CN107382991A - two-photon fluorescent material benzoxazolyl pyridine salt and preparation method and application thereof - Google Patents
two-photon fluorescent material benzoxazolyl pyridine salt and preparation method and application thereof Download PDFInfo
- Publication number
- CN107382991A CN107382991A CN201710671589.1A CN201710671589A CN107382991A CN 107382991 A CN107382991 A CN 107382991A CN 201710671589 A CN201710671589 A CN 201710671589A CN 107382991 A CN107382991 A CN 107382991A
- Authority
- CN
- China
- Prior art keywords
- benzoxazolyl
- preparation
- pyridiniujm
- photon
- photon fluorescence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- WELSCYIRWKBEBZ-UHFFFAOYSA-N 2-pyridin-2-yl-1,3-benzoxazole Chemical class N1=CC=CC=C1C1=NC2=CC=CC=C2O1 WELSCYIRWKBEBZ-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000047 product Substances 0.000 claims description 31
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003384 imaging method Methods 0.000 claims description 8
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000000183 1,3-benzoxazoles Chemical class 0.000 claims description 2
- UTMZWCTVPHAOJZ-UHFFFAOYSA-N 2-(4-methylphenyl)-1,3-benzoxazole Chemical class C1=CC(C)=CC=C1C1=NC2=CC=CC=C2O1 UTMZWCTVPHAOJZ-UHFFFAOYSA-N 0.000 claims description 2
- LFOXZOBJWYTCTG-UHFFFAOYSA-N 2-[4-(bromomethyl)phenyl]-1,3-benzoxazole Chemical class C1=CC(CBr)=CC=C1C1=NC2=CC=CC=C2O1 LFOXZOBJWYTCTG-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- TZRQRSOGELDRBK-AATRIKPKSA-N N1=CC=C(C=C1)/C=C/C1=CC=C(C=C1)C=1OC2=C(N1)C=CC=C2 Chemical class N1=CC=C(C=C1)/C=C/C1=CC=C(C=C1)C=1OC2=C(N1)C=CC=C2 TZRQRSOGELDRBK-AATRIKPKSA-N 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 description 22
- 210000004027 cell Anatomy 0.000 description 21
- 239000000243 solution Substances 0.000 description 18
- 230000005284 excitation Effects 0.000 description 13
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 210000001519 tissue Anatomy 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000006059 cover glass Substances 0.000 description 4
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 210000000805 cytoplasm Anatomy 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 239000006143 cell culture medium Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- -1 pyridine salt compounds Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003325 tomography Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic 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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a two-photon fluorescent material benzoxazolyl pyridine salt, a preparation method and application thereof. The structural formula of the two-photon fluorescent material benzoxazolyl pyridine salt is as follows:
Description
Technical field
The present invention relates to fluorescent material field, relates in particular to a kind of two-photon fluorescence material benzoxazolyl pyridiniujm
And its preparation method and application.
Background technology
In recent years, organic two-photon material numerous areas, especially two-photon fluorescence it is micro- and imaging in applying
Extensive concern is arrived.Two-photon Laser Scanning Confocal Microscope has many advantages compared with single photon Laser Scanning Confocal Microscope：(1) double light
Sub- Laser Scanning Confocal Microscope can use longer wavelengths of (near infrared region), in biological tissues penetration capacity it is stronger it is infrared swash
Light can greatly reduce absorption and scattering of the biological tissue to exciting light, can obtain stronger fluorescent as excitation source
And solves the problems, such as the tomography of biological tissue's mid-deep strata material.(2) because two-photon fluorescence launch wavelength is away from excitation light wave
It is long, it is possible to achieve dark-field imaging.(3) two-photon fluorescence can avoid common fluorescent be imaged in fluorescent bleach problem and to biology
The toxicity of cell.(4) two photon transition has very strong selective exitation, is advantageous to enter some particular matters in biological tissue
Row imaging research.(5) two-photon Laser Scanning Confocal Microscope has higher lateral resolution and longitudinal frame, the two-photon of material
Absorption intensity it is square related to excitation light intensity, under conditions of copolymerization is burnt, two-photon absorption is limited only at object focal point
Small space volume range in, make the design of Laser Scanning Confocal Microscope greatly simplified, it is easily operated.
