CN103242355A - BODIPY (Boron Dipyrromethene) compound-based lysosome fluorescence probe as well as preparation method and applications thereof - Google Patents
BODIPY (Boron Dipyrromethene) compound-based lysosome fluorescence probe as well as preparation method and applications thereof Download PDFInfo
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- CN103242355A CN103242355A CN2013101740456A CN201310174045A CN103242355A CN 103242355 A CN103242355 A CN 103242355A CN 2013101740456 A CN2013101740456 A CN 2013101740456A CN 201310174045 A CN201310174045 A CN 201310174045A CN 103242355 A CN103242355 A CN 103242355A
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- LZQPWYLEDZOGDF-FQHZWJPGSA-N CCOC(/C(/C#N)=C/c1ccc(C(c(cc2)cc3c2OCCOCCOCCOCCO3)=C2[N+]3=C(/C=C(/C(OCC)=O)\C#N)C=C2)[n]1B3F)=O Chemical compound CCOC(/C(/C#N)=C/c1ccc(C(c(cc2)cc3c2OCCOCCOCCOCCO3)=C2[N+]3=C(/C=C(/C(OCC)=O)\C#N)C=C2)[n]1B3F)=O LZQPWYLEDZOGDF-FQHZWJPGSA-N 0.000 description 1
- 0 CCOC(C(C#N)=CC(C=C1)=[N+](B([n]2c3ccc2C=C(*)C#N)F)C1=C3c1ccccc1)=O Chemical compound CCOC(C(C#N)=CC(C=C1)=[N+](B([n]2c3ccc2C=C(*)C#N)F)C1=C3c1ccccc1)=O 0.000 description 1
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Abstract
The invention provides a near infrared BODIPY (Boron Dipyrromethene) compound-based molecular fluorescence probe which has the following structure, wherein the substituent group Ar is one of the following four substituent groups described in the specification. The BODIPY probe with an alpha bit containing a strong electrondrawing group is synthesized for the first time, the absorption spectrum red shift of the fluorescence probe can achieve 606-633nm through the introduced substituent group, and the emission peak can achieve 616-646nm. The BODIPY molecule is a favorable fluorescence, can be used for specifically marking lysosome in biological cells, and can emit light through the self molecules, and the absorption and emission of the BODIPY molecule are close to the near-infrared zone; and in addition, the fluorescence probe has the advantages of high mole extinction coefficient, acute emission peak, high fluorescence quantum yield and the like, and has attractive application prospects on the lysosome marking application.
Description
Technical field
The present invention relates to that near infrared BODIPY and the method for making thereof of strong electron-withdrawing group group contained in a series of α position and it is as fluorescent probe lysosomal application in labeled cell.
Background technology
Lysosome is a kind of very important organoid in the eukaryotic cell, and its internal medium is slightly acidic (pH4-6), contains the multiple acid hydrolase that can decompose the interior waste material of cell and fragment, participates in intracellular digestive process directly.In addition, lysosome also has direct correlation with the generation of the autophagy of cell, apoptosis, immune defense, cancer.
