CN105669734A - BCPA-BODIPY fluorescent molecules and preparation method and application thereof - Google Patents
BCPA-BODIPY fluorescent molecules and preparation method and application thereof Download PDFInfo
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- CN105669734A CN105669734A CN201610151356.4A CN201610151356A CN105669734A CN 105669734 A CN105669734 A CN 105669734A CN 201610151356 A CN201610151356 A CN 201610151356A CN 105669734 A CN105669734 A CN 105669734A
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- bodipy
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- fluorine boron
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- 238000002360 preparation method Methods 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000003384 imaging method Methods 0.000 claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000000975 dye Substances 0.000 claims abstract description 9
- 150000003233 pyrroles Chemical class 0.000 claims description 38
- DRYYVMCHFVXCFD-UHFFFAOYSA-N [B].[F].C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [B].[F].C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 DRYYVMCHFVXCFD-UHFFFAOYSA-N 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001044 red dye Substances 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical compound CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 claims description 5
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000377 silicon dioxide Substances 0.000 abstract description 10
- 239000007850 fluorescent dye Substances 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 5
- 238000001215 fluorescent labelling Methods 0.000 abstract description 3
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000029918 bioluminescence Effects 0.000 abstract 1
- 238000005415 bioluminescence Methods 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 125000003367 polycyclic group Chemical group 0.000 abstract 1
- DKACXUFSLUYRFU-UHFFFAOYSA-N tert-butyl n-aminocarbamate Chemical compound CC(C)(C)OC(=O)NN DKACXUFSLUYRFU-UHFFFAOYSA-N 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 239000012620 biological material Substances 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000012447 hatching Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000799 fluorescence microscopy Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 2
- 208000026310 Breast neoplasm Diseases 0.000 description 2
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- YSGZPEILUZVKDO-UHFFFAOYSA-N [F].C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [F].C1(=CC=CC=C1)N(C1=CC=CC=C1)C1=CC=CC=C1 YSGZPEILUZVKDO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- -1 carbazole triphenylamine-fluorine boron Chemical compound 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 1
- 238000002073 fluorescence micrograph Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1491—Heterocyclic containing other combinations of heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses BCPA-BODIPY fluorescent molecules and further discloses a preparation method and application thereof. The novel compound BCPA-BODIPY is rigid polycyclic long-wavelength red fluorochrome containing three types of fluorophore, namely tert-butyl carbazate, triphenylamine and 1, 3, 5, 7-tetramethyl bodipy, emits red fluorescence when the compound is in the solid state and in an aqueous solution and has good gathering induction and fluorescence enhancement performance. The BCPA-BODIPY fluorescent molecules can serve as long-wavelength red fluorochrome which is excellent in performance and are used for preparing dye loaded with silica fluorescent nanoparticles and have wide application in the fields such as cell imaging, fluorescent sensors, bioluminescence analysis and fluorescence labeling.
Description
Technical field
The present invention relates to fluorescent chemicals and its preparation method and application field, be specifically related to a kind of carbazyl triphenAmine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY and its preparation method and application.
Background technology
The molar extinction coefficient of fluorine boron two pyrroles's fluorescence molecules is large, and fluorescence quantum yield is high, and sensitivity is good, stableGood, can reach near infra-red light region through its fluorescent emission wavelength of structural modification, there is good optical property,Can be used for fluorimetric assay for biological materials field. Carbazyl triphenylamine-fluorine boron two pyrroles's red dyes rarely have report in the literatureRoad, its fluorescence property excellence, fluorescence quantum efficiency is high, has good aggregation inducing fluorescence and strengthens the property, and sends outPenetrate very strong red fluorescence, the red dye that can be used as long wavelength is received for the preparation of dye load silica fluorescentRice corpuscles, extensively should have in fields such as cell imaging, fluorescent optical sensor, fluorimetric assay for biological materials, fluorescence labelingsWith.
Summary of the invention
Goal of the invention: first technical problem to be solved by this invention be to provide a kind of carbazyl triphenylamine-Fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY.
Second technical problem to be solved by this invention is that a kind of carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence divideThe preparation method of sub-BCPA-BODIPY.
