CN108117770A - A kind of blue light excitation fluorescent dye and preparation method and application - Google Patents
A kind of blue light excitation fluorescent dye and preparation method and application Download PDFInfo
- Publication number
- CN108117770A CN108117770A CN201611085861.XA CN201611085861A CN108117770A CN 108117770 A CN108117770 A CN 108117770A CN 201611085861 A CN201611085861 A CN 201611085861A CN 108117770 A CN108117770 A CN 108117770A
- Authority
- CN
- China
- Prior art keywords
- fluorescent dye
- blue
- preparation
- stirring
- hours
- 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
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 230000005284 excitation Effects 0.000 title claims description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 5
- 238000003384 imaging method Methods 0.000 claims abstract description 4
- 239000000990 laser dye Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 51
- 239000013078 crystal Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000005457 ice water Substances 0.000 claims description 16
- 238000002386 leaching Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 10
- GPBKEFWZTVGDDM-UHFFFAOYSA-N (10-boronoanthracen-9-yl)boronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=C(B(O)O)C2=C1 GPBKEFWZTVGDDM-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- -1 cyano, phenyl Chemical group 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 13
- 238000000295 emission spectrum Methods 0.000 abstract description 3
- 238000000695 excitation spectrum Methods 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000006862 quantum yield reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 235000010265 sodium sulphite Nutrition 0.000 description 6
- 0 COC(C(C1)O)=C(*)C=C1c1cc(-c2c(cccc3)c3c(-c3cc(-c(cc4O)cc(OC)c4OC)cc(-c(cc4OC)cc(O)c4OC)c3)c3c2CC=CC=C3)cc(-c2cc(O)c(*)c(OC)c2)c1 Chemical compound COC(C(C1)O)=C(*)C=C1c1cc(-c2c(cccc3)c3c(-c3cc(-c(cc4O)cc(OC)c4OC)cc(-c(cc4OC)cc(O)c4OC)c3)c3c2CC=CC=C3)cc(-c2cc(O)c(*)c(OC)c2)c1 0.000 description 5
- 235000015497 potassium bicarbonate Nutrition 0.000 description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 5
- 239000011736 potassium bicarbonate Substances 0.000 description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 5
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 5
- 235000019252 potassium sulphite Nutrition 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000000684 flow cytometry Methods 0.000 description 2
- 238000000799 fluorescence microscopy Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 238000003018 immunoassay Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- AKYHKWQPZHDOBW-UHFFFAOYSA-N (5-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol Chemical compound OS(O)(=O)=O.C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 AKYHKWQPZHDOBW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000001576 FEMA 2977 Substances 0.000 description 1
- VIEADTMAOZPEIQ-UHFFFAOYSA-N O=C=Nc(c(Oc1ccccc1)cc(-c1cc(-c2c(cccc3)c3c(-c3cc(-c(cc4Oc5ccc[s]5)cc(Oc5ccccc5)c4N=C=O)cc(-c(cc4Oc5ccccc5)cc(Oc5ccc[s]5)c4N=C=O)c3)c3c2cccc3)cc(-c(cc2Oc3ccccc3)cc(Oc3ccc[s]3)c2N=C=O)c1)c1)c1Oc1ccc[s]1 Chemical compound O=C=Nc(c(Oc1ccccc1)cc(-c1cc(-c2c(cccc3)c3c(-c3cc(-c(cc4Oc5ccc[s]5)cc(Oc5ccccc5)c4N=C=O)cc(-c(cc4Oc5ccccc5)cc(Oc5ccc[s]5)c4N=C=O)c3)c3c2cccc3)cc(-c(cc2Oc3ccccc3)cc(Oc3ccc[s]3)c2N=C=O)c1)c1)c1Oc1ccc[s]1 VIEADTMAOZPEIQ-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229960003110 quinine sulfate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
-
- 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
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to field of optical functional material, and in particular to and blue light excites fluorescent dye, has the structure as shown in formula (I), wherein, R1、R2、R3Selected from hydrogen, C1‑C10One kind in alkyl, cyano, aromatic radical or heterocycle, but R1、R2、R3It is asynchronously hydrogen.The fluorescent dye has higher emissive porwer and quantum efficiency, emission spectrum main peak is between 460nm~500nm, with very wide excitation spectrum, and good light stability, trace detection, sensitivity is high, available for the different applications such as cell imaging, fluorescence probe, laser dye, fluorescent optical sensor field, shows good practicability.Preparation method cost of material provided by the invention is low, pollution-free, simple for process, yield is high, fluorescent dye structure novel, the function admirable of preparation, suitable in the extensive use in the fields such as biology, environment.
