting the flask to a double-row pipe with an argon bottle, switching the cock position of the solution under vacuum, introducing argon, raising the temperature of the flask to 320 ℃, keeping for 1 hour, then cooling to room temperature, centrifuging the reaction product after the reaction is finished, removing supernatant, ultrasonically dissolving the obtained solid part by using cyclohexane for precipitation, washing with absolute ethyl alcohol for three times to obtain the NadF coated with oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nanoparticles on the nano core-shell structure.
(2) DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Preparation process of nano core-shell structure material
0.05g of oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Dissolving the up-conversion nano particles with the nano core-shell structure in 5mL of trichloromethane, mixing the obtained up-conversion nano particle trichloromethane solution with 4mL of DHCA tetrahydrofuran solution of 0.03g/mL, stirring at 47 ℃ for 12h at the stirring speed of 600rpm/min, and then centrifugally separating the DHCA-modified NaGdF from the obtained reaction product according to ethanol and N, N-dimethylformamide of 1:5 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
2. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature of the aqueous solution by the nano core-shell structure material comprises the following steps:
1.25mg/mL DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the aqueous solution of the nano core-shell structure material at constant temperature of 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C and 70 deg.C for 15min, respectively, and measuring DHCA-modified NaGdF at 25-70 deg.C under 980nm laser excitation by fluorescence spectrometer 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Luminous intensity I of nano core-shell structure material aqueous solution at the wavelength of 525nm and 812nm 525 And I 812 Calculating the linear relationship Ln (I) of the emitted light intensity and the temperature according to the Boltzmann formula 525 /I 812 )＝-2.28819-0.31825×(1/T)，R 2 ＝0.99。
3. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature of the aqueous solution by the nano core-shell structure material comprises the following steps:
1.25mg/mL of DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the water solution of the nano core-shell structure material in constant temperature conditions of 30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃ and 60 ℃ for 15min respectively, imaging under 980nm laser excitation on a total internal reflection imaging platform, deriving the luminous intensity by the formula photon number = (ADU-offset) x gain/QE according to the quantitative image analysis method, deriving the luminous intensity of a single particle by software ImageJ, and deriving the luminous intensity according to the wavelength of 525nm and 812nmPlotting the relationship between the ratio of light intensity and temperature to obtain a linear relationship Ln (I) 525 /I 812 )＝3.06815-2.07908×(1/T)，R 2 ＝0.99。
4. NaGdF modified with DHCA 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The process of detecting the temperature in the living cell body by the nano core-shell structure material is as follows:
1.25mg/mL of DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nano core-shell structure material aqueous solution and the HeLa cell in constant temperature conditions of 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 41 ℃ and 43 ℃ for 14h respectively, imaging on a total internal reflection imaging platform under the excitation of 980nm laser, deriving the luminous intensity by the formula photon number = (ADU-offset). Times.gain/QE according to the quantitative image analysis method, deriving the luminous intensity of a single particle by software ImageJ, and drawing a linear relation Ln (I) according to the change relation between the ratio of the luminous intensity at the wavelength of 525nm and the wavelength of 812nm and the temperature 525 /I 812 )＝15.23783-4.80306×(1/T)，R 2 ＝0.99。
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related fields can be directly or indirectly applied thereto.
Claims (10)
1. A preparation method of DHCA modified up-conversion luminescent nano-materials is characterized by comprising the following steps:
(1) Preparation of Yb and Er doped NaGdF coated with oleic acid 4 The up-conversion nano particle is a core, and the core is coated with NaGdF doped with Yb and Tm 4 A first shell layer, and the outside of the first shell layer is wrapped with NaYF 4 Oleic acid-coated NaGdF of second shell 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano-core-shell structure up-conversion nanoparticles;
(2) Coating the oleic acid with NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano core-shell structureDissolving the up-conversion nanoparticles in chloroform, mixing the obtained up-conversion nanoparticle chloroform solution with a DHCA tetrahydrofuran solution, stirring, and centrifuging the obtained reaction product to obtain DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 A nano core-shell structure material.
2. The method of claim 1, wherein the step (1) comprises the steps of:
1) Comprises gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid, 1-octadecene, and NH 4 Mixing the solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain the NaGdF coated with the oleic acid and doped with the Yb and the Er 4 An upconverting nanoparticle core;
2) Oleic acid coated Yb and Er doped NaGdF 4 The up-conversion nano particle inner core cyclohexane solution and the solution contain gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid, 1-octadecene and NH 4 Mixing the mixed solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain NaGdF with the oleic acid-coated kernel wrapped by Yb and Tm doped 4 Converting nanoparticles on the first shell;
3) Wrapping the oleic acid-coated inner core with NaGdF doped with Yb and Tm 4 The first shell layer is converted into nano particle cyclohexane solution and contains yttrium acetate, oleic acid, 1-octadecene and NH 4 Mixing the mixed solution of F and NaOH, and reacting by adopting a coprecipitation method to obtain NaGdF coated with oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 And (3) converting the nanoparticles on the nano core-shell structure.