But at present, the two photon absorption cross section number generally more small than Single Photon Absorption section of general material
Magnitude, the practical application of two-photon absorption is caused to be subject to many limitations.Two photon absorption cross section increasing degree and conjugation chain bridge class
Type is relevant, and for most of organic molecules, their two photon absorption cross section shows wavelength dependency.From theory and in fact
Test and find and synthesize with the new of sufficiently large two photon absorption cross section, two-photon fluorescence effect and up conversion lasing efficiency
Compound, study correlation rule and intramolecular between the structure of organic molecule and two-photon absorption, two-photon fluorescence characteristic
Energy transmission mechanism etc., it has also become the hot issue during currently two-photon material is studied in the world.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of water solubility, hypotoxicity, have two-photoninduced fluorescence hair
Penetrate two-photon fluorescence material benzoxazolyl pyridiniujm of ability and its preparation method and application.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：Two-photon fluorescence material benzoxazolyl
Pyridiniujm, its structural formula are as follows：
Application provided by the invention is above-mentioned two-photon fluorescence material benzoxazolyl pyridiniujm answering in cell imaging
With.
Benzooxazole kind compound has higher fluorescence quantum yield, but because the dipole structure of its own is not enough to produce
Obvious ICT processes strengthen its absorption to light radiation, and inventor find to modify push-and-pull such as on its 2- position or 6- positions it is electric
Subbase group adjusts molecular polarity, can produce abundant optical property.By proving and testing repeatedly, inventor from pyridine sun from
Son is modified, and pyridylium has a superior membrane penetrating as strong electron withdraw group, can be in the short time
Interior penetration cell film enters cell, and pyridine salt compounds generally have good water solubility, possesses the prerequisite of bio-imaging
Condition.
The preparation method of above-mentioned two-photon fluorescence material benzoxazolyl pyridiniujm, comprises the following steps：
A, intermediate M1 (2- (p-methylphenyl) benzoxazoles) preparations
P-methylbenzoic acid, o-aminophenol are mixed with polyphosphoric acids, flow back 4~7h at 210~240 DEG C, obtains
Reaction solution intermediate M1 is obtained after extracting, dry, recrystallize；
B, intermediate M2 (2- (4- (bromomethyl) phenyl) benzoxazoles) preparations
M1 and N- bromo-succinimides are dissolved in benzene, add initiator benzoyl peroxide, it is anti-at 60~80 DEG C
6~8h is answered, obtained reaction solution obtains intermediate M2 through standing, filter, wash, after drying；
C, intermediate M3 (2- (4- ((triphenylphosphinebromide) methyl) phenyl) benzoxazoles) preparations
M2 is dissolved in benzene, adds PPh3, at 40~80 DEG C react 6~8h, obtained reaction solution through filtering while hot,
Intermediate M3 is obtained after drying；
D, intermediate M4 (E-2- (4- (2- (pyridin-4-yl) vinyl) phenyl) benzoxazoles) preparations
M3,4- pyridine carboxaldehyde and potassium carbonate are added in DMA, 10~14h is reacted at 140 DEG C,
Dichloromethane is added into obtained reaction solution warp, then is filtered, filtrate obtains intermediate M4 through washing, after drying；
E, intermediate M5 (E-4- (4- (2- benzoxazolyls) -2- styryls)-N- picolines salt compounded of iodine) preparation
M4 is dissolved in tetrahydrofuran, adds CH3I, 3~6h is reacted at 40~60 DEG C, obtained reaction solution is through taking advantage of
Heat obtains intermediate M5 after filtering；
F, the preparation of target product L two-photon fluorescences material benzoxazolyl pyridiniujm
M5 is dissolved in ethanol, adds NaBPh4, 4~7h is reacted at 60~90 DEG C, obtained reaction solution is through while hot
Target product L is obtained after suction filtration.
Further, in step A, the mole dosage ratio of p-methylbenzoic acid and o-aminophenol is 1:2.2.
Further, in step B, the mole dosage ratio of intermediate M1 and N- bromo-succinimide is 13.3:30.
Further, in step C, intermediate M2 and PPh3Mole dosage ratio be 32.3:50.
Further, in step D, the mole dosage ratio of intermediate M3,4- pyridine carboxaldehyde and potassium carbonate is 9.4:13.5:
36。
Further, in step E, intermediate M4 and CH3I mole dosage ratio is 3.1:5.5.
Further, in step F, intermediate M5 and NaBPh4Mole dosage ratio be 1:2.
In implementing the present invention, it may, inventor has found, each raw material uses above-mentioned mole dosage ratio, each intermediate product and
The yield of target product is higher.
Beneficial effects of the present invention are embodied in：
1. two-photon fluorescence material benzoxazolyl pyridiniujm of the present invention has good single photon fluorescence in 510nm or so
Property, there is good two-photon fluorescence property (see Fig. 2 and Fig. 3) in 530nm or so, and two photon absorption cross section value can reach
103GM, in fluorescence co-focusing micro-imaging, Hela cells are contaminated by two-photon fluorescence material benzoxazolyl pyridiniujm of the present invention
After color, the cytoplasm that two-photon fluorescence material benzoxazolyl pyridiniujm of the present invention is positioned at Hela cells can be clearly observed
In, design, preparation and life science of this result of study for two-photon material are significant.
