CN104356680B - Water solublity PnO2-PODIPY/PnO2-azaPODIPY fluorescent dye and preparation method thereof - Google Patents
Water solublity PnO2-PODIPY/PnO2-azaPODIPY fluorescent dye and preparation method thereof Download PDFInfo
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Abstract
Water solublityPnO2‑PODIPY/PnO2AzaPODIPY fluorescent dye and preparation method thereof, relates to a kind of dyestuff and preparation method thereof, and described fluorescent dye is to develop with methine two pyrroles/aza-methylene two pyrroles complexation PnO2 (Pn=P, As, Sb, Bi)PnO2‑PODIPY/PnO2AzaPODIPY is novel a series of dyestuffs of parent nucleus.Its formula is as shown in Formulas I/II.This fluorescent dye has the advantages such as classical conventional dyes BODIPY/azaBODIPY spectrum property.Although central atom Pn is hexa-coordinate, but this dyestuff is stable in air and aqueous solution, does not decomposes.The characteristic that this compounds highlights is excellent water solublity, has certain cell-permeant simultaneously, can be used for biological stain.This kind of new dye of the present invention has relatively new spectral characteristic, can apply to fluorescence imaging aspect.
Description
Technical field
The present invention relates to a kind of dyestuff and preparation method thereof, particularly relate to a kind of water solublity PnO2-PODIPY/PnO2-
AzaPODIPY fluorescent dye and preparation method thereof.
Background technology
The noinvasive that carries out life or internal physiology, pathological process on molecule and cellular level, realtime imaging, can be
Disease is i.e. made the great meaning of Accurate Diagnosis before not yet there is morphological change by body.Fluorescent dye is as functional type dyestuff
It is used widely in this field, gets most of the attention.
In numerous dyestuffs, fluorine boron two pyrroles's methine (BF2-dipyrrolemethene is called for short BODIPY) class fluorescence dye
Material, has fluorescence quantum yield height, good light stability, absorbs and launch wavelength and be positioned at visible region, it is easy to regulation and control etc. are many excellent
Putting and be widely studied, its molecule is easily modified.
Azepine fluorine boron two pyrroles's methine (BF2-azadipyrrolemethene is called for short azaBODIPY) dyestuff is in recent years
The novel near infrared fluorescent dye of class received significant attention, such dyestuff has absorption and transmitting wavelength is long, good light stability,
The features such as half-peak width, quantum yield are high, molar extinction coefficient is big, have broad application prospects at field of bioanalysis,
Through becoming the focus of Recent study.But there is the deficiency that molecule difficulty is modified.
In recent years, dipyrromethene/aza-methylene two pyrroles complexation BF2 and the BODIPY/azaBODIPY that generates obtain
To developing widely, Shen research group and Burgess research group have done systematic account.And the BODIPY/ now reported
AzaBODIPY, due to its hydrophobicity, limits its internal/external application.Dipyrromethene/aza-methylene two pyrroles is as joining
Body, complexation Si and transition metal, also there are some to report.The such as compound of the SiR3-BODIPY centered by Si, but stability
Very poor；And the M-BODIPY's centered by metal ion (such as Zn, Ni, Sn, Cu, Co, Fe etc.) is metal-dislocated, stablize the most not
Good, quantum yield is the lowest.Their actual application is the most impossible.But, dipyrromethene/aza-methylene two pyrroles makees
For part, the dyestuff of complexation PnO2 (Pn=P, As, Sb, Bi) was never reported and investigated.
Long wavelength's fluorescent dye, reduces self-absorption and the interference of autofluorescence of biological substance in vivo, improves the spirit of detection
Sensitivity and selectivity, raising fluorescence imaging (treatment) efficiency.The universal quantum yield of long wavelength's fluorescent dye is low, but it is firm to increase molecule
Property/freeze rotation can be effectively improved fluorescence quantum yield.Therefore, seeking breakthrough is modified in parent nucleus rigidity.Here, we introduce
New strategy design, the new dye PnO2-PODIPY/PnO2-developed from the BODIPY/azaBODIPY that classics are traditional
(PnO2-phosphorusdipyrrolemethene is called for short PnO2-PODIPY to azaPODIPY; PnO2-
Azaphosphorusdipyrrolemethene, is called for short PnO2-azaPODIPY).This dyestuff is with dipyrromethene/nitrogen
The PO2-BODIPY/PO2-azaBODIPY dyestuff of miscellaneous dipyrromethene complexation PnO2 development.It is anticipated that design novel
PnO2-PODIPY/PnO2-azaPODIPY dyestuff provides new-type dyestuff for the development further applying biological study, abundant
The kind of dye families.As new-type dyestuff, at the spectrum property possessing classical traditional BODIPY/azaBODIPY dyestuff
Outside advantage, maximum feature is good water solublity.
