CN102924531B - Iridium-selenium multi-pyridine ligand and its preparation method and application - Google Patents
Iridium-selenium multi-pyridine ligand and its preparation method and application Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003446 ligand Substances 0.000 title claims abstract description 42
- DKZXLKGTIOYQTI-UHFFFAOYSA-N [Ir]=[Se] Chemical compound [Ir]=[Se] DKZXLKGTIOYQTI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 229910006400 μ-Cl Inorganic materials 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000011669 selenium Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 claims description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 7
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000002438 mitochondrial effect Effects 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- RIYPENPUNLHEBK-UHFFFAOYSA-N phenanthro[9,10-b]pyridine Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 RIYPENPUNLHEBK-UHFFFAOYSA-N 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 description 25
- 229910052741 iridium Inorganic materials 0.000 description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 14
- 239000000975 dye Substances 0.000 description 12
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- RUVJFMSQTCEAAB-UHFFFAOYSA-M 2-[3-[5,6-dichloro-1,3-bis[[4-(chloromethyl)phenyl]methyl]benzimidazol-2-ylidene]prop-1-enyl]-3-methyl-1,3-benzoxazol-3-ium;chloride Chemical compound [Cl-].O1C2=CC=CC=C2[N+](C)=C1C=CC=C(N(C1=CC(Cl)=C(Cl)C=C11)CC=2C=CC(CCl)=CC=2)N1CC1=CC=C(CCl)C=C1 RUVJFMSQTCEAAB-UHFFFAOYSA-M 0.000 description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- CWHJIJJSDGEHNS-MYLFLSLOSA-N Senegenin Chemical compound C1[C@H](O)[C@H](O)[C@@](C)(C(O)=O)[C@@H]2CC[C@@]3(C)C(CC[C@]4(CCC(C[C@H]44)(C)C)C(O)=O)=C4[C@@H](CCl)C[C@@H]3[C@]21C CWHJIJJSDGEHNS-MYLFLSLOSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- SSABEFIRGJISFH-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=CC=N1 SSABEFIRGJISFH-UHFFFAOYSA-N 0.000 description 2
- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
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- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003342 selenium Chemical class 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000006144 Dulbecco’s modified Eagle's medium Substances 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VYVIOMJSKUGJLV-UHFFFAOYSA-N [Ir+2] Chemical class [Ir+2] VYVIOMJSKUGJLV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses iridium-selenium multi-pyridine ligand and its preparation method and application.The invention discloses a kind of iridium-selenium multi-pyridine ligand, its chemical formula is [Ir (N-C)
2(phenSe)]
+(N-C=ppy, dfppy, btp, 2-pq or dbq), it is the compound derived by selenium-5,6-diamines-1,10-phenanthroline, this title complex has good viable cell plastosome coloring properties, stronger cell membrane penetration and lower cytotoxicity, will have great application potential in biomarker and cell imaging.
Description
Technical field
The present invention relates to viable cell staining technique field, be specifically related to a series of new iridium-selenium multi-pyridine ligand, and its preparation method and application.
Background technology
Along with day by day deep to cell research of people, the biomedical optical imaging techniques such as Magnetic resonance imaging (MRI), PET (PET), single photon emission fault imaging (SPECT) and laser confocal fluorescence microscope technology also obtain development, and the exploitation of applicable bio-imaging reagent is a current study hotspot.At present, the commercial fluorescence dye major part being applied to cell imaging field is some organic molecules, as PI, DAPI, EB, Hoechst, MitoTracker, JC-1 etc.But, there is some shortcomings (V.Fernandez-Moreira in these organic molecules, F.L.Thorp-GreenwoodandM.P.Coogan.Chem.Commun.2010,46,186-202): water-soluble poor, water surrounding (as in substratum) easily produce precipitation or with cytosis after at once separate out, affect Color; There is higher cytotoxicity, after dyestuff and cytosis, cause the death of cell, affect the observation to cell standard state; Light stability is low, because of the effect by promoting agent group (singlet oxygen etc.) in air or in medium, dyestuff is after excitation wavelength is irradiated, fluorescence constantly weakens, and light drifts phenomenon seriously, is unfavorable for image stabilization (M.S.Lowry, W.R.Hudson, R.A.Pascal andS.Bernhard.J.Am.Chem.Soc.2004,126,14129-14135); Stoke displacement between excitation spectrum and emmission spectrum is little, generally at tens ran, is unfavorable for the self-quenching distinguished endogenous fluorescence and reduce dyestuff itself.Based on organic dye exist some shortcomings, people more sight is turned to there is excellent electro optic properties transition metal complex on.