In recent years, because it has more convenience and susceptibility, the synthetic molecules fluorescent probe has been paid much attention to and has been widely used in detecting intracellular different ions.[referring to: (a) T.Hirano, K.Kikuchi, Y.Urano, T.Higuchi, T.Nagano, Angew.Chem.2000,112,1094 – 1096; (b) Z.H.Lin, M.Wu, M.Schaferling, O.S.Wolfbeis, Angew.Chem.2004,116,1767 – 1770; (c) H.Komatsu, T.Miki, D.Citterio, T.Kubota, Y.Kitamura, K.Oka, K.Suzuki, J.Am.Chem.Soc.2005,127 (31), 10798-10799. (d) N.Umezawa, K.Tanaka, Y.Urano, K.Kikuchi, T.Higuchi, T.Nagano, Angew.Chem.Int.Ed.1999,38,2899-2901. (e) X.Y.Qu, Q.Liu, X.N.Ji, H.C.Chen, Z.K.Zhou, Z.Shen, Chem.Commun.2012,48,4600-4602.] in these intracellular ions, proton is one of them very important object ion.As everyone knows, intracellular pH is the important parameter of numerous physiological activities.Intracellular proton distributes and heterogeneity, is about 7.2 in tenuigenin, at plastosome meta-alkalescence more then.[referring to: (a) C.Hunte, E.Screpanti, M.Venturi, A.Rimon, E.Padan, H.Michel, Nature2006,435,1197-1202. (b) H.Izumi, T.Torigoe, H.Ishiguchi, H.Uramoto, Y.Yoshida, M.Tanabe, T.Ise, T.Murakami, T.Yoshida, M.Nomoto, K.Kohno, Cancer Treat.Rev.2003,29,541 – 549. (c) M.Chesler, Physiol.Rev.2003,83,1183 – 1221. (d) A.M.Paradiso, R.Y.Tsien, T.E.Machen, Nature1987,325,447 – 450. (e) I.Yuli, A.Oplatka, Science1987,235,340 – 342.] and lysosomal pH is about 4.5-5.5, existing most of pH fluorescent probes are not suitable for studying the acid organoid of this class.This is because of their quenching of fluorescence under neutrality or strong acidic condition, the perhaps accumulation of non preference in acid organoid.In addition, desirable probe also should be avoided the interference of other species in the cell.[referring to: (a) J.E.Whitaker, R.P.Haugland, F.G.Prendergast, Anal.Biochem.1991,194,330-344. (b) C.C.Overly, K.D.Lee, E.Berthiaume, P.J.Hollenbeck, Proc.Natl.Acad.Sci.USA1995,92,3156-3160. (c) V.Sandhu, M.Miller, A.K.Grover, Mol. Cell.Biochem.1998,178,77-80. (d) J.X.Liu, Z.Diwu, W.-Y.Leung, Bioorg.Med.Chem.Lett.2001,11,2903 – 2905.]
Boron-two pyrroles methylene base class (BODIPY) molecule is a kind of polar fluorescent dyestuff with high degree of rigidity, class methyne, nonionic.Its structure is coupled together by boron bridged bond and methylene radical bridged bond by two pyrrole rings, and this mode of connection is fixing at grade the parent fraction of such dyestuff, makes molecule have the rigidity of height.The molecule mother nucleus structure of BODIPY is as follows:
Named each atom of BODIPY parent nucleus as usual with Arabic numerals according to International Union of Pure and Applied Chemistry(IUPAC) (IUPAC), but we select each atom in the more convenient efficient manner understanding BODIPY parent nucleus usually for use in real work: the meso-position, alpha-position, β-position.Compare with other pigment as fluorescence carrier, it has some row advantages such as high molar extinction coefficient (ε ≈ 7*104～7*105L.mol-1.cm-1), sharp-pointed fluorescence emission peak, high fluorescence quantum yield (Ф〉0.5) and light stability.[referring to: (a) Loudet, A.; Burgess, K.Chem.Rev.2007,107,4891. (b) Ulrich, G.; Ziessel, R.; Harriman, A.Angew.Chem.2008,120,1202; Angew.Chem.Int.Ed.2008,47,1184. (c) Ziessel, R.; Ulrich, G.; Harriman, A.New J.Chem.2007,31,496. (d) Boens, N.; Leen, V.; Dehaen, W.Chem.Soc.Rev.2012,41,1130. (d) Qu, X.; Liu, Q.; Ji, X.; Chen, H.; Zhou, Z.; Shen, Z.Chem.Commun.2012,48,4600. (e) Shen, Z.; Rohr, H.; Rurack, K.; Uno, H.; Spieles, M.; Schulz, B.; Reck, G.; Ono, N.Chem.Eur.J.2004,10,4853.] this experiment invention improves the structure of existing hydrogen ion fluorescent probe, and the boron pyrroles dimethyl quasi-molecule fluorescent probe that is applicable to the lysosomal excellent property of detection of acidic organoid in the detection viable cell has been synthesized in design.
Summary of the invention
Content of the present invention is to design and provide near infrared fluorine boron two pyrroles (BODIPY) of containing ester group cyano group electron-withdrawing group in a series of α position and its production and use.
