CN112300164A - Rare earth samarium cryptand ether fluorescent complex and preparation method thereof - Google Patents
Rare earth samarium cryptand ether fluorescent complex and preparation method thereof Download PDFInfo
- Publication number
- CN112300164A CN112300164A CN202011216540.5A CN202011216540A CN112300164A CN 112300164 A CN112300164 A CN 112300164A CN 202011216540 A CN202011216540 A CN 202011216540A CN 112300164 A CN112300164 A CN 112300164A
- Authority
- CN
- China
- Prior art keywords
- formula
- compound shown
- rare earth
- cryptate
- room temperature
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 51
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 47
- 229910052772 Samarium Inorganic materials 0.000 title claims abstract description 40
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 title claims abstract description 40
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002739 cryptand Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 72
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 75
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000004007 reversed phase HPLC Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- ZGXJTSGNIOSYLO-UHFFFAOYSA-N 88755TAZ87 Chemical compound NCC(=O)CCC(O)=O ZGXJTSGNIOSYLO-UHFFFAOYSA-N 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 229960002749 aminolevulinic acid Drugs 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000013375 chromatographic separation Methods 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- UHNSRFWQBVXBSK-UHFFFAOYSA-N methanol;2,2,2-trifluoroacetic acid Chemical compound OC.OC(=O)C(F)(F)F UHNSRFWQBVXBSK-UHFFFAOYSA-N 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 12
- 239000007850 fluorescent dye Substances 0.000 abstract description 5
- 230000008033 biological extinction Effects 0.000 abstract description 4
- 108091005461 Nucleic proteins Proteins 0.000 abstract description 3
- 102000039446 nucleic acids Human genes 0.000 abstract description 3
- 108020004707 nucleic acids Proteins 0.000 abstract description 3
- 150000007523 nucleic acids Chemical class 0.000 abstract description 3
- 102000004169 proteins and genes Human genes 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 5
- ZMXDDKWLCZADIW-YYWVXINBSA-N N,N-dimethylformamide-d7 Chemical compound [2H]C(=O)N(C([2H])([2H])[2H])C([2H])([2H])[2H] ZMXDDKWLCZADIW-YYWVXINBSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 3
- -1 crown ether rare earth Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000002372 labelling Methods 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000002877 time resolved fluorescence resonance energy transfer Methods 0.000 description 2
- CWGFSQJQIHRAAE-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.OCC(N)(CO)CO CWGFSQJQIHRAAE-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 125000006360 carbonyl amino methylene group Chemical group [H]N(C([*:1])=O)C([H])([H])[*:2] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 238000007877 drug screening Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002868 homogeneous time resolved fluorescence Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RXNXLAHQOVLMIE-UHFFFAOYSA-N phenyl 10-methylacridin-10-ium-9-carboxylate Chemical compound C12=CC=CC=C2[N+](C)=C2C=CC=CC2=C1C(=O)OC1=CC=CC=C1 RXNXLAHQOVLMIE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
-
- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a rare earth samarium cryptand fluorescent complex and a preparation method thereof, wherein the complex has a chemical structural formula shown as the following formula (I): the chemical structural formula of MO is shown as the following formula (II):
the molar extinction coefficient of the rare earth samarium cryptand fluorescent complex provided by the invention can be improved by about 4 times (80000M) compared with that of the existing product‑1cm‑1) The fluorescent dye is suitable for being used as fluorescent dye molecule to mark biomolecules such as nucleic acid and protein for detection in the field of biomedicine, and can improve the sensitivity and accuracy of detection.
Description
Technical Field
The invention relates to the technical field of preparation of coordination compounds, in particular to a rare earth samarium cryptand fluorescent complex and a preparation method thereof.
Background
Time-Resolved Fluorescence resonance energy transfer (Homogeneous Time-Resolved Fluorescence) utilizes energy transfer of two fluorophores, called (energy) donor and (energy) acceptor, respectively, the donor being excited by an external energy source (e.g., a flash lamp or laser) and being capable of transferring energy to the acceptor in resonance if it is within a sufficiently close distance from the acceptor; the receptor is excited to emit light of a specific wavelength. The technology mainly utilizes a long-life fluorescence donor combined with a time-resolved detection method to eliminate biological autofluorescence (fluorescence lifetime of a few nanoseconds) interference. Its advantages are high sensitivity and reliability, and low false positive rate of test result. And the experimental mode is simple to operate, and the experimental time and the cost are saved. The key point of the technology is how to select a proper fluorescent marker as a donor, and the fluorescent markers which are researched more at home and abroad can be divided into organic molecular fluorescent compounds (such as acridinium ester and luminol for chemiluminescence) Quantum Dots (QDs) and metal fluorescent complexes (such as terpyridyl ruthenium for electrochemiluminescence). The organic compound type fluorescent marker generally has the problems of high quenching rate, instability under the illumination condition and the like. The quantum dots have the problems of much nonspecific adsorption and poor interference resistance in complex biological samples.