2. two-photon fluorescence material benzoxazolyl pyridiniujm of the present invention is a kind of water miscible two-photoninduced fluorescence material
Material, toxicity is low, and the membrane penetrating having had can enter in cell, can apply to two-photon fluorescence confocal microscopic image.
3. preparation method raw material of the present invention is easy to get, cost is low, and synthesis step is simple, easily operated.
4. the present invention is with the Ben Bing Evil with stronger photochemical light physical stability and special asymmetric dipole structure
Oxazolyl group is used as main body, is reacted by Wittig and introduces 4 pyridine groups, forms pyridiniujm using methylation reaction, finally leads to
Cross anion exchange reaction and prepare tetraphenylboron acid group pyridiniujm, obtain can apply to the water solubility of cell imaging, hypotoxicity, tool
There is the benzoxazolyl pyridiniujm of two-photoninduced fluorescence emissivities.
Brief description of the drawings
Fig. 1 is the route map of the preparation method of two-photon fluorescence material benzoxazolyl pyridiniujm of the present invention.
Fig. 2 a and Fig. 2 b are uv-visible absorption spectras and fluorescence spectra of the target product L in different solvents.
Fig. 3 a and Fig. 3 b are two-photoninduced fluorescence spectrum of the target product L in water and output fluorescent energy (Iout) with
Input laser energy (Iin) logistic fit curve map.
Fig. 4 is two photon absorption cross section values (GM) of the target product L in water.
Fig. 5 is target product L to the single, double photon fluorescence confocal microscopic image of Hela cells：(a) target product L is coloured
The single photon fluorescences of Hela cells be copolymerized burnt microphoto；(b) light field action diagram；(c) the Hela cells of target product L colorings
Two-photon fluorescence be copolymerized burnt microphoto；(d) photo of overlapping.
Embodiment
This part carries out general description to the material and experimental method that are arrived used in present invention experiment.Although it is
Realize that many materials used in the object of the invention and operating method are it is known in the art that still the present invention makees as far as possible herein
It is described in detail.It will be apparent to those skilled in the art that hereinafter, if not specified, material therefor, equipment and operation of the present invention
Method is well known in the art.
Embodiment 1
The preparation method of two-photon fluorescence material benzoxazolyl pyridiniujm, referring to Fig. 1, comprises the following steps：
A, intermediate M1 preparation
20.4g (0.15mol) paratolunitrile is weighed, 35.97g (0.33mol) o-aminophenol, is placed in the necks of 250mL tri-
In flask, 1500mL polyphosphoric acids is added, nitrogen is protected, flow back 6h at 220 DEG C, and obtained reaction solution is cooled into 80 afterwards
DEG C, pour into the large beaker equipped with frozen water, the appropriate saturation NaOH aqueous solution is added dropwise and adjusts pH value of solution to 7~8, with 300mL second
Acetoacetic ester is repeatedly extracted, and is spin-dried for ethyl acetate afterwards, then carries out ethyl alcohol recrystallization, obtains solid 9.84g, i.e. intermediate
M1, yield 31%.
Intermediate M1's1H NMR:(400MHz,CD2Cl2):δ(ppm)8.17(s,2H),7.77(s,1H),7.63(s,
1H),7.38(s,4H),2.48(s,2H).13C NMR:(100MHz,CD2Cl2):δ(ppm)163.58,151.15,142.67,
130.05,127.86,125.26,124.81,120.07,110.84,21.75.FT-IR(KBr,cm-1):3058.30(w),
2919.16(m),2870.11(w),1621.99(s),1555.47(vs),1345.57(m),1243.21(vs),1198.73
(m),1177.50(s),1116.39(m),1055.18(m),1000.15(w),926.47(s),820.77(vs),785.82
(w),745.62(s),726.69(m),692.70(w),501.44(vs).MS(ESI):m/z,calcd:209.0841,
found:209.0908.
B, intermediate M2 preparation
Weigh 2.78g (13.30mmol) M1 and 5.34g (30mmol) N- bromo-succinimides (NBS) and be placed in 250mL circles
In the flask of bottom, 100mL benzene and 0.5g initiator benzoyl peroxides are added, 80 DEG C are warming up under nitrogen protection, and in this temperature
Lower reaction 8h, obtained reaction solution are stood at normal temperatures, separate out a large amount of white solids, then through filtering, filter cake is dry through washing,
Obtain yellow crystalline solid 2.26g, i.e. intermediate M2, yield 59%.