Technical scheme of the present invention is as follows:
One class is based near infrared fluorine boron two azole compounds (BODIPY), and it has following structure:
Wherein: substituent A r is a kind of in following four kinds of substituting groups:
A kind ofly prepare the method that near infrared fluorine boron two azole compounds (BODIPY) of ester group cyano group electron-withdrawing group are contained in above-mentioned α position, it comprises the steps:
In reaction vessel, add phenyl aldehyde and the 2-(2-cyano group-2-ethoxycarbonyl vinyl that R-replaces)-1H-pyrroles, formaldehyde and 2-(2-cyano group-2-ethoxycarbonyl vinyl that R-replaces)-1H-pyrroles's mol ratio is 1:2, be dissolved in the anhydrous methylene chloride, the formaldehyde that described R-replaces is phenyl aldehyde, the 4-nitrobenzaldehyde, the 4-(dimethylamino) phenyl aldehyde or 4 '-aldehyde radical phendioxin 5-hat-5, add catalytic amount trifluoroacetic acid (TFA) catalysis, catalyst levels is about three times of substituted benzaldehyde, stir under the condition of anhydrous lucifuge, backflow 4-7 days, the point plate detects up to 2-(2-cyano group-2-ethoxycarbonyl vinyl)-1H-pyrroles exhausts fully, to wait 2 of mole number then, 3-two chloro-5,6-dicyano-1,4-benzoquinones (DDQ) adds in the reaction soln, stirred 30 minutes under the room temperature, add excessive triethylamine (TEA) and boron trifluoride-diethyl ether solution (BF afterwards
3Et
2O), continue stirring and refluxing reaction one hour, the water cancellation is reacted after obtaining blue solution, reaction mixture washs successively with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, evaporation concentration behind the subsequent drying is separated with 100-140 order silica gel dress post, and eluent is methylene dichloride, after the solvent evaporated, obtain target compound with methylene dichloride/normal hexane recrystallization.
The amount of catalyzer and the control in reaction times are played crucial effects for this step of BODIPY.The TFA catalyzed reaction of synthetic BODIPY must be carried out under the anhydrous and oxygen-free condition.For the consumption of the oxidation that suppresses pyrroles self and the polymerization TFA under the acidic conditions too much unsuitable.And in order to accelerate reaction process and raising productive rate, the consumption of TFA is also unsuitable very few.And because the pyrroles is contained strong electron-withdrawing group group, make this reaction make slow progress, compare this reaction needed higher temperature with a few hours of common BODIPY and just can make with time a couple of days and react completely.
With
1H-NMR, UV-Vis, fluorescence spectral, MALDI-TOF MASS and crystalline structure characterize and have confirmed the structure (seeing accompanying drawing and subordinate list) of this BODIPY fluorescent probe.Bruker DRX500 type nuclear magnetic resonance analyser, in be designated as TMS, solvent is CDCl
3Tianjin, island UV-4500 type ultraviolet-visible spectrophotometer, CH
2Cl
2, DMF, CH
3CN, CH
3OH is solvent, and sweep limit is 300-900nm, slit width 2.0nm, and light source Wavelength-converting 360nm, CH2Cl2, DMF, CH3CN, CH3OH are solvent; ABI Voyager MALDI-TOF mass spectrum workstation is substrate with the alpha-cyano-4-hydroxycinnamic acid of ABI company; Bruker Smart Apex CCD diffractometer, MoK
ω-2 θ scan pattern.
This class pH lysosome probe of the present invention's design, two strong electron-withdrawing group cyano group and ester groups have been introduced in the α position at the BODIPY parent nucleus of novelty, make it to absorb emission wavelength all red shift is near near infrared region that and the molar absorptivity molar extinction coefficient has reached 10
5The order of magnitude also has higher fluorescence quantum yield.The strong electron-withdrawing substituent in α position makes the BODIPY molecule that does not have the typical group of being combined with hydrogen ion have the characteristic of pH fluorescent probe.Synthesized the meso bit substituent in addition and given the different a series of compounds of electronic property, proved that by theory and practice this series compound is functional ground lysosome fluorescent probe, has huge using value.