The rare earth fluorescent complex is an ideal material as a fluorescence donor in the time-resolved fluorescence resonance energy transfer technology due to the characteristics of small molecular weight, easy modification, good light excitation stability, strong anti-interference capability and the like. The rare earth fluorescent complex can be divided into crown ether rare earth complex, beta-diketone rare earth complex, cryptand ether rare earth complex, calixarene rare earth complex and the like. The cryptate has a three-dimensional cavity, metal ions can be strongly pulled into a space lattice to form a stable rare earth complex, and the cryptate has strong fluorescence. The complex formed by the cryptand and the rare earth metal is an ionic compound, and the cryptand structure contains hydrophilic oxygen atoms, so that the cryptand is easy to label in a cell environment and is an ideal material of a fluorescence donor.
At present, although various cave-shaped coordination compounds have been reported at home and abroad, the practical application is not so much, and an ideal cave-shaped coordination compound must have high molar absorption coefficient, high luminous efficiency, long fluorescence life, good water solubility and excited state chemical stability (difficult to quench by ocean gas, water and the like), and easy biomolecule labeling. The rare earth cryptate fluorescent complexes which have been commercialized are very few, such as developed by Cisbio of France and applied to drug screening Eu3+,Tb3+The cryptate complex can be sold, but the price is very expensive, the price is more than 1 ten thousand/mg, and the complex has more synthesis steps and extremely low yield; furthermore, the solubility of the compound is not ideal, which complicates the labeling process. For example, the rare earth cryptand ether fluorescent complex shown in the formula A has a molar extinction coefficient of 20000M-1cm-1Left and right, the detection limit can only reach 10 when the method is used for detecting the index-9g/L, can not meet the requirements of partial detection indexes.
In order to meet the requirements of more detection indexes, a novel fluorescent material which is high in molar extinction coefficient and easy to mark is urgently needed to be provided.
Disclosure of Invention
The invention aims to solve the technical problem of providing a rare earth samarium cryptate fluorescent complex and a preparation method thereof aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the technical scheme that: the rare earth samarium cryptand ether fluorescent complex is provided, and has a chemical structural formula shown as the following formula (I):
wherein, the chemical structural formula of MO is shown as the following formula (II):
the invention also provides a preparation method of the rare earth samarium cryptate fluorescent complex, and the synthesis route of the MO is as follows:
preferably, the preparation method of MO comprises the following steps:
1) adding a compound shown in a formula (II-1), a compound shown in a formula (II-2), anhydrous sodium carbonate and HPLC-grade acetonitrile into a dehydrated and deoxidized two-neck flask, refluxing under the protection of argon, standing and cooling after the reaction is finished, filtering, spin-drying filtrate, adding diethyl ether for pumping, and washing with diethyl ether to obtain a compound shown in a formula (II-3);
2) adding SmCl into the dehydrated and deoxidized two-neck flask after the reaction in the step 1) under the protection of argon3And dehydrated and deoxidized acetonitrile, refluxing, and dropwise adding an acetonitrile solution of tris- (bipyridine) cryptate sodium salt into the obtained white suspension; refluxing overnight, standing and cooling after the reaction is finished; filtering, and washing the solid with diethyl ether to obtain a compound shown as a formula (II-4);
3)N2under protection, adding trifluoroacetic acid into the compound shown in the formula (II-4), stirring at room temperature, slowly dissolving the solid, cleaning the solution, pumping out the trifluoroacetic acid solution after the reaction is completed, adding ether for washing, and pumping out by using an oil pump;
dissolving the obtained solid with ultra-dry anhydrous methanol, and performing N treatment under ice bath condition2Slowly dripping ethylenediamine into the protective atmosphere, and slowly adding the solutionTurbid, after complete reaction at room temperature, draining the solvent, adjusting the pH value by using a trifluoroacetic acid methanol solution, stirring, centrifuging, and draining the liquid; separating the obtained solid with reversed phase high performance liquid chromatography column, and collecting the product to obtain compound shown as formula (II), i.e. MO.