Transition metal complex, particularly iridium multi-pyridine ligand, the optical physics excellent due to it and spectrochemical property, have the advantage of its uniqueness in cell imaging reagent.Compared with other transition metal complexes, iridium multi-pyridine ligand has high cell migration rate, easily by Cell uptake.In addition, iridium metal complex seems more excellent in luminosity and light stability etc., therefore receives more many concerns.The hyperfluorescenceZeng Yongminggaoyingguang of iridium metal complex dependence usually itself, is positioned certain position of cell, thus becomes good cell dye.The Cell uptake of these title complexs and cell dyeing research thereof tentatively start.Reported for work the first iridium multi-pyridine ligand [Ir (dfpy) being applied to cell imaging for 2008
2(bpy)] (PF
6) and [Ir (dfpy)
2(quqo)] (PF
6), wherein the introducing of F element adds the lipotropy of title complex, makes it more easily by cytolemma.Laser co-focusing experiment shows that title complex is positioned tenuigenin, and having the anti-light bleaching effect being better than DAPI, is good cytoplasmic dye (M.Yu, Q.Zhao, L.Shi, F.Li, Z.Zhou, H.Yang, T.Yi and C.Huang, Chem.Commun., 2008,2115-2117).The alkyl (-C modifying different lengths is carried out to the dipyridyl ring of part
2h
6,-C
10h
21,-C
18h
37), can be strengthened it to nuclear membrane perviousness, show roughly the same Color.This kind of title complex all tends to tenuigenin location, particularly core Zhou Dingwei, this strong effective locating effect infers the hydrophobic tissue deriving from long alkyl chain and core week, as the interaction (K.K.W.Lo between endoplasmic reticulum and golgi body etc., P.K.Lee and J.S.Y.Lau, Organometallics, 2008,27,2998 – 3006).The complex of iridium that a class contains dipyridyl quinoxaline part is also studied by this working group, finds that this kind of complex of iridium can enter nucleus, interacts with DNA, dye to nucleus, this is the first nucleus fluorescent probe (K.Y.Zhang, S.P.Y.Li in this kind of complex of iridium, N.Zhu, L.W.S.Or, M.S.H.Cheung, Y.W.Lam, and K.K.W.Lo, Inorg.Chem., 2010,49,2530-2540).In general, all kinds of iridium metal complexes being applied to cell dyeing imaging reported at present, the overwhelming majority dyes and is positioned tenuigenin, and the iridium metal complex being applied to the dyeing of viable cell plastosome has no report at present.
Summary of the invention
The object of the invention is to following several: the preparation method and application that a series of iridium-selenium multi-pyridine ligand is provided.
The present invention is achieved through the following technical solutions above-mentioned purpose:
Invention provides a kind of iridium-selenium multi-pyridine ligand, chemical formula [Ir (N-C)
2(phenSe)]
2+(N-C=ppy, dfppy, btp, 2-pq or dbq), structural formula is as shown in the formula any one in I, II, III, IV and V:
Invention provides the preparation method of above-mentioned iridium-selenium multi-pyridine ligand simultaneously, comprises the following steps:
By chlorine bridging dimer [(N-C)
2ir (μ-Cl)]
2(such as formula VI) and the many pyridine ligands of selenium join in ethanol/methylene mixed solvent, heating reflux reaction under protection of inert gas.
