CN114057931A - Temperature response polymer material with iridium complex and europium chelate as monomers, and preparation method and application thereof - Google Patents
Temperature response polymer material with iridium complex and europium chelate as monomers, and preparation method and application thereof Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 25
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 24
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000002861 polymer material Substances 0.000 title claims abstract description 18
- 230000004044 response Effects 0.000 title claims abstract description 16
- 229910052741 iridium Inorganic materials 0.000 title claims description 28
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims description 27
- 239000013522 chelant Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- -1 europium ions Chemical class 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 16
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims abstract description 14
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 12
- XKFCVCJBXJFJEO-UHFFFAOYSA-N OC(C(C=C1)=CC=C1C(C=C1)=NC=C1C1=CC=CC=C1)=O Chemical compound OC(C(C=C1)=CC=C1C(C=C1)=NC=C1C1=CC=CC=C1)=O XKFCVCJBXJFJEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003287 optical effect Effects 0.000 claims abstract description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002503 iridium Chemical class 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 81
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000004809 thin layer chromatography Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 5
- 229910016644 EuCl3 Inorganic materials 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 5
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920000208 temperature-responsive polymer Polymers 0.000 claims description 5
- GMECCVFSBLSIKE-UHFFFAOYSA-N tert-butyl 2-[4,7-bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]-1,4,7,10-tetrazacyclododec-1-yl]acetate;hydrobromide Chemical compound Br.CC(C)(C)OC(=O)CN1CCNCCN(CC(=O)OC(C)(C)C)CCN(CC(=O)OC(C)(C)C)CC1 GMECCVFSBLSIKE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000003039 volatile agent Substances 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 7
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 3
- LYOPWQIAHLWERL-UHFFFAOYSA-N [Eu].[Ir] Chemical compound [Eu].[Ir] LYOPWQIAHLWERL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 230000004660 morphological change Effects 0.000 abstract 1
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- 230000006870 function Effects 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 230000005284 excitation Effects 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
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- 239000012452 mother liquor Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000004624 confocal microscopy Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- DEXIAIVWKNJLGP-UHFFFAOYSA-N n-(1,10-phenanthrolin-5-yl)prop-2-enamide Chemical compound C1=CC=C2C(NC(=O)C=C)=CC3=CC=CN=C3C2=N1 DEXIAIVWKNJLGP-UHFFFAOYSA-N 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
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- 230000036962 time dependent Effects 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
- G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
A temperature response polymer material taking iridium complexes and europium chelates as monomers comprises: an iridium (III) complex monomer taking 4- (5-phenylpyridine-2-yl) benzoic acid as a main ligand, wherein: the N ^ N ligand is selected from bipyridine, 1, 10-phenanthroline, bipyridine-2-methane and derivatives thereof. The invention has shorter synthetic route and simple preparation condition; through reasonable molecular structure design, an iridium (III) complex with a main ligand containing carboxyl is synthesized, and through the coordination of the carboxyl and europium ions, the europium center excited by 523nm yellow-green light is emitted; the polymer main chain can generate spontaneous curling or stretching under the temperature change by introducing an N-isopropyl acrylamide monomer; by utilizing the morphological change, the regulation and control of the iridium-europium coordination degree are realized, so that the regulation and control of the luminescence performance are realized; the polymer has good water solubility, low biotoxicity, high-resolution and high-accuracy temperature optical sensing characteristics, and can realize real-time monitoring of temperature in a biological microenvironment.
Description
Technical Field
The invention relates to the field of bio-optical probes, in particular to a temperature response polymer material taking an iridium complex and a europium chelate as monomers, a preparation method and application thereof.
Background
An environmentally responsive polymer is a polymer that is responsive to environmental factors. They can change their conformation or state under the stimulation of external environment, such as pH value, mechanical force, temperature, magnetic field intensity, light radiation, electric field intensity, organic/inorganic molecules and biological proteins, etc., and then show the corresponding detection and identification functions. Such stimuli-responsive polymers have found applications in a wide variety of fields, such as information encryption devices, biological detection, drug-targeted delivery, and self-healing materials. At present, temperature is a common physical index, and has become a research focus in the field of environment-responsive polymers.