Intermediate M2's1H NMR(400MHz,CDCl3):δ (ppm) 8.28-8.26 (d, J=8.00Hz, 2H), 7.90-
7.82 (m, 1H), 7.62-7.59 (m, 1H), 7.58-7.56 (d, J=8.00Hz, 2H), 7.40-7.36 (m, 2H), 7.55 (s,
2H).13C NMR(100MHz,CDCl3):δ(ppm)162.44,150.72,141.71,129.66,128.13,126.93,
125.44,124.82,120.05,110.69,32.45.FT-IR(KBr,cm-1):3026.33(w),2924.14(vw),
2852.01(vw),1618.40(w),1552.15(s),1497.27(vs),1451.23(vs),1411.89(vs),1244.17
(s),1227.47(m),1197.50(m),1169.28(w),1126.28(w),1106.83(w),1053.27(vs),
1013.26(m),925.74(s),846.85(w),824.39(s),759.30(s),746.30(vs),699.83(s),
647.87(w),609.96(s),499.07(w).MS(APCI):m/z,calcd:286.9946,found:288.9991.
C, intermediate M3 preparation
9.29g (32.3mmol) M2 are weighed in 250mL round-bottomed flasks, adding the backflow of 100mL benzene makes its dissolving, adds
12.24g(50mmol)PPh3In reaction system, flow back 6h at 80 DEG C, and white solid separates out, and obtained reaction solution through taking out while hot
Filter, gained solid is dried in vacuo, obtains white solid 13.71g, i.e. intermediate M3, yield 77%.
Intermediate M3's1H NMR(400MHz,CDCl3):δ (ppm) 7.89-7.80 (m, 9H), 7.77-7.73 (t, J=
12.0Hz, 3H), 7.64-7.60 (m, 7H), 7.43-7.41 (m, 1H), 7.32-7.29 (d, J=12.00Hz, 2H), 7.26-
7.24 (m, 1H), 5.81-5.77 (d, J=16.00Hz, 2H)13C NMR(100MHz,CDCl3):δ(ppm)162.18,
150.52,141.70,134.90,134.60,132.34,131.29,127.53,125.16,124.48,119.83,118.16,
117.31,110.49,30.31.FT-IR(KBr,cm-1):3048.72(m),3004.26(w),2988.26(w),2964.25
(w),2842.70(vs),2764.35(vs),1613.10(m),1587.13(m),1550.58(s),1493.63(s),
1450.84(w),1435.93(s),1344.59(m),1244.35(s),1179.21(w),1110.32(vs),1064.34
(s),1013.20(m),995.73(m),868.64(s),802.10(m),746.15(s),720.87(m),685.74(m),
561.73(m),508.50(s).MS(ESI):m/z,calcd:549.0857,found:469.1654(M-Br)+.
D, intermediate M4 preparation
Weigh 5.17g (9.41mmol) M3,1.45g (13.53mmol) 4- pyridine carboxaldehydes, 4.98g (36mmol) potassium carbonate,
It is added sequentially in 20mL DMAs (DMA), nitrogen is protected, after the 12h that flowed back at 140 DEG C, is cooled to room temperature,
60mL dichloromethane is added into obtained reaction solution and is stirred, filters to obtain filtrate, filtrate adds a large amount of water and repeatedly washed, then
With anhydrous calcium chloride dry methylene chloride layer, it is spin-dried for dichloromethane and obtains 1.71g white solids, i.e. intermediate M4, yield 61%.
Intermediate M4's1H NMR:(400MHz,DMSO-d6),δ(ppm):8.60-8.58 (d, J=8.00Hz, 2H),
8.26-8.24 (d, J=8.00Hz, 2H), 7.91-7.89 (d, J=8.00Hz, 2H), 7.84-7.80 (t, J=8.00Hz,
2H), 7.69-7.64 (d, J=16.00Hz, 1H), 7.62-7.61 (d, J=4.00Hz, 2H), 7.47-7.41 (m, 3H)13C
NMR:(100MHz,DMSO-d6),δ(ppm):161.96,150.11,143.82,141.55,139.59,131.85,128.30,
127.81,127.71,126.00,125.61,124.94,121.04,119.81,110.91.
E, intermediate M5 preparation
0.93g (3.1mmol) M4 is weighed, is placed in 100mL round-bottomed flasks, adds 50mL tetrahydrofurans (THF), at room temperature
Stirring makes its dissolving, adds 0.78g (5.5mmol) CH3I, it is warming up to 60 DEG C and reacts 4h at this temperature, solution becomes muddy
It is turbid, there are a large amount of yellow solids, obtained reaction solution obtains yellow powder 0.99g, i.e. intermediate M5, yield is through filtering while hot
72%.