Wherein N-C is 2-(2-pyridyl) thionaphthene (btp), 2-(2,4-difluorophenyl) pyridine (dfppy), dibenzo [f, h] quinoline Nuo Xilin (dbq), 2-phenylquinoline (2-pq) and 2-phenylpyridine (ppy), the respectively corresponding compound obtaining above-mentioned formula I-formula V.[(N-C)
2ir (μ-Cl)]
2can be synthesized by existing method, concrete preparation method can refer to document S.Sprouse, K.A.King, P.J.Spellane, and R.J.Watts, J.Am.Chem.Soc., 1984,106,6647-6653.
The many pyridine ligands of selenium are wherein such as formula shown in VII.The many pyridine ligands of this selenium, be called for short phen-Se, its chemical name is selenium-5,6-diamines-1,10-phenanthroline.The preparation method of the many pyridine ligands of this selenium is with reference to existing document (Qian Li, DongdongSun, Yanhui Zhou, Du Liu, Qianling Zhang and Jie Liu, Inorg.Chem.Commun., 2012,20,142) method, carry out part to its synthetic route to optimize and revise, decrease synthesis step.Step is as follows: by the mixture heated and stirred of 1,10-phenanthroline-5,6-diketone, tin anhydride, ammonium acetate and Glacial acetic acid, and be cooled to room temperature after backflow 6h, filter, filtrate is poured in frozen water, hold over night, suction filtration; Repeatedly wash with water and ether respectively, vacuum-drying.Wherein 1,10-phenanthroline-5,6-diketone the mature technology of many pyridine ligands can prepare, as reference literature (M.Yamada with common synthesis, Y.Tanaka, Y.Yoshimato, S.Kuroda and I.Shimao, Bull.Chem.Soc.Jpn., 1992,65,1006.) method.The many pyridine ligands of selenium can be applicable to prepare viable cell mitochondrial dye.
Ethanol/methylene mixed solvent described in the inventive method is ethanol/methylene (v/v=2:1).Reflux time is 6-10h.
After above-mentioned back flow reaction terminates, be cooled to room temperature, filter, in filtrate, add NH
4pF
6methyl alcohol saturated solution, revolve steaming, the precipitation of generation is dry after filtering, crosses neutral alumina column, the ratio wash-out increased gradually in polarity with methylene dichloride and acetone mixture, obtains and dissolves the elutriant of pure products, be drying to obtain described iridium-selenium multi-pyridine ligand.
As a kind of specific embodiment, above-mentioned iridium-selenium multi-pyridine ligand can be obtained by following steps: first synthesize [(N-C)
2ir (μ-Cl)]
2, join in ethanol/methylene (v/v=2:1) together with selenium many pyridine ligands phen-Se, the lower 65 DEG C of reflux 6h of argon shield, are cooled to room temperature, Filtration Filtration, NH
4pF
6methyl alcohol saturated solution add in filtrate, spin off part methyl alcohol, the precipitation of generation is dry through suction filtration final vacuum, and cross neutral alumina column, be methylene dichloride and the acetone mixture drip washing of 5:1 by volume ratio, namely vacuum-drying obtain described iridium-selenium multi-pyridine ligand; ; Wherein N-C is 2-(2,4-difluorophenyl) pyridine (dfppy), 2-(2-pyridyl) thionaphthene (btp), dibenzo [f, h] quinoline Nuo Xilin (dbq), 2-phenylquinoline (2-pq) or 2-phenylpyridine (ppy).
Methylene dichloride and the acetone mixture of described methylene dichloride and acetone mixture to be volume ratio be 1:2 to 5:1.
Iridium of the present invention-selenium multi-pyridine ligand is applied to prepares viable cell mitochondrial dye reagent.