Description
Technical Field
The invention relates to the field of optical functional materials, in particular to a blue light excited fluorescent dye and a preparation method and application thereof.
Background
Dyes that strongly absorb and emit fluorescence in the visible range are called fluorochromes, which emit visible fluorescence after absorption of blue light by the substance molecules and emit visible fluorescence of longer wavelength after absorption of visible light of shorter wavelength. Each molecule has a series of strict discrete energy levels, and the molecules of substances are mostly in a ground state at room temperature, and when the substances absorb light energy under the irradiation of light, the substances enter a new state, called an excited state, and the molecular weight in the excited state is unstable, and can pass through 10-9～10-7The emitted light quanta return to the ground state within a very short time of seconds, a process which fluoresces. Fluorescent dyes have been widely used in various industries such as textile, plastic dyeing, printing pigments, etc. since the 20 th century. In recent years, fluorescent dyes have been widely used to label, detect, and/or quantify components in samples, and various methods for such detection and/or quantification include fluorescence microscopy, fluorescence immunoassay, flow cytometric analysis of cells, mass spectrometry, and the like,As well as a variety of other applications.
For many applications that utilize blue-light fluorescent dyes as detection tools, it is necessary to conjugate the fluorescent dye to ligands such as proteins, antibodies, enzymes, nucleotides, nucleic acids, and other biological and non-biological molecules to prepare the dye-labeled ligand. The choice of blue-light fluorescent dye is particularly important in applications where multiple, multi-color assays are employed, as well as in a variety of other applications, such as fluorescence microscopy, fluorescence immunoassay, flow cytometry. The dye molecule has high thermal stability, so that the rapid degradation of the dye structure caused by the irradiation of exciting light, the rise of temperature or the change of detection environment in the fluorescence analysis process of the dye can be avoided, and the stability of a spectrum analysis signal is ensured. Moreover, the blue-light fluorescent dye has the advantages of higher molar absorption coefficient, high fluorescence quantum yield, insensitivity of a fluorescence signal to solvent polarity and pH, narrow fluorescence spectrum peak, long fluorescence life and the like, and has certain chemical activity and an easily modified structure. Therefore, such dyes have been one of the preferred fluorophores for fluorescent molecular detection.
However, most of the current blue light excited fluorescent dyes have the disadvantages of multiple synthesis steps, high difficulty, low yield and poor solubility, so that the further application of the blue light excited fluorescent dyes in the fields of biology, environment and the like is limited. The invention designs and synthesizes a novel blue light excitation fluorescent dye with novel structure, simple preparation method and excellent performance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of difficult synthesis of the blue light excitation fluorescent dye in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the blue light excited fluorescent dye has a structure shown as a formula (I):
wherein,
R1、R2r3 is selected from hydrogen and C1-C10One of alkyl, cyano, aryl or heterocyclic aromatic hydrocarbon, R1、R2、R3Not hydrogen at the same time.
Optionally, the R is1、R2、R3One selected from methyl, cyano, phenyl and 2-thienyl.
Alternatively, the structural formula is shown in (II) (III) (IV) (V) (VI) (VIII):
optionally, the method comprises the following steps:
(1) preparation of intermediate 1
Adding arylsulfonyl chloride, sulfite and bicarbonate into an eggplant-shaped bottle at a molar ratio of 1: 1.5, adding deionized water, and stirring and reacting at 95-98 ℃ for 2.5-3.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5-3.0 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
Adding bromoarylsulfonyl chloride, sulfite and bicarbonate into an eggplant-shaped bottle at a molar ratio of 1: 1.5, adding deionized water, and stirring and reacting at 95-98 ℃ for 3.5-4.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5-3.0 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
Adding the intermediate 1, the intermediate 2 and palladium chloride into a 250ml eggplant-shaped bottle at a molar ratio of 1: 1.5, adding into an ester solvent, and stirring and reacting at 70-75 ℃ for 1.5-2.0 hours. After the reaction is finished, directly distilling to remove the solvent, and recrystallizing by adopting ethyl acetate and isopropanol to obtain white crystals, namely the intermediate 3.
(4) Preparation of Compound I
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into an eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, starting to dropwise add the solution of the intermediate 3, continuing to heat to 70-75 ℃ after dropwise addition is finished, stirring and reacting for 3.0-3.5 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting ethyl acetate and isopropanol to obtain a white crystal, namely the compound I.