3. The method according to claim 2, wherein the step 1) comprises the steps of:
mixing a mixed solution containing gadolinium acetate, erbium acetate, ytterbium acetate, oleic acid and 1-octadecene, heating to 150-180 ℃, and keeping for 40-60min; cooling to 50-55 deg.C, adding NH respectively 4 Keeping the methanol solution of F and the methanol solution of NaOH at 50-55 ℃ for 30-40min, and then heating to 100-120 ℃ for 20-40min; then in a vacuum stripIntroducing inert gas under the reaction conditions, heating to 280-320 ℃, keeping for 50-80min, centrifuging the reaction product after the reaction is finished, dissolving and washing the obtained solid part to obtain the NaGdF coated by oleic acid and doped with Yb and Er 4 An upconverting nanoparticle core;
preferably, the gadolinium acetate, erbium acetate, ytterbium acetate, NH 4 The molar ratio of the F to the NaOH is 45-55:1:44-54:300-360:20-30 parts of;
preferably, the ratio of the molar amount of erbium acetate to the volume of oleic acid is 1mmol:900-1100mL; the dosage ratio of the molar weight of erbium acetate to the volume of the 1-octadecene is 1mmol:1400-1600mL;
preferably, the NH is 4 The concentration of the methanol solution F is 0.30-0.50mol/L; the concentration of the NaOH methanol solution is 0.90-1.10mol/L.
4. The method according to claim 2, wherein the step 2) comprises the steps of:
mixing mixed solution containing gadolinium acetate, ytterbium acetate, thulium acetate, oleic acid and 1-octadecene, heating to 150-180 deg.C, and maintaining for 40-60min; cooling to 50-55 deg.C, adding NH respectively 4 Yb and Er doped NaGdF coated with F methanol solution, naOH methanol solution and oleic acid 4 Up-converting the nano particle inner core cyclohexane solution, keeping the temperature at 50-55 ℃ for 30-40min, and then heating to 100-120 ℃ and keeping the temperature for 20-40min; then introducing inert gas under the vacuum condition, heating to 280-320 ℃, keeping for 50-80min, centrifuging the reaction product after the reaction is finished, dissolving and washing the obtained solid part to obtain the NaGdF with the oleic acid-coated kernel and the Yb and Tm doped outside the kernel 4 Converting nanoparticles on the first shell;
preferably gadolinium acetate, ytterbium acetate, thulium acetate, NH 4 The molar ratio of the F to the NaOH is 45-55:44-54:1:300-360:20-30 parts of;
preferably, the ratio of the molar amount of the thulium acetate to the volume of the oleic acid is 1mmol:900-1100mL; the dosage ratio of the molar weight of the thulium acetate to the volume of the 1-octadecene is 1mmol:1400-1600mL;
preferably, the NH is 4 The concentration of the methanol solution F is 0.30-0.50mol/L; the concentration of the NaOH methanol solution is 0.90-1.10mol/L;
the oleic acid-coated Yb and Er doped NaGdF 4 The concentration of the cyclohexane solution in the up-conversion nano particle inner core is 30-50mg/mL.
5. The method according to claim 2, wherein the step 3) comprises the steps of:
mixing the mixed solution containing yttrium acetate, oleic acid and 1-octadecene, heating to 150-180 deg.C, and maintaining for 40-60min; cooling to 50-55 deg.C, adding NH respectively 4 The kernel coated by the F methanol solution, the NaOH methanol solution and the oleic acid is wrapped by the Yb and Tm doped NaGdF 4 Converting the nano-particle cyclohexane solution on the first shell layer, keeping the temperature at 50-55 ℃ for 30-40min, and then heating to 100-120 ℃ for 20-40min; then introducing inert gas under the vacuum condition, heating to 280-320 ℃, keeping the temperature for 50-80min, centrifuging the reaction product after the reaction is finished, and dissolving and washing the obtained solid part to obtain the NaGdF coated with the oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Nano-core-shell structure up-conversion nanoparticles;
preferably, yttrium acetate, NH 4 The molar ratio of the F to the NaOH is 1:3.0-3.6:0.20-0.30;
preferably, the ratio of the molar amount of the yttrium acetate to the volume of the oleic acid is 1mmol:7.0-8.0mL; the dosage ratio of the molar weight of the yttrium acetate to the volume of the 1-octadecene is 1mmol:17.0-18.0mL;
preferably, the NH 4 The concentration of the methanol solution F is 0.30-0.50mol/L; the concentration of the NaOH methanol solution is 0.90-1.10mol/L;
preferably, the oleic acid-coated inner core is coated with Yb and Tm doped NaGdF 4 The concentration of the cyclohexane solution of the converted nanoparticles on the first shell is 30-50mg/mL.