The 3rd technical problem to be solved by this invention has been to provide a kind of carbazyl triphenylamine-fluorine boron two pyrrolesThe application of fluorescence molecule BCPA-BODIPY.
The present invention prepares a kind of novel carbazole base triphen-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY.This fluorescence molecule has no report in the prior art, its fluorescence property excellence, and fluorescence quantum efficiency is high, has goodGood aggregation inducing fluorescence is enhanced propertied, launches very strong red fluorescence, and the red dye that can be used as long wavelength is usedIn the silica fluorescent nanoparticle of preparation dye load, at cell imaging, fluorescent optical sensor, bioluminescenceThe fields such as analysis, fluorescence labeling have extensive use.
Technical scheme: in order to solve the problems of the technologies described above, the invention provides a kind of carbazyl triphenylamine-fluorine boronTwo pyrroles's fluorescence molecule BCPA-BODIPY, are made up of following structural formula:
The preparation method of above-mentioned carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY, described inCarbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY are with 4-{N, N-bis-[4-(the tertiary fourth of 3,6-bis-Base-9-carbazyl) phenyl] amino benzaldehyde (BCPA) is raw material, under nitrogen protection with 2,4-dimethyl pyrrolePrepare through multistep reaction. Specifically comprise the steps: under nitrogen protection and magnetic agitation, to being dissolved with chemical combinationThing 4-{N, N-bis-[4-(3,6-di-t-butyl-9-carbazyl) phenyl] amino } nothing of benzaldehyde and 2,4-dimethyl pyrroleIn water dichloromethane solution, drip trifluoroacetic acid, lucifuge reaction under room temperature; Then be dissolved with to injecting in reaction systemThe anhydrous methylene chloride solution of tetrachloroquinone, lucifuge reaction; Finally in ice bath, slowly drip triethylamine and trifluoroChange borate ether complex compound, remove under ice bath room temperature and react, finish reaction, through extraction, dry, column chromatography is purified,Obtain carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY. Concrete reaction equation is as follows:
. Wherein, compound 4-{N, N-bis-[4-(3,6-di-t-butyl-9-carbazyl) phenyl] amino } benzaldehyde (BCPA)Press literature method preparation (YongchangJinandYingQian.Photophysicalproperties,aggregation-inducedfluorescenceinnanoaggregatesandcellimagingof2,5-bisaryl1,3,4-oxadiazoles.NewJournalofChemistry.2015,39,2872～2880)。
Compound 2,4-dimethyl pyrrole is pressed literature method preparation (GeMeng, Mei-LinZheng, andMeiWang.Animprovedtwo-steppreparationof2,4-dimethylpyrrole.Organicprepararionsandproceduresinternational.2011,43,308～311)。
New compound of the present invention is to comprise tert-butyl group carbazole, triphenylamine and 1,3,5,7-tetramethyl fluorine boron, two pyrrolesCough up the rigidity of 3 kinds of fluorophors and encircle fluorescence molecule more, its proportion of composing fluorine boron two pyrroles: triphenylamine: the tert-butyl groupCarbazole is 1:1:2.
Above-mentioned carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY are as dye loadFluorescent nano particles is prepared the application of aspect.
Above-mentioned carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY are as aggregation inducingThe application of luminescent material aspect.
Above-mentioned carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY are red as long wavelength'sThe application of photoinitiator dye aspect cell imaging.
Beneficial effect: the present invention has the following advantages: rigidity of the present invention is encircled ruddiness molecule moreThe structure of BCPA-BODIPY, synthetic, photoluminescent property and application have no report, its fluorescence in the prior artExcellent performance, launches very strong red fluorescence, and fluorescence quantum efficiency is high, and fluorescent emission wavelength is greater than 600nm,And having good aggregation inducing fluorescence strengthens the property. Red-emitting when BCPA-BODIPY is solid-state, maximumEmission wavelength is 633nm; In the pure organic solvents such as oxolane, launch red fluorescence, maximum emission wavelengthFor 656nm; In water/oxolane mixed solvent, launch red fluorescence, and increase fluorescence enhancing with water content,In water content 90% mixed solvent, fluorescence is the strongest, and maximum emission wavelength is 620nm; LoadThe very strong red fluorescence of silica fluorescent nanoparticle transmitting of BCPA-BODIPY dyestuff, emission maximum rippleLong is 635nm. Carbazyl triphenylamine-fluorine boron of the present invention two pyrroles can be used as red dye for the preparation of dyestuffThe silica fluorescent nanoparticle of load, at cell imaging, fluorescent optical sensor, fluorimetric assay for biological materials, fluorescenceThe fields such as mark have extensive use.