Optionally, in the step (1) and (2), M is one of sodium and potassium.
Optionally, in the step (3), the ester solvent is one of ethyl acetate, methyl acetate and diethyl oxalate.
Optionally, in the step (3) recrystallization, the volume ratio of the ethyl acetate to the isopropanol is 7: 10.
Optionally, in the step (4) of recrystallization, the volume ratio of the ethyl acetate to the isopropanol is 1: 3.
Optionally, the method for exciting the fluorescent dye by blue light is applied to cell imaging, fluorescent probes, laser dyes, organic nonlinear optical materials and photoelectric functional devices.
The technical scheme of the invention has the following advantages:
1. the blue light excited fluorescent dye provided by the embodiment of the invention contains benzene ring or heterocycle and has conjugated double bond, and non-bonding electrons of O or N atoms can be excited to pi when in an excited state*The bond is expressed as a large pi bond which enlarges the organic fluorescent molecule, so that the conjugated system of the whole organic fluorescent molecule is enlarged, and the function of enhancing the fluorescence of the organic molecule is achieved.
2. The blue light excited fluorescent dye provided by the embodiment of the invention has a simple synthesis process, adopts palladium as a catalyst, does not need to add a phosphine ligand, has high selectivity, is not easy to polymerize, has high fluorescence quantum yield and good light stability, can greatly reduce the interference of self-absorption and autofluorescence of substances in organisms when being used for detecting the substances in the organisms, improves the sensitivity and selectivity of detection, and can reduce the damage to lives.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an excitation and emission spectrum of blue-light excited fluorescent dye in ethanol according to examples 1-6 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The basic chemical raw materials such as the reagent used in the embodiment of the invention can be purchased in the domestic chemical product market or customized in the relevant intermediate preparation plant.
Example 1
The preparation method of the blue light excitation fluorescent dye (II) provided in this example:
has the structure of formula (II):
the preparation method comprises the following steps:
(1) preparation of intermediate 1
50mmol of arylsulfonyl chloride, 75mmol of sodium sulfite and 75mmol of sodium bicarbonate are added to a 250ml eggplant-shaped bottle, 100ml of deionized water is added, and the mixture is stirred and reacted at 95-98 ℃ for 2.5 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
50mmol of bromoarylsulfonyl chloride, 75mmol of sodium sulfite and 75mmol of sodium bicarbonate are added into a 250ml eggplant-shaped bottle, 100ml of deionized water is added, and the mixture is stirred and reacted for 3.5 hours at 95-98 ℃. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
30mmol of intermediate 1, 45mmol of intermediate 2 and 0.5mmol of palladium chloride are added into a 250ml eggplant-shaped bottle, 200ml of ethyl acetate are added, and the mixture is stirred and reacted for 1.5 hours at 70-75 ℃. After the reaction is finished, ethyl acetate is directly distilled and removed, and white crystals, namely the intermediate 3, are obtained by recrystallization by adopting the volume ratio of ethyl acetate to isopropanol of 7: 10.
(4) Preparation of Compound (II)
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into a 250ml eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, beginning to dropwise add the tetrahydrofuran solution of the intermediate 3, continuing to heat to 70-75 ℃ after the dropwise adding is finished, stirring and reacting for 3.0 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting the volume ratio of ethyl acetate to isopropanol of 1: 3 to obtain a white crystal, namely the compound (II).
In this example, the detection and characterization data for the blue-light excited fluorescent dye (II) of the present invention are as follows:
calculated elemental analysis (CHO): c58H50O12
Mass spectrum (MS +): 938.33(M +)
m/z：938.33(100.0％)，939.33(63.2％)，940.34(20.0％)，941.34(5.7％)，940.33(2.5％)，942.34(1.1％)
Elemental analysis: c, 74.19; h, 5.37; o, 20.45.