Summary of the invention
It is an object of the invention to provide a kind of water solublity PnO2-PODIPY/PnO2-azaPODIPY fluorescent dye and
Preparation method, this fluorescent dye has a characteristic that central atom is to join with the six of Pn (Pn=P, As, Sb, Bi) complexation
The fluorescent dye of position, has good water solublity, and dyestuff the most of the present invention has good cell in terms of biologic applications
Permeable membrane.
It is an object of the invention to be achieved through the following technical solutions:
A first aspect of the present invention, the present invention is directed to the deficiency of the BODIPY/azaBODIPY dyestuff of existing existence, at it
On the basis of improve, it is provided that a class formation is simple, long wavelength, and has the new compound PnO2-of good cell-permeant
PODIPY/PnO2-azaPODIPY.The having structure formula I/II that it has:
Wherein, R1-R7 is selected from-H ,-Ph ,-Me ,-Et ,-OH ,-OMe ,-OEt ,-N (Me)2、-N(Et)2Deng group；
R8Selected from R8-1、R8-2、R8-3、R8-4、R8-5、R8-6、R8-7And R8-8Deng group.
R1-R7 is selected from groups such as-Ph ,-Me ,-Ar, naphthyl, pyrenyls.
Dotted line, represents and does not fuse phenyl ring and fusion two kinds of molecular structures of phenyl ring.
The novel fluorescence dyestuff with above-mentioned formula I/II can be used for biological stain, cell imaging, enumerates in examples of implementation
By one of them application in cell imaging, demonstrate that this compounds has good stability, have well
Water solublity, has certain permeable membrane simultaneously.This fluorochrome of the present invention the most also has the spectral characteristic of novelty.
Another aspect of the present invention is the brand-new PnO2-PODIPY/PnO2-of hexa-coordinate centered by Pn atom
AzaPODIPY fluorescent dye, prominent features is good water solublity.
Another aspect of the invention: a kind of new-type method preparing fluorescent dye of the present invention, described method are provided
Comprise the steps:
(1) under argon shield, corresponding aldehyde and corresponding pyrroles are dissolved in dichloromethane, add a trifluoro second
Acid, is stirred at room temperature, reaction overnight.After terminating with TLC detection reaction, add DDQ, stir 30 minutes.Reactant liquor ice cancellation.With
Dichloromethane extracts, decompression distillation, and residue silicagel column purifies, and developing solvent is dichloromethane/normal hexane, obtains methylene two
Pyrroles's III solid.
Wherein, R1-R7 is selected from-H ,-Ph ,-Me ,-Et ,-OH ,-OMe ,-OEt ,-N (Me)2、-N(Et)2Deng group；
R8Selected from R8-1、R8-2、R8-3、R8-4、R8-5、R8-6、R8-7And R8-8Deng group.
(2) under unlimited system, step (1) is obtained solid III and is dissolved in dichloromethane, be subsequently adding three second
Amine, reacts half an hour.Finally, PnOCl is added3 ((Pn=P, As, Sb, Bi)), reacts 3 hours.Mixture ice cancellation.
Extracting with dichloromethane, decompression distillation, it is dichloromethane/normal hexane that residue silicagel column purifies developing solvent, obtains solid I.
(3) under open system, add the substituted pyrroles of phenyl, glacial acetic acid (, acetic anhydride, under ice bath add sodium nitrite, room
Temperature reaction 0.5 h, is transferred to 80 ° of C and reacts 0.5 h, and reaction terminates.It is slowly added to frozen water cancellation reaction, has solid and separate out,
Filter out solid.Filter cake dichloromethane dissolves, and with dichloromethane as eluent, crosses post with aluminium oxide mutually for fixing, is spin-dried for molten
Agent, obtains azepine methine two pyrroles's IV solid.
R1-R7 is selected from groups such as-Ph ,-Me ,-Ar, naphthyl, pyrenyls.