Intermediate M5's1H NMR:(400MHz,DMSO-d6),δ(ppm):8.92-8.91 (d, J=4.00Hz, 2H),
8.33-8.27 (m, 4H), 8.12-8.08 (d, J=16.00Hz, 1H), 7.99-7.97 (d, J=8.00Hz, 2H), 7.86-
7.82 (t, J=8.00Hz, 2H), 7.72-7.68 (d, J=16.00Hz, 1H), 7.50-7.43 (m, 2H), 4.28 (s, 3H)13C
NMR(100MHz,DMSO-d6),δ(ppm):161.66,151.91,150.24,145.25,141.49,139.07,138.30,
128.80,127.88,127.40,125.86,125.31,125.05,123.84,119.94,110.99,47.05.MS
(APCI):m/z 313.1335[(M-I-)+,calcd 313.1337].
F, target product L preparation
0.3g (0.68mmol) M5 are weighed in 250mL round-bottomed flasks, add 150mL ethanol, heating makes its dissolving, then claims
Take 0.46g (1.36mmol) NaBPh4It is added in reaction system, 6h, solution turned cloudy, obtained reaction is reacted at 80 DEG C
Liquid obtains 0.2743g yellow solids, i.e. target product L, target product L that is to say two-photon fluorescence material benzo through filtering while hot
Oxazolyl pyridiniujm, yield 63%.
Target product L's1H NMR:(400MHz,DMSO-d6),δ(ppm):8.90-8.88 (d, J=8.00Hz, 2H),
8.33-8.31 (d, J=8.00Hz, 2H), 8.27-8.25 (d, J=8.00Hz, 2H), 8.11-8.07 (d, J=16.00Hz,
1H), 7.99-7.97 (d, J=8.00Hz, 2H), 7.86-7.81 (t, J=10.00Hz, 2H), 7.71-7.67 (d, J=
16.00Hz, 1H), 7.50-7.43 (m, 2H), 7.18 (s, 8H), 6.94-6.90 (t, J=8.00Hz, 8H), 6.80-6.77 (t,
J=6.00Hz, 4H), 4.26 (s, 3H)13C NMR(100MHz,DMSO-d6),δ(ppm):164.02,163.56,162.56,
161.57,151.91,150.26,145.27,141.49,139.09,138.30,135.49,128.804,127.91,
127.43,125.88,125.28,123.84,121.47,119.95,111.00,47.02.MS(APCI):m/z 313.1335
[(M-NO3 -)+,calcd 313.1333].
Embodiment 2
The preparation method of two-photon fluorescence material benzoxazolyl pyridiniujm
The present embodiment is similar to Example 1, for the sake of succinct description, therefore is illustrated only for deviation.Their difference
It is different to be：It is the 7h that flowed back at 210 DEG C, M1 yield is 30.5%, is to be warming up in step B in the step A of the present embodiment
70 DEG C, and 6h is reacted at this temperature, M2 yield is 58%, is the 8h that flowed back at 40 DEG C, M3 yield is in step C
It is the 10h that flowed back at 140 DEG C, M4 yield is 59%, is to be warming up to 50 DEG C and in this temperature in step E in 75%, step D
Lower reaction 3h, M5 yield are 70%, are that 7h is reacted at 60 DEG C in step F, and target product L yield is 61%.
Embodiment 3
The preparation method of two-photon fluorescence material benzoxazolyl pyridiniujm
The present embodiment is similar to Example 1, for the sake of succinct description, therefore is illustrated only for deviation.Their difference
It is different to be：It is the 4h that flowed back at 240 DEG C, M1 yield is 30%, is to be warming up to 60 in step B in the step A of the present embodiment
DEG C, and 7h is reacted at this temperature, M2 yield is 56%, is the 7h that flowed back at 60 DEG C in step C, and M3 yield is 76%,
It is the 14h that flowed back at 140 DEG C in step D, M4 yield is 58%, is to be warming up to 40 DEG C and anti-at this temperature in step E
6h is answered, M5 yield is 69%, is that 4h is reacted at 90 DEG C in step F, and target product L yield is 59%.
Embodiment 4
Target product L performance test
2.1 target product L single photon properties
Can be seen that target product L from Fig. 2 a has two absworption peaks in the range of 267-290nm and 362-378nm, the former
π-π * the transition of benzoxazole ring can be belonged to, and the latter can then be attributed to the ICT transition of whole intramolecular；Target product L
The electric charge transfer from benzoxazole core to pyridine groups be present in intramolecular.Target product L is can be seen that in 501nm- from Fig. 2 b
There is single emission peak between 512nm, thus it is speculated that the emission peak is launched caused by can belonging to Intramolecular electron transfer transition.