Show after deliberation, above-mentioned 5 kinds of title complex [Ir (N-C) containing phenanthroline diketone-selenium part of the present invention
2(phenSe)]
+(N-C=ppy, dfppy, btp, 2-pq or dbq), has strong fluorescence intensity and fluorescence lifetime under aqueous conditions.Thus iridium-selenium multi-pyridine ligand can be used for the cell mitochondrial dyestuff preparing viable cell.MTT and flow cytometry tests result show that the cytotoxicity of title complex is low under low consistency conditions, little to cell injury.
Compared with prior art, the present invention has following beneficial effect:
Iridium of the present invention-selenium multi-pyridine ligand simple and stable structure, in this iridium (II) title complex, selenium element and the combination of phenanthroline diketone reduce title complex becomes hydrogen bond ability with water molecules, greatly strengthen the fluorescent characteristic of title complex, simultaneously, as one of human essential elements, the introducing of selenium element also enhances the cell transmembrane ability of title complex.Under the condition without the need to cell pretreatment (as electroporation or solvent are fixed), this title complex can be successfully painted to the plastosome in viable cell, and there is the feature of short, the stoke displacement highly sensitive, Premeabilisation of cells ability is strong, large of dyeing of cultivation time, low cytotoxicity and resistance to photobleaching, great application potential will be had in biomarker and cell imaging.
Accompanying drawing explanation
Fig. 1 selenium many pyridine ligands molecular structural formula;
Fig. 2 iridium-selenium multi-pyridine ligand molecular structural formula;
The route of synthesis of the many pyridine ligands of Fig. 3 selenium;
Fig. 4 chlorine bridging dimer [(N-C)
2ir (μ-Cl)]
2molecular structural formula;
The route of synthesis of Fig. 5 iridium-selenium multi-pyridine ligand;
The fluorescence spectrum of Fig. 6 iridium-selenium multi-pyridine ligand, [Ir]=10mM, (L=Phen-Se);
The title complex [Ir (ppy) 2 (phenSe)] of Fig. 7 HeLa cell difference 10 μMs
+(PF
6 -) (A), [Ir (dfppy) 2 (phenSe)]
+(PF
6 -) (B), [Ir (btp) 2 (phenSe)]
+(PF
6 -) (C), [Ir (2-pq) 2 (phenSe)]
+(PF
6 -) (D), [Ir (dbq) 2 (phenSe)]
+(PF
6 -) (E) cultivate 30min, contaminate cell imaging result afterwards altogether with Mitotracker-Green (1 μM).A () Mitotracker-Green is to the fluorogram after cell color; B () title complex is to the fluorogram after cell color; (c) bright field visible ray cell color figure; (d) a, the superposition of b, c; A, B, C, D and E in bracket represent this five kinds of title complexs respectively.
Embodiment
The preparation of embodiment 1 part selenium-5,6-diamines-1,10-phenanthroline (phen-Se)
The synthesis of part phen-Se can with reference to existing document (Qian Li, Dongdong Sun, Yanhui Zhou, Du Liu, Qianling Zhang and Jie Liu, Inorg.Chem.Commun., 2012,20,142) prepare, part has been carried out to its synthetic route and has optimized and revised, decreased synthesis step, make it synthesize more simple and fast, productive rate is high.Only need through two steps, wherein the first step is the reaction of the technology maturation of the common many pyridine ligands of synthesis.
(1) 1,10-phenanthroline-5,6-diketone
Can the preparation of reference literature (M.Yamada, Y.Tanaka, Y.Yoshimato, S.Kuroda and I.Shimao, Bull.Chem.Soc.Jpn., 1992,65,1006) method.Under ice cooling, 4, in the three neck round-bottomed flasks that 4.0g o-phenanthroline and 4.0g Potassium Bromide be housed, 40cm is dripped
3the vitriol oil and 20cm
3the mixed solution of concentrated nitric acid, simultaneously induction stirring.After dropwising, remove ice bath, be warming up to 85 DEG C of reactions 3 hours.After reaction terminates, stop heating and removing prolong, allow bromine escape and go.Complete cooled orange-yellow reaction soln pours 200cm into
3in frozen water, neutralize pH=7 carefully with the sodium hydroxide solution of 10M, have a large amount of yellow mercury oxides to produce.By this suspension liquid 4 ' 100cm
3chloroform extraction.Merge organic phase, use 50cm
3spend the night with anhydrous sodium sulfate drying again after water washing.Boil off chloroform after filtration, solid product ethyl alcohol recrystallization, obtain orange-yellow needle-like crystal, fusing point is 258 DEG C.