The rare earth elements have abundant electronic energy levels and excellent physical properties such as sound, light, electricity, magnetism and the like. In the optical field, rare earth materials have multiple light emission wavelengths, narrow emission spectra, long light emission lifetimes, and the like. By applying the rare earth elements to the field of biological imaging by using a confocal microscopy technology and a time-resolved optical imaging technology, an imaging result with high accuracy and high signal-to-noise ratio can be obtained. However, rare earth elements are difficult to be excited directly due to their f-f transition steric hindrance. The organic aromatic compound has strong absorption in a near ultraviolet region, and can effectively transfer excited state energy to an excited state energy level of the rare earth ions after the organic aromatic compound is close to or coordinated with the rare earth ions to form a complex, so that the rare earth ions can emit light. This phenomenon of ligand-sensitized rare earth ion luminescence is called antenna effect.
At present, although the number of rare earth biological probes is relatively large, the excitation wavelength of most materials is in the ultraviolet region. Ultraviolet excitation results in penetration that exists during detection and imagingThe defects of insufficient capability, light source damage and the like, so the development of the rare earth complex with visible light sensitization has important significance. The phosphorescent iridium complex has the advantages of adjustable excited state, long emission life, high quantum efficiency and the like. By reasonable structural design, the existence of the phosphorescent iridium complex metal center and the organic ligand is utilized3In the MLCT state, the effective regulation and control of the rare earth ion luminescence can be realized.
Disclosure of Invention
The invention aims to solve the defects in the prior art and develop a synthetic route with low cost and simple process to prepare the iridium-europium-sensitized temperature optical probe material. The polymer optical material has high water solubility and low biotoxicity, and has high application value in micro-environment temperature monitoring.
In order to solve the technical problems, the invention adopts the following technical scheme: a temperature response polymer material taking an iridium complex and a europium chelate as monomers comprises an iridium (III) complex monomer taking 4- (5-phenylpyridine-2-yl) benzoic acid as a main ligand, and has a structure shown in a formula (I):
wherein: the N ^ N ligand is selected from bipyridine, 1, 10-phenanthroline, bipyridine-2-methane and derivatives thereof; the material has luminescent characteristics.
Further, the material has the luminescent characteristic that the rare earth ions are excited to emit light at 523nm of yellow-green light, and the temperature optical response can be realized in a biological microenvironment.
A preparation method of a temperature response polymer material taking an iridium complex and a europium chelate as monomers is characterized by comprising the following steps:
the method comprises the following steps: dissolving tri-tert-butyl-1, 4,7, 10-tetraazacyclododecane-1, 4, 7-triacetate hydrobromide in an excess of a mixed solution of acetonitrile and potassium carbonate, then slowly adding acryloyl chloride to the solution, reacting the solution at room temperature for 24 hours, finally removing the excess of the acryloyl chloride from the reacted solution by distillation, extracting the crude product with a large amount of dichloromethane and water, taking a dichloromethane layer, removing the solvent by rotary evaporation, and purifying by column chromatography to obtain (7, 10-bis {2- [ (2-methylpropan-2-yl) oxy ] -2-oxoethylidene } -4- (1-oxoethylidene prop-2-enyl) -1,4,7, 10-tetraazacyclododecan-1-yl) acetic acid-2-methylpropan-2-yl ester, the feeding molar ratio of the tri-tert-butyl-1, 4,7, 10-tetraazacyclododecane-1, 4, 7-triacetate hydrobromide to the acryloyl chloride is 1: 5;
step two: the compound obtained in the first step above was dissolved in dichloromethane (5mL), an excess of trifluoroacetic acid was added dropwise with stirring for 24 hours, all volatiles were removed by reduced pressure after the reaction was completed, the crude product was extracted with a large amount of dichloromethane and water, the dichloromethane layer was collected, and the solvent was removed by rotary evaporation. Then dissolving the residue in a small amount of methanol and adding a large amount of diethyl ether to obtain a precipitate, filtering to obtain a precipitate, dissolving the precipitate with a small amount of methanol and washing with diethyl ether for 3 times to obtain white solid (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecan-1-yl) acetic acid;
