CN102675348A - Selenium polypyridine ligand, ruthenium-selenium polypyridine complex, and preparation methods and applications of selenium polypyridine ligand and ruthenium-selenium polypyridine complex - Google Patents
Selenium polypyridine ligand, ruthenium-selenium polypyridine complex, and preparation methods and applications of selenium polypyridine ligand and ruthenium-selenium polypyridine complex Download PDFInfo
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- CN102675348A CN102675348A CN2012100664376A CN201210066437A CN102675348A CN 102675348 A CN102675348 A CN 102675348A CN 2012100664376 A CN2012100664376 A CN 2012100664376A CN 201210066437 A CN201210066437 A CN 201210066437A CN 102675348 A CN102675348 A CN 102675348A
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Abstract
The invention discloses a selenium polypyridine ligand, a ruthenium-selenium polypyridine complex, and preparation methods and applications of the selenium polypyridine ligand and ruthenium-selenium polypyridine complex. The chemical name of the selenium polypyridine ligand provided by the invention is selenium-5,6-diketone-1,10-phenanthroline, which is prepared through the following steps of: taking 1,10-phenanthroline-5,6-diketone and selenium dioxide as the raw materials, and carrying out cooling filtering, washing, drying and the like after a heated reflux reaction. The invention also discloses a ruthenium-selenium polypyridine complex having a chemical formula as follows: [Ru(N-N)2(phendione)Se]2+(N-N=bpy, phen, dip or dpa); the ruthenium-selenium polypyridine complex is a compound derived from selenium-5,6-diketone-1,10-phenanthroline; the complex has excellent live cell nucleus coloring properties, high cell membrane penetrability and low cytotoxicity, and has great application potential in the aspects of biomarker and cell imaging.
Description
Technical field
The present invention relates to viable cell staining technique field, be specifically related to a kind of new many pyridine ligands of compound selenium, by this part deutero-ruthenium-selenium multi-pyridine ligand.
Background technology
It is deep day by day that the Along with people's pair cell is studied; Biomedical optical image technologies such as zeugmatography (MRI), PET (PET), single photon emission fault imaging (SPECT) and laser co-focusing fluorescence microscopy are also constantly developed, and the exploitation of the bio-imaging reagent that is fit to is a current research focus.At present, the commercial optical dye major part that is applied to the cell imaging field is some organic molecules, like PI, DAPI, EB, Hoechst etc.Yet; There are some shortcoming (V.Fernandez-Moreira in these organic molecules; F.L.Thorp-Greenwood and M.P.Coogan.Chem.Commun.2010,46,186-202): water-soluble relatively poor; Be easy to generate deposition in water surrounding (in substratum) and perhaps with after the cytosis separate out at once, influence Color; Have than higher cytotoxicity, after dyestuff and the cytosis, cause the death of cell, influence the observation of pair cell standard state; Light stability is low, and because of receiving in the air or the effect of promoting agent group (singlet oxygen etc.) in the medium, dyestuff is after the excitation wavelength irradiation; Fluorescence constantly weakens, and it is serious that light is drifted phenomenon, is unfavorable for the stable (M.S.Lowry of imaging; W.R.Hudson; R.A.Pascal and S.Bernhard.J.Am.Chem.Soc.2004,126,14129-14135); Excite and the intersection of emmission spectrum serious (stoke shif is little), generally about tens nanometers, be unfavorable for distinguishing endogenous fluorescence and the self-quenching that reduces dyestuff itself.Based on some shortcomings that organic dye exists, people more turn to sight on the transition metal complex with good photoelectricity attribute.