(2) selenium-5,6-diamines-1,10-phenanthroline
By 1,10-phenanthroline-5,6-diketone (2.1g, 10mmol), tin anhydride (2.1g, 19mmol), ammonium acetate (7.7g, 100mmol) and the mixture heated and stirred of 100mL Glacial acetic acid, be cooled to room temperature after backflow 6h, filter, filtrate is poured in 600mL frozen water, after leaving standstill a night, if precipitate less, available ammoniacal liquor regulates pH to neutral, suction filtration.Repeatedly wash with water and ether respectively, vacuum-drying, obtain brown solid 2.3g, be i.e. selenium-5,6-diamines-1,10-phenanthroline.Productive rate: 79.6%.ES-MS(CH
3OH):m/z 287.2[M+1]
+，595.3[M-Na
+]
2+
Embodiment 2 title complex [Ir (ppy)
2(phenSe)]
+(PF
6)
-, [Ir (dfppy)
2(phenSe)]
+(PF
6)
-, [Ir (btp)
2(phenSe)]
+(PF
6)
-, [Ir (2-pq)
2(phenSe)]
+(PF
6)
-, [Ir (dbq)
2(phenSe)]
+(PF
6)
-synthetic method:
(1) [(dfppy)
2ir (μ-Cl)]
2synthesis
The synthesis of this compound can be prepared with reference to existing document (T.Peng, Y.Yang, Y.Liu, D.Ma, Z.Hou and Y.Wang, Chem.Commun., 2011,47,3150).Take IrCl
30.33g (about 1.1mmol); 2-(2; 4-difluorophenyl) pyridine (dfppy) 0.501g (2.62mmol), in the mixed solution of 40mL ethylene glycol ethyl ether and water (V1:V2=3:1), the lower 120 DEG C of backflows of argon shield about 24 hours.After being chilled to room temperature, add suitable quantity of water, collected by suction solid precipitation, with normal hexane, ether repeatedly washs, and dries and obtains yellow greenish powder, productive rate 53.5%.
(2) [(ppy)
2ir (μ-Cl)]
2synthesis
Synthetic method is with [(dfppy)
2ir (μ-Cl)]
2, ppy (0.426g, 2.75mmol) is replaced dfpy, and other steps are identical.Productive rate 67.7%.
(3) [(btp)
2ir (μ-Cl)]
2synthesis
Synthetic method is with [(ppy)
2ir (μ-Cl)]
2synthesis, btp (0.580g, 2.75mmol) is replaced dfppy, and other steps are identical.Productive rate 45.6%.
(4) [(2-pq)
2ir (μ-Cl)]
2synthesis
Synthetic method is with [(ppy)
2ir (μ-Cl)]
2synthesis, 2-pq (0.564g, 2.75mmol) is replaced dfppy, and other steps are identical.Productive rate 65.4%.
(5) [(dbq)
2ir (μ-Cl)]
2synthesis
Synthetic method is with [(ppy)
2ir (μ-Cl)]
2synthesis, dbq (0.506g, 2.2mmol) is replaced dfppy, and other steps are identical.Productive rate 50.6%.