step three: reacting the compound obtained in the second step with EuCl3˙6H2Dissolving O in 10mL of methanol, adjusting the pH value of a reaction system to 6 by using a dilute sodium hydroxide solution, heating the reaction system to 50 ℃, refluxing for 24 hours, cooling to room temperature after the reaction is finished, re-precipitating for many times by using a small amount of methanol and a large amount of diethyl ether, filtering and drying to obtain a white solid (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecane-1-yl) europium acetate, and mixing the compound obtained in the second step and EuCl3˙6H2The molar ratio of O feeding is 2: 1;
step four: IrCl is added3·3H2Adding O and 4- (5-phenylpyridine-2-yl) benzoic acid into a 50mL flask, carrying out nitrogen protection, mixing 2-ethoxyethanol and water in a volume ratio of 3:1, carrying out nitrogen bubbling for 30 minutes, taking 10mL of mixed solvent, injecting the mixed solvent into a reaction system through an injector, heating the mixture to reflux for 24 hours, cooling to normal temperature after the reaction is finished, filtering out precipitate, washing with water and ethanol to obtain orange yellow solid precipitate, namely crude orange solid precipitateIridium dichloride bridge, the mixture of the above obtained dichloride bridge and ancillary ligand compound is vacuumized through double row pipes in a 50mL round bottom flask and nitrogen is blown, then dichloromethane and methanol mixed solution (25mL, 2:1v/v) after being blown with nitrogen and oxygen is injected, then the mixture is heated and refluxed for 12 hours, after being cooled to room temperature, excess potassium hexafluorophosphate is added, the mixture is stirred for 4 hours at room temperature and then is rotated to be evaporated to dryness, then the mixture is cooled to room temperature, water and dichloromethane are used for washing, organic layers are collected and evaporated, and after the orange yellow solid is separated through thin layer chromatography. IrCl3·3H2The feeding molar ratio of O to 4- (5-phenylpyridin-2-yl) benzoic acid is 1: 2.3 the feeding ratio of the dichloro bridge to the auxiliary ligand compound is 1: 2.2, the auxiliary ligand compound is one of derivatives of bipyridyl, 1, 10-phenanthroline and bipyridyl-2-methane;
step five: NIPAM, an iridium complex, europium (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecan-1-yl) acetate and AIBN were placed in a 50mL reaction tube, the gas of the reaction system was exhausted and filled with nitrogen (three times to-and-fro), Tetrahydrofuran (THF) was bubbled with nitrogen for 1 hour and 3mL was taken out and injected into the reaction tube through an injector. The reaction was stirred at 80 ℃ for 12 hours under nitrogen atmosphere, after cooling, the mixture was added dropwise to 150mL of diethyl ether to give a temperature-sensitive polymeric material, and the precipitated polymer was collected by filtration and further purified by dialysis for 1 day. The feeding molar ratio of the NIPAM to the iridium complex, the (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecane-1-yl) acetic acid europium to the AIBN is 1600: 1: 24: 18.
further, in the purification method of the iridium (III) complex monomer in the fourth step, the crude iridium (III) complex monomer product is subjected to thin layer chromatography separation by acidic alumina, and the developing solvent is methanol: dichloromethane: ethyl acetate was 1: 20: 10.
further, in the fifth step, the feeding molar ratio of the NIPAM, the iridium complex, the europium (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecane-1-yl) acetate and the AIBN is 1600: 1: 24: 18.
an application of a temperature response polymer material taking an iridium complex and a europium chelate as monomers in a biological microenvironment temperature detection reagent is characterized in that: the iridium complex and europium chelate-based temperature-responsive polymer material as claimed in any one of claims 1 or 2, applied to a biological microenvironment temperature detection reagent.
Has the advantages that: compared with the prior art, the preparation method of the temperature response polymer material taking the iridium complex and the europium chelate as monomers can be completed under the conditions of normal temperature and normal pressure, the synthetic route is short, and the preparation conditions are simple.
Through reasonable molecular structure design, the iridium (III) complex with the carboxyl group as the main ligand is synthesized, and through the coordination of the carboxyl group and europium ions, the europium center luminescence excited by 523nm yellow-green light is realized.
The N-isopropyl acrylamide monomer is introduced, so that the polymer main chain can generate spontaneous curling or stretching under the temperature change. By utilizing the form change, the regulation and control of the iridium-europium coordination degree are realized, thereby realizing the regulation and control of the luminescence performance.
In addition, the polymer has good water solubility, low biotoxicity, high resolution and high-accuracy temperature optical sensing characteristics, and can realize real-time monitoring of temperature in a biological microenvironment.