Transition metal complex, particularly Ru-polypyridine complex are because its good optical physics and spectrochemical property have its unique advantage aspect the cell imaging reagent.Ru-polypyridine complex as the cell imaging agent roughly can be divided into two kinds; The first kind is the Ru-polypyridine complex with tangible photoswitch effect; Promptly this compounds in the aqueous solution fluorescence by cancellation, emitting fluorescence not, but with the DNA effect after; Receive the protection of DNA hydrophobic structure, fluorescence strengthens greatly.This ruthenium complexe with molecular light switch effect has that background fluorescence is low, Stability Analysis of Structures, water-soluble strong, excite big and with emmission spectrum stoke displacement in the characteristics of long-wavelength region; Can directly be used for the dyeing of intracellular nucleic acid; Be the good DNA staining reagent of potential (M.Matson, F.R.Svensson, B.Norden and P.Lincoln.J.Phys.Chem.B 2011; 115,1706-1711; F.R.Svensson, M.Abrahamsson, N.Stromberg, A.G.Ewing and P.Lincoln.J.Phys.Chem.Lett.2011,2,397-401).
These cells with molecular light switch character title complex absorb and cell dyeing research tentatively begins.Research [the Ru (bpy) of Barton J.K. working group
2Dppz]
2+[Ru (phen)
2Dppz]
2+Cell absorb the back and find, it is relatively poor that title complex passes through the ability of cytolemma, its ability that gets into cell is directly proportional with its hydrophobicity.Title complex mainly concentrates on the tenuigenin position, and not discovery enhancing of fluorescence in the nucleus (A.Puckett Cindy and K.Barton Jacqueline.J.Am.Chem.Soc.2007,129,46-47).Palaniandavar M. working group finds [Ru (phen)
2Dppz]
2+Can get into dead cell apace, can be used for distinguishing the different cells component, be good dead cell dyestuff (V.Rajendiran, M.Palaniandavar, V.S.Periasamy and M.A.Akbarsha.J.Inorg.Biochem.2010,104,217-220).After modifying alkyl oxide on the dppz part, can strengthen its cell membrane permeability (F.R.Svensson, M.Li, B.Nord é n and P.Lincoln.J.Phys.Chem.B 2008,112,10969-10975; F.R.Svensson, M.Matson, M.Li and P.Lincoln.Biophys.Chem.2010,149,102-106).Alkyl oxide (OC with the end modified different lengths of phenyl ring of dppz
2H
5,-OC
4H
9,-OC
6H
13) its performance different dyeing effect.Cell to methyl alcohol after fixing, the title complex (OC that lipotropy is the strongest
6H
13) tend to transfect cell film, medium lipophilic title complex (OC
4H
9) be enriched in the RNA zone of kernel, and the most weak (OC of lipotropy
2H
5) the DNA zone of specially dying kernel.Relevant (M.Matson, F.R.Svensson, B.Norden and P.Lincoln.J.Phys.Chem.B2011,115,1706-1711 of localized selectivity in its cell with the selectivity of bonding; M.Ardhammar, P.Lincoln and B.Norden.J.Phys.Chem.B2001,105,11363-11368).In addition; Double-core Ru-dppz title complex can be to tenuigenin dyeing (the M.E.Jim é nez-Hern á ndez of V79Chinese hamster cells viable cell under the condition of electroporation as two reagent that insert of DNA; G.Orellana; F.Montero and M.T.Portol é s.Photochem.Photobiol.2000,72,28-34; B.Onfelt, L.Gostring, P.Lincoln, B.Norden and A.Onfelt.Mutagenesis 2002,17,317-320.).With the dppz verivate be bridgingligand double-core Ru-polypyridine complex [Ru (phen) 2tpphz] (tpphz=tetrapyrido [and 3,2-a:2 ', 3 '-c:3 ", 2 " h:2 " '; 3 " '-j] phenazine), can be used as viable cell DNA dyestuff (M.R.Gill, J.Garcia-Lara; S.J.Foster, C.Smythe, G.Battaglia and J.A.Thomas.Nat.Chem.2009; 1,662-667), be good viable cell imaging agents.
Second type is the hyperfluorescence of dependence itself, is positioned certain position of cell.But, therefore limit of the research of this type title complex in viable cell bio-imaging field because Ru-polypyridine complex because of its more weak cell migration rate, is difficult to surmount complete cytolemma.The monokaryon Ru-polypyridine complex is less at present as the painted report of viable cell, as at [Ru (bpy)
3]
2+Or [Ru (phen)
3]
2+Behind middle one or two carboxyl of introducing, title complex is permeates cell membranes successfully, the nucleus of dyeing of ground, location and viable cell; Be a kind of low toxicity, the good agent of viable cell nuclear imaging (E.Musatkina, H.Amouri, M.Lamoureux; T.Chepurnykh and C.Cordier, J.Inorg.Biochem., 2007; 101,1086).
Summary of the invention
The objective of the invention is to following several: provide a kind of selenium many pyridine ligands, by this many pyridine ligands of selenium deutero-ruthenium-selenium multi-pyridine ligand, and preparation method of the two and application.
The present invention realizes above-mentioned purpose by the following technical programs:
The many pyridine ligands of a kind of selenium are called for short phendione-Se, and its chemical name is a selenium-5,6-diketone-1, and the 10-phenanthroline, structural formula is suc as formula shown in the I:
The preparation method of the many pyridine ligands of above-mentioned selenium, step is following: with mass ratio be 1: 11,10-phenanthroline-5,6-diketone and tin anhydride add the Glacial acetic acid min. 99.5 post-heating and stir, backflow 6h postcooling filters to room temperature, filtrating is poured in the frozen water hold over night, suction filtration into; Water and ether repeatedly wash respectively, and vacuum-drying gets the many pyridine ligands of the said selenium of claim 1.Wherein 1,10-phenanthroline-5, the 6-diketone can prepare with the mature technology of common synthetic many pyridine ligands, like reference literature (M.Yamada; Y.Tanaka, Y.Yoshimato, S.Kuroda and I.Shimao, Bull.Chem.Soc.Jpn.; 1992,65,1006.) method.
Among the preparation method of the many pyridine ligands of said selenium, 1,10-phenanthroline-5; The weight ratio of 6-diketone and tin anhydride mixture and Glacial acetic acid min. 99.5 is preferably 4～5: 95～105; If precipitate lessly in the above-mentioned steps after the hold over night, can be preferably regulate pH value to neutral, with the increase precipitation capacity with ammoniacal liquor.
The application of the many pyridine ligands of selenium in preparation viable cell nuclear dyestuff.
A kind of ruthenium-selenium multi-pyridine ligand, chemical formula [Ru (N-N)
2(phendione) Se]
2+(N-N=bpy, phen, dip or dpa), structural formula are as shown in the formula among II, III, IV or the V any one:
Brief note is [Ru (bpy)
2(phendione) Se]
2+Brief note is [Ru (phen)
2(phendione) Se]
2+
Brief note is [Ru (dip)
2(phendione) Se]
2+Brief note is [Ru (dpa)
2(phendione) Se]
2+
The preparation method of above-mentioned ruthenium-selenium multi-pyridine ligand is earlier synthetic cis-[Ru (N-N)
2Cl
2] 2H
2O, phendione-Se joins in the terepthaloyl moietie with many pyridine ligands of selenium, and the following 120 ℃ of reflux 6h of argon shield are cooled to room temperature, add the water after-filtration, remove insolubles, slowly add excessive N aClO again
4, the deposition of generation is water and ether washing respectively behind suction filtration, crosses the neutral alumina post, and the use volume ratio is 1: 1 toluene and the drip washing of acetonitrile mixed solution, and vacuum-drying promptly gets said ruthenium-selenium multi-pyridine ligand; Wherein N-N is 2,2-dipyridyl (bpy), 1,10-o-phenanthroline (phen), 4,7-phenylbenzene-1,10-o-phenanthroline (dip) or 2,2 '-two pyridine amine (dpa).
The preparation method of said ruthenium-selenium multi-pyridine ligand, cis-[Ru (N-N)
2Cl
2] 2H
2The weight ratio of O and the many pyridine ligands of selenium is 5～6: 3～4.
Show above-mentioned 4 kinds of title complex [Ru (N-N) that contain phenanthroline diketone-selenium part of the present invention after deliberation
2(phendione) Se]
2+(N-N=bpy, phen, dip or dpa), the fluorescence intensity under aqueous conditions, life-span all are better than parent Ru-polypyridine complex [Ru (bpy)
3]
2+, diketone-the selenium part is good chromophore to this explanation phenanthroline.Thereby ruthenium-selenium multi-pyridine ligand can be used for preparing the nucleus dyestuff of viable cell.MTT and flow cytometry experimental result show that the cytotoxicity of title complex is very low, and the pair cell damage is little.
Compared with prior art, the present invention has following beneficial effect:
Many pyridine ligands of selenium molecular structure of the present invention is little; Compound method is simple, and by its deutero-ruthenium-selenium multi-pyridine ligand simple and stable structure, selenium element and the combination of phenanthroline diketone have weakened title complex becomes hydrogen bond with water molecules ability in this ruthenium (II) title complex; Strengthened the fluorescent characteristic of title complex greatly; Simultaneously, as one of human essential elements, the introducing of selenium element has also strengthened the cell transmembrane ability of title complex.Under the condition that need not cell pre-treatment (like electroporation or solvent fixing etc.); This title complex can be successfully painted to the nucleus in the viable cell; And have the characteristics of the cultivation time is short, dyeing is highly sensitive, the Premeabilisation of cells ability is strong, big stoke displacement, low cytotoxicity and fast light bleaching, will have great application potential aspect biomarker and the cell imaging.
Description of drawings
Many pyridine ligands of Fig. 1 selenium molecular structural formula.
Fig. 2 ruthenium-selenium multi-pyridine ligand molecular structural formula.
The route of synthesis of the many pyridine ligands of Fig. 3 selenium.
The route of synthesis of Fig. 4 ruthenium-selenium multi-pyridine ligand.
The fluorescence spectrum of Fig. 5 ruthenium-selenium multi-pyridine ligand, [Ru]=10 μ M, (L=Phendione-Se).
Fig. 6 HeLa cell respectively with the title complex [Ru (bpy) of 10 μ M
2(phendione-Se)]
2+(A), [Ru (phen)
2(phendione-Se)]
2+(B), [Ru (dip)
2(phendione-Se)]
2+(C), [Ru (dpa)
2(phendione-Se)]
2+(D) cultivate 30min, dye back cell imaging result altogether with DAPI (5 μ M).(a) fluorogram of DAPI pair cell after painted; (b) fluorogram of title complex pair cell after painted; (c) bright field visible light cell color-patch map; (d) a, b, the stack of c.
Embodiment
Embodiment 1 part selenium-5,6-diketone-1, the preparation of 10-phenanthroline (phendione-Se)
Part phendione-Se is the many pyridine ligands that completely newly do not appear in the newspapers, its synthetic simple and fast, and productive rate is high.Only need through two steps, wherein the first step is the reaction of the technology maturation of common synthetic many pyridine ligands.
(1) 1,10-phenanthroline-5, the 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 the ice bath cooling, in the three neck round-bottomed flasks that 4.0g o-phenanthroline and 4.0g Potassium Bromide are housed, drip 40cm
3The vitriol oil and 20cm
3The mixed solution of concentrated nitric acid, induction stirring simultaneously.After dropwising, remove ice bath, be warming up to 85 ℃ of reactions 3 hours.After reaction finishes, stop heating and remove prolong, let the bromine ease go.Cooled orange-yellow reaction soln is poured 200cm into fully
3In the frozen water,, there is a large amount of yellow mercury oxides to produce with the sodium hydroxide solution of the 10M pH=7 that neutralizes carefully.With this suspension liquid with 4 * 100cm
3Chloroform extraction.Merge organic phase, use 50cm
3Spend the night with anhydrous sodium sulfate drying again after the water washing.Boil off chloroform after the filtration, solid product is used ethyl alcohol recrystallization, gets orange-yellow needle-like crystal, and fusing point is 258 ℃.
