CN101928472A - Organic boron fluorescent dyes based on 1, 8-naphthyridine - Google Patents
Organic boron fluorescent dyes based on 1, 8-naphthyridine Download PDFInfo
- Publication number
- CN101928472A CN101928472A CN2009101480522A CN200910148052A CN101928472A CN 101928472 A CN101928472 A CN 101928472A CN 2009101480522 A CN2009101480522 A CN 2009101480522A CN 200910148052 A CN200910148052 A CN 200910148052A CN 101928472 A CN101928472 A CN 101928472A
- Authority
- CN
- China
- Prior art keywords
- naphthyridines
- fluorescence
- organic boron
- naphthyridine
- fluorescent dyes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to organic boron fluorescent dyes based on 1, 8-naphthyridine, belonging to the technical field of chemistry. The structural general formula of organic boron fluorescent dyes based on the 1, 8-naphthyridine is shown in the specification, wherein R1-R15 is hydrogen or the same or different substituent groups. The invention researches and develops the new fluorescent dyes which have high fluorescence quantum yield and larger two-photon absorption cross-section, contain 1, 8-naphthyridine groups with bioactivity, and can be applied to the fields of fluorescent probes and molecule fluorescent development as a new fluorogen.
Description
Technical field
The present invention relates to a class based on 1, the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines belong to technical field of chemistry.
Background technology
Boron fluoride complexing two pyrroles's methines (Boron-dipyrrolemethene, be called for short BODIPY) fluorochrome is just to grow up in nearly twenties years, and is subjected to the extensively a kind of new fluorescent chemicals of attention.The precursor structure of dyestuff as shown in the figure, its core be about two pyrrole rings, a middle boron nitrogen five or hexa-member heterocycles, three are encircled into extraordinary conjugate planes structure, two fluorine atoms that link to each other with the boron atom are positioned at BODIPY core planar both sides.
The BODIPY fluorochrome has very excellent optical physics performance
[1-3]Show the following aspects:
The one, has higher molar absorptivity in visible and near-infrared region, usually ε＞80000cm
-1M
-1, thereby be the luminescent dye that a class has the better photosensitivity energy, be convenient to be applied in the bioanalysis field.
The 2nd, has very high fluorescence quantum yield, generally can reach more than 0.6.The quantum yield of many such dyestuffs is near 1, and still keeps the characteristic of high-fluorescence quantum yield in water, can be by the water molecules cancellation.By contrast, quantum yield may be very high in organic solvent for the fluorescence dye of many other classes, but but only show faint fluorescence in water.
The spectral quality of the 3rd .BODIPY dyestuff is highly stable, is not vulnerable to the influence of solvent polarity and pH value, the molecular probe particularly important that this character shows in different solvents for design.The BODIPY dye molecule is insensitive for pH, and this performance makes dyestuff be fit to be applied in dna sequencing and dna marker field, because all can run into the step of acid dissociation in the separation and purification process of this type of probe molecule, need guarantee that dye molecule is not destroyed.
The fluorescence spectrum peak width of the 4th .BODIPY dyestuff is narrower, and this makes dyestuff be applied to its detection sensitivity height of analysis field.When having only micro-testing sample to exist, fluorescent probe molecule just can present the existence that significant spectral response indicates sample.
The 5th .BODIPY dyestuff has higher light stability, can not cause the rapid photodegradation of dye structure because of the irradiation of stimulated luminescence in the fluorometric analysis process, thereby the variation that has guaranteed spectral signal only comes from examined sample.
Do not contain ionic charge in the 6th .BODIPY molecular structure of dye.Avoided like this having reduced interfering source because the existence of electric charge causes the possibility of other interionic electrostatic interaction in dye molecule and the solution.
Therefore, boron fluoride complexing two pyrroles's methine class fluorescence or phosphorescent coloring optical physics performance brilliance, be fit to be applied in various bioluminescence analysis fields, and innovated and developed the research focus that always becomes organic chemist round the BODIPY molecular structure of dye in recent years.The BODIPY dyestuff has high-fluorescence quantum yield, long-wave band absorbs and bigger some good photophysical properties such as molar absorptivity, they all have practical application at aspects such as fluorescent probe, laser dyes, fluorescence molecule switch, information storage, but get seldom about their two-photon absorption property research
[4-8]
Summary of the invention
In order to remedy this vacancy, we have invented the first based on 1, the organic boron fluorescence dye of the double-core of 8-naphthyridines C1.The present invention solves the experimental program that its technical problem adopts: our design is new 1 at synthetic, introduces BF on the basis of 8-naphthyridines part
2Nuclear is modified molecular structure by the space and the electronic effect that change molecule, makes novel title complex possess high-fluorescence quantum yield, wide spectral absorption, bigger molar absorptivity and bigger optical physics characteristics such as two photon absorption cross section.Based on 1, the synthetic route of novel organic boron fluorescence dye C1 of 8-naphthyridines such as figure below (synthesis step is seen the embodiment part in detail).Conventional synthetic method is inapplicable for synthetic C1, be solvent promptly at methylene dichloride or with toluene, boron trifluoride diethyl etherate is excessive, organic bases as: though in the presence of triethylamine or the diisopropyl ethyl amine be prolong the reaction times, rising temperature of reaction system or control concentration of reactants all can only obtain seldom, even can not get target product C1.But we adopt 2, and the 6-lutidine is solvent as organic alkali catalyst with a large amount of ether, obtains target title complex C1 under the condition of ice bath.
One class is based on 1, and the organoboron compound of 8-naphthyridines is characterized in that: 1, and the structure of 8-7-naphthyridine derivatives is as follows
R
1-R
10For hydrogen or be identical, different substituents.1, the 8-7-naphthyridine derivatives also can be following structure:
R
1-R
15For hydrogen or be identical, different substituents.
This class is based on 1, and the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines can be applicable to fields such as luminescent material, biological fluorescent labeling, bioluminescence video picture.
The first that relates in this patent is based on 1, and organic boron fluorescence dye C1 of 8-naphthyridines has good photophysical property:
(1) have bigger fluorescence quantum yield, fluorine boron complexes C1 shows very strong fluorescent emission (Fig. 1) in dichloromethane solution, and two emission peaks that intensity is suitable are positioned at 472 and the 518nm place, and fluorescence quantum yield is 0.975, is 0.767 in DMSO solution.In addition, C1 presents very strong yellow green light emission (Fig. 2) under solid-state.
(2) has bigger two photon absorption cross section, the maximum absorption cross section of the two-photon absorption of title complex C1 (two-photon absorption (TPA)) appears at the 730nm place and reaches 100GM (Fig. 3), the acromion (Fig. 1) at this absorption peak mapping 375nm place in single photon absorption (single-photon absorption (SPA)).And the absorption mapping at 850nm place is positioned at the maximum absorption band at 440nm place in the two-photon absorption in single photon absorbs.In part 5, introduce BF
2Nuclear has increased the symmetry charge transfer of intramolecularly from the centre to two ends, has also increased intermolecular interaction, i.e. intermolecular hydrogen bonding simultaneously.This is highly profitable to the two photon absorption cross section that increases molecule
[9,10]The two-photon absorption character of title complex C1 reports that with nearest Prasad their the two-photon absorption character of the synthetic BODIPY of research group dyestuff is suitable
[5], because title complex C1 intramolecularly contains 1 of biologically active, the 8-naphthyridinyl
[11-15]So, having more the potential using value aspect the two-photon microcosmic video picture of biomass cells.
(3) has stronger two-photon emission, the one-photon excitation fluorescence of title complex C1 (single-photon-excitedfluorescence (SPEF)) is compared with two-photon fluorescence excitation (two-photon-excited fluorescence (TPEF)), the position at emission peak type and peak all very similar (Fig. 4), though this show molecule by single photon or two-photon excitation to different excited state, finally all get back to identical fluorescence excitation attitude.The acromion on the left side is littler than corresponding emission peak in the single photon fluorescent signal in the two-photon fluorescence signal, and this may be because the cause of self-absorption.In addition, the relation of the up-conversion fluorescence intensity of C1 and excitating light strength can well be used secondary relational expression y=a+bx
2Match (Fig. 5).Square being directly proportional of the intensity of two-photon fluorescence and incident intensity, slope is 2.19, and this is a very important feature of two-photon fluorescence excitation, and this shows does not have linear absorption to take place.
The most outstanding beneficial effect of this patent is, synthesized the first based on 1, the organic boron fluorescence dye of the double-core of 8-naphthyridines, significant photophysical property makes its actual application prospect with fluorescent probe, bioluminescence video picture etc., for the development and the exploitation of fluorescence or phosphorescent coloring provides new approaches.
Description of drawings
Fig. 1 .C1 is in dichloromethane solution (10
-5Single photon absorption (-) and single photon fluorescent emission M) (---), excite at 440nm
The solid state fluorescence emmission spectrum of Fig. 2 .C1 excites at 470nm
Fig. 3 .C1 is in acetonitrile solution (1.4 * 10
-5M) two-photon absorption
The single photon emission of Fig. 4 .C1 (methylene dichloride, 10
-6M) and two-photon emission (acetonitrile, 10
-5M, λ
Ex=780nm)
The up-conversion fluorescence intensity of Fig. 5 .C1 and the graph of a relation of excitating light strength
The crystalline structure figure of Fig. 6 .C1
Embodiment
Title complex C1 is a brand-new compound, and the synthetic of its raw material is to improve to some extent on the synthetic method of bibliographical information
[10]Part 5 (0.15g 0.43mmol) is dissolved in anhydrous diethyl ether (100mL) adds 2, slowly drip BF after 6-lutidine (2mL), ice bath are cooled to 5 ℃ with system
3Et
2O (4mL), drip half an hour.System adds saturated NaHCO react 5h under ice bath after
3The aqueous solution (50mL), water extracted with diethyl ether (3 * 100mL).Merge organic phase, it is inferior to give a baby a bath on the third day after its birth with deionized water, anhydrous MgSO
4Drying is filtered, and column chromatography for separation is used CHCl
3As eluent.Finally obtaining C1 is the glassy yellow powder, productive rate: 40%.Dichloromethane solution by Skellysolve A diffusion C1 obtains being used for the pale yellow crystals (Fig. 6) that the X-ray single crystal diffraction is analyzed.
1H?NMR(400MHz，CDCl
3，298K，relative?to?Me
4Si)δ2.60(s，3H，4-Me?of?naphthyridylrings)，2.70(s，3H，2-Me?of?naphthyridyl?rings)，7.06(s，1H，naphthyridyl?proton)，7.16(d，J＝9.1Hz，1H，naphthyridyl?proton)，8.16(d，J＝9.3Hz，1H，naphthyridyl?proton)；EI?mass?spectrum：m/z440.
Reference
1.R.P.Haugland，Handbook?of?Fluorescent?Probes?and?Research?Chemicals，6th?ed.1996.
2.J.Karolin，L.B.A.Johansson，L.Strandberg?and?T.Ny，J.Am.Chem.Soc.，1994，116，7801-7806.
3.N.J.Meltola，A.E.Soini?and?P.E.Hanninen，Journal?of?Fluorescence，2004，14，129-138.
4.G.Zhang，J.Chen，S.J.Payne，S.E.Kooi，J.N.Demas，and?C.L.Fraser，J.Am.Chem.Soc.，2007，129，8942-8943.
5.Q.Zheng，G.Xu，and?P.N.Prasad，Chem.Eur.J.，2008，14，5812-5819.
6.E.Cogné-Laage，J.F.Allemand，O.Ruel，J.B.Baudin，V.Croquette，M.Blanchard-Desce?and?L.Jullien，Chem.Eur.J.，2004，10，1445-1455.
7.L.Porrès，O.Mongin?and?M.Blanchard-Desce，Tetra.Lett.，2006，47，1913-1917.
8.M.Halik，W.Wenseleers，C.Grasso，F.Stellacci，E.Zojer，S.Barlow，J.L.Brédas，J.W.Perry?and?S.R.Marder，Chem.Commun.，2003，1490-1491.
9.M.Albota，D.Beljonne，J.-L.Brédas，J.E.Ehrlich，J.-Y.Fu，A.A.Heikal，S.E.Hess，T.Kogej，M.D.Levin，W.W.Webb，X.-L.Wu?and?C.Xu，Science，1998，281，1653-1656.
10.Z.Liu，P.Shao，Z.Huang，B.Liu，T.Chen?and?J.Qin，Chem.Comm.，2008，2260-2262.
11.P.C.Appelbaum?and?P.A.Hunter，International?J.Antimicrobial?Agents，2000，16，5-15.
12.P.L.Ferrarini，C.Manera?and?C.Mori，et?al.，Il?Farmaco?1998，53，741-746.
13.M.Badawneh，C.Manera?and?C.Mori，et?al.，Il?Farmaco?2002，57，631-639.
14.K.Tomita，Y.Tsuzuki?and?K.Shibamori，et?al.，J.Med.Chem.2002，45，5564-5575.
15.E.J.Barreiro，C.A.Camara?and?H.Verli，et?al.，J.Med.Chem.2003，46，1144-1152.
Claims (5)
1. a class is based on 1, and the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines is characterized in that 1,8-naphthyridines analog derivative and fluorine boron caryogamy position.
2. a class according to claim 1 is based on 1, and the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines is characterized in that 1, and the structure of 8-naphthyridines analog derivative is as follows:
R
1-R
10For hydrogen or be identical or different substituting group.
3. a class according to claim 1 is based on 1, and the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines is characterized in that 1, and the structure of 8-naphthyridines analog derivative can also be as follows:
R
1-R
15For hydrogen or be identical or different substituting group.
4. a class according to claim 1 is based on 1, and the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines is characterized in that 1,8-naphthyridines analog derivative and single, double or polyfluoro boron caryogamy position.
5. a class according to claim 1 is based on 1, and the organic boron fluorescence or the phosphorescent coloring of 8-naphthyridines is characterized in that can be applicable to fields such as luminescent material, biological fluorescent labeling, bioluminescence video picture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101480522A CN101928472A (en) | 2009-06-24 | 2009-06-24 | Organic boron fluorescent dyes based on 1, 8-naphthyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101480522A CN101928472A (en) | 2009-06-24 | 2009-06-24 | Organic boron fluorescent dyes based on 1, 8-naphthyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101928472A true CN101928472A (en) | 2010-12-29 |
Family
ID=43367918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101480522A Pending CN101928472A (en) | 2009-06-24 | 2009-06-24 | Organic boron fluorescent dyes based on 1, 8-naphthyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101928472A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8715529B1 (en) * | 2012-01-23 | 2014-05-06 | Arrowhead Center, Inc. | Synthesis and applications of triazaborolopyridinium compounds and substituted triazaborolopyridinium compounds and methods of use |
| CN108059638A (en) * | 2017-02-16 | 2018-05-22 | 昆明医科大学 | Fluorescence probe of one kind mark amyloid and preparation method and application |
-
2009
- 2009-06-24 CN CN2009101480522A patent/CN101928472A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8715529B1 (en) * | 2012-01-23 | 2014-05-06 | Arrowhead Center, Inc. | Synthesis and applications of triazaborolopyridinium compounds and substituted triazaborolopyridinium compounds and methods of use |
| CN108059638A (en) * | 2017-02-16 | 2018-05-22 | 昆明医科大学 | Fluorescence probe of one kind mark amyloid and preparation method and application |
| CN108059638B (en) * | 2017-02-16 | 2019-12-31 | 昆明医科大学 | Amyloid-labeled fluorescent probe and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tao et al. | Tuning the photo-physical properties of BODIPY dyes: Effects of 1, 3, 5, 7-substitution on their optical and electrochemical behaviours | |
| CN102702768B (en) | Novel red BODIPY fluorescent dye and preparation method and application thereof | |
| Gareis et al. | Phenol/phenolate-dependent on/off switching of the luminescence of 4, 4-difluoro-4-bora-3a, 4a-diaza-s-indacenes | |
| CN102993763B (en) | Single charge boron fluroride complexing dipyrrole methenyl fluorochrome and application thereof | |
| Yang et al. | Organic nanostructure-based probes for two-photon imaging of mitochondria and microbes with emission between 430 nm and 640 nm | |
| Aranda et al. | Vinyl-diazine triphenylamines and their N-methylated derivatives: synthesis, photophysical properties and application for staining DNA | |
| Zhou et al. | Dicyanoboron diketonate dyes: Synthesis, photophysical properties and bioimaging | |
| CN107098923A (en) | One class feux rouges targets fluorescent dye and preparation method thereof and purposes near infrared emission lysosome | |
| CN107353302A (en) | A kind of carborane derivative material based on carbazole and preparation method and application | |
| CN103194085A (en) | Novel BODIPY flourescent dye with adjustable emission wavelength and preparation method thereof | |
| Yang et al. | Synthesis, spectroscopic characterization, one and two-photon absorption properties, and electrochemistry of truxene π-expanded BODIPYs dyes | |
| Lakshmi et al. | Synthesis, spectral and electrochemical properties of phenylated boron-dipyrromethenes | |
| Zhang et al. | Chiral benzo-fused Aza-BODIPYs with optical activity extending into the NIR range | |
| Chen et al. | Two novel two-photon excited fluorescent pH probes based on the A-π-D-π-A system for intracellular pH mapping | |
| Wang et al. | Design and synthesis of an AIEgen with multiple functions: Solvatochromism, chromism, lipid droplet imaging | |
| Willis et al. | NIR‐Circularly Polarized Luminescence from Chiral Complexes of Lanthanides and d‐Metals | |
| CN104650610A (en) | Asymmetric near-infrared BODIPY fluorescent dye as well as preparation method and application thereof | |
| Balzani et al. | A comparison of shuttling mechanisms in two constitutionally isomeric bistable rotaxane-based sunlight-powered nanomotors | |
| CN107011213B (en) | Multi-channel luminous fluorescent probe and preparation method and application thereof | |
| CN101928472A (en) | Organic boron fluorescent dyes based on 1, 8-naphthyridine | |
| CN102786550A (en) | Iridium complex possessing open-type phosphorescent light emission, its preparation method and its application | |
| Zhang et al. | Enhanced brightness and electron affinity of terrylenediimide with sulfone-bridged substituents on the bay region | |
| Rao et al. | Synthesis of boron-dipyrromethene–ferrocene conjugates | |
| Kálai et al. | Synthesis of paramagnetic BODIPY dyes as new double (spin and fluorescence) sensors | |
| Mishra et al. | New push–pull type dendritic stilbazolium dyes: synthesis, photophysical and electrochemical investigation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101229 |