Drawings
FIG. 1 is a general structural diagram of the present invention;
FIG. 2 is a scheme showing the synthesis scheme of europium chelate obtained in example 1 of the present invention;
FIG. 3 is a scheme showing the synthesis scheme of iridium complex 1 obtained in example 2 of the present invention;
FIG. 4 is a synthesis scheme of iridium complex 2 obtained in example 3 of the present invention;
FIG. 5 is a synthesis scheme of iridium complex 3 obtained in example 4 of the present invention;
FIG. 6 is a scheme showing the synthesis scheme of temperature sensitive polymer 1 obtained in example 5 of the present invention;
FIG. 7 is a scheme showing the synthesis scheme of temperature sensitive polymer 2 obtained in example 6 of the present invention;
FIG. 8 is a scheme showing the synthesis of temperature sensitive polymer 3 obtained in example 7 of the present invention;
FIG. 9 is a graph showing an emission spectrum of a polymer sample obtained in example 8 of the present invention;
FIG. 10 is a graph showing a lifetime spectrum of a polymer sample obtained in example 8 of the present invention;
FIG. 11 is a graph showing a temperature titration spectrum of a polymer sample obtained in example 8 of the present invention;
FIG. 12 is a diagram showing intracellular temperature time-resolved lifetime imaging obtained in example 9 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying drawings. The invention may be embodied in different forms and is not limited to the embodiments described herein. Rather, the embodiments are provided so that this disclosure will be thorough and complete.
A temperature response polymer material taking iridium complexes and europium chelates as monomers is characterized in that: comprises the following steps: an iridium (III) complex monomer taking 4- (5-phenylpyridine-2-yl) benzoic acid as a main ligand has a structure shown in figure 1:
wherein: the N ^ N ligand is selected from bipyridine, 1, 10-phenanthroline, bipyridine-2-methane and derivatives thereof; the material has luminescent characteristics. The material has the luminescent characteristic that the material excites rare earth ions to emit light at 523nm of yellow-green light, and can realize temperature optical response in a biological microenvironment.
Example 1: preparation of europium chelate:
(1) tri-tert-butyl-1, 4,7, 10-tetraazacyclododecane-1, 4, 7-triacetate hydrobromide (0.50g, 0.83mmol) was dissolved in a mixed solution of acetonitrile (10mL) and an excess of potassium carbonate, and the solution was stirred constantly. Then, acryloyl chloride (0.30g, 3.31mmol) was slowly added to the solution, and the solution was reacted at room temperature for 24 hours. Finally, distilling the reacted solution to remove redundant acryloyl chloride, extracting the crude product by using a large amount of dichloromethane and water, taking a dichloromethane layer, and removing the solvent by rotary evaporation; and purifying by column chromatography;
(2) compound 1(0.20g, 0.35mmol) obtained above was dissolved in dichloromethane (5mL), and trifluoroacetic acid (5mL) was added dropwise with stirring for 24 hours. After the reaction was complete, all volatiles were removed by reduced pressure, the crude product was extracted with copious amounts of dichloromethane and water and the dichloromethane layer was collected and the solvent was removed by rotary evaporation. The residue was then dissolved in a small amount of methanol and a large amount of diethyl ether was added to give a precipitate. Filtering to obtain precipitate, dissolving with small amount of methanol, and washing with diethyl ether for 3 times to obtain white solid;
(3) compound 2(0.10mg, 0.25mmol) was reacted with EuCl3˙6H2O (0.44g, 0.12mmol) was dissolved in 10mL of methanol. The pH of the reaction system was adjusted to 6 with dilute sodium hydroxide solution. The reaction was warmed to 50 ℃ and refluxed for 24 hours. After the reaction is finished, cooling to room temperature, re-precipitating for many times by using a small amount of methanol and a large amount of diethyl ether, filtering and drying to obtain a white solid. As shown in fig. 2.
Example 2: preparation of Iridium (III) Complex 1:
IrCl is added3·3H2O (0.50g, 1.4mmol) and 4- (5-phenylpyridin-2-yl) benzoic acid (0.85g, 3.08mmol) were charged to a 50mL flask under nitrogen. 2-ethoxyethanol and water were mixed at a volume ratio of 3:1 and purged with nitrogen for 30 minutes, and 10mL of the mixed solvent was injected into the reaction system through a syringe. The mixture was then heated to reflux for 24 hours. After the reaction is finished, cooling to normal temperature, filtering out precipitate, washing with water and ethanol to obtain orange yellow solid precipitate, namely the crude iridium dichloro-bridge. A mixture of the dichloro-bridge (0.50g, 0.40mmol) obtained above and 2-propenoic acid (2- (pyridin-2-yl) pyridin-4-yl) methyl ester (0.21g, 0.88mmol) was purged through a double row vacuum drum with nitrogen in a 50mL round bottom flask, then a mixed solution of dichloromethane and methanol (25mL, 2:1v/v) deoxygenated with nitrogen was injected, and then the mixture was heated under reflux for 12 hours. After cooling to room temperature, an excess of potassium hexafluorophosphate was added. The mixture was stirred at room temperature for 4 hours and then rotary evaporated to dryness. The mixture was then cooled to room temperature and washed with water and dichloromethane. After collection and evaporation of the organic layer, compound 1 was isolated by acidic alumina thin layer chromatography. As shown in fig. 3.