Dotted line, represents and does not fuse phenyl ring and fusion two kinds of molecular structures of phenyl ring.
(4) solid IV will be obtained, and under open system, add dichloromethane, triethylamine, continue stirring 30 minutes.Slowly
Instill and add PnOCl3 ((Pn=P, As, Sb, Bi)), is stirred at room temperature reaction 8 hours.Add frozen water cancellation reaction, dichloro
Methane separatory extracts, and organic layer is washed, and anhydrous sodium sulfate is dried, and is spin-dried for, column chromatography, and developing solvent is dichloromethane/normal hexane,
To the solid II having metallic luster.
Wherein in II structure, R " selected from-H ,-OH ,-OMe ,-OEt ,-N (Me)2With-N (Et)2；Dotted line, represents and does not fuse benzene
Ring and fusion two kinds of molecular structures of phenyl ring.
The present invention improves existing BODIPY/azaBODIPY fluorescent dye deficiency spectrally, the PnO2 of design synthesizing new
The PnO2-PODIPY/PnO2-azaPODIPY fluorescent dye of complexation.This fluorochrome has the feature of good light stability, with
Time this kind of dyestuff have have excellence water solublity, there is cell-permeant, in terms of can apply to biological dye, cell imaging
Research.
Accompanying drawing explanation
Fig. 1 is the general structure I of the novel fluorescence dyestuff of the present invention.
Fig. 2 is the general structure II of the novel fluorescence dyestuff of the present invention.
Fig. 3 is the phosphorus spectrum of the novel fluorescence dyestuff I-1 of the present invention.
Fig. 4 is the absorption (λ of the novel fluorescence dyestuff III-1 of the present inventionabs = 450 nm in CH2Cl2).
Fig. 5 is the absorption spectrum (a: λ of the novel fluorescence dyestuff I-1 of the present inventionabs = 513 nm in CH2Cl2; b:
λabs = 505 nm in H2O) with fluorescence spectrum (c: λem = 520 nm in H2O).Spectrum before and after main contrast's PO2 complexation
The performance of behavior.
Fig. 6 is the CH of the fluorescent dye III-1 of the present invention2Cl2Color (left figure) in solution；Fluorescent dye I-1 of the present invention
The color (right figure) dissolved in pure water.
Fig. 7 is the phosphorus spectrum of the novel fluorescence dyestuff IIa-1 of the present invention.
Fig. 8 is the absorption (λ of the novel fluorescence dyestuff IVa-1 of the present inventionabs = 597 nm in CH2Cl2).
Fig. 9 is the absorption (a: λ of the novel fluorescence dyestuff IIa-1 of the present inventionabs = 625 nm in H2O) with fluorescence light
Spectrum (b: λem = 675 nm in H2O).The performance of spectrum behavior before and after main contrast's PO2 complexation.
Figure 10 is the CH of the novel fluorescence dyestuff IVa-1 of the present invention2Cl2In color (left figure)；Fluorescent dye of the present invention
The color (right figure) that IIa-1 dissolves in pure water.
Figure 11 is the fluorescence micrograph to living cells Hep-2 cell dyeing of the novel fluorescence dyestuff IIa-1 of the present invention.
Instrument used is confocal laser scanning microscope, CLSM.Model: ArrayScan VTI HCS Reader.Lasing fluorescence leads to
Road: 590 nm.
Detailed description of the invention
Illustrated embodiment below in conjunction with the accompanying drawings, the invention will be further described.
Unless otherwise indicated, term used herein has following implication.
Wherein, R1-R7 is selected from-H ,-Ph ,-Me ,-Et ,-OH ,-OMe ,-OEt ,-N (Me)2、-N(Et)2Deng group, preferentially
Elect-Me as；R8Selected from R8-1、R8-2、R8-3、R8-4、R8-5、R8-6、R8-7And R8-8Deng group, R8Preferentially elect p-nitrophenyl as.
In formula II of the present invention, R1-R7 is selected from groups such as-Ph ,-Me ,-Ar, naphthyl, pyrenyls；Dotted line, represents and does not fuses
Phenyl ring (a) and fusion phenyl ring (b) two kinds of molecular structures.R1-R7 preferentially elects-Ph as;Preferential employing does not fuse the molecule of phenyl ring
Structure.