6. The method of claim 1The method is characterized in that in the step (2), the NaGdF coated with the oleic acid 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The dosage ratio of the weight of the conversion nanoparticles on the nano core-shell structure to the volume of the trichloromethane is 1mg:0.05-0.20mL;
preferably, the oleic acid-coated NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The weight ratio of the dosage of the upconversion nanoparticles to DHCA on the nano core-shell structure is 1:2-3;
preferably, the concentration of the DHCA tetrahydrofuran solution is 0.01-0.03g/mL.
7. The method of claim 1, wherein in step (2), the conditions of agitation comprise: the stirring temperature is 45-47 ℃; stirring for 12-13h; the stirring speed is 300-700rpm/min;
preferably, in step (2), the reagents used in the centrifugation include a precipitant and a purifying agent, and the ratio of the weight of the reaction product to the volume of the precipitant is 1mg:0.020-0.030mL, wherein the volume ratio of the dosage of the precipitator to the dosage of the purifying agent is 1:2-5;
preferably, the precipitant is ethanol and the purifying agent is N, N-dimethylformamide.
8. DHCA modified NaGdF prepared by any one of the methods of claims 1-7 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature of the aqueous solution by using the nano core-shell structure material is characterized by comprising the following steps of: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the water solution of the nano core-shell structure material at a constant temperature of 25-70 ℃, and imaging by using a fluorescence spectrometer under 980nm laser excitation to obtain the luminous intensity I at the wavelength of 525nm and 812nm 525 And I 812 Is a linear relationship between the ratio of (A) to (B) and the temperature, the linear relationship being as shown in formula (1), R of formula (1) 2 ＝0.99，
Ln(I 525 /I 812 ) = -2.28819-0.31825 × (1/T) formula (1);
preferably, the time of the constant temperature condition is more than or equal to 10min; more preferably, the time of the constant temperature condition is 10-15min;
preferably, the DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The concentration of the nano core-shell structure material aqueous solution is 1-1.25mg/mL.
9. DHCA modified NaGdF prepared by any one of the methods of claims 1-7 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature of the aqueous solution by using the nano core-shell structure material is characterized by comprising the following steps of: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the nano core-shell structure material aqueous solution at a constant temperature of 30-60 ℃, and imaging by using a total internal reflection imaging platform under 980nm laser excitation to obtain a linear relation between the ratio of luminous intensity at the wavelength of 525nm to that at the wavelength of 812nm and the temperature, wherein the linear relation is shown as a formula (2), and R of the formula (2) 2 ＝0.99，
Ln(I 525 /I 812 ) =3.06815-2.07908 × (1/T) formula (2).
10. DHCA modified NaGdF prepared by any one of the methods of claims 1-7 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 The method for detecting the temperature in the living cell body by using the nano core-shell structure material is characterized by comprising the following steps: DHCA-modified NaGdF 4 :Yb,Er@NaGdF 4 :Yb,Tm@NaYF 4 Placing the water solution of the nano core-shell structure material and cells at a constant temperature of 31-43 ℃ for 12-14h, and imaging by utilizing a total internal reflection imaging platform under the excitation of 980nm laser to obtain a linear relation between the ratio of luminous intensity at the wavelength of 525nm and 812nm and the temperature, wherein the linear relation is shown as a formula (3), and R of the formula (3) 2 ＝0.99，
Ln(I 525 /I 812 ) =15.23783-4.80306 × (1/T) formula (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211210457.6A CN115595140A (en) | 2022-09-30 | 2022-09-30 | Preparation method of DHCA (dehydroepiandrosterone) -modified upconversion luminescent nano material and method for detecting solution and cell temperature by using DHCA-modified upconversion luminescent nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211210457.6A CN115595140A (en) | 2022-09-30 | 2022-09-30 | Preparation method of DHCA (dehydroepiandrosterone) -modified upconversion luminescent nano material and method for detecting solution and cell temperature by using DHCA-modified upconversion luminescent nano material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115595140A true CN115595140A (en) | 2023-01-13 |
Family