Example 3: preparation of Iridium (III) Complex 2:
ir is addedCl3·3H2O (0.50g, 1.4mmol) and 4- (5-phenylpyridin-2-yl) benzoic acid (0.85g, 3.08mmol) were charged to a 50mL flask under nitrogen. 2-ethoxyethanol and water were mixed at a volume ratio of 3:1 and purged with nitrogen for 30 minutes, and 10mL of the mixed solvent was injected into the reaction system through a syringe. The mixture was then heated to reflux for 24 hours. After the reaction is finished, cooling to normal temperature, filtering out precipitate, washing with water and ethanol to obtain orange yellow solid precipitate, namely the crude iridium dichloro-bridge. A mixture of the dichloro-bridge (0.50g, 0.40mmol) obtained above and N- (pyrido (3, 2-h) quinolin-5-yl) prop-2-enamide (0.22g, 0.88mmol) was purged with nitrogen via a double row vacuum drum in a 50mL round bottom flask, then a mixed solution of dichloromethane and methanol (25mL, 2:1v/v) deoxygenated by drum nitrogen was injected, and then the mixture was heated under reflux for 12 hours. After cooling to room temperature, an excess of potassium hexafluorophosphate was added. The mixture was stirred at room temperature for 4 hours and then rotary evaporated to dryness. The mixture was then cooled to room temperature and washed with water and dichloromethane. After collection and evaporation of the organic layer, compound 1 was isolated by acidic alumina thin layer chromatography. As shown in fig. 4.
Example 4: preparation of Iridium (III) Complex 3:
IrCl is added3·3H2O (0.50g, 1.4mmol) and 4- (5-phenylpyridin-2-yl) benzoic acid (0.85g, 3.08mmol) were charged to a 50mL flask under nitrogen. 2-ethoxyethanol and water were mixed at a volume ratio of 3:1 and purged with nitrogen for 30 minutes, and 10mL of the mixed solvent was injected into the reaction system through a syringe. The mixture was then heated to reflux for 24 hours. After the reaction is finished, cooling to normal temperature, filtering out precipitate, washing with water and ethanol to obtain orange yellow solid precipitate, namely the crude iridium dichloro-bridge. A mixture of the dichloro-bridge (0.50g, 0.40mmol) obtained above and 2-propenoic acid (2- (pyridin-2-yl) pyridin-4-yl) methyl ester (0.19g, 0.88mmol) was purged through a double row vacuum drum with nitrogen in a 50mL round bottom flask, then a mixed solution of dichloromethane and methanol (25mL, 2:1v/v) deoxygenated with nitrogen was injected, and then the mixture was heated under reflux for 12 hours. After cooling to room temperature, an excess of potassium hexafluorophosphate was added. The mixture was stirred at room temperature for 4 hours and then rotary evaporated to dryness. Then mixing the mixtureThe mixture was cooled to room temperature and washed with water and dichloromethane. After collection and evaporation of the organic layer, compound 1 was isolated by acidic alumina thin layer chromatography. As shown in fig. 5.
Example 5: preparation of temperature-sensitive polymer 1:
NIPAM (391.0mg, 1.62mmol), Complex 1(1.14mg, 1.01. mu. mol), Compound 3(13.4mg, 24.3. mu. mol), and AIBN (2.9mg, 17.6. mu. mol) were placed in a 50mL reaction tube. The reaction system was purged and filled with nitrogen (three times). Tetrahydrofuran (THF) was sparged with nitrogen for 1 hour and 3mL was injected into the reaction tube via syringe. The reaction was stirred at 80 ℃ for 12 hours under nitrogen. After cooling, the mixture was added dropwise to 150mL of diethyl ether to give polymer 1. The precipitated polymer was collected by filtration and further purified by dialysis for 1 day. As shown in fig. 6.
Example 6: preparation of temperature-sensitive polymer 2:
NIPAM (391.0mg, 1.62mmol), Complex 2(1.15mg, 1.01. mu. mol), Compound 3(13.4mg, 24.3. mu. mol), and AIBN (2.9mg, 17.6. mu. mol) were placed in a 50mL reaction tube. The reaction system was purged and filled with nitrogen (three times). Tetrahydrofuran (THF) was sparged with nitrogen for 1 hour and 3mL was injected into the reaction tube via syringe. The reaction was stirred at 80 ℃ for 12 hours under nitrogen. After cooling, the mixture was added dropwise to 150mL of diethyl ether to give polymer 2. The precipitated polymer was collected by filtration and further purified by dialysis for 1 day. As shown in fig. 7.