Example 2
The preparation method of the blue light excitation fluorescent dye (III) provided in this example:
has the structure of formula (III):
the preparation method comprises the following steps:
(1) preparation of intermediate 1
40mmol of arylsulfonyl chloride, 60mmol of sodium sulfite and 60mmol of sodium bicarbonate are added into a 500ml eggplant-shaped bottle, 150ml of deionized water is added, and the mixture is stirred and reacted for 3.0 hours at 95-98 ℃. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
Adding 30mmol of bromoarylsulfonyl chloride, 45mmol of sulfite and 45mmol of bicarbonate into a 500ml eggplant-shaped bottle, adding 100ml of deionized water, and stirring for reaction at 95-98 ℃ for 3.5-4.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5-3.0 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
10mmol of intermediate 1, 15mmol of intermediate 2 and 0.2mmol of palladium chloride are added into a 250ml eggplant-shaped bottle, 100ml of ethyl acetate is added, and the mixture is stirred and reacted for 2.0 hours at 70-75 ℃. After the reaction is finished, ethyl acetate is directly distilled and removed, and white crystals, namely the intermediate 3, are obtained by recrystallization by adopting the volume ratio of ethyl acetate to isopropanol of 7: 10.
(4) Preparation of Compound (III)
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into a 250ml eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, beginning to dropwise add the tetrahydrofuran solution of the intermediate 3, continuing to heat to 70-75 ℃ after the dropwise adding is finished, stirring and reacting for 3.5 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting the volume ratio of ethyl acetate to isopropanol of 1: 3 to obtain a white crystal, namely the compound (III).
In this example, the detection and characterization data for the blue-light excited fluorescent dye (III) of the present invention are as follows:
calculated elemental analysis (CHNO): c58H38N4O12
Mass spectrum (MS +): 982.94(M +)
m/z：982.25(100.0％)，983.25(65.1％)，984.26(19.9％)，985.26(5.6％)，984.25(3.4％)，986.26(1.2％)
Elemental analysis: c, 70.87; h, 3.90; n, 5.70; and O, 19.53.
Example 3
The preparation method of the blue light excitation fluorescent dye (IV) provided in this example:
has the structure of formula (IV):
the preparation method comprises the following steps:
(1) preparation of intermediate 1
Adding 20mmol of aryl sulfonyl chloride, 30mmol of potassium sulfite and 30mmol of potassium bicarbonate into a 100ml eggplant-shaped bottle, adding 50ml of deionized water, and stirring for reaction at 95-98 ℃ for 2.5 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 3.0 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
20mmol of bromoarylsulfonyl chloride, 30mmol of sodium sulfite and 30mmol of sodium bicarbonate are added into a 100ml eggplant-shaped bottle, 50ml of deionized water is added, and the mixture is stirred and reacted for 4.0 hours at the temperature of 95-98 ℃. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
Adding 20mmol of intermediate 1, 30mmol of intermediate 2 and 0.3mmol of palladium chloride into a 100ml eggplant-shaped bottle, adding 50ml of diethyl oxalate, and stirring for reaction at 70-75 ℃ for 2.0 hours. After the reaction, diethyl oxalate is directly distilled and removed, and white crystals, namely the intermediate 3, are obtained by recrystallization by adopting the volume ratio of ethyl acetate to isopropanol of 7: 10.
(4) Preparation of Compound (IV)
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into a 100ml eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C after the solid is completely dissolved, stirring and reacting for 20 minutes, and beginning to dropwise addAnd (3) after the tetrahydrofuran solution of the intermediate 3 is dripped, continuously heating to 70-75 ℃, stirring and reacting for 3.0 hours, filtering out solids, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting the volume ratio of ethyl acetate to isopropanol of 1: 3 to obtain white crystals, namely the compound (IV).
In this example, the detection and characterization data for the blue-light excited fluorescent dye (IV) of the present invention are as follows:
calculated elemental analysis (CHNO): c78H46N4O12
Mass spectrum (MS +): 1231.22(M +)
m/z：1230.31(100.0％)，1231.31(85.8％)，1232.32(38.4％)，1233.32(12.1％)，1234.32(3.0％)，1232.31(1.3％)
Elemental analysis: c, 76.09; h, 3.77; n, 4.55; and O, 15.59.
Example 4
The preparation method of the blue light excitation fluorescent dye (V) provided in this example:
has a structure of formula (V):
the preparation method comprises the following steps:
(1) preparation of intermediate 1
Adding 300mmol of aryl sulfonyl chloride, 450mmol of potassium sulfite and 450mmol of potassium bicarbonate into a 1000ml eggplant-shaped bottle, adding 500ml of deionized water, and stirring and reacting at 95-98 ℃ for 3.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
250mmol of bromoarylsulfonyl chloride, 375mmol of sodium sulfite and 375mmol of sodium bicarbonate are added into a 1000ml eggplant-shaped bottle, 500ml of deionized water is added, and the mixture is stirred and reacted for 3.5 hours at 95-98 ℃. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 3.0 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
50mmol of intermediate 1, 75mmol of intermediate 2 and 1.0mmol of palladium chloride are added into a 1000ml eggplant-shaped bottle, and the mixture is added into 300ml of methyl acetate and stirred for reaction for 2.0 hours at 70-75 ℃. After the reaction is finished, methyl acetate is directly distilled and removed, and white crystals, namely the intermediate 3, are obtained by recrystallization by adopting the volume ratio of ethyl acetate to isopropanol of 7: 10.