(2) selenium-5,6-diketone-1,10-phenanthroline
With 1,10-phenanthroline-5, the 6-diketone (2.1g, 10mmol); Tin anhydride (2.1g, 19mmol) mixture heating up with the 100mL Glacial acetic acid min. 99.5 stirs, and backflow 6h postcooling is to room temperature; Filter, filtrating is poured in the 600mL frozen water, leave standstill after the night; If deposition is less, available ammoniacal liquor is regulated pH to neutral, suction filtration.Water and ether repeatedly wash respectively, vacuum-drying, brown solid 2.3g, i.e. selenium-5,6-diketone-1,10-phenanthroline.Productive rate: 79.6%.
(1) cis-[Ru (bpy)
2Cl
2] 2H
2O's is synthetic
The synthetic of this compound can prepare with reference to existing document (B.P.Sullivan, D.J.Salmn and T.J.Meyer, Inorg.Chem., 1978,17,3334).Take by weighing RuCl
3NH
2O 1.56g (about 6mmol), 2,2 '-dipyridyl 1.87g (12mmol), lithium chloride 1.68g (28mmol) is in 10cm
3In the N, reflux is about 8 hours under the argon shield.After being chilled to room temperature, add 50cm
3Acetone, freeze overnight.After suction filtration, deposition were cleaned with frozen water, cold acetone, vacuum-drying got the atropurpureus crystallite.Average yield 80%.
(2) cis-[Ru (phen)
2Cl
2] 2H
2O's is synthetic
The synthetic of this compound can prepare with reference to existing document (B.P.Sullivan, D.J.Salmn and T.J.Meyer, Inorg.Chem., 1978,17,3334).The same cis-of compound method [Ru (bpy)
2Cl
2] 2H
2O, (2.16g 12mmol) replaces bpy, and other steps are identical with phen.Productive rate 74%.
(3) cis-[Ru (dip)
2Cl
2] 2H
2O's is synthetic
The same cis-of compound method [Ru (bpy)
2Cl
2] 2H
2O, (3.98g 12mmol) replaces bpy, and other steps are identical with dip.Productive rate 82%.
(4) cis-[Ru (dpa)
2Cl
2] 2H
2O's is synthetic
The same cis-of compound method [Ru (bpy)
2Cl
2] 2H
2O, (2.05g 12mmol) replaces bpy, and other steps are identical with dpa.Productive rate 76%.
(5) [Ru (bpy)
2(phendione-Se)] (ClO
4)
2Synthetic
With cis-[Ru (bpy)
2Cl
2] 2H
2O (0.52g, 1mmol) and phendione-Se (0.32g 1.1mmol), joins in the 40mL terepthaloyl moietie, argon shield, 120 ℃ of reflux 6 hours, the reddish black clear liquid.Be cooled to room temperature, behind the elimination insolubles, add 200mL water excessively, slowly add excessive N aClO again
4, promptly produce a large amount of red-brown precipitations.Suction filtration, successively water, ether washing.The neutral alumina post, V (toluene): V (acetonitrile)=1: 1 drip washing purifying.Vacuum-drying gets dark red solid 0.62g, productive rate 68%.Anal.Calcd.for?C
32H
22Cl
2N
6O
10RuSe(％)：C，42.63；H，2.46；N，9.32.Found(％)：C，42.59；H，2.48；N，9.30.ES-MS(CH
3OH)m/z：351[M-2ClO
4]
2+，802[M-ClO
4]
+。
(6) [Ru (phen)
2(phendione-Se)] (ClO
4)
2Synthetic
Compound method is with [Ru (bpy)
2(phendione-Se)] (ClO
4)
2With cis-[Ru (phen)
2Cl
2] 2H
2(0.57g 1mmol) substitutes cis-[Ru (bpy) to O
2Cl
2] 2H
2O.Get red solid 0.57g, productive rate 60%.Anal.Calcd.for?C
36H
22Cl
2N
6O
10RuSe(％)：C，45.54；H，2.34；N，8.85.Found(％)：C，45.58；H，2.30；N，8.82.ES-MS(CH
3OH)m/z：376[M-2ClO
4]
2+，850[M-ClO
4]
+。
(7) [Ru (dip)
2(phendione-Se)] (ClO
4)
2Synthetic
Compound method is with [Ru (bpy)
2(phendione-Se)] (ClO
4)
2With cis-[Ru (dip)
2Cl
2] 2H
2(0.87g 1mmol) substitutes cis-[Ru (bpy) to O
2Cl
2] 2H
2O.Get red solid 0.68g, productive rate 55%.Anal.Calcd.for?d.for?C
60H
38Cl
2N
6O
10RuSe(％)：C，57.47；H，3.05；N，6.70.Found(％)：C，54.51；H，2.99；N，6.73.ES-MS(CH
3OH)m/z：528[M-2ClO
4]
2+，577[M-ClO
4]
+。
(8) [Ru (dpa)
2(phendione-Se)] (ClO
4)
2Synthetic
Compound method is with [Ru (bpy)
2(phendione-Se)] (ClO
4)
2With cis-[Ru (dpa)
2Cl
2] 2H
2(0.55g 1mmol) substitutes cis-[Ru (bpy) to O
2Cl
2] 2H
2O.Get red solid 0.45g, productive rate 48%.Anal.Calcd.for?C
32H
24Cl
2N
8O
10RuSe(％)：C，41.26；H，2.60；N，12.03.Found(％)：C，41.30；H，2.57；N，11.98.ES-MS(CH
3OH)m/z：366[M-2ClO
4]
2+，416[M-ClO
4]
+。
Complex fluorescent spectral detection result sees table 1 and Fig. 5.
The fluorescence data of each title complex of table 1
| ?Complex | λ MLCT，nm | λ em，nm | τ，ns | Φ em/Φ ref |
| ?[Ru(bpy) 3] 2+ | 450 | 600 | 225 | 1 |
| ?[Ru(bpy) 2(phendione-Se)] 2+ | 449 | 608 | 293 | 1.2 |
| ?[Ru(phen) 2(phendione-Se)] 2+ | 450 | 608 | 295 | 1.2 |
| ?[Ru(dip) 2(phendione-Se)] 2+ | 452 | 610 | 312 | 1.4 |
| ?[Ru(dpa) 2(phendione-Se)] 2+ | 451 | 606 | 276 | 1.2 |
The laser co-focusing experiment of embodiment 3Ru (II) title complex
Cell cultures: the Hela cell is cultivated in containing the DMEM substratum of 10% foetal calf serum, cell (5 * 10
8/ L) be seeded at the bottom of the special-purpose glass of Laser Scanning Confocal Microscope in the petridish petridish diameter 35mm, cover-glass thickness 0.085～0.13mm wherein, ware center micro-pore diameter 10mm, 5%CO
2Under 95% air conditions, 37 ℃ of cultivations, adherent growth 24 hours.
Laser Scanning Confocal Microscope-cell imaging: Hela cell and title complex { 10 μ M, [Ru (bpy) 2 (phendione-Se)]
2+(A), [Ru (phen) 2 (phendione-Se)]
2+(B), [Ru (dip) 2 (phendione-Se)]
2+(C), [Ru (dpa) 2 (phendione-Se)]
2+(D) } cultivate 30min; Again with and DAPI (5 μ M) cultivate the regular hour, the sucking-off nutrient solution washs 3～4 times with the PBS damping fluid then; On Leica TCS SP5 laser scanning co-focusing microscope, form images; Use 63 */1.4 oily mirrors, as excitation light source, collect the fluorescence in 560～630nm scope with 458nm light.Experimental result sees that (DAPI excites with emission wavelength and is respectively 405 Fig. 6, and 460nm, ruthenium complexe excite, emission wavelength is respectively 458,600nm, scale: 50 μ m).
Embodiment 4MTT vitro cytotoxicity analysis experiment
Select human cervical carcinoma cell (Hela), human liver cancer cell (HepG-2) for use, lung carcinoma cell tumour cells such as (A549) and people's normal breast epithelial cell (MCF-10A) carry out this research.Well-grown cell is become single cell suspension with 0.25% tryptic digestion, adopt blood counting chamber to carry out viable count, the adjustment viable cell concentrations is 5 * 10
4/ mL is inoculated in 96 well culture plates, and every hole 160 μ L cultivated after 24 hours, added the medicine of different concns more respectively, placed 37 ℃, were containing 5%CO
2Incubator in hatched 48 hours, in finishing to add in preceding 4 hours MTT 20 μ L/ holes, abandoning supernatant after 4 hours; Add DMSO100 μ L/ hole; Vibrated about 10 minutes, and placed multi-functional ELIASA, for avoiding the inhalation effects of Ru-polypyridine complex itself; Measure 570nm and 607nm wavelength OD value, calculate survival rate by following formula:
The average OD value of the average OD value/control wells in survival rate %=dosing hole * 100%
Half casualty-producing concentrations (IC is tried to achieve in mapping simultaneously
50), estimate medicine extracorporeal anti-tumor cytoactive with this, and compare with the effect of existing medicines such as cis-platinum.Experimental result is seen table 2.
Table 2MTT method is analyzed title complex to HeLa, HepG-2, A549, the cytotoxicity of MCF-10A cell
Claims (6)
1. the many pyridine ligands of selenium is characterized in that chemical name is a selenium-5,6-diketone-1, and the 10-phenanthroline, structural formula is suc as formula shown in the I:
2. the preparation method of the many pyridine ligands of the said selenium of claim 1 is characterized in that step is following: with mass ratio be 1: 11,10-phenanthroline-5; 6-diketone and tin anhydride add the Glacial acetic acid min. 99.5 post-heating and stir, and backflow 6h postcooling filters to room temperature; Filtrating is poured in the frozen water hold over night, suction filtration into; Water and ether repeatedly wash respectively, and vacuum-drying gets the many pyridine ligands of the said selenium of claim 1.
3. the application of the many pyridine ligands of the said selenium of claim 1 in preparation viable cell nuclear dye reagent.
4. ruthenium-selenium multi-pyridine ligand is characterized in that structural formula is as shown in the formula among II, III, IV or the V any one:
5. the preparation method of the said ruthenium of claim 4-selenium multi-pyridine ligand is characterized in that earlier synthetic cis-[Ru (N-N)
2Cl
2] 2H
2O joins in the terepthaloyl moietie with the many pyridine ligands of the said selenium of claim 1, and the following 120 ℃ of reflux 6h of argon shield are cooled to room temperature, add the water after-filtration, remove insolubles, slowly add excessive N aClO again
4, the deposition of generation is water and ether washing respectively behind suction filtration, crosses the neutral alumina post, and the use volume ratio is 1: 1 toluene and the drip washing of acetonitrile mixed solution, and vacuum-drying promptly gets said ruthenium-selenium multi-pyridine ligand;
Wherein N-N is 2,2-dipyridyl, 1,10-o-phenanthroline, 4,7-phenylbenzene-1,10-o-phenanthroline or 2,2 '-two pyridine amine.
6. the application of the said ruthenium of claim 4-selenium multi-pyridine ligand in preparation viable cell nuclear dye reagent.
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|---|---|---|---|---|
| CN102924531A (en) * | 2012-11-22 | 2013-02-13 | 中山大学 | Iridium-selenium polypyridine complex as well as preparation method and application thereof |
| CN104910211A (en) * | 2015-05-07 | 2015-09-16 | 中山大学 | Cyclometalated iridium (III) complex and preparation method and application thereof in living cell mitochondria dyeing |
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| CN102924531A (en) * | 2012-11-22 | 2013-02-13 | 中山大学 | Iridium-selenium polypyridine complex as well as preparation method and application thereof |
| CN102924531B (en) * | 2012-11-22 | 2015-10-07 | 中山大学 | Iridium-selenium multi-pyridine ligand and its preparation method and application |
| CN104910211A (en) * | 2015-05-07 | 2015-09-16 | 中山大学 | Cyclometalated iridium (III) complex and preparation method and application thereof in living cell mitochondria dyeing |
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