Example 7: preparation of temperature-sensitive polymer 3:
NIPAM (391.0mg, 1.62mmol), Complex 3(1.11mg, 1.01. mu. mol), Compound 3(13.4mg, 24.3. mu. mol), and AIBN (2.9mg, 17.6. mu. mol) were placed in a 50mL reaction tube. The reaction system was purged and filled with nitrogen (three times). Tetrahydrofuran (THF) was sparged with nitrogen for 1 hour and 3mL was injected into the reaction tube via syringe. The reaction was stirred at 80 ℃ for 12 hours under nitrogen. After cooling, the mixture was added dropwise to 150mL of diethyl ether to give polymer 3. The precipitated polymer was collected by filtration and further purified by dialysis for 1 day. As shown in fig. 8.
Example 8: plotting of the temperature titration curve of Polymer 1 in aqueous solution:
Example 9: use of Polymer 1 for intracellular temperature monitoring:
hela cells grown in log phase were seeded at the appropriate concentration into confocal dishes until they adhered. Polymer 1 was added to the confocal dish of each experimental group at a concentration of 60. mu.g/mL, and Hela cells were incubated at 37 ℃ and 5% CO2Incubate under atmosphere for 2 hours. After PBS washing, the polymer incubated Hela cells were excited at 405nm using a semiconductor laser equipped on a confocal microscope. Luminescence signals at 500-590nm and 600-680nm are collected by a charge coupled device module, and the lifetime signals are processed by a time-dependent single photon counting module. The temperature lifetime imaging photograph results are shown in fig. 12.
In summary, the invention provides a material of a polymer luminescent probe with temperature response, and provides a preparation method of the material. The material has excellent luminescence property, and is suitable to be used as an optical probe material in the fields of biomedical imaging and treatment. The material provided by the invention has better efficacy when being used as a core functional material in a biomedical detection kit.
It is characterized in that:
1. through reactions such as suzuki, dichloro bridge coordination and the like, a temperature response type polymer material taking iridium (III) complex, europium (III) chelate and N-isopropylacrylamide as monomers is synthesized.
2. The material also has good optical performance, can excite europium ions by 523nm yellow-green light, has longer luminescent life and has better rate responsiveness to ambient temperature.
3. The material can be used as a functional material to realize real-time monitoring of the temperature in the cell.
In the above embodiments, all functions may be implemented, or a part of the functions may be implemented as necessary.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and variations of the embodiment of the present invention may occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A temperature response polymer material taking iridium complexes and europium chelates as monomers is characterized in that: the method comprises the following steps: the iridium (III) complex monomer taking 4- (5-phenylpyridine-2-yl) benzoic acid as a main ligand has a structure shown in a formula (I):
wherein: the N ^ N ligand is selected from bipyridine, 1, 10-phenanthroline, bipyridine-2-methane and derivatives thereof; the material has luminescent characteristics.
2. The temperature-responsive polymeric material of claim 1, wherein the iridium complex and europium chelate are selected from the group consisting of: the material has the luminescent characteristic that the material excites rare earth ions to emit light at 523nm of yellow-green light, and can realize temperature optical response in a biological microenvironment.