The present invention provides a kind of and new-type prepares fluorescent dye PnO2-PODIPY/PnO2-azaPODIPY of the present invention
Method, first prepare intermediate III/IV, the intermediate of secondly preparation and PnOCl3 (Pn=P, As, Sb, Bi) network
Close, finally hydrolyze, obtain compound of the present invention.Specific embodiments is as described below.
(1) under argon shield, corresponding aldehyde and corresponding pyrroles are dissolved in dichloromethane, add a trifluoro second
Acid, is stirred at room temperature, reaction overnight.Terminating with TLC detection reaction, DDQ adds, and stirs 30 minutes.Reactant liquor ice cancellation.With two
Chloromethanes extracts, decompression distillation, and residue silicagel column purifies, and developing solvent is dichloromethane/normal hexane, obtains solid III.
2-15 hour response time.Corresponding aldehyde is 1:2 with the molar ratio of corresponding pyrroles.
(2) under unlimited system, will obtain solid III and be dissolved in dichloromethane, and be subsequently adding triethylamine, reaction half is little
Time.Finally, PnOCl is added3 (Pn=P, As, Sb, Bi), reacts 8 hours under room temperature.Frozen water is slowly added to, carries out water
Solve reaction.Then extracting with dichloromethane, decompression distillation, it is dichloromethane/normal hexane that residue silicagel column purifies developing solvent,
Obtain solid I.
In a preferred embodiment, reaction temperature 25 degree, room temperature.1-5 hour response time.
Solid III is 1:5 with the molar ratio of triethylamine；Solid III and PnOCl3 (Pn=P, As, Sb, Bi)
Molar ratio be 1:10.Being slowly added to frozen water, be hydrolyzed reaction, completes the complexation of PnO2, generates dyestuff I.
(3) open wide under system, add the substituted pyrroles of phenyl, glacial acetic acid, acetic anhydride, under ice bath, add sodium nitrite, room
Temperature reaction 0.5 h, is transferred to 80 ° of C and reacts 0.5 h, and reaction terminates.Add frozen water cancellation reaction, have solid and separate out, filter
Go out solid.Filter cake dichloromethane dissolves, and with dichloromethane as eluent, crosses post with aluminium oxide mutually for fixing, is spin-dried for solvent,
To solid IV.
Pyrroles is strictly 2:1 with the molar ratio of sodium nitrite.
(4) solid IV will be obtained, and under open system, add dichloromethane, triethylamine, continue stirring 50 minutes.Slowly drip
Enter PnOCl3 (Pn=P, As, Sb, Bi), is stirred at room temperature reaction 3 hours.Add frozen water cancellation reaction, dichloromethane separatory
Extraction, organic layer washing, anhydrous sodium sulfate is dried, and is spin-dried for, column chromatography, and developing solvent is dichloromethane/normal hexane, obtains there is metal
The solid II of gloss.
Solid IV is 1:5 with the molar ratio of triethylamine；Solid IV and PnOCl3 (Pn=P, As, Sb, Bi's)
Molar ratio is 1:8.Being slowly added to frozen water, be hydrolyzed reaction, completes the complexation of PnO2, generates solid II.
The present invention is used the compound of the novel fluorescence dyestuff that said method synthesizes, uses nuclear magnetic resonance map to include1H
NMR and31P NMR, mass spectrum determines its structure.
PnO2-PODIPY/PnO2-azaPODIPY fluorescent dye of the present invention has a characteristic that
Described compound great advantage is to have good water solublity, can be used for the cell imaging under physiological environment.
The fluorescence emission wavelengths of described compound II is more than 600 nm, can be used for cell imaging, it is to avoid biology self
Fluorescence background disturbs.
Described compound has the light stability of excellence.
Described compound side effect is little, and raw material is easy to get, and structure is classical, simply, it is easy to preparation, easy industrialization, through two steps
Reaction i.e. can get target compound.
These features of the invention and advantage and other feature and advantage are concrete with the present invention with reference to the following drawings
Will become clear from after embodiment.
During in consideration of it, fluorescent dye of the present invention carries out biological stain, need other components, such as solvent, pH regulator
Agent.
After the compounds of this invention carries out biological sample dyeing, sample is analyzed in fluorescence-activated cell sorter device,
The transmitting light that determinator is produced by the fluorescent dye excited.
The above-mentioned fluorescent dye of the present invention can be formulated directly into aqueous solution, it is possible to stable existence.