Brief description of the drawings
Fig. 1 is the Solid fluorescene spectrum of carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY;
Fig. 2 is the silica of carbazyl triphenylamine-fluorine boron two pyrroles's fluorescent dye BCPA-BODIPY loads(BCPA-BODIPY concentration is 10 to the fluorescence spectrum of nano particle in pure water solution-6mol/L)；
Fig. 3 is carbazyl triphenylamine-fluorine boron two pyrroles's fluorescent dye BCPA-BODIPY and breast cancer cellsLaser co-focusing fluorescence micrograph (ruddiness region cell imaging) after the common hatching of MCF-7.
Detailed description of the invention:
By specific embodiment, the present invention is described in further detail below.
Embodiment 1: the preparation of carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPYUnder nitrogen protection and magnetic agitation, to being dissolved with compound 4-{N, N-bis-[4-(3,6-di-t-butyl-9-carbazyl) benzeneBase] amino } benzaldehyde BCPA (1.66g, 2.0mmol) and 2,4-dimethyl pyrrole (0.43g, 4.5mmol) dryIn dry dichloromethane solution, drip 3 trifluoroacetic acids, under room temperature, lucifuge stirs 13h, then in reaction systemThe dry methylene chloride solution that injection is dissolved with tetrachloroquinone (0.54g, 2.2mmol) continues to stir 6h, finally existsIn ice bath, slowly drip triethylamine 5mL and boron trifluoride etherate 5mL, remove under ice bath room temperature and react10h. Finish reaction, add 250mL water to reaction system, extraction, dry, column chromatography is purified, and obtainsCarbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY.
The preparation of embodiment 2 carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY
Under nitrogen protection and magnetic agitation, to being dissolved with compound 4-{N, N-bis-[4-(3,6-di-t-butyl-9-carbazyl)Phenyl] amino } benzaldehyde BCPA (0.828g, 1.0mmol) and 2,4-dimethyl pyrrole (0.209g, 2.2mmol)Dry methylene chloride solution in drip 3 trifluoroacetic acids, under room temperature, lucifuge stirs 12h, then to reaction bodyIn system, inject the dry methylene chloride solution continuation stirring 5h that is dissolved with tetrachloroquinone (0.268g, 1.1mmol),After in ice bath, slowly drip triethylamine 3mL and boron trifluoride etherate 4mL, remove under ice bath room temperatureReaction 8h. Finish reaction, add 200mL water to reaction system, extraction, dry, column chromatography is purified,Obtain carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY.
The synthetic route of the compd B CPA-BODIPY of above-described embodiment 1～2 is as follows:
Wherein, compound 4-{N, N-bis-[4-(3,6-di-t-butyl-9-carbazyl) phenyl] amino } benzaldehyde(BCPA) press literature method preparation (YongchangJinandYingQian.Photophysicalproperties,aggregation-inducedfluorescenceinnanoaggregatesandcellimagingof2,5-bisaryl1,3,4-oxadiazoles.NewJournalofChemistry.2015,39,2872～2880)。
Compound 2,4-dimethyl pyrrole is pressed literature method preparation (GeMeng, Mei-LinZheng, andMei Wang.Animprovedtwo-steppreparationof2,4-dimethylpyrrole.Organicprepararionsandproceduresinternational.2011,43,308～311)。
Analyze gained compd B CPA-BODIPY:
Proton nmr spectra1HNMR(CDCl3,ppm):δ8.17(s,4H),7.56(s,2H),7.53(s,4H),7.49(t,J1＝1.2Hz,J2＝12.0Hz,6H),7.41(t,J1＝3.9Hz,J2＝4.5Hz,6H),7.29(s,2H),2.59(s,6H),1.65(s,6H),1.49(s,36H)。
Carbon-13 nmr spectra13CNMR(CDCl3,ppm):δ154.98,145.27,142.43,138.82,133.08,128.89,127.34,124.91,123.64,123.11,120.80,115.77,108.72,76.93,76.51,76.08,34.24,31.52,14.12。
High resolution mass spectrum HRMSCalcdforC71H75BF2N5[M+H]+1046.6078
found1046.6021。
The structural formula of the compd B CPA-BODIPY that obtains is:
The red solid fluorescence of embodiment 3 carbazyl triphenylamine-fluorine boron two pyrroles BCPA-BODIPY
Carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY red-emitting when solid-state, maximumEmission wavelength is 633nm. Under the medium ultraviolet lamp of darkroom, BCPA-BODIPY solid state is sent very strong rednessFluorescence. Carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecules that accompanying drawing 1 is prepared for the embodiment of the present invention 1The Solid fluorescene spectrum of BCPA-BODIPY.