3. A method for preparing a temperature responsive polymer material using an iridium complex and a europium chelate as monomers according to any one of claims 1 or 2, wherein: the method comprises the following steps:
the method comprises the following steps: dissolving tri-tert-butyl-1, 4,7, 10-tetraazacyclododecane-1, 4, 7-triacetate hydrobromide in an excess of a mixed solution of acetonitrile and potassium carbonate, then slowly adding acryloyl chloride to the solution, reacting the solution at room temperature for 24 hours, finally removing the excess of the acryloyl chloride from the reacted solution by distillation, extracting the crude product with a large amount of dichloromethane and water, taking a dichloromethane layer, removing the solvent by rotary evaporation, and purifying by column chromatography to obtain (7, 10-bis {2- [ (2-methylpropan-2-yl) oxy ] -2-oxoethylidene } -4- (1-oxoethylidene prop-2-enyl) -1,4,7, 10-tetraazacyclododecan-1-yl) acetic acid-2-methylpropan-2-yl ester, the feeding molar ratio of the tri-tert-butyl-1, 4,7, 10-tetraazacyclododecane-1, 4, 7-triacetate hydrobromide to the acryloyl chloride is 1: 5;
step two: dissolving the compound obtained in the first step in dichloromethane (5mL), dropwise adding excess trifluoroacetic acid with stirring for 24 hours, removing all volatiles by reduced pressure after the reaction is finished, extracting the crude product with dichloromethane and water, collecting dichloromethane layer, removing solvent by rotary evaporation, dissolving the residue in a small amount of methanol and adding a large amount of diethyl ether to obtain a precipitate, filtering to obtain a precipitate, dissolving with a small amount of methanol and washing with diethyl ether for 3 times to obtain white solid (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecan-1-yl) acetic acid;
step three: reacting the compound obtained in the second step with EuCl3˙6H2Dissolving O in 10mL of methanol, adjusting the pH value of a reaction system to 6 by using a dilute sodium hydroxide solution, heating the reaction system to 50 ℃, refluxing for 24 hours, cooling to room temperature after the reaction is finished, re-precipitating for many times by using a small amount of methanol and a large amount of diethyl ether, filtering and drying to obtain a white solid (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecane-1-yl) europium acetate, and mixing the compound obtained in the second step and EuCl3˙6H2The molar ratio of O feeding is 2: 1;
step four: IrCl is added3·3H2Adding O and 4- (5-phenylpyridin-2-yl) benzoic acid into a 50mL flask, mixing 2-ethoxyethanol and water in a volume ratio of 3:1 under the protection of nitrogen, bubbling nitrogen for 30 minutes, taking 10mL of mixed solvent, injecting the mixed solvent into a reaction system through an injector, and then mixingHeating the mixture to reflux for 24 hours, cooling to normal temperature after the reaction is finished, filtering out the precipitate, washing the precipitate with water and ethanol to obtain an orange yellow solid precipitate, namely a crude iridium dichloro bridge, injecting a dichloromethane and methanol mixed solution (25mL, 2:1v/v) obtained by removing oxygen from the mixture of the dichloro bridge and an auxiliary ligand compound in a 50mL round bottom flask through double-row vacuum drum nitrogen, heating and refluxing the mixture for 12 hours, cooling to room temperature, adding excessive potassium hexafluorophosphate, stirring the mixture at room temperature for 4 hours, then rotating to evaporate to dryness, cooling the mixture to room temperature, washing with water and dichloromethane, collecting and evaporating an organic layer, and separating the orange yellow solid by thin layer chromatography, wherein the IrCl is IrCl3·3H2The feeding molar ratio of O to 4- (5-phenylpyridin-2-yl) benzoic acid is 1: 2.3, the feeding ratio of the dichloro bridge to the auxiliary ligand compound is 1: 2.2, the auxiliary ligand compound is one of derivatives of bipyridyl, 1, 10-phenanthroline and bipyridyl-2-methane;
step five: NIPAM, iridium complex, (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecan-1-yl) acetic acid europium and AIBN were put into a 50mL reaction tube, the reaction system was purged and filled with nitrogen, Tetrahydrofuran (THF) was bubbled with nitrogen for 1 hour and 3mL was taken and injected into the reaction tube through a syringe, stirring the reaction at 80 ℃ for 12 hours under nitrogen atmosphere, cooling, dropwise adding the mixture into 150mL of diethyl ether to obtain a temperature-sensitive polymer material, the precipitated polymer was collected by filtration and further purified by dialysis for 1 day with a molar ratio of input of NIPAM, iridium complex, (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecan-1-yl) europium acetate and AIBN of 1600: 1: 24: 18.
4. the method of claim 3, wherein the iridium complex and europium chelate are used as monomers for preparing the temperature-responsive polymer material, and the method comprises the following steps: fourthly, the iridium (III) complex monomer purification method is characterized in that the iridium (III) complex monomer crude product is subjected to thin-layer chromatography separation by acidic alumina, and the developing solvent is methanol: dichloromethane: ethyl acetate was 1: 20: 10.
5. the method of claim 3, wherein the iridium complex and europium chelate are used as monomers for preparing the temperature-responsive polymer material, and the method comprises the following steps: in the fifth step, the feeding molar ratio of NIPAM, iridium complexes, europium (4-acetyl-7, 10-bis (carboxymethyl) -1,4,7, 10-tetraazacyclododecane-1-yl) acetate and AIBN is 1600: 1: 24: 18.