2.2 target product L two-phpton properties
(1) tester and condition
Two-photoninduced fluorescence (TPEF) is tested with locked mode ti sapphire laser (Coherent Mira 900F, pulse
140fs, frequency 80MHz) it is pump light source, using physical interference method, there is provided 680-1080nm variable wavelength laser.
Target product L solution concentration is 1 × 10 during experiment-4M, test are the aqueous solution with mother liquor.With 1 × 10-4M's
The fluorescein NaOH aqueous solution (wherein NaOH concentration is 1M) is used as reference.Solvent for use is chromatogram pure reagent, sample cell 1.0
× 1.0cm four sides thang-kng quartz colorimetric utensil.Laser light source power is controlled in 300mW, wave-length coverage 720-980nm, wavelength
It is spaced 20nm.
(2) determination of maximum excitation wavelength
The determination of two-photoninduced fluorescence maximum excitation wavelength is the laser excitation molecule using firm power different wave length
Two-photon absorption is produced, then records its fluorescent emission intensity, the most strong excitation wavelength of two-photon fluorescence is optimum excitation wave
It is long.In order to determine target product L maximum excitation wavelength, the laser light source power of use is all controlled in 300mW, excitation wavelength
Scope is 720-900nm, 20nm is spaced, 1 × 10-4Its two-photoninduced fluorescence spectrum is determined in the M aqueous solution, as a result sees figure
Shown in 3a.
(3) two-photon is verified
In this experiment, two-photon checking is to measure it by changing excitating light strength under compound maximum excitation wavelength
The two-photon for (100-700mW power bracket being chosen in experiment, interval 100mW is measured) under different capacity exciting light lures
Fluorescence intensity is led to be verified.The two-photon checking slopes of target product L in aqueous preferably meet double 1.80 or so
The feature of photon excitation, as a result as shown in Fig. 3 b.
(4) two photon absorption cross section calculates
The measure of two photon absorption cross section (δ) uses two-photoninduced fluorescence method.Using the method for two-photoninduced fluorescence
To calculate the two photon absorption cross section (δ of compound2PA), the reference reagent of selection is pH=11 fluorescein (fluorescein)
The aqueous solution, it is as follows to calculate publicity：
In formula, ref represents reference, and (fluorescein here is matched somebody with somebody in the NaOH aqueous solution, concentration c=1 × 10-3M, Ф are
Two-photon quantum yield (is generally replaced) with single photon fluorescence quantum yield, the two photon absorption cross section (Ф of reference sampleref=
0.95) absolute value derives from document, and c is the concentration of solution, and n is the refractive index of solvent, and F is corresponding under different excitation wavelengths
Two-photon fluorescence integrated area value, δrefIt is the two photon absorption cross section value of reference.
Two photon absorption cross sections of the target product L in water is calculated, its result is as shown in figure 4, target product L
There is maximum at 760nm in two photon absorption cross section in aqueous, and two photon absorption cross section value is：103GM.
The test of 2.3 target product L single photons, two-photon cell developing effect
The cover glass for cleaning up and sterilizing is put into 6 hole tissue culturing plates, liver cancer tissue cell (Hela cells) 5 ×
105The density in individual/hole is seeded in diameter 35mm 6 orifice plate culture dishes, and carries out cell training by the use of DMEM as cell culture medium
Support, hyclone (10%), penicillin (100 μ g/mL) and streptomysin (100ug/mL) are contained in cell culture medium.Cell culture
Ware is placed in containing 5%CO2And 95%O2Incubator in maintain 37 DEG C of temperature progress cell culture 24h, with PBS (phosphate buffer,
PH=7.4, Gibco Reagent Company produce) wash Hela cells three times, wash away culture medium.It is then respectively adding 4 μ L target chemical combination
Thing L DMSO solution (1mM), 0.5h is cultivated, rinse cover glass 6~7 times with PBS cushioning liquid (pH=7.4), drip 1mL 4%
Paraformaldehyde/PBS solution fixes cell 10min, distilled water flushing cover glass 6~7 times.Cover glass is stuck in clean glass slide
On, it is placed under laser confocal microscope (LSM-710, Zeiss, Germany) and observes cellular morphology and fluorescence intake situation, as a result
See Fig. 5.
It is clear from fig. 5 that target product L passes through the cell membrane of Hela cells, and into cytoplasm, and it is complete to it
Complete uniform coloring, illustrates that target product has very high stationkeeping ability to the cytoplasm of Hela cells.This two-photon material
For the selecting of cell developing material, prepare, important meaning is suffered from for life science, material science etc..