Preferably, the preparation method of MO comprises the following steps:
1) adding a compound shown in a formula (II-1), a compound shown in a formula (II-2), anhydrous sodium carbonate and HPLC-grade acetonitrile into a dehydrated and deoxidized two-neck flask, refluxing for 2-3 days under the protection of argon, standing and cooling after the reaction is finished, filtering, spin-drying filtrate, adding diethyl ether for pumping, and washing with diethyl ether to obtain a compound shown in a formula (II-3);
2) adding SmCl into the dehydrated and deoxidized two-neck flask after the reaction in the step 1) under the protection of argon3And dehydrating and deoxidizing the treated acetonitrile, refluxing for half an hour, and then dropwise adding an acetonitrile solution of tris- (bipyridine) cryptate sodium salt into the obtained white suspension; refluxing at 80 ℃ overnight, standing and cooling after the reaction is finished; filtering, and washing the solid with diethyl ether to obtain a compound shown as a formula (II-4);
3)N2under protection, adding trifluoroacetic acid into the compound shown in the formula (II-4), stirring at room temperature, slowly dissolving the solid, allowing the solution to become clear, reacting for 5h, draining the trifluoroacetic acid solution, adding ether for washing, and draining by using an oil pump;
dissolving the obtained solid with ultra-dry anhydrous methanol, and performing N treatment under ice bath condition2Slowly dripping ethylenediamine in a protective atmosphere, slowly making the solution turbid, reacting at room temperature for 3h, draining the solvent, neutralizing with 1% trifluoroacetic acid methanol solution until the pH value is 5, stirring, centrifuging, and draining the liquid; separating the obtained solid with reversed phase high performance liquid chromatography column, and collecting the product to obtain compound shown as formula (II-5), i.e. MO.
Preferably, the synthetic route of the rare earth samarium cryptate fluorescent complex is as follows:
preferably, the preparation method of the rare earth samarium cryptate fluorescent complex comprises the following steps:
step 2, dissolving the compound shown as the formula (I-1) and KOH in DMSO, dropwise adding bromo-ester into the DMSO, reacting at room temperature, continuously reacting at room temperature after dropwise adding, adding the product into water after the reaction is finished, then adjusting the pH value with HCl, precipitating, filtering and drying to obtain the compound shown as the formula (I-2);
step 3, dissolving the compound shown as the formula (I-2) and the complex MO in ultra-dry dichloromethane at room temperature, dripping dichloromethane solution of DCC, stirring, draining the solvent, and carrying out chromatographic separation to obtain the compound shown as the formula (I-3);
and 4, dissolving the compound I shown as the formula (I-3) by using ultra-dry anhydrous methanol, and carrying out N treatment under the ice bath condition2Slowly dripping ethylenediamine in a protective atmosphere, slowly becoming turbid, finishing the reaction at room temperature, and draining the solvent; separating and collecting the obtained solid by using a reversed-phase high performance liquid chromatography preparation column to obtain a compound shown as a formula (I), namely the rare earth samarium cryptand fluorescent complex.
Preferably, the preparation method of the rare earth samarium cryptate fluorescent complex comprises the following steps:
step 2, dissolving the compound shown as the formula (I-1) and KOH in DMSO, dropwise adding bromo-ester into the DMSO, reacting for 8 hours at room temperature, continuing to react for 14 hours at room temperature after dropwise adding, adding the product into water after the reaction is finished, then adjusting the pH value to 1-2 by using HCl, precipitating a precipitate, filtering, and drying to obtain the compound shown as the formula (I-2);
step 3, dissolving the compound shown as the formula (I-2) and the complex MO in ultra-dry dichloromethane at room temperature, dropwise adding a dichloromethane solution of DCC, stirring for 2 hours, draining the solvent, and carrying out chromatographic separation to obtain the compound shown as the formula (I-3);
and 4, dissolving the compound I shown as the formula (I-3) by using ultra-dry anhydrous methanol, and carrying out N treatment under the ice bath condition2Slowly dripping ethylenediamine in a protective atmosphere, slowly becoming turbid, reacting at room temperature for 3 hours, and draining the solvent; separating and collecting the obtained solid by using a reversed-phase high performance liquid chromatography preparation column to obtain a compound shown as a formula (I), namely the rare earth samarium cryptand fluorescent complex.
The invention has the beneficial effects that:
the molar extinction coefficient of the rare earth samarium cryptand fluorescent complex provided by the invention can be improved by about 4 times (80000M) compared with that of the existing product-1cm-1) The fluorescent dye is suitable for being used as fluorescent dye molecules to mark biomolecules such as nucleic acid, protein and the like, and can improve the sensitivity and the accuracy of detection;
drawings
FIG. 1 shows the results of H-NMR detection of a compound (II-3) in example 2 of the present invention;
FIG. 2 is a result of H-NMR measurement of compound (I-1) in example 2 of the present invention;
FIG. 3 is a result of H-NMR measurement of the compound (I-2) in example 2 of the present invention;
FIG. 4 is an absorption spectrum of a rare earth samarium cryptate fluorescent complex in example 3 of the present invention;
FIG. 5 is an emission spectrum of a rare earth samarium cryptate fluorescent complex in example 3 of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
The embodiment provides a rare earth samarium cryptate fluorescent complex, which has a chemical structural formula shown as the following formula (I):
wherein, the chemical structural formula of MO is shown as the following formula (II):
example 2
The embodiment provides a preparation method of a rare earth samarium cryptand fluorescent complex, and the synthetic route of the rare earth samarium cryptand fluorescent complex is as follows:
wherein the synthesis route of the MO is as follows:
the preparation method of the rare earth samarium cryptate fluorescent complex comprises the following steps:
first, synthesis of MO
The method specifically comprises the following steps:
1) adding 103.4mg (0.176mmol) of the compound shown in the formula (II-1), 189.7mg (0.351mmol) of the compound shown in the formula (II-2), 0.26g of anhydrous sodium carbonate and 300 mLHPLC-grade acetonitrile into a dehydrated and deoxidized two-necked flask, refluxing for 2-3 days under the protection of argon, standing and cooling after the reaction is finished, filtering, spin-drying the filtrate, adding diethyl ether, pumping out (repeatedly), and washing with diethyl ether to obtain the compound shown in the formula (II-3); the results of H-NMR measurement are shown in FIG. 1, and the data for structural confirmation are:1H NMR(DMF-d7):8.73(s,1H,Hbpy),8.28(m,2H,Hbpy),7.76(s,2H,Hbpy), 7.58(s,1H,Hbpy),3.95(s,9H,-OCH3),1.54(s,9H,-C(CH3)3)；
2) adding SmCl into a dehydrated and deoxidized 100mL two-neck flask after the reaction in the step 1) under the protection of argon3(38.6mg, 0.1496mmol) and dehydrated deoxygenated acetonitrile (30mL) were refluxed for half an hour, and then to the resulting white suspension was added dropwise a solution of tris- (bipyridyl) cryptate sodium salt (59.5mg, 0.0499mmol) in acetonitrile (20 mL); refluxing at 80 ℃ overnight, standing and cooling after the reaction is finished; filtering, washing the solid twice with diethyl ether to obtain the compound shown in the formula (II-4), and directly carrying out the next reaction without further treatment;
3)N2under protection, adding 10mL of trifluoroacetic acid into the compound shown in the formula (II-4), stirring at room temperature, slowly dissolving the solid, allowing the solution to become clear, reacting for 5h, draining the trifluoroacetic acid solution, adding ether, washing for three times, and draining by using an oil pump;
the obtained solid was dissolved in ultra-dry anhydrous methanol (20mL) under ice bath condition, N2Slowly dropwise adding ethylenediamine (1.0mL, 15mmol, 100 equivalents, which can be diluted with about 2mL of methanol) in a protective atmosphere, slowly making the solution turbid, reacting at room temperature for 3h, draining the solvent, neutralizing with 1% trifluoroacetic acid methanol solution until the pH value is 5, stirring, centrifuging, and draining the liquid; the obtained solid was separated and collected by reverse phase High Performance Liquid Chromatography (HPLC) preparative column to give a compound represented by the formula (II-5), i.e., MO, in this example, in a yield of 6-8%.
Secondly, synthesizing rare earth samarium cryptand ether fluorescent complex
The method specifically comprises the following steps:
step 2, dissolving the compound (0.55mmol) shown in the formula (I-1) and 3g of KOHDissolving in 15ml of DMSO, dropwise adding 0.556mmol of bromo-ester (dissolved in 5ml of DMSO), reacting for 8h at room temperature, continuing to react for 14h at room temperature after dropwise adding, adding the product into 150ml of water after the reaction is finished, adjusting the pH value to 1-2 by using 1M HCl, precipitating, filtering, and drying to obtain a compound shown as a formula (I-2); the results of H-NMR measurement are shown in FIG. 3, and the data for structure confirmation are:1H-NMR(200MHz,CDCl3):2.42(m,CH2OOCH3),3.21,4.26(d, COCH2C),3.64,3.76(OCH2),4.04,4.41,4.55(m,COOHCH2NH),6.73(d,NHCO)
step 3, dissolving the compound (0.1mmol) shown in the formula (I-2) and the complex MO (0.3mmol) in 100ml of ultra-dry dichloromethane at room temperature, dropwise adding a dichloromethane solution of DCC (0.3mmol of DCC in 50ml of ultra-dry dichloromethane), stirring for 2 hours, draining the solvent, and carrying out chromatographic separation to obtain the compound shown in the formula (I-3);
and 4, dissolving the compound I (0.1mol) shown as the formula (I-3) by using ultra-dry absolute methanol (20mL), and carrying out N treatment under ice bath conditions2Slowly dropwise adding ethylenediamine (1.0mL, 15mmol, 100 equivalents, which can be diluted by about 2mL of methanol) in a protective atmosphere, slowly making the solution turbid, reacting at room temperature for 3h, and draining the solvent; separating and collecting the obtained solid by using a reversed-phase High Performance Liquid Chromatography (HPLC) preparative column to obtain a compound shown as a formula (I), namely the rare earth samarium cryptand fluorescent complex.
Example 3 fluorescence Spectroscopy detection of rare earth samarium cryptate fluorescent Complex
The detection method comprises the following steps: a10.0 mL volumetric flask was charged with the dimethyl sulfoxide stock solution (10. mu.g/mL, 1mL) of the rare earth samarium cryptate fluorescent complex synthesized in example 2, and Tris (hydroxymethyl) aminomethane-hydrochloric acid (Tris-HCl) buffer solution (1X 10)-3mol/L, 1mL) and double distilled water (3mL), diluted to the scale with dimethyl sulfoxide solution, shaken well, left at room temperature for L0min, transferred to an lcm quartz cuvette (Cary Eclipse fluorescence spectrophotometer, VARIAN, USA) for fluorescence spectroscopy.
The detection result is shown in fig. 4-5, fig. 4 is an absorption spectrum diagram of the rare earth samarium cryptand ether fluorescent complex, and fig. 5 is a diagram of the rare earth samarium cryptand ether fluorescent complexEmission spectrum of the compound. It can be seen that the fluorescence emission signal is stable, a fluorescence emission spectrum with a specific peak shape can be formed, and the peak value of the fluorescence emission peak is high, which indicates that the trimer in the rare earth samarium cryptand fluorescent complex is used for Sm in rare earth metal ions3+The rare earth samarium cryptand ether fluorescent complex is suitable for being used as a fluorescent dye molecule to mark biomolecules such as nucleic acid, protein and the like for detection in the field of biomedicine.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (7)
1. A rare earth samarium cryptate fluorescent complex is characterized by having a chemical structural formula shown as the following formula (I):
wherein, the chemical structural formula of MO is shown as the following formula (II):
2. a method for preparing the rare earth samarium cryptate fluorescent complex of claim 1, wherein the MO is synthesized by the following steps:
3. the method for preparing rare earth samarium cryptate fluorescent complex according to claim 2, wherein the MO comprises the following steps:
1) adding a compound shown in a formula (II-1), a compound shown in a formula (II-2), anhydrous sodium carbonate and HPLC-grade acetonitrile into a dehydrated and deoxidized two-neck flask, refluxing under the protection of argon, standing and cooling after the reaction is finished, filtering, spin-drying filtrate, adding diethyl ether for pumping, and washing with diethyl ether to obtain a compound shown in a formula (II-3);
2) adding SmCl into the dehydrated and deoxidized two-neck flask after the reaction in the step 1) under the protection of argon3And dehydrated and deoxidized acetonitrile, refluxing, and dropwise adding an acetonitrile solution of tris- (bipyridine) cryptate sodium salt into the obtained white suspension; refluxing overnight, standing and cooling after the reaction is finished; filtering, and washing the solid with diethyl ether to obtain a compound shown as a formula (II-4);
3)N2under protection, adding trifluoroacetic acid into the compound shown in the formula (II-4), stirring at room temperature, slowly dissolving the solid, cleaning the solution, pumping out the trifluoroacetic acid solution after the reaction is completed, adding ether for washing, and pumping out by using an oil pump;
dissolving the obtained solid with ultra-dry anhydrous methanol, and performing N treatment under ice bath condition2Slowly dripping ethylenediamine in a protective atmosphere, slowly making the solution turbid, draining the solvent after complete reaction at room temperature, adjusting the pH value with a trifluoroacetic acid methanol solution, stirring, centrifuging, and draining the liquid; separating the obtained solid with reversed phase high performance liquid chromatography column, and collecting the product to obtain compound shown as formula (II), i.e. MO.
4. The method for preparing rare earth samarium cryptate fluorescent complex according to claim 3, wherein the MO is prepared by the following steps:
1) adding a compound shown in a formula (II-1), a compound shown in a formula (II-2), anhydrous sodium carbonate and HPLC-grade acetonitrile into a dehydrated and deoxidized two-neck flask, refluxing for 2-3 days under the protection of argon, standing and cooling after the reaction is finished, filtering, spin-drying filtrate, adding diethyl ether for pumping, and washing with diethyl ether to obtain a compound shown in a formula (II-3);
2) adding SmCl into the dehydrated and deoxidized two-neck flask after the reaction in the step 1) under the protection of argon3And dehydrating and deoxidizing the treated acetonitrile, refluxing for half an hour, and then dropwise adding an acetonitrile solution of tris- (bipyridine) cryptate sodium salt into the obtained white suspension; refluxing at 80 ℃ overnight, standing and cooling after the reaction is finished; filtering, and washing the solid with diethyl ether to obtain a compound shown as a formula (II-4);
3)N2under protection, adding trifluoroacetic acid into the compound shown in the formula (II-4), stirring at room temperature, slowly dissolving the solid, allowing the solution to become clear, reacting for 5h, draining the trifluoroacetic acid solution, adding ether for washing, and draining by using an oil pump;
dissolving the obtained solid with ultra-dry anhydrous methanol, and performing N treatment under ice bath condition2Slowly dripping ethylenediamine in a protective atmosphere, slowly making the solution turbid, reacting at room temperature for 3h, draining the solvent, neutralizing with 1% trifluoroacetic acid methanol solution until the pH value is 5, stirring, centrifuging, and draining the liquid; separating the obtained solid with reversed phase high performance liquid chromatography column, and collecting the product to obtain compound shown as formula (II-5), i.e. MO.
5. The method for preparing rare earth samarium cryptate fluorescent complex according to any one of claims 2 to 4, wherein the synthetic route of the rare earth samarium cryptate fluorescent complex is as follows:
6. the method for preparing a rare earth samarium cryptate fluorescent complex according to claim 5, wherein the method for preparing the rare earth samarium cryptate fluorescent complex comprises the following steps:
step 1, adding 2-hydroxypropane-1, 2, 3-tricarboxylic acid, 5-aminolevulinic acid and EDC into toluene, refluxing and heating, cooling, standing, and separating to obtain a compound shown as a formula (I-1);
step 2, dissolving the compound shown as the formula (I-1) and KOH in DMSO, dropwise adding bromo-ester into the DMSO, reacting at room temperature, continuously reacting at room temperature after dropwise adding, adding the product into water after the reaction is finished, then adjusting the pH value with HCl, precipitating, filtering and drying to obtain the compound shown as the formula (I-2);
step 3, dissolving the compound shown as the formula (I-2) and the complex MO in ultra-dry dichloromethane at room temperature, dripping dichloromethane solution of DCC, stirring, draining the solvent, and carrying out chromatographic separation to obtain the compound shown as the formula (I-3);
and 4, dissolving the compound I shown as the formula (I-3) by using ultra-dry anhydrous methanol, and carrying out N treatment under the ice bath condition2Slowly dripping ethylenediamine in a protective atmosphere, slowly becoming turbid, finishing the reaction at room temperature, and draining the solvent; separating and collecting the obtained solid by using a reversed-phase high performance liquid chromatography preparation column to obtain a compound shown as a formula (I), namely the rare earth samarium cryptand fluorescent complex.
7. The method for preparing a rare earth samarium cryptate fluorescent complex according to claim 6, wherein the method for preparing the rare earth samarium cryptate fluorescent complex comprises the following steps:
step 1, adding 2-hydroxypropane-1, 2, 3-tricarboxylic acid, 5-aminolevulinic acid and EDC into toluene, refluxing and heating at 90 ℃, cooling, standing and separating to obtain a compound shown as a formula (I-1);
step 2, dissolving the compound shown as the formula (I-1) and KOH in DMSO, dropwise adding bromo-ester into the DMSO, reacting for 8 hours at room temperature, continuing to react for 14 hours at room temperature after dropwise adding, adding the product into water after the reaction is finished, then adjusting the pH value to 1-2 by using HCl, precipitating a precipitate, filtering, and drying to obtain the compound shown as the formula (I-2);
step 3, dissolving the compound shown as the formula (I-2) and the complex MO in ultra-dry dichloromethane at room temperature, dropwise adding a dichloromethane solution of DCC, stirring for 2 hours, draining the solvent, and carrying out chromatographic separation to obtain the compound shown as the formula (I-3);
step 4, conversion as shown in formula (I-3)Dissolving the compound I in ultra-dry absolute methanol under ice bath condition, and N2Slowly dripping ethylenediamine in a protective atmosphere, slowly becoming turbid, reacting at room temperature for 3 hours, and draining the solvent; separating and collecting the obtained solid by using a reversed-phase high performance liquid chromatography preparation column to obtain a compound shown as a formula (I), namely the rare earth samarium cryptand fluorescent complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011216540.5A CN112300164A (en) | 2020-11-04 | 2020-11-04 | Rare earth samarium cryptand ether fluorescent complex and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011216540.5A CN112300164A (en) | 2020-11-04 | 2020-11-04 | Rare earth samarium cryptand ether fluorescent complex and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112300164A true CN112300164A (en) | 2021-02-02 |
Family
ID=74325895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011216540.5A Pending CN112300164A (en) | 2020-11-04 | 2020-11-04 | Rare earth samarium cryptand ether fluorescent complex and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112300164A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552238A (en) * | 2020-11-04 | 2021-03-26 | 中国科学院苏州生物医学工程技术研究所 | Novel trimeric rare earth europium complex and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058912A2 (en) * | 2002-12-24 | 2004-07-15 | Elam-T Limited | Electroluminescent materials and devices |
| US6878552B1 (en) * | 1999-04-08 | 2005-04-12 | Cis Bio International French Joint Stock Company | Homogeneous detection and/or determination method for a chemical or physico-chemical interaction |
| WO2010070232A1 (en) * | 2008-12-19 | 2010-06-24 | Cis Bio International | Novel rare earth element cryptates including a tetraazatriphenylene unit |
| CN105218570A (en) * | 2015-07-30 | 2016-01-06 | 中国科学院苏州生物医学工程技术研究所 | A kind of lanthanide series compound and its preparation method and application |
| CN106432298A (en) * | 2016-09-05 | 2017-02-22 | 中国科学院苏州生物医学工程技术研究所 | Lanthanide metal ether complex and preparation method and application thereof |
-
2020
- 2020-11-04 CN CN202011216540.5A patent/CN112300164A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6878552B1 (en) * | 1999-04-08 | 2005-04-12 | Cis Bio International French Joint Stock Company | Homogeneous detection and/or determination method for a chemical or physico-chemical interaction |
| WO2004058912A2 (en) * | 2002-12-24 | 2004-07-15 | Elam-T Limited | Electroluminescent materials and devices |
| WO2010070232A1 (en) * | 2008-12-19 | 2010-06-24 | Cis Bio International | Novel rare earth element cryptates including a tetraazatriphenylene unit |
| CN105218570A (en) * | 2015-07-30 | 2016-01-06 | 中国科学院苏州生物医学工程技术研究所 | A kind of lanthanide series compound and its preparation method and application |
| CN106432298A (en) * | 2016-09-05 | 2017-02-22 | 中国科学院苏州生物医学工程技术研究所 | Lanthanide metal ether complex and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| JOHN H. BURNS: "Crystal and Molecular Structure of a Cryptate Complex of Samarium:C18H3606N2Sm2(N03)6-H20", 《INORGANIC CHEMISTRY》 * |
| WENKUI DONG等: "Synthesis and characterization of cryptates of Sm(II)，Eu(III)，Tb(III)，Dy(III) chlorides with macrobicyclic cryptand", 《INDIAN JOURNAL CHEMISTRY》 * |
| 余江等: "新型铕(III)、穴醚[2.2]与α-噻吩甲酰三氟丙酮三元荧光配合物的合成与表征", 《化学学报》 * |
| 胡学雷等: "含吡啶基的多氮亚胺穴醚稀土配合物的合成与表征", 《稀土》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552238A (en) * | 2020-11-04 | 2021-03-26 | 中国科学院苏州生物医学工程技术研究所 | Novel trimeric rare earth europium complex and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2449072T3 (en) | Borocarbons of unsaturated boron dipyrrometenes | |
| CN105017300B (en) | A perylene diimide-fluoroboron dipyrrole fluorescent dendrimer and its preparation method and application | |
| JPH115796A (en) | Indacene derivative | |
| CN105859778A (en) | Pure organic phosphorescent material with afterglow luminescence performance and ultra-long service life, method for preparing pure organic phosphorescent material and application thereof | |
| CN108516950B (en) | Tetraphenylethylene-based subcellular organelle viscosity probe and preparation method and application thereof | |
| JP5090731B2 (en) | Fluorescent probe | |
| CN105669734A (en) | BCPA-BODIPY fluorescent molecules and preparation method and application thereof | |
| CN112341462A (en) | Rare earth dysprosium cryptate ether fluorescent complex and preparation method thereof | |
| CN112300164A (en) | Rare earth samarium cryptand ether fluorescent complex and preparation method thereof | |
| Safir Filho et al. | Visualization of intracellular lipid droplets using lipophilic benzothiazole-based push-pull fluorophores at ultralow concentration | |
| KR101298553B1 (en) | Fluorescence probe for selective cyanide detection, method for preparing the same and method for selective cyanide detection | |
| CN113717231B (en) | AIE active force-induced light five-membered six-membered heterocyclic platinum complex, and preparation method and application thereof | |
| CN112174988B (en) | Tertiary rare earth terbium trimer and its preparation method | |
| CN113387905A (en) | Organic room temperature phosphorescent material, preparation method and application | |
| CN109336932B (en) | Amphiphilic platinum(Ⅱ) complexes and their applications in their preparation and construction of white light-emitting systems | |
| CN115894521B (en) | Fluorescent molecule based on caged oxacalixarene, and preparation method and application thereof | |
| CN110330532A (en) | A kind of novel phosphorescent iridium complex and the preparation method and application thereof | |
| CN113735864B (en) | A kind of D-benzothiadiazole-TB (-D) derivative and its synthetic method and application | |
| CN110862420B (en) | Energy transfer luminescent material based on triplet donor material and acceptor material and application thereof | |
| CN112552238A (en) | Novel trimeric rare earth europium complex and preparation method thereof | |
| CN111349067B (en) | Aggregation-induced emission type fluorescent material and preparation method thereof | |
| CN112812088A (en) | Near-infrared luminescent triphenylamine derivative fluorescent molecule and preparation method and application thereof | |
| CN107266472B (en) | A kind of homogeneous phase time discrimination fluorescence immunity analysis intermediate, chelating agent and preparation method | |
| JP4545370B2 (en) | Chiral sensor | |
| JP7479667B2 (en) | Compound having a sulfonylaniline skeleton or a salt thereof, or organic fluorescent material having the same |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221212 Address after: Room 401, building 3, R & D platform area, Jinan pharmaceutical Valley, No.1, north section of Gangxing Third Road, high tech Zone, Jinan City, Shandong Province Applicant after: Jinan Guoke Medical Engineering Technology Development Co.,Ltd. Applicant after: Suzhou Guoke medical technology development (Group) Co.,Ltd. Address before: Room 401, building 3, R & D platform area, Jinan pharmaceutical Valley, No.1, north section of Gangxing Third Road, high tech Zone, Jinan City, Shandong Province Applicant before: Jinan Guoke Medical Engineering Technology Development Co.,Ltd. Applicant before: Suzhou Guoke medical technology development (Group) Co.,Ltd. Applicant before: Jilin Guoke Medical Technology Development Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210202 |