6. an application of a temperature response polymer material taking an iridium complex and a europium chelate as monomers in a biological microenvironment temperature detection reagent is characterized in that: the iridium complex and europium chelate-based temperature-responsive polymer material as claimed in any one of claims 1 or 2, applied to a biological microenvironment temperature detection reagent.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265407A (en) * | 2008-04-24 | 2008-09-17 | 江南大学 | Polymer electroluminescence material containing amides iridium metal complexes and preparation method thereof |
| CN102268250A (en) * | 2011-05-31 | 2011-12-07 | 江西理工大学 | Novel electrically-neutral tridentate iridium [III] complex red luminescent material and preparation method |
| CN102321468A (en) * | 2011-06-03 | 2012-01-18 | 上海师范大学 | Cationic iridium complex phosphorescene probe as well as preparation method and application thereof |
| CN105934498A (en) * | 2013-11-27 | 2016-09-07 | 华盛顿大学商业中心 | Encoded chromophoric polymer particles |
| US20160340463A1 (en) * | 2014-01-31 | 2016-11-24 | Newsouth Innovations Pty Limited | Process for preparing a polymer |
| CN106432348A (en) * | 2016-09-05 | 2017-02-22 | 南京邮电大学 | Visible light excitable ratio fluorescence thermosensitive probe based on europium complex and preparation method and application of probe |
| US20200062871A1 (en) * | 2017-01-30 | 2020-02-27 | Massachusetts Institute Of Technology | Reactions enabled by thermoresponsive and photoresponsive gels |
| CN111960988A (en) * | 2020-10-21 | 2020-11-20 | 南京工业职业技术大学 | Novel thermal activation delayed fluorescence material based on excimer luminescence and application thereof |
| CN112661777A (en) * | 2020-12-25 | 2021-04-16 | 天津工业大学 | Photochromic and photoluminescent nano-microsphere with core-shell structure and preparation method thereof |
| US20210115328A1 (en) * | 2018-06-22 | 2021-04-22 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie | Fluorescent particles with molecularly imprinted fluorescent polymer shells for cell staining applications in cytometry and microscopy |
-
2021
- 2021-12-06 CN CN202111511378.4A patent/CN114057931A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265407A (en) * | 2008-04-24 | 2008-09-17 | 江南大学 | Polymer electroluminescence material containing amides iridium metal complexes and preparation method thereof |
| CN102268250A (en) * | 2011-05-31 | 2011-12-07 | 江西理工大学 | Novel electrically-neutral tridentate iridium [III] complex red luminescent material and preparation method |
| CN102321468A (en) * | 2011-06-03 | 2012-01-18 | 上海师范大学 | Cationic iridium complex phosphorescene probe as well as preparation method and application thereof |
| CN105934498A (en) * | 2013-11-27 | 2016-09-07 | 华盛顿大学商业中心 | Encoded chromophoric polymer particles |
| US20160340463A1 (en) * | 2014-01-31 | 2016-11-24 | Newsouth Innovations Pty Limited | Process for preparing a polymer |
| CN106432348A (en) * | 2016-09-05 | 2017-02-22 | 南京邮电大学 | Visible light excitable ratio fluorescence thermosensitive probe based on europium complex and preparation method and application of probe |
| US20200062871A1 (en) * | 2017-01-30 | 2020-02-27 | Massachusetts Institute Of Technology | Reactions enabled by thermoresponsive and photoresponsive gels |
| US20210115328A1 (en) * | 2018-06-22 | 2021-04-22 | Bundesrepublik Deutschland, Vertreten Durch Den Bundesminister Für Wirtschaft Und Energie | Fluorescent particles with molecularly imprinted fluorescent polymer shells for cell staining applications in cytometry and microscopy |
| CN111960988A (en) * | 2020-10-21 | 2020-11-20 | 南京工业职业技术大学 | Novel thermal activation delayed fluorescence material based on excimer luminescence and application thereof |
| CN112661777A (en) * | 2020-12-25 | 2021-04-16 | 天津工业大学 | Photochromic and photoluminescent nano-microsphere with core-shell structure and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KARSON KA-SHUN TSO，等: "Strategic Applications of Luminescent Iridium(III) Complexes as Biomolecular Probes, Cellular Imaging Reagents, and Photodynamic Therapeutics", 《IRIDIUM(III) IN OPTOELECTRONIC AND PHOTONICS APPLICATIONS》 * |
| 蒋嘉洋: "基于能量传递的含金属功能聚合物的设计、合成及其生物应用", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
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