Useful achievement of the present invention
The present invention compared with prior art, its remarkable advantage is: 1. the BODIPY dyestuff of taking by storm electronics ester group and cyano group is contained in the α position first, makes its absorption peak and emission peak reach about 630nm, with simple BODIPY(λ
Max≈ 500nm) dyestuff is compared, red shift 130nm, successfully the ruddiness zone has been arrived in the maximum absorption band red shift, can better improve imaging (treatment) efficient, improve penetration depth, reduce photic tissue injury.2.BODIPYA1 fluorescence takes place in molecule self, and optionally accumulates in the lysosome, does not need and other material acting in conjunction.3. fluorescence molecule BODIPY A1 has high molar extinction coefficient and has reached 10
5The order of magnitude and have sharp-pointed fluorescence emission peak, higher fluorescence quantum yield.4. highly sensitive, the fluorescence of compd B ODIPY A1 has increased by 17 times at pH from the process that 6.0-4.1 changes, and color is changed to blue fairly obviously by yellow, is pH bore hole probe well.Our designed molecule is suitable for use in labeled cell inner acidic organoid lysosome very much, is class lysosome fluorescent probe efficiently.
Description of drawings
Fig. 1-4 is the nuclear magnetic spectrogram spectrum of fluorescent probe BODIPY A1-A4;
Fig. 5 is the crystalline structure collection of illustrative plates of fluorescent probe BODIPY A1;
Fig. 6 is the fluorescence picture in different time points with the KB cell alive of 15 μ M fluorescent probe BODIPY A1 hatching;
Fig. 7 is the fluorescent three-dimensional image with the KB cell alive of 15 μ M probe BODIPY A1 hatching;
Fig. 8 is for hatching the fluoroscopic image of cell jointly with commercially available lysosome fluorescent probe Lyso-Traker and synthetic lysosome fluorescent probe BODIPY A1; Wherein, (a: λ ex=488nm; B: λ ex=543; C is the two composograph);
Fig. 9 is for hatching the fluorescent three-dimensional image of cell jointly with commercially available lysosome fluorescent probe Lyso-Traker and synthetic lysosome fluorescent probe BODIPY A1.
Embodiment
Embodiment 1.BODIPY A1's is synthetic:
In reaction vessel, add phenyl aldehyde (0.106g, 1mmol) and 2-(2-cyano group-2-ethanoyl ester group)-(0.380g 2mmol), is dissolved in the 50ml anhydrous methylene chloride 1H-pyrroles.Extract trifluoroacetic acid (TFA) catalyzer 0.5ml injection system with syringe, put into magneton under the condition of anhydrous lucifuge and stir, refluxing, the detection of some plate exhausts fully up to the pyrroles after 4 days.Add 2,3-, two chloro-5 then, 6-dicyano-1, (DDQ:0.227g 1mmol) adds in the reaction soln 4-benzoquinones, stirs 30 minutes under the room temperature, adds afterwards after excessive triethylamine (TEA) 3ml stirs, and divides adding boron trifluoride-diethyl ether solution (BF three times
3Et
2O) 6ml continues stirring and refluxing reaction one hour, obtains the solution that blueness has intense red fluorescence, and the some plate detects to coordination product not and exhausts the reaction of water cancellation subsequently.Reaction mixture washs successively with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, and organic layer uses anhydrous sodium sulfate drying to concentrate by Rotary Evaporators.Separate with 100-140 order silica gel dress post, eluent is methylene dichloride, obtains target compound A1 with methylene dichloride/normal hexane recrystallization then after the solvent evaporated.A1 is the green crystal that has metalluster, (298.2mg, productive rate 58%).MALDI TOF MS:Calc.for C27H21BF2N4O4[M]-=514.162; Found:[M]-=514.316. ultraviolet 627nm, fluorescence 635nm.Its nuclear magnetic spectrum is seen accompanying drawing 1, and the A1 crystalline structure is seen accompanying drawing 5, and its parameter sees Table 1, table 2.