Embodiment 1
Prepare fluorescent dye I-1
(1) synthesis of intermediate compound III-1.
Under argon shield, p-nitrophenyl aldehyde (300 mg, 0.19 mmol) and 2,4-dimethyl pyrrole (0.51 ml,
0.49 mmol) it is dissolved in dichloromethane (20 ml), add a trifluoroacetic acid, be stirred at room temperature, react 12 h.Examine with TLC
Measured reaction terminates, DDQ(900 mg) add, stir 30 minutes.Reactant liquor ice cancellation.Extract with dichloromethane, decompression distillation,
Residue silicagel column purifies, and developing solvent is dichloromethane/normal hexane, obtains yellow solid III-1(183.2 mg, 30 %).
(2) synthesis of PO2-PODIPY dyestuff I-1.
Under unlimited system, solid III-1(64.2 mg will be obtained) it is dissolved in dichloromethane (20 ml), it is subsequently adding
Triethylamine (0.7 ml), reacts 10 minutes.Then, add phosphorus oxychloride (1.2 ml), react 1 hour under room temperature.Frozen water is delayed
Slow addition, be hydrolyzed reaction.Then extract with dichloromethane (50 ml), MgSO4It is dried, distillation of then reducing pressure, surplus
It is dichloromethane/normal hexane that excess silicagel column purifies developing solvent, obtains pink solid I-1 (58.1 mg, 76%).1H
NMR (500 MHz, CDCl3) 8.46 (d, J = 7.5 Hz, 2H), 7.69 (d, J = 7.5 Hz, 2H),
6.25 (s, 2H),2.77 (s, 6H), 2.54 (s, 6H). 31P NMR (202 MHz, CDCl3) -0.5. ESI-
MS: m/z = 383.1.
Embodiment 2
Prepare fluorescent dye IIa-1
(1) synthesis of midbody compound IVa-1
Under open system, add 2,4-Diphenyl Pyrrole (43.8 mg, 0.2 mmol), glacial acetic acid (1 ml), acetic anhydride
(0.4 ml), adds sodium nitrite (6.9 mg, 0.1 mmol), room temperature reaction 0.5 h under ice bath, be transferred to 80 ° of C reactions
0.5 h, reaction terminates.Add frozen water cancellation reaction, have solid and separate out, filter out solid.Filter cake dichloromethane dissolves, with
Dichloromethane is eluent, crosses post with aluminium oxide mutually for fixing, is spin-dried for solvent, obtains bluish violet solid IVa-1(35.9 mg,
80%).1H NMR (400 MHz, CDCl3) 8.04-8.08 (m, 4H), 7.94-7.97 (m, 4H), 7.33-
7.57 (m, 12H), 7.21 (s, 2H) (NH not observed). 13C NMR (CDCl3) 155.1, 149.6,
142.7, 133.7, 132.2, 130.1, 129.2, 129.1, 128.3, 128.0, 126.6, 114.9.
(2) synthesis of PO2-azaPODIPY dyestuff IIa-1.
Under unlimited system, solid IVa-1(20.3 mg will be obtained) it is dissolved in dichloromethane (20 ml), it is subsequently adding
Triethylamine (0.5 ml), reacts 10 minutes.Then, add phosphorus oxychloride (1 ml), react 1 hour under room temperature.Frozen water is slow
Adding, be hydrolyzed reaction.Then extract with dichloromethane (50 ml), MgSO4It is dried, distillation of then reducing pressure, residue
It is dichloromethane/normal hexane that thing silicagel column purifies developing solvent, obtains blue solid IIa-1(19.6 mg, 85%).1H NMR
(500 MHz, CDCl3) 8.14-8.17 (m, 4H), 7.69 (d, J = 7.0 Hz, 4H), 7.63 (d, J =
7.0 Hz, 6H), 7.48 (t, J = 7.0 Hz, 2H), 7.32-7.35 (m, 6H). 31P NMR (202 MHz,
CDCl3) 0.3. ESI-MS: m/z =511.2.