(6) [Ir (dfppy)
2(phenSe)]
+(PF
6)
-synthesis
By [(dfppy)
2ir (μ-Cl)]
2(0.244g, 0.2mmol) and phenSe (0.114g, 0.4mmol), be dissolved in 48ml ethanol/methylene (v/v=2:1), and the lower 65 DEG C of reaction 6h of argon atmosphere, are cooled to room temperature, filter, ammonium hexafluorophosphate (NH
4pF
6) methyl alcohol saturated solution add in filtrate, spin off part methyl alcohol, separate out a large amount of yellow mercury oxide, filtering vacuum is dry.The a small amount of methylene dichloride of thick product dissolves, load about 15cm neutral alumina (200 order) post to be separated, with methylene dichloride/acetone mixed solvent (increasing solvent polarity gradually) drip washing, collect the component under the drip washing of 5:1 dichloromethane-acetone, pressure reducing and steaming solvent, obtain yellow powder solid, productive rate 49.8%.ES-MS(CH
3OH):m/z 857.1[M-PF
6 -]
+.
1H NMR(300MHz,d6-DMSO)δ9.21(d,J＝7.6Hz,1H),8.27(t,J＝7.4Hz,2H),8.10–7.93(m,2H),7.67(d,J＝5.8Hz,1H),7.10(t,J＝6.6Hz,1H),7.05–6.91(m,1H),5.66(dd,J＝8.4,2.2Hz,1H).
(7) [Ir (ppy)
2(phenSe)]
+(PF
6)
-synthesis
Synthetic method is with [Ir (dfppy)
2(phenSe)]
+(PF
6)
-synthesis.By [(ppy)
2ir (μ-Cl)]
2(0.215g, 0.2mmol) substitutes [(dfppy)
2ir (μ-Cl)]
2.Obtain orange-yellow powdery solid, productive rate 48.4%.ES-MS(CH
3OH):m/z 785.2[M-PF
6 -]
+.
1H NMR(300MHz,Acetonitrile)δ9.17(d,J＝6.8Hz,1H),8.29(d,J＝5.2Hz,1H),8.06(d,J＝8.1Hz,1H),7.90–7.75(m,3H),7.57(d,J＝5.8Hz,1H),7.07(t,J＝7.5Hz,1H),6.99–6.85(m,2H),6.35(d,J＝7.5Hz,1H)。
(8) [Ir (btp)
2(phenSe)]
+(PF
6)
-synthesis
Synthetic method is with [Ir (dfppy)
2(phenSe)]
+(PF
6)
-synthesis.By [(btp)
2ir (μ-Cl)]
2(0.259g, 0.2mmol) substitutes [(dfppy)
2ir (μ-Cl)]
2.Red powdery solid, productive rate 54.9%.ES-MS(CH
3OH):m/z 899.1[M-PF
6 -]
+.
1HNMR(300MHz,d6-DMSO)δ9.24–9.17(m,1H),8.21–8.12(m,1H),8.04(dd,J＝8.1,5.3Hz,1H),8.00–7.86(m,3H),7.66(d,J＝5.8Hz,1H),7.23(t,J＝7.6Hz,1H),6.98–6.84(m,2H),5.97(d,J＝8.0Hz,1H).
(9) [Ir (2-pq)
2(phenSe)]
+(PF
6)
-synthesis
Synthetic method is with [Ir (dfppy)
2(phenSe)]
+(PF
6)
-synthesis.By [(2-pq)
2ir (μ-Cl)]
2(0.255g, 0.2mmol) substitutes [(dfppy)
2ir (μ-Cl)]
2.Orange red powdery solid, productive rate 50.4%.Dissolve a small amount of title complex completely with methylene dichloride, add a small amount of toluene, solvent is slowly volatilized in atmosphere, obtains complex monocrystal.ES-MS(CH
3OH):m/z 887.2[M-PF
6 -]
+.
1H NMR(300MHz,Acetonitrile)δ8.98(dd,J＝8.1,1.4Hz,1H),8.55(dd,J＝5.3,1.3Hz,1H),8.39–8.29(m,2H),8.18(d,J＝7.8Hz,1H),7.85(dd,J＝8.1,5.3Hz,1H),7.71(d,J＝7.2Hz,1H),7.26–7.16(m,3H),6.91–6.79(m,2H),6.60(d,J＝7.6Hz,1H).