Table 1A1 crystal data and structural modifications parameter
Table 2A1 crystal block section bond distance
And bond angle (°)
Embodiment 2.BODIPY A2's is synthetic:
In reaction vessel, add paranitrobenzaldehyde (0.151g, 1mmol) and 2-(2-cyano group-2-ethanoyl ester group)-(0.380g 2mmol), is dissolved in the 50ml dry methylene chloride 1H-pyrroles.Extract trifluoroacetic acid (TFA) catalyzer 0.5ml injection system with syringe, put into magneton under the condition of anhydrous lucifuge and stir, refluxing, the detection of some plate exhausts fully up to the pyrroles after 7 days.Add 2,3-, two chloro-5 then, 6-dicyano-1, (DDQ:0.227g 1mmol) adds in the reaction soln 4-benzoquinones, stirs 30 minutes under the room temperature, adds afterwards after excessive triethylamine (TEA) 3ml stirs, and divides adding boron trifluoride-diethyl ether solution (BF three times
3Et
2O) 9ml continues stirring and refluxing reaction one hour, obtains blue solution, and the some plate detects to coordination product not and exhausts the reaction of water cancellation subsequently.Reaction mixture washs successively with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, and organic layer uses anhydrous sodium sulfate drying to concentrate by Rotary Evaporators.Separate with 100-140 order silica gel dress post, eluent is methylene dichloride, obtains target compound A2 with methylene dichloride/normal hexane recrystallization then after the solvent evaporated.A2 is green metal gloss crystal, (290.7mg, productive rate 52%).MALDI TOF MS:Calc.for C27H20BF2N5O6[M]-=559.148; Found:[M]-=559.488. ultraviolet 633nm, fluorescence 646nm.Its nuclear magnetic spectrum is seen accompanying drawing 2.
Embodiment 3.BODIPY A3's is synthetic:
In reaction vessel, add paradimethy laminobenzaldehyde (0.149g; 1mmol) and 2-(2-cyano group-2-ethanoyl ester group)-1H-pyrroles (0.380g; 2mmol); be dissolved in the 50ml anhydrous methylene chloride; extract trifluoroacetic acid (TFA) catalyzer 0.5ml injection system with syringe; put into magneton under the condition of anhydrous lucifuge and stir, refluxing, the detection of some plate exhausts fully up to the pyrroles after 7 days.Add 2,3-, two chloro-5 then, 6-dicyano-1, (DDQ:0.227g 1mmol) adds in the reaction soln 4-benzoquinones, stirs 30 minutes under the room temperature, adds afterwards after excessive triethylamine (TEA) 3ml stirs, and divides adding boron trifluoride-diethyl ether solution (BF three times
3Et
2O) 9ml continues stirring and refluxing reaction one hour, obtains blue solution, and the some plate detects to coordination product not and exhausts the reaction of water cancellation subsequently.Reaction mixture washs successively with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, and organic layer uses anhydrous sodium sulfate drying to concentrate by Rotary Evaporators.Separate with 100-140 order silica gel dress post, eluent is methylene dichloride, obtains target compound A3 with methylene dichloride/normal hexane recrystallization then after the solvent evaporated.A3 is the sap green crystal, (267.4mg, productive rate 48%).MALDI TOF MS:Calc.for C29H26BF2N5O4[M]-=557.205; Found:[M]-=557.359. ultraviolet 606nm, fluorescence 616nm.Its nuclear magnetic spectrum is seen accompanying drawing 3.
Embodiment 4.BODIPY A4's is synthetic:
In reaction vessel, add benzo 15-5 phenyl aldehyde (0.296g; 1mmol) and 2-(2-cyano group-2-ethanoyl ester group)-1H-pyrroles (0.380g; 2mmol); be dissolved in the 50ml anhydrous methylene chloride and extract trifluoroacetic acid (TFA) catalyzer 0.5ml injection system with syringe; put into magneton under the condition of anhydrous lucifuge and stir, refluxing, the detection of some plate exhausts fully up to the pyrroles after 7 days.Add 2,3-, two chloro-5 then, 6-dicyano-1, (DDQ:0.227g 1mmol) adds in the reaction soln 4-benzoquinones, stirs 30 minutes under the room temperature, adds afterwards after excessive triethylamine (TEA) 3ml stirs, and divides adding boron trifluoride-diethyl ether solution (BF three times
3Et
2O) 9ml continues stirring and refluxing reaction one hour, obtains blue solution, and the some plate detects to coordination product not and exhausts the reaction of water cancellation subsequently.Reaction mixture washs successively with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, and organic layer uses anhydrous sodium sulfate drying to concentrate by Rotary Evaporators.Separate with 100-140 order silica gel dress post, eluent is methylene dichloride, obtains target compound A4 with methylene dichloride/normal hexane recrystallization then after the solvent evaporated.A4 is blue powder, (70.5mg, productive rate 10%).MALDI TOF MS:Calc.for C35H35BF2N4O9[M]-=704.246; Found:[M]-=704.533. high resolution mass spectrum m/z ([M+H]+)=705.2540, C35/35, H36/36, O9/9, N4/4, F2/2, B1/1.Ultraviolet 619nm, fluorescence 639nm.Its nuclear magnetic spectrum is seen accompanying drawing 4.