The aggregation inducing fluorescence of embodiment 4 carbazyl triphenylamine-fluorine boron two pyrroles BCPA-BODIPY strengthens
Carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY are pure organic molten at oxolane etc.In agent, launch red fluorescence, maximum emission wavelength is 656nm; In water/oxolane mixed solvent, launch redLook fluorescence, and increase fluorescence enhancing with water content, when in mixed solvent, water content reaches 90%, fluorescence is the strongest,Large emission wavelength is 620nm; The silica fluorescent nanoparticle transmitting of load BCPA-BODIPY dyestuffVery strong red fluorescence, maximum emission wavelength is 635nm. Accompanying drawing 2 is carbazyl triphenylamine-fluorine boron two pyrrolesThe fluorescence spectrum of the Nano particles of silicon dioxide of fluorescent dye BCPA-BODIPY load in pure water solution.
During the silica fluorescent nanoparticle of load BCPA-BODIPY dyestuff is soluble in water, rich surface is containing largeAmount active amino, is easy to modify, good biocompatibility, and photoluminescent property is good, can be used as biomolecule fluorescence and visitsPin is for life sciences such as fluorimetric assay for biological materials, medicament high flux screenings.
Embodiment 5 carbazole triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY are for cell fluorescence imaging
By carbazyl triphenylamine-fluorine boron two pyrroles's fluorescent dye BCPA-BODIPY and breast cancer cell MCF-7After common hatching at the micro-Microscopic observation MCF-7 of binary channels confocal fluorescent cell imaging photo. Accompanying drawing 3 isLaser co-focusing fluorescence imaging photo after the common hatching of MCF-7 cell and fluorescent dye BCPA-BODIPY.In MCF-7 cell, add after the common hatching of fluorescence molecule BCPA-BODIPY, red dye enters MCF-7Cell interior, at ruddiness region blur-free imaging. Carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence moleculesBCPA-BODIPY can be used as the red dye of function admirable for cell imaging.
Instantiation compound carbazyl triphenylamine-fluorine boron of the present invention two pyrroles's fluorescence molecule BCPA-BODIPY,Fluorescence property is good, and transmitting red fluorescence, has that aggregation inducing is luminous strengthens the property, and can be used for preparing dyestuff negativeThe silica fluorescent nanoparticle carrying, can be used as long wavelength's red dye for tumour cell fluorescence imaging,The fields such as cell imaging, fluorescent optical sensor, fluorimetric assay for biological materials, fluorescence labeling, medicament high flux screening haveExtensive use.
The above is only the preferred embodiment of the present invention, is noted that the technology people for the artMember, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvementAlso should be considered as protection scope of the present invention with retouching.