(4) Preparation of Compound (V)
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into a 1000ml eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, beginning to dropwise add the tetrahydrofuran solution of the intermediate 3, continuing to heat to 70-75 ℃ after the dropwise adding is finished, stirring and reacting for 3.0 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting the volume ratio of ethyl acetate to isopropanol of 1: 3 to obtain a white crystal, namely the compound (V).
In this example, the detection and characterization data for the blue-light excited fluorescent dye (V) of the present invention are as follows:
calculated elemental analysis (CHNO): c82H54N4O12
Mass spectrum (MS +): 1287.33(M +)
m/z：1286.37(100.0％)，1287.38(89.8％)，1288.38(42.3％)，1289.38(14.2％)，1290.39(2.5％)，1287.37(1.5％)，1288.37(1.3％)，1290.38(1.2％)
Elemental analysis: c, 76.51; h, 4.23; n, 4.35; and O, 14.91.
Example 5
The preparation method of the blue light excitation fluorescent dye (VI) provided in this example:
has the structure of formula (VI):
the preparation method comprises the following steps:
(1) preparation of intermediate 1
150mmol of arylsulfonyl chloride, 225mmol of sodium sulfite and 225mmol of sodium bicarbonate are added to a 500ml eggplant-shaped bottle, 250ml of deionized water is added, and the reaction is stirred at 95 to 98 ℃ for 3.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
100mmol of bromoarylsulfonyl chloride, 150mmol of potassium sulfite and 150mmol of potassium bicarbonate are added into a 500ml eggplant-shaped bottle, 200ml of deionized water is added, and the mixture is stirred and reacted for 4.0 hours at the temperature of 95-98 ℃. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
30mmol of intermediate 1, 45mmol of intermediate 2 and 0.5mmol of palladium chloride are added into a 250ml eggplant-shaped bottle, and the mixture is added into 100ml of ethyl acetate and stirred for reaction for 1.5 to 2.0 hours at 70 to 75 ℃. After the reaction is finished, ethyl acetate is directly distilled and removed, and white crystals, namely the intermediate 3, are obtained by recrystallization by adopting the volume ratio of ethyl acetate to isopropanol of 7: 10.
(4) Preparation of Compound (VI)
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into a 250ml eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, beginning to dropwise add the tetrahydrofuran solution of the intermediate 3, continuing to heat to 70-75 ℃ after the dropwise adding is finished, stirring and reacting for 3.0 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting the volume ratio of ethyl acetate to isopropanol of 1: 3 to obtain a white crystal, namely the compound (VI).
In this example, the detection and characterization data for the blue light-excited fluorescent dye (VI) of the present invention are as follows:
calculated elemental analysis (CHNOS): c74H46N4O12S4
Mass spectrum (MS +): 1311.44(M +)
m/z：1310.20(100.0％)，1311.20(85.2％)，1312.21(32.4％)，1312.20(24.4％)，1313.20(15.3％)，1313.21(11.6％)，1314.20(6.9％)，1314.21(2.9％)，1315.21(1.9％)，1314.19(1.3％)，1315.19(1.0％)
Elemental analysis: c, 67.77; h, 3.54; n, 4.27; o, 14.64; and S, 9.78.
Example 6
The preparation method of the blue light excitation fluorescent dye (VII) provided in this example:
has the structure of formula (VII):
the preparation method comprises the following steps:
(1) preparation of intermediate 1
Adding 60mmol of aryl sulfonyl chloride, 90mmol of potassium sulfite and 90mmol of potassium bicarbonate into a 500ml eggplant-shaped bottle, adding 100ml of deionized water, and stirring for reaction at 95-98 ℃ for 3.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 3.0 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
100mmol of bromoarylsulfonyl chloride, 150mmol of potassium sulfite and 150mmol of potassium bicarbonate are added into a 500ml eggplant-shaped bottle, 200ml of deionized water is added, and the mixture is stirred and reacted for 3.5 hours at the temperature of 95-98 ℃. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 3.0 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
70mmol of intermediate 1, 105mmol of intermediate 2 and 0.1mmol of palladium chloride are added into a 250ml eggplant-shaped bottle, and then the mixture is added into 150ml of diethyl oxalate and stirred for reaction for 1.5 hours at 70-75 ℃. After the reaction, diethyl oxalate is directly distilled and removed, and white crystals, namely the intermediate 3, are obtained by recrystallization by adopting the volume ratio of ethyl acetate to isopropanol of 7: 10.