Embodiment 5 cell cultures
The KB cell strain is provided by Institute Of Biochemistry And Cell Biology, Shanghai Institutes For Biological Sciences, Chinese Academy Of Sciences.The KB cell is cultivated in being mixed with the serum-free cell cryopreservation substratum (RPMI) 1640 of 10% foetal calf serum (FBS).Be placed in the CO2gas incubator, cultivate 4h for 37 ℃.Scanning imagery after cell uses phosphate buffered saline buffer PBS to clean three times.
By 3D viable cell imaging technique synthetic fluorescent probe BODIPY A1 and mark lysosome have been done further research.Molecular probe and the cell incubated cell 20min that will contain 15 μ M.Use commercially available lysosome fluorescent probe Lyso-Tracker Green(DND-26 subsequently) 10 μ M hatching cell 20min.488 and 543nm under excite the acquisition image respectively.With the synthetic lysosome fluorescent probe probe BODIPY A1 hatching of 15 μ M (37 ℃, the fluoroscopic image in different time points of KB cell alive 20min) (λ ex=543nm, λ em=560-660nm) is seen accompanying drawing 6,3-D view is seen accompanying drawing 7.Synthetic lysosome probe BODIPY A1 and Lyso-Traker are hatched cell 20min fluoroscopic image jointly.(a: λ ex=488nm; B: λ ex=543) see accompanying drawing 8,3-D view is seen accompanying drawing 9.
Claims (3)
1. a class is characterized in that based near infrared fluorine boron two azole compounds (BODIPY) that contain ester group cyano group electron-withdrawing group it has following structure:
Wherein: substituent A r is a kind of in following four kinds of substituting groups:
2. one kind prepares the described method based near infrared fluorine boron two azole compounds (BODIPY) that contain ester group cyano group electron-withdrawing group of claim 1, it is characterized in that it comprises the steps:
In reaction vessel, add formaldehyde and the 2-(2-cyano group-2-ethoxycarbonyl vinyl that R-replaces)-1H-pyrroles, formaldehyde and 2-(2-cyano group-2-ethoxycarbonyl vinyl that R-replaces)-1H-pyrroles's mol ratio is 1:2, be dissolved in the anhydrous methylene chloride, the formaldehyde that described R-replaces is phenyl aldehyde, the 4-nitrobenzaldehyde, the 4-(dimethylamino) phenyl aldehyde or 4 '-aldehyde radical phendioxin 5-hat-5, add catalytic amount trifluoroacetic acid (TFA) catalysis, catalyst levels is about three times of substituted benzaldehyde, stir under the condition of anhydrous lucifuge, backflow 4-7 days, the point plate detects up to 2-(2-cyano group-2-ethoxycarbonyl vinyl)-1H-pyrroles exhausts fully, to wait 2 of mole number then, 3-two chloro-5,6-dicyano-1,4-benzoquinones (DDQ) adds in the reaction soln, stirred 30 minutes under the room temperature, add excessive triethylamine (TEA) and boron trifluoride-diethyl ether solution (BF afterwards
3Et
2O), continue stirring and refluxing reaction one hour, the water cancellation is reacted after obtaining blue solution, reaction mixture washs successively with distilled water, saturated sodium bicarbonate aqueous solution, saturated aqueous common salt, evaporation concentration behind the subsequent drying is separated with 100-140 order silica gel dress post, and eluent is methylene dichloride, after the solvent evaporated, obtain target compound with methylene dichloride/normal hexane recrystallization.
3. the application of described fluorine boron two azole compounds of claim 1 (BODIPY) in preparation lysosome fluorescent probe.
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