The compound IIa-1 dyeing to living cells Hep-2 cell is observed: by compound under confocal laser scanning microscope, CLSM
IIa-1(concentration 5.0 × 10-5M, 40PBS solution) add the DMEM culture fluid (10% that the Hep-2 cell of 2 ml is conventional
Hyclone, 0.2%NaHCO3Aqueous solution, penicillin 100 U/mL).Adjusting cell concentration is 1 × 105mL-1, it is placed in sterility cover
In the culture dish of slide, 37 DEG C of 5%CO2Incubator places 1 h, cleans 3 times with the DMPE not having serum, and removing does not has adherent
Cell, obtains adherent Hep-2 cell for experiment.Before fluorescence imaging, rinse with PBS buffer solution.Embodiment 2 compound pair
The laser confocal imaging of Hep-2 cell.As seen from the figure, after compound dyes, one group of cell of 30 minutes is fostered at 37 DEG C
Presenting strong fluorescence, cell is high-visible.Illustrate that this kind of dyestuff has good imaging effect to Hep-2 cell.Instrument
Confocal laser scanning microscope, CLSM, model ArrayScan VTI HCS Reader.Laser emission channel 561 nm.
Above content is to combine concrete optimal enforcement mode further description made for the present invention, it is impossible to assert
Being embodied as of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
Core idea of the present invention with the parts such as methine two pyrroles/aza-methylene two pyrroles and PnO2 (Pn=P, As, Sb,
Bi) on the premise of complexation, it is also possible to make some simple deductions and replacement, all should be considered as belonging to protection scope of the present invention.
For the those of ordinary skill in the territory of the technical field of the invention, in the phase being used for dyeing based on fluorescent dye of the present invention
Under the consideration of same-action mechanism, it is also possible to make some simple inferences, obtain other application purpose of the compound of the present invention, all
Protection scope of the present invention should be considered as belonging to.
Claims (1)
1. water solublity PnO2The preparation method of-PODIPY fluorescent dye, it is characterised in that described method comprises the steps:
(1) under argon shield, corresponding aldehyde and corresponding pyrroles are dissolved in dichloromethane, add a trifluoroacetic acid, room
Temperature stirring, reaction overnight；After terminating with TLC detection reaction, add DDQ, stir 30 minutes；Reactant liquor ice cancellation, uses dichloro
Methane extracts, decompression distillation, and residue silicagel column purifies, and developing solvent is dichloromethane/normal hexane, obtains methine two pyrroles
III solid；
Wherein, wherein R1-R7Selected from-H ,-Ph ,-Me ,-Et ,-OH ,-OMe ,-OEt ,-N (Me)2、-N(Et)2Group；R8It is selected from
R8-2、R8-3、R8-4、R8-5、R8-6、R8-7And R8-8Group；
(2) under open system, step (1) is obtained solid III and is dissolved in dichloromethane, be subsequently adding triethylamine, reaction half
Hour；Finally, PnOCl is added3 , Pn=P, As, Sb, Bi, react 3 hours；Mixture ice cancellation, extracts with dichloromethane
Taking, decompression distillation, it is dichloromethane/normal hexane that residue silicagel column purifies developing solvent, obtains solid I；
Described solid I formula is:；
In Formulas I, wherein R1-R7Selected from-H ,-Ph ,-Me ,-Et ,-OH ,-OMe ,-OEt ,-N (Me)2、-N(Et)2Group；R8It is selected from
R8-2、R8-3、R8-4、R8-5、R8-6、R8-7And R8-8Group；Central atom Pn is selected from P, As, Sb, Bi；
。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702768A (en) * | 2012-06-04 | 2012-10-03 | 天津理工大学 | Novel red BODIPY fluorescent dye and preparation method and application thereof |
| CN103333682A (en) * | 2013-07-24 | 2013-10-02 | 南京大学 | Proportional near-infrared fluorescent probe as well as preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702768A (en) * | 2012-06-04 | 2012-10-03 | 天津理工大学 | Novel red BODIPY fluorescent dye and preparation method and application thereof |
| CN103333682A (en) * | 2013-07-24 | 2013-10-02 | 南京大学 | Proportional near-infrared fluorescent probe as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Aluminium complexes of N2O2-type dipyrrins: the first hetero-multinuclear complexes of metallo-dipyrrins with high fluorescence quantum yields;Chusaku Ikeda et al.;《Chem. Commun.》;20090316;第2544-2546页 * |
| Synthesis of Triple-Stranded Complexes Using Bis(dipyrromethene) Ligands;Zhan Zhang et al.;《Inorg. Chem.》;20101111;第49卷;第11550-11555页 * |
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