It should be understood that example as described herein and embodiment are not intended to limit the invention, this area only for explanation
Technical staff can make various modifications or change according to it, within the spirit and principles of the invention, any modification for being made,
Equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (9)
1. two-photon fluorescence material benzoxazolyl pyridiniujm, it is characterised in that its structural formula is as follows：
2. application of the two-photon fluorescence material benzoxazolyl pyridiniujm as claimed in claim 1 in cell imaging.
3. the preparation method of two-photon fluorescence material benzoxazolyl pyridiniujm as claimed in claim 1, it is characterised in that bag
Include following steps：
A, intermediate M1 (2- (p-methylphenyl) benzoxazoles) preparations
P-methylbenzoic acid, o-aminophenol are mixed with polyphosphoric acids, flow back 4~7h at 210~240 DEG C, and what is obtained is anti-
Liquid is answered to obtain intermediate M1 after extracting, dry, recrystallize；
B, intermediate M2 (2- (4- (bromomethyl) phenyl) benzoxazoles) preparations
M1 and N- bromo-succinimides are dissolved in benzene, add initiator benzoyl peroxide, at 60~80 DEG C react 6~
8h, obtained reaction solution obtain intermediate M2 through standing, filter, wash, after drying；
C, intermediate M3 (2- (4- ((triphenylphosphinebromide) methyl) phenyl) benzoxazoles) preparations
M2 is dissolved in benzene, adds PPh3, 6~8h is reacted at 40~80 DEG C, obtained reaction solution through filtering while hot, drying
After obtain intermediate M3；
D, intermediate M4 (E-2- (4- (2- (pyridin-4-yl) vinyl) phenyl) benzoxazoles) preparations
M3,4- pyridine carboxaldehyde and potassium carbonate are added in DMA, 10~14h, Xiang get are reacted at 140 DEG C
To reaction solution warp in add dichloromethane, then filtered, filtrate through washing, dry after obtain intermediate M4；
E, intermediate M5 (E-4- (4- (2- benzoxazolyls) -2- styryls)-N- picolines salt compounded of iodine) preparation
M4 is dissolved in tetrahydrofuran, adds CH3I, 3~6h is reacted at 40~60 DEG C, obtained reaction solution through filtering while hot
After obtain intermediate M5；
F, the preparation of target product L two-photon fluorescences material benzoxazolyl pyridiniujm
M5 is dissolved in ethanol, adds NaBPh4, 4~7h is reacted at 60~90 DEG C, obtained reaction solution after filtering while hot
Obtain target product L.
4. the preparation method of two-photon fluorescence material benzoxazolyl pyridiniujm as claimed in claim 3, it is characterised in that step
In rapid A, the mole dosage ratio of p-methylbenzoic acid and o-aminophenol is 1:2.2.
5. the preparation method of the two-photon fluorescence material benzoxazolyl pyridiniujm as described in claim 3 or 4, its feature exist
In in step B, the mole dosage ratio of intermediate M1 and N- bromo-succinimide is 13.3:30.
6. the preparation method of the two-photon fluorescence material benzoxazolyl pyridiniujm as described in claim 3 or 4, its feature exist
In, in step C, intermediate M2 and PPh3Mole dosage ratio be 32.3:50.
7. the preparation method of the two-photon fluorescence material benzoxazolyl pyridiniujm as described in claim 3 or 4, its feature exist
In in step D, the mole dosage ratio of intermediate M3,4- pyridine carboxaldehyde and potassium carbonate is 9.4:13.5:36.
8. the preparation method of the two-photon fluorescence material benzoxazolyl pyridiniujm as described in claim 3 or 4, its feature exist
In, in step E, intermediate M4 and CH3I mole dosage ratio is 3.1:5.5.