(10) [Ir (dbq)
2(phenSe)]
+(PF
6)
-synthesis
Synthetic method is with [Ir (dfppy)
2(phenSe)]
+(PF
6)
-synthesis.By [(dbq)
2ir (μ-Cl)]
2(0.275g, 0.2mmol) substitutes [(dfppy)
2ir (μ-Cl)]
2.Obtain orange-yellow powdery solid, productive rate 31.5%.Dissolve a small amount of title complex completely with methylene dichloride, add a small amount of toluene, solvent is slowly volatilized in atmosphere, obtains complex monocrystal.ES-MS(CH
3OH):m/z 938.1[M-PF
6 -]
+.
1H NMR(300MHz，d6-DMSO)δ9.20(d，J＝8.2Hz，1H)，9.14(d，J＝8.0Hz，1H)，8.82(d，J＝8.2Hz，1H)，8.75(d，J＝3.1Hz，1H)，8.35(d，J＝8.2Hz，1H)，8.26-8.13(m，2H)，8.03-7.90(m，2H)，7.90-7.80(m，1H)，7.34(t，J＝7.7Hz，1H)，6.52(d，J＝7.2Hz，1H).
Complex fluorescent spectral detection the results are shown in Table 1 and Fig. 6.
The fluorescence data of table 1 title complex
| Complex | λ MLCT，nm | λ em，nm | Φ em |
| [Ir(ppy) 2(phenSe)] + | 473 | 589 | 0.049 |
| [Ir(dfppy) 2(phenSe)] + | 360 | 528 | 0.957 |
| [Ir(btp) 2(phenSe)] + | 438 | 665 | 0.058 |
| [Ir(2-pq) 2(phenSe)] + | 434 | 585 | 0.055 |
| [Ir(dbq) 2(phenSe)] + | 346 | 547 | 0.227 |
The laser co-focusing experiment of embodiment 3 complex of iridium
Cell cultures: Hela cell is cultivated in containing the DMEM substratum of 10% foetal calf serum, cell (5 ' 10
8/ L) be seeded in culture dish at the bottom of the special glass of Laser Scanning Confocal Microscope, culture dish diameter 35mm, wherein cover-glass thickness 0.085 ~ 0.13mm, ware center micro-pore diameter 10mm, 5%CO
2with under 95% air conditions, 37 DEG C of cultivations, adherent growth 24 hours.
Laser Scanning Confocal Microscope-cell imaging: Hela cell and title complex 5 μMs, [Ir (ppy) 2 (phenSe)]
+(PF
6 -) (A), [Ir (dfppy) 2 (phenSe)]
+(PF
6 -) (B), [Ir (btp) 2 (phenSe)]
+(PF
6 -) (C), [Ir (2-pq) 2 (phenSe)]
+(PF
6 -) (D), [Ir (dbq) 2 (phenSe)]
+(PF
6 -) (E) cultivate 30min, the regular hour is cultivated again with plastosome Green fluorescent dye Mitotracker-Green (50nM), sucking-off nutrient solution, then PBS buffer solution is used 3 ~ 4 times, imaging on Leica TCS SP5 laser scanning co-focusing microscope, use 63 '/1.4 oily mirrors, with 405nm light as excitation light source, collect the fluorescence within the scope of 560 ~ 630nm.Experimental result is shown in that (MitoTracker-Green excites and is respectively 490,516nm with emission wavelength Fig. 7, and complex of iridium excites, emission wavelength is respectively 458,600nm, scale: 50mm).Plastosome Green fluorescent dye Mitotracker-Green wherein can not affect by mitochondrial membrane potential the plastosome be positioned in viable cell, from Fig. 6 experimental result, a figure is the image that 490nm wavelength excites lower MitoTracker-Green dyestuff to be positioned in Hela cell mitochondrial, b figure is the image that 458nm wavelength excites lower title complex to be positioned in Hela cell, c figure is the Hela cell imaging under light field, d figure is all image coverage diagrams, can see that a figure and b figure luminous position overlap, illustrate that title complex is also positioned Hela cell mitochondrial, there is good viable cell plastosome coloring properties.