(4) Preparation of Compound (VII)
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into a 500ml eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, beginning to dropwise add the tetrahydrofuran solution of the intermediate 3, continuing to heat to 70-75 ℃ after the dropwise adding is finished, stirring and reacting for 3.0 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by adopting the volume ratio of ethyl acetate to isopropanol of 1: 3 to obtain a white crystal, namely the compound (VII).
In this example, the detection and characterization data for the blue-light excited fluorescent dye (VII) of the present invention are as follows:
calculated elemental analysis (CHNOS): c94H54N4O12S4
Mass spectrum (MS +): 1559.71(M +):
m/z：1559.27(100.0％)，1558.26(97.3％)，1560.27(53.3％)，1560.26(22.3％)，1561.27(21.7％)，1561.26(18.6％)，1562.26(10.2％)，1559.26(4.6％)，1562.28(4.3％)，1563.27(3.8％)，1562.27(2.4％)，1563.26(1.7％)，1563.28(1.2％)，1562.25(1.2％)，1564.27(1.1％)
elemental analysis: c, 72.39; h, 3.49; n, 3.59; o, 12.31; and S, 8.22.
Examples of the experiments
In order to verify the fluorescence property of the blue light excited fluorescent dye, the fluorescence spectrum, the molar extinction coefficient and the fluorescence quantum yield of the blue light excited fluorescent dye are measured, and the specific measurement method of each parameter is as follows:
experimental example 1 measurement of absorption Spectroscopy of blue-light-excited fluorescent dye
Accurately weighing the compound to be measured, respectively transferring into 5mL volumetric flasks, diluting with dichloromethane to constant volume, and making into the product with concentration of 1.0 × 10-4mol/L solution. 0.5mL of the solution was transferred into a 5mL volumetric flask. Blowing dichloromethane with nitrogen, diluting with ethanol to desired volume, dissolving the sample completely, and making into the product with concentration of 1.0 × 10-5The absorption spectrum of the solution in mol/L was measured, as shown in FIG. 1.
Experimental example 2 measurement of fluorescence Spectroscopy of blue-light-excited fluorescent dye
The fluorescence spectrum is measured using the maximum absorption wavelength in the measured blue spectrum as the excitation wavelength of the fluorescence spectrum. The test compound was weighed to a concentration of 1.0X 10-6The emission spectrum was measured on a solution of ethanol/L in water (50: 50, v/v), as shown in FIG. 1.
EXAMPLE 3 determination of molar extinction coefficient of blue-excited fluorescent dye
The molar extinction coefficient of the compound was determined by uv-vis absorption spectroscopy. The calculation formula is shown as formula (1):
a ═ ε cl formula (1)
Wherein A represents the absorption intensity,. epsilon.is the molar absorption coefficient, c is the concentration of the compound, and l is the thickness of the quartz cell for detection.
EXAMPLE 4 measurement of fluorescence Quantum yield of blue-excited fluorescent dye
The fluorescence quantum yield of the blue-excited fluorescent dye was measured at 20 ℃ with quinine sulfate (0.1M H as solvent)2SO4Quantum yield of 0.56) as a reference, and the fluorescence quantum yield was calculated by measuring the integrated intensity of fluorescence obtained under the same excitation conditions and the ultraviolet absorption value at the excitation wavelength of a dilute solution of the blue-light-excited fluorescent dye and the reference. The product was dissolved in absolute ethanol.
The calculation formula is shown in formula (2):
wherein phi is the quantum yield of the object to be detected, subscript R represents reference substance, I is fluorescence integral intensity, A is ultraviolet absorption value, η is solvent refractive index, and the general requirement absorbance A, ARAre all less than 0.1.