ID=84845807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211210457.6A Pending CN115595140A (en) | 2022-09-30 | 2022-09-30 | Preparation method of DHCA (dehydroepiandrosterone) -modified upconversion luminescent nano material and method for detecting solution and cell temperature by using DHCA-modified upconversion luminescent nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115595140A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185978A (en) * | 2020-09-24 | 2021-07-30 | 杭州美迪生物医药技术开发有限公司 | Nanocrystalline material for cell temperature detection, preparation method thereof and detection kit |
| CN114214069A (en) * | 2021-12-20 | 2022-03-22 | 桂林理工大学 | Core-shell double-doped nanoparticle material for improving sensitivity of non-contact temperature sensor and preparation method and application thereof |
-
2022
- 2022-09-30 CN CN202211210457.6A patent/CN115595140A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185978A (en) * | 2020-09-24 | 2021-07-30 | 杭州美迪生物医药技术开发有限公司 | Nanocrystalline material for cell temperature detection, preparation method thereof and detection kit |
| CN114214069A (en) * | 2021-12-20 | 2022-03-22 | 桂林理工大学 | Core-shell double-doped nanoparticle material for improving sensitivity of non-contact temperature sensor and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| BO LING等: "Multimodal Imaging and Synergetic Chemodynamic/Photodynamic Therapy Achieved Using an NaGdF4, Yb, Er@ NaGdF4, Yb, Tm@NaYF4@Fe-MOFs Nanocomposite", CHEM ASIAN J., vol. 17, no. 14, 18 May 2022 (2022-05-18), pages 202200161 * |
| 王国凤: "稀土氟化物纳米晶的制备及性质", vol. 2015, 31 January 2015, 黑龙江大学出版社, pages: 28 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Nd3+-sensitized upconversion nanostructure as a dual-channel emitting optical probe for near infrared-to-near infrared fingerprint imaging | |
| Xu et al. | High-resolution fluorescence diffuse optical tomography developed with nonlinear upconverting nanoparticles | |
| Yan et al. | Lanthanide ion doped upconverting nanoparticles: synthesis, structure and properties | |
| Chen et al. | Core/shell NaGdF4: Nd3+/NaGdF4 nanocrystals with efficient near-infrared to near-infrared downconversion photoluminescence for bioimaging applications | |
| Li et al. | Influence of the TGA modification on upconversion luminescence of hexagonal-phase NaYF4: Yb3+, Er3+ nanoparticles | |
| Cao et al. | Energy transfer highway in Nd3+-sensitized nanoparticles for efficient near-infrared bioimaging | |
| CN103589432B (en) | Rear-earth-doped lithium lutetium fluoride nano material and its preparation and application | |
| Lim et al. | In vivo and scanning electron microscopy imaging of upconverting nanophosphors in Caenorhabditis elegans | |
| Wang et al. | Upconversion luminescence of monodisperse CaF2: Yb3+/Er3+ nanocrystals | |
| Abel et al. | Analysis of the shell thickness distribution on NaYF4/NaGdF4 core/shell nanocrystals by EELS and EDS | |
| Liu et al. | Sub-10 nm hexagonal lanthanide-doped NaLuF4 upconversion nanocrystals for sensitive bioimaging in vivo | |
| Li et al. | Nd3+ sensitized up/down converting dual-mode nanomaterials for efficient in-vitro and in-vivo bioimaging excited at 800 nm | |
| CN106867509B (en) | A kind of Nd3+It is sensitized conversion nano crystalline substance material and preparation method thereof and water detection application on nucleocapsid | |
| Yi et al. | Strong red-emitting near-infrared-to-visible upconversion fluorescent nanoparticles | |
| Yin et al. | Synthesis of a novel core–shell nanocomposite Ag@ SiO2@ Lu2O3: Gd/Yb/Er for large enhancing upconversion luminescence and bioimaging | |
| Fang et al. | Surface-protected high-efficiency nanophosphors via space-limited ship-in-a-bottle synthesis for broadband near-infrared mini-light-emitting diodes | |
| Park et al. | Comparative study of upconverting nanoparticles with various crystal structures, core/shell structures, and surface characteristics | |
| Lv et al. | Lutecium fluoride hollow mesoporous spheres with enhanced up-conversion luminescent bioimaging and light-triggered drug release by gold nanocrystals | |
| Rafiei Miandashti et al. | Effect of temperature and gold nanoparticle interaction on the lifetime and luminescence of NaYF4: Yb3+: Er3+ upconverting nanoparticles | |
| CN103013520B (en) | Water-soluble near-infrared quantum dot, preparation method and application thereof | |
| Wei et al. | A single component self-assembled thermally activated delayed fluorescence nanoprobe | |
| Lebret et al. | Synthesis and characterization of fluorescently doped mesoporous nanoparticles for two-photon excitation | |
| Kömpe et al. | Spectroscopic distinction of surface and volume ions in cerium (III)-and terbium (III)-containing core and core/shell nanoparticles | |
| Maurya et al. | Assessment of colloidal NaGdF4: Er3+/Yb3+ upconversion phosphor as contrast enhancer for optical coherence tomography | |
| Fan et al. | Solvatochromism of high-efficient and long-wavelength emissive carbon dots for wide-range water-sensing in organic solvents |
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 |