Embodiment 4MTT vitro cytotoxicity analysis design mothod
Select human cervical carcinoma cell (Hela), human liver cancer cell (HepG-2), the tumour cells such as lung carcinoma cell (A549) and people's normal mammary epithelial (MCF-10A) carry out this research.Well-grown cell 0.25% tryptic digestion is become single cell suspension, adopts blood counting chamber to carry out viable count, adjustment viable cell concentrations is 5 ' 10
4/ mL is inoculated in 96 well culture plates, every hole 160mL, cultivates after 24 hours, then adds the medicine of different concns respectively, be placed in 37 DEG C, is containing 5%CO
2incubator in hatch 48 hours, within first 4 hours, MTT 20mL/ hole is added in end, abandoning supernatant after 4 hours, add DMSO 100mL/ hole, vibrate about 10 minutes, be placed in multi-functional microplate reader, for avoiding the inhalation effects of iridium multi-pyridine ligand itself, measure 570nm and 607nm wavelength place OD value, by following formulae discovery survival rate:
Survival rate %=medicine feeding hole mean OD value/control wells mean OD value ' 100%
Experimental result is in table 2.MTT experiment result shows that the cell survival rate of title complex is high under low consistency conditions, and cytotoxicity is low, little to cell injury.
Table 2MTT method analyzes 5mM title complex to the cytotoxicity of HeLa, HepG-2, A549, MCF-10A cell
The laser co-focusing experiment of complex of iridium and MTT vitro cytotoxicity analysis design mothod illustrate that this title complex has good viable cell plastosome coloring properties, stronger cell membrane penetration and lower cytotoxicity, will have great application potential in biomarker and cell imaging.
Claims (7)
1. iridium-selenium multi-pyridine ligand, is characterized in that, the structural formula of the cationic moiety of described iridium-selenium multi-pyridine ligand is as shown in the formula any one of I, II, III, IV and V:
。
2. the preparation method of iridium-selenium multi-pyridine ligand as claimed in claim 1, is characterized in that comprising the following steps:
By chlorine bridging dimer [(N-C)
2ir (μ-Cl)]
2join in ethanol/methylene mixed solvent with the many pyridine ligands of selenium, heating reflux reaction under protection of inert gas;
N-C is wherein 2-(2,4 difluorobenzene base) pyridine, 2-(2-pyridyl) thionaphthene, dibenzo [f, h] quinoline Nuo Xilin, 2-phenylquinoline or 2-phenylpyridine;
Selenium many pyridine ligands structural formula is wherein as follows:
。
3. the preparation method of iridium-selenium multi-pyridine ligand as claimed in claim 2, is characterized in that: in described ethanol/methylene mixed solvent, the volume ratio of methyl alcohol and methylene dichloride is 2:1.
4. the preparation method of iridium-selenium multi-pyridine ligand as claimed in claim 2, is characterized in that: described reflux time is 6-10h.
5. the preparation method of iridium-selenium multi-pyridine ligand as claimed in claim 2, is characterized in that: after reaction terminates, be cooled to room temperature, filters, add NH in filtrate
4pF
6methyl alcohol saturated solution, revolve steaming, the precipitation of generation is dry after filtering, crosses neutral alumina column, the ratio wash-out increased gradually in polarity with methylene dichloride and acetone mixture, obtains and dissolves the elutriant of pure products, be drying to obtain described iridium-selenium multi-pyridine ligand.
6. the preparation method of iridium-selenium multi-pyridine ligand as claimed in claim 5, is characterized in that: methylene dichloride and the acetone mixture of described methylene dichloride and acetone mixture to be volume ratio be 1:2-5:1.
7. iridium-selenium multi-pyridine ligand is preparing the application in viable cell mitochondrial dye reagent as claimed in claim 1.
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