TABLE 1 spectroscopic Properties of blue-excited fluorescent dyes described in examples 1-6
As shown in table 1, the blue-light excited fluorescent dye (VII) described in example 6 has the maximum absorption wavelength, and corresponds to the maximum emission wavelength of 500nm, the maximum molar absorption coefficient of 4.9 and the maximum fluorescence quantum yield of 89.26%, which indicates that the molecular structure of the blue-light excited fluorescent dye described in example 6 has spectral properties superior to other compounds, thereby indicating that the compounds have advantages for cell imaging, fluorescent probes, laser dyes and fluorescent sensors.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A blue-light excited fluorescent dye, which has a structure represented by formula (I):
wherein,
R1、R2r3 is selected from hydrogen and C1-C10One of alkyl, cyano, aryl or heterocyclic aromatic hydrocarbon, R1、R2、R3Not hydrogen at the same time.
2. The blue-light excited fluorescent dye according to claim 1, wherein R is1、R2And R3 is selected from one of methyl, cyano, phenyl and 2-thienyl.
3. The blue-excited fluorescent dye according to claim 1 or 2, which has a structural formula shown in the following formula:
4. a method of preparing a blue-excitable fluorescent dye according to any one of claims 1 to 3, comprising the steps of:
(1) preparation of intermediate 1
Adding arylsulfonyl chloride, sulfite and bicarbonate into an eggplant-shaped bottle at a molar ratio of 1: 1.5, adding deionized water, and stirring and reacting at 95-98 ℃ for 2.5-3.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5-3.0 hours to obtain an intermediate 1.
(2) Preparation of intermediate 2
Adding bromoarylsulfonyl chloride, sulfite and bicarbonate into an eggplant-shaped bottle at a molar ratio of 1: 1.5, adding deionized water, and stirring and reacting at 95-98 ℃ for 3.5-4.0 hours. Slowly cooling to the ice-water bath until crystals are separated out, continuously stirring for 0.5 hour, filtering, leaching with deionized water for three times to obtain white crystals, and drying at the set temperature of 120-125 ℃ and the pressure of-0.098 MPa for 2.5-3.0 hours to obtain an intermediate 2.
(3) Preparation of intermediate 3
Adding the intermediate 1, the intermediate 2 and palladium chloride into an eggplant-shaped bottle at a molar ratio of 1: 1.5, adding into an ester solvent, and stirring and reacting at 70-75 ℃ for 1.5-2.0 hours. After the reaction is finished, directly distilling to remove the solvent, and recrystallizing by adopting ethyl acetate and isopropanol to obtain white crystals, namely the intermediate 3.
(4) Preparation of Compound I
In N2Under protection, adding anthracene-9, 10-diyl diboronic acid, tetrabutylammonium bromide, potassium carbonate and tetrahydrofuran into an eggplant-shaped bottle, stirring and dissolving at 65-70 ℃, adding 5% Pd/C when the solid is completely dissolved, stirring and reacting for 20 minutes, starting to dropwise add the tetrahydrofuran solution of the intermediate 3, continuing to heat to 70-75 ℃ after the dropwise addition is finished, stirring and reacting for 3.0-3.5 hours, filtering out the solid, adding ethyl acetate and deionized water for extraction, distilling to remove the solvent, and recrystallizing by using ethyl acetate and isopropanol to obtain a white crystal, namely the compound I.
5. The method for preparing a blue-light excited fluorescent dye according to any one of claims 1 to 4, wherein in the step (1) (2), M is one of sodium and potassium.
6. The method for preparing a blue-light excited fluorescent dye according to any one of claims 1 to 5, wherein in the step (3), the ester solvent is one of ethyl acetate, methyl acetate and diethyl oxalate.
7. The method for preparing a blue-light excited fluorescent dye according to any one of claims 1 to 6, wherein the volume ratio of the ethyl acetate to the isopropanol is 7: 10 during the recrystallization in the step (3).
8. The method for preparing a blue-light excited fluorescent dye according to any one of claims 1 to 7, wherein the volume ratio of the ethyl acetate to the isopropanol is 1: 3 during the recrystallization in the step (4).
9. Use of the method of any one of claims 1-4 for blue-light excitation of fluorescent dyes in cell imaging, fluorescent probes, laser dyes, organic nonlinear optical materials, and optoelectronic functional devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611085861.XA CN108117770A (en) | 2016-11-30 | 2016-11-30 | A kind of blue light excitation fluorescent dye and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611085861.XA CN108117770A (en) | 2016-11-30 | 2016-11-30 | A kind of blue light excitation fluorescent dye and preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108117770A true CN108117770A (en) | 2018-06-05 |
Family
ID=62227275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611085861.XA Pending CN108117770A (en) | 2016-11-30 | 2016-11-30 | A kind of blue light excitation fluorescent dye and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108117770A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423426A (en) * | 2019-12-26 | 2020-07-17 | 江西科技师范大学 | Asymmetric 9- (N-tert-butyloxycarbonyl-2-pyrrolyl) -10-five-membered heterocyclic anthracene compound and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010051285A1 (en) * | 1998-12-09 | 2001-12-13 | Jianmin Shi | Electroluminescent device with improved hole transport layer |
| JP2006137956A (en) * | 2005-12-05 | 2006-06-01 | Toppan Printing Co Ltd | Luminescent material and organic thin film el element |
-
2016
- 2016-11-30 CN CN201611085861.XA patent/CN108117770A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010051285A1 (en) * | 1998-12-09 | 2001-12-13 | Jianmin Shi | Electroluminescent device with improved hole transport layer |
| JP2006137956A (en) * | 2005-12-05 | 2006-06-01 | Toppan Printing Co Ltd | Luminescent material and organic thin film el element |
Non-Patent Citations (2)
| Title |
|---|
| MOTOYUKI UEJIMA 等: "Quantum yield in blue-emitting anthracene derivatives: vibronic coupling density and transition dipole moment density", 《PHYS. CHEM. CHEM. PHYS.》 * |
| 何仁等: "《金属有机化学》", 30 September 2007 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111423426A (en) * | 2019-12-26 | 2020-07-17 | 江西科技师范大学 | Asymmetric 9- (N-tert-butyloxycarbonyl-2-pyrrolyl) -10-five-membered heterocyclic anthracene compound and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1078023B1 (en) | Luminescent compounds | |
| Mahendran et al. | Tetraphenylethene–2-pyrone conjugate: Aggregation-induced emission study and explosives sensor | |
| CN106543213A (en) | A kind of infrared Novel BODIPY flourescent dye and its preparation method and application | |
| CN101343420A (en) | Unsymmetrical cyanines fluorochrome | |
| CN103497121B (en) | The equal preparation of benzene three formyl hydrazone series derivates and the application as probe molecule identification fluorion thereof | |
| CN108130070A (en) | A kind of feux rouges excitation fluorescent dye and preparation method and application | |
| CN102618060A (en) | Method for preparing asymmetrical cyanine dye and method for detecting bovine serum albumin by asymmetrical cyanine dye | |
| CN108130072A (en) | A kind of near infrared light excitation fluorescent dye and preparation method and application | |
| CN105348176A (en) | Amphiphilic molecules with aggregation-induced emission effects, preparing method thereof and uses of the amphiphilic molecules | |
| WO2015077427A1 (en) | Highly Fluorescent Pyrrole-BF2 Chromophores | |
| CN110256218A (en) | A kind of aggregation-induced emission dye molecule and its synthetic method | |
| CN104151867B (en) | Temperature response type cyclodextrin probe double with pH and preparation method thereof | |
| CN104327846B (en) | A kind of Hg containing rigid structure rhodamine 2+ratio fluorescent probe and preparation method | |
| CN101712866B (en) | Nanometer europium fluorescent particle with performance of visible light excitation, preparation method and application thereof | |
| CN107759504B (en) | Dual-phase organic fluorescent material with strong fluorescence in solid and liquid states and preparation method thereof | |
| CN102731479B (en) | Organic ligand, rare earth organic fluorescent probe material thereof and preparation method thereof | |
| CN108117770A (en) | A kind of blue light excitation fluorescent dye and preparation method and application | |
| CN108440441B (en) | AIE fluorescent probe molecule and method for detecting p-nitroaniline and fluorine ions | |
| CN107903220B (en) | Fluorescent probe for visually detecting ozone and preparation method thereof | |
| CN105778897A (en) | PH sensitive fluorochrome and preparation method and application thereof | |
| CN108516984A (en) | It is a kind of to be used to detect fluorescence probe of cytimidine and preparation method thereof | |
| JP7010290B2 (en) | Fluorescent dyes and their manufacturing methods and applications | |
| CN112341453A (en) | Fluorescent probe based on coumarin and preparation method and application thereof | |
| CN108117871A (en) | A kind of green light excitation fluorescent dye and preparation method and application | |
| CN105461755B (en) | Platinum complex with aggregation-induced red light emission and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180605 |
|
| RJ01 | Rejection of invention patent application after publication |