Claims (5)
1. carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY，It is characterized in thatFormed by following structural formula:
2. carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY claimed in claim 1Preparation method, is characterized in that, comprises the steps: under nitrogen protection and magnetic agitation, to being dissolved with compound4-{N, N-bis-[4-(3,6-di-t-butyl-9-carbazyl) phenyl] amino } benzaldehyde and 2,4-dimethyl pyrrole anhydrousIn dichloromethane solution, drip trifluoroacetic acid, lucifuge reaction under room temperature; Then be dissolved with four to injecting in reaction systemThe anhydrous methylene chloride solution of chloranil, lucifuge reaction; Finally in ice bath, slowly dripping triethylamine and three fluoridizesBorate ether complex compound, removes under ice bath room temperature and reacts, and finishes reaction, and through extraction, dry, column chromatography is purified,Obtain carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY.
3. carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY claimed in claim 1 existPrepare the application of aspect as red dye load fluorescent nano particles.
4. carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY claimed in claim 1 existAs the application of gathering induced luminescence material aspect.
5. carbazyl triphenylamine-fluorine boron two pyrroles's fluorescence molecule BCPA-BODIPY claimed in claim 1 doFor long wavelength's red fluorescence dyestuff is in the application aspect cell imaging.
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| CN106046376A (en) * | 2016-06-16 | 2016-10-26 | 上海交通大学 | Tert-butyl B'B2-containing triamine monomer, hyperbranched polyimide thereof and preparation method |
| CN106221280A (en) * | 2016-08-09 | 2016-12-14 | 东莞理工学院 | Novel organic dye sensitizer containing BODIPY conjugated units and preparation method thereof |
| CN106496260A (en) * | 2016-09-23 | 2017-03-15 | 东南大学 | Two pyrroles ruddiness compound OPA BODIPY of a kind of diazole triphenylamine fluorine boron and its preparation method and application |
| CN109180715A (en) * | 2018-10-12 | 2019-01-11 | 东北师范大学 | A kind of boron-dipyrromethene derivative, nanoparticle, preparation method and application |
| CN109320536A (en) * | 2018-11-20 | 2019-02-12 | 南京工业大学 | Aza-BODIPY based near-infrared two-window fluorescent probe and preparation and application thereof |
| CN109762557A (en) * | 2019-01-14 | 2019-05-17 | 天津理工大学 | Inorganic fluorescent nanoparticle and its preparation method and application |
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| CN106046376A (en) * | 2016-06-16 | 2016-10-26 | 上海交通大学 | Tert-butyl B'B2-containing triamine monomer, hyperbranched polyimide thereof and preparation method |
| CN106046376B (en) * | 2016-06-16 | 2019-02-22 | 上海交通大学 | The B of the B ' containing tert-butyl2Type Triamine monomer and its super-branched polyimide and preparation method |
| CN106221280A (en) * | 2016-08-09 | 2016-12-14 | 东莞理工学院 | Novel organic dye sensitizer containing BODIPY conjugated units and preparation method thereof |
| CN106221280B (en) * | 2016-08-09 | 2017-10-13 | 东莞理工学院 | Organic dye sensitizer containing BODIPY conjugated units and preparation method thereof |
| CN106496260A (en) * | 2016-09-23 | 2017-03-15 | 东南大学 | Two pyrroles ruddiness compound OPA BODIPY of a kind of diazole triphenylamine fluorine boron and its preparation method and application |
| CN106496260B (en) * | 2016-09-23 | 2018-03-23 | 东南大学 | Pyrroles feux rouges compound OPA BODIPY of Yi Zhong oxadiazole triphenylamine fluorine boron two and its preparation method and application |
| CN109180715A (en) * | 2018-10-12 | 2019-01-11 | 东北师范大学 | A kind of boron-dipyrromethene derivative, nanoparticle, preparation method and application |
| CN109180715B (en) * | 2018-10-12 | 2020-12-11 | 东北师范大学 | Boron-dipyrromethene derivative, nanoparticle, preparation method and application |
| CN109320536A (en) * | 2018-11-20 | 2019-02-12 | 南京工业大学 | Aza-BODIPY based near-infrared two-window fluorescent probe and preparation and application thereof |
| CN109762557A (en) * | 2019-01-14 | 2019-05-17 | 天津理工大学 | Inorganic fluorescent nanoparticle and its preparation method and application |
| CN109762557B (en) * | 2019-01-14 | 2022-01-11 | 天津理工大学 | Inorganic fluorescent nano particle and preparation method and application thereof |
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