9. the preparation method of the two-photon fluorescence material benzoxazolyl pyridiniujm as described in claim 3 or 4, its feature exist
In, in step F, intermediate M5 and NaBPh4Mole dosage ratio be 1:2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710671589.1A CN107382991B (en) | 2017-08-08 | 2017-08-08 | Two-photon fluorescent material benzoxazolyl pyridine salt and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710671589.1A CN107382991B (en) | 2017-08-08 | 2017-08-08 | Two-photon fluorescent material benzoxazolyl pyridine salt and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107382991A true CN107382991A (en) | 2017-11-24 |
| CN107382991B CN107382991B (en) | 2020-11-06 |
Family
ID=60355109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710671589.1A Active CN107382991B (en) | 2017-08-08 | 2017-08-08 | Two-photon fluorescent material benzoxazolyl pyridine salt and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107382991B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440965A (en) * | 2003-01-23 | 2003-09-10 | 安徽大学 | Pyridine salt derivative as strong two-photon absorbing material and its prepn process |
| CN105272974A (en) * | 2014-06-24 | 2016-01-27 | 爱科来株式会社 | Styryl pyridinium derivative and nonlinear optical material using the same |
| CN106496102A (en) * | 2016-10-31 | 2017-03-15 | 安徽大学 | Mitochondrial two-photon fluorescence viscosity probe and preparation method thereof |
-
2017
- 2017-08-08 CN CN201710671589.1A patent/CN107382991B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1440965A (en) * | 2003-01-23 | 2003-09-10 | 安徽大学 | Pyridine salt derivative as strong two-photon absorbing material and its prepn process |
| CN105272974A (en) * | 2014-06-24 | 2016-01-27 | 爱科来株式会社 | Styryl pyridinium derivative and nonlinear optical material using the same |
| CN106496102A (en) * | 2016-10-31 | 2017-03-15 | 安徽大学 | Mitochondrial two-photon fluorescence viscosity probe and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHAN F. ZHAO ET AL.: "Newly Synthesized Dyes and Their Polymer/Glass Composites for One- and Two-Photon Pumped Solid-state Cavity Lasing", 《CHEM. MATER》 * |
| 桑言奎: "一些D-π-A型吡啶盐的分子设计、合成、表征及其光学性质初探", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
| 葛新萍: "双光子吸收苯胺类衍生物的合成、光学性质及生物应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107382991B (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Structural modification strategies for the rational design of red/NIR region BODIPYs | |
| Baruah et al. | Solvent and pH dependent fluorescent properties of a dimethylaminostyryl borondipyrromethene dye in solution | |
| CA3045485A1 (en) | Near-ir glucose sensors | |
| Rodrigues et al. | Two-photon absorption properties of push–pull oxazolones derivatives | |
| Janiga et al. | Quadrupolar, emission-tunable π-expanded 1, 4-dihydropyrrolo [3, 2-b] pyrroles–synthesis and optical properties | |
| Owens et al. | A microwave-assisted and environmentally benign approach to the synthesis of near-infrared fluorescent pentamethine cyanine dyes | |
| EP3126451A1 (en) | Azetidine-substituted fluorescent compounds | |
| Wu et al. | Asymmetric boron-complexes containing keto-isoindolinyl and pyridyl groups: solvatochromic fluorescence, efficient solid-state emission and DFT calculations | |
| Patil et al. | ESIPT-inspired benzothiazole fluorescein: Photophysics of microenvironment pH and viscosity | |
| Petchprayoon et al. | Rational design, synthesis, and characterization of highly fluorescent optical switches for high-contrast optical lock-in detection (OLID) imaging microscopy in living cells | |
| Zhang et al. | Long-wavelength boradiazaindacene derivatives with two-photon absorption activity and strong emission: versatile candidates for biological imaging applications | |
| Sun et al. | Non-symmetric thieno [3, 2-b] thiophene-fused BODIPYs: synthesis, spectroscopic properties and providing a functional strategy for NIR probes | |
| Zhou et al. | Dicyanoboron diketonate dyes: Synthesis, photophysical properties and bioimaging | |
| Xu et al. | meso-C6F5 substituted BODIPYs with distinctive spectroscopic properties and their application for bioimaging in living cells | |
| CN108069908A (en) | Fluorescence probe and its application | |
| Wang et al. | Synthesis, two-photon absorption properties and bioimaging applications of mono-, di-and hexa-branched pyrimidine derivatives | |
| Rodrigues et al. | Unsaturated oxazolones as nonlinear fluorophores | |
| CN108864056A (en) | Near infrared fluorescent compound and its preparation method and application with AIE performance | |
| Yang et al. | BODIPY derivatives bearing borneol moieties: Enhancing cell membrane permeability for living cell imaging | |
| CN108864733A (en) | A kind of near-infrared carbon rhodamine fluorescent dyes and its synthetic method | |
| Sun et al. | The synthesis, two-photon absorption and blue upconversion fluorescence of novel, nitrogen-containing heterocyclic chromophores | |
| Yamaguchi et al. | A Benzophosphole P-oxide with an electron-donating group at 3-position: enhanced fluorescence in polar solvents | |
| CN102286213A (en) | Near-infrared aza-BODIPY dye as well as preparation method and application thereof | |
| Liu et al. | Water-soluble two-photon absorption benzoxazole-based pyridinium salts with the planar cationic parts: crystal structures and bio-imaging | |
| Shu et al. | Small molecules based benzothiazole-pyridinium salts with different anions: Two-photon fluorescence regulation and difference in cell imaging application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |