CN102464676B - Ruthenium (II)-polypyridine complex, and preparation method and application thereof - Google Patents
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Abstract
The invention provides a ruthenium (II)-polypyridine complex. For the ruthenium (II)-polypyridine complex, bipyridyl (bpy) or phenanthroline hydrate (phen) is used as an ancillary ligand, and dipyridine[3,2-a:2',3'-c]phenazine-11,12-imidazole (dppzi) is used as a main ligand. The preparation method comprises the following steps: preparing 5,6-dinitrobenzimidazole from 5,6-nitrobenzimidazole; reducing 5,6-dinitrobenzimidazole into 5,6-diaminobenzimidazole by using hydrazine hydrate and palladium/carbon; preparing dppzi from phenanthroline hydrate-5,6-dione and 5,6-diaminobenzimidazole and preparing cis-[Ru(bpy)2Cl2].2H2O from ruthenium trichloride, bpy and lithium chloride; preparing cis-[Ru(phen)2Cl2].3H2O from ruthenium trichloride, phen and lithium chloride; carrying out a heating reflux reaction on dppzi and cis-[Ru(bpy)2Cl2].2H2O or cis-[Ru(phen)2Cl2].3H2O under the protection of argon, carrying out cooling, adding ammonium hexafluorophosphate, allowing precipitate to deposit and carrying out filtration and column chromatography so as to obtain a target product. The ruthenium (II)-polypyridine complex provided in the invention can be used as an optical switch for G-quadruplex DNA molecules.
Description
Technical field
The present invention relates to metal complexes, be specifically related to a kind of ruthenium (II) multi-pyridine ligand and its preparation method and application.
Background technology
Ruthenium outermost layer has 4d
75s
1structure, its common valence state is Ru (I), Ru (II) and Ru (III), and is easy to form the title complex of hexa-coordinate.Transition metal ruthenium (II) multi-pyridine ligand has unique DNA binding ability, good electrochemistry, photochemistry, Photophysics and abundant fluorescent property, and there is hypotoxicity, the feature that easily absorbs and easily drain.The aspects such as charge transfer, DNA footprint reagent, DNA break reagent and anticarcinogen at DNA structure probe, DNA have a wide range of applications, and have caused widely and have paid close attention to, and become very active forward position and crossing domain.[1] the particularly discovery of DNA-molecular light switch ruthenium complexe, causes the concern that people are larger.These title complexs in water, do not have or fluorescence very weak, but in aqueous dna, there is strong fluorescent emission, so these title complexs are called DNA-molecular light switch title complex.[2,3] are well-known, [Ru (phen)
2dppz]
2+[Ru (bpy)
2dppz]
2+the extensive good DNA molecular photoswitch title complex of approval, however the large quantity research of relative engagement thing and double-stranded DNA bonding, and [Ru(bpy)2(dppzi) is as G-tetra-serobila DNA molecular photoswitches rarely seen report also.
Summary of the invention
Object of the present invention, exactly for provide a kind of can be as ruthenium (II) multi-pyridine ligand of G-tetra-serobila DNA molecular photoswitches and preparation method thereof.
In order to achieve the above object, the present invention has adopted following technical scheme: a kind of ruthenium (II) multi-pyridine ligand, be characterized in, described ruthenium (II) multi-pyridine ligand is with two pyridines [3,2-a:2 ', 3 '-c] and azophenlyene-11,12-imidazoles is main part, using dipyridyl or phenanthroline as ruthenium (II) title complex of assistant ligand, and the chemical formula of this ruthenium (II) multi-pyridine ligand is [Ru (bpy)
2dppzi] (PF
6)
2or [Ru (phen)
2dppzi] (PF
6)
2, wherein, [Ru (bpy)
2dppzi] (PF
6)
2following (1) formula of structural formula shown in, [Ru (phen)
2dppzi] (PF
6)
2shown in following (2) formula of structural formula;
Bpy represents dipyridyl, and phen represents phenanthroline, and dppzi represents two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11,12-imidazoles.
The preparation method of above-mentioned ruthenium (II) multi-pyridine ligand, comprises the following steps:
1) 5,6-dinitrobenzene benzo imidazoles synthetic
By 5-nitrobenzimidazole reacting by heating under the vitriol oil and nitrosonitric acid environment, cooling rear with sodium hydroxide neutralization, prepare 5,6-dinitrobenzene benzo imidazoles;
2) 5,6-diamino benzo imidazoles synthetic
By step 1) gained 5,6-dinitrobenzene benzo imidazoles is usingd palladium carbon as catalyzer, usings hydrazine hydrate as reductive agent, usings ethanol as solvent, under argon shield, reacts, and reaction product activated carbon decolorizing, filters, and prepares 5,6-diamino benzo imidazoles;
3) phenanthroline-5,6-diketone synthetic
With phenanthroline and Potassium Bromide, under the effect of vitriol oil concentrated nitric acid, prepare phenanthroline-5,6-diketone;
4) two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11, the main part of 12-imidazoles synthetic
By phenanthroline-5,6-diketone and 5,6-dinitrobenzene benzo imidazoles, with the mixed in molar ratio of 1:1, add methyl alcohol or ethanol as solvent, and reflux is prepared two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11, the main part of 12-imidazoles;
5) cis-[Ru (bpy)
2cl
2] .2H
2o's is synthetic
Use RuCl
3, dipyridyl and lithium chloride in DMF, reflux under argon shield, adds acetone after cooling, prepares cis-[Ru (bpy)
2cl
2] .2H
2o;
6) cis-[Ru (phen)
2cl
2] .3H
2o's is synthetic
Use RuCl
3, phenanthroline and lithium chloride in DMF, argon shield reflux, adds acetone after cooling, prepares cis-[Ru (phen)
2cl
2] .3H
2o;
7) [Ru (bpy)
2dppzi] (PF
6)
2synthetic
By cis-[Ru (bpy)
2cl
2] .2H
2o and two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11,12-imidazoles, with the mixed in molar ratio of 1:1, adds ethylene glycol, at argon shield and 120 ℃, reacts 6h, and cooling, thin up, adds NH
4pF
6saturated solution, obtains red precipitate, suction filtration, and water and ether washing precipitation, will precipitate and be dried, and with acetonitrile, dissolve, and use neutral alumina column chromatography for separation, by main red part under eluent wash-out, boil off solvent, obtain red powder for [Ru (bpy)
2dppzi] (PF
6)
2product;
8) [Ru (phen)
2dppzi] (PF
6)
2synthetic
By cis-[Ru (phen)
2cl
2] .3H
2o and two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11,12-imidazoles, with the mixed in molar ratio of 1:1, adds ethylene glycol, at argon shield and 120 ℃, reacts 6h, is chilled to room temperature, and thin up, adds NH
4pF
6saturated solution, obtains red precipitate, suction filtration, and water and ether washing precipitation, will precipitate and be dried, and with acetonitrile, dissolve, and use neutral alumina column chromatography for separation, by main red part under eluent wash-out, boil off solvent, obtain red powder for [Ru (phen)
2dppzi] (PF
6)
2product.
The concentration of the vitriol oil described in step 1) is 98%.
The weight percentage of the Pd in palladium-carbon catalyst step 2) is 5%.
RuCl in step 5)
3with the mol ratio of dipyridyl be 1:2, RuCl in step 6)
3with the mol ratio of phenanthroline be 1:2.
Eluent described in step 7) and step 8) is mixed and forms by the volume ratio of 1:3 by toluene and acetonitrile.
As telomere G-tetra-serobila DNA molecular photoswitches.
The telomere G-tetra-serobila DNA that described telomere G-tetra-serobila DNA are people.
Described telomere G-tetra-serobila DNA contain 22 Nucleotide.
The nucleotides sequence of described telomere G-tetra-serobila DNA is classified 5 '-AGGGTTAGGGTTAGGGTTAGGG-3 ' as, is called for short AG
3(T
2aG
3)
3.
Ruthenium in the present invention (II) multi-pyridine ligand has good G-tetra-serobila DNA molecular photoswitch performances; Can be used as G-tetra-serobila DNA molecular photoswitches.
Accompanying drawing explanation
Figure 1 shows that [Fe (CN)
6]
4-titration Ru-polypyridine complex [Ru (bpy)
2dppzi]
2+fluorescent quenching figure;
Figure 2 shows that G-tetra-serobila DNA titration Ru-polypyridine complex [Ru (bpy)
2dppzi]
2+the luminescent spectrum figure of the aqueous solution.
Embodiment
The preparation method of ruthenium of the present invention (II) multi-pyridine ligand, specifically comprises the following steps:
1, main part two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11, the preparation of 12-imidazoles (dppzi)
1) 5,6-dinitrobenzene benzo imidazoles synthetic
Under condition of ice bath, 2.0g5-nitrobenzimidazole and 30mL nitrosonitric acid are added in 250mL three-necked bottle, stir until dissolve completely, 98% the vitriol oil and the nitrosonitric acid (volume ratio is 1:1) that add again 15mL, at 110 ℃, stir 6h, add ice cube that reaction is stopped, the NaOH solution neutralization with 37%.Produce a large amount of faint yellow precipitations, filter, obtain thick product.With acetic acid ethyl dissolution, with silicagel column separated (ethyl acetate and toluene for eluent), obtain 5,6-dinitrobenzene benzo imidazoles.
2) 5,6-diamino benzo imidazoles synthetic
In 50mL three-necked bottle, add 2.08g(10mmol) 5,6-dinitrobenzene benzo imidazoles, 35ml ethanol and 5% palladium-carbon catalyst 0.25g; magnetic agitation; with separating funnel, drip 10mL hydrazine hydrate down nitrogen protection, frozen water are cooling, remove ice-water bath, be warming up to 40 ℃ and continue reaction 10h.Standing, filter, obtain red-brown clear solution, add gac, at 60-80 ℃, heated and stirred is 1 hour, and filtered while hot obtains colourless solution, and decompression is spin-dried for solvent, and with ethyl alcohol recrystallization, vacuum-drying, obtaining white plates crystal is 5,6-diamino benzo imidazoles.
3) phenanthroline-5,6-diketone synthetic
Mix and be placed in 4.0g phenanthroline and 4.0g Potassium Bromide thoroughly round-bottomed flask, then drip the mixing acid of the cold vitriol oil (40mL) and concentrated nitric acid (20mL).Drip after mixing acid, holding temperature is after 80-85 ℃ of reaction 3h, cooling.Be poured in 500mL frozen water, then with 10mol/L sodium hydroxide solution, be carefully neutralized to neutrality, with chloroform, solution is extracted.Merge after organic phase, wash with water.Finally with anhydrous sodium sulfate drying, spend the night.After filtration, decompression steams chloroform, solid product ethyl alcohol recrystallization, and obtaining yellow or orange-yellow needle-like crystal is phenanthroline-5,6-diketone.
4) main part is synthetic
By phenanthroline-5,6-diketone (0.42g, 2mmol), 5,6-diamino benzo imidazoles (0.30g, 2mmol) adds in three-necked bottle, adds 20ml methyl alcohol, reflux 2h, cooling, filter, by recrystallizing methanol, obtaining yellow crystals is main part two pyridines [3,2-a:2 ', 3 '-c] and azophenlyene-11,12-imidazoles (dppzi).
2. ruthenium (II) multi-pyridine ligand [Ru (bpy)
2dppzi] (PF
6)
2preparation
1) cis-[Ru (bpy)
2cl
2] .2H
2o's is synthetic
Take 1.56g (about 6mmol) RuCl
3.nH
2o, 1.87g(12mmol) dipyridyl (bpy) and 1.68g(28mmol) lithium chloride be placed in three-necked bottle, add 10ml DMF(N, dinethylformamide), reflux 8h under argon shield, is chilled to after room temperature, adds 50ml acetone, freeze overnight.Suction filtration, frozen water and cold washing with acetone several for precipitation, vacuum-drying, obtaining atropurpureus crystallite is cis-[Ru (bpy)
2cl
2] .2H
2o.
2) [Ru (bpy)
2dppzi] (PF
6)
2synthetic
Take 0.16g(0.3mmol) Cis-[Ru (bpy)
2cl
2] .2H
2o and 0.094g(0.3mmol) dppzi mixes, and adds 20mL ethylene glycol, at argon shield and 120 ℃, reacts 6h, is chilled to room temperature, adds the dilution of 50ml water, adds NH
4pF
6saturated solution, produces a large amount of red precipitates, suction filtration, and water and ether washing are for several times, dry.With acetonitrile, dissolve, with neutral alumina column separated (200 order).By main red part under toluene acetonitrile eluent (volume ratio 1:3) wash-out, boil off solvent, obtain red powder for [Ru (bpy)
2dppzi] (PF
6)
2product.
3.[Ru (phen)
2dppzi] (PF
6)
2preparation
1) cis-[Ru (phen)
2cl
2] .3H
2o's is synthetic
Take 1.56g (about 6mmol) RuCl
3.nH
2o, 2.40g(12mmol) phenanthroline (phen) and 1.68g(28mmol) lithium chloride in three-necked bottle, add 10mL DMF, reflux 8h under argon shield, is chilled to after room temperature, adds 50mL acetone, freeze overnight.Suction filtration, precipitation frozen water, cold washing with acetone several, vacuum-drying, obtaining atropurpureus crystallite is cis-[Ru (phen)
2cl
2] .3H
2o.
2) [Ru (phen)
2dppzi] (PF
6)
2synthetic
Take 0.17g(0.3mmol) cis-[Ru (phen)
2cl
2] .3H
2o and 0.094g(0.3mmol) dppzi mixes, and adds 20mL ethylene glycol, at argon shield and 120 ℃, reacts 6h, is chilled to room temperature, adds the dilution of 50mL water, adds NH
4pF
6saturated solution, produces a large amount of red precipitates, suction filtration, and water and ether washing are for several times, dry.With acetonitrile, dissolve, with neutral alumina column separated (200 order).By main red part under toluene acetonitrile eluent (volume ratio 1: 3) wash-out, boil off solvent, obtain red powder for [Ru (phen)
2dppzi] (PF
6)
2product.
Ruthenium of the present invention (II) multi-pyridine ligand, as the application of G-tetra-serobila DNA molecular photoswitches, is specifically implemented as follows:
One, the preparation of damping fluid:
Formulated by 10mM Tris and 100mM KCl, PH=7.0.
Two, the preparation of G-tetra-serobila DNA and title complex and concentration are determined
1) preparation of G-tetra-serobila DNA and concentration are determined
Get the rich G single stranded DNA (nucleotides sequence is classified 5 '-AGGGTTAGGGTTAGGGTTAGGG-3 ' as) of certain mass, be dissolved in damping fluid, be heated to seal to 90 ℃, and keep 5 minutes.Then naturally cool to room temperature, put into 4 ℃ of refrigerators and keep 24 hours, prepare G-tetra-serobila DNA.By its concentration of ultraviolet spectrometer measure and calculation.
[G]=K×A
260/228500(M)
In above formula, [G] represents the concentration of four serobila DNA, and K is extension rate.While measuring DNA absorbancy, as DNA excessive concentration, can cause absorbancy inaccurate, generally should be diluted to A and be advisable between 0.5-1.
2) preparation of title complex and concentration are determined
The preparation method of title complex is the same, and the concentration of title complex is calculated according to corresponding quality and molecular weight.
Three, title complex and the interactional fluorometric assay of G-tetra-serobila DNA
Sweep limit: 500-800nm, excitation wavelength: 450nm, slit width: (10,10), voltage: 500V.
Preparation Ru-polypyridine complex solution 5uM, with excited by visible light, observes luminous situation.Drip [the Fe (CN) of 100mM
6]
4-, make fluorescent quenching.With micro sample adding appliance, at every turn toward the G-tetra-serobila DNA storing solutions that add same volume in sample pool, concentration ratio [DNA]/[Ru] of G-tetra-serobila DNA and title complex increases by a certain percentage, until saturated.Mix after approximately 5 minutes, the fluorescence spectrum of observing at 500-800nm scope monitoring title complex changes with about 450nm light source activation, records utilizing emitted light crest and luminous intensity at every turn.
Result shows: G-tetra-serobilas add after Ru-polypyridine complex, and fluorescence significantly strengthens.
Figure 1 shows that [Fe (CN)
6]
4-titration Ru-polypyridine complex [Ru (bpy)
2dppzi]
2+fluorescent quenching figure;
Figure 2 shows that G-tetra-serobila DNA titration Ru-polypyridine complex [Ru (bpy)
2dppzi]
2+the luminescent spectrum figure of the aqueous solution.
Claims (10)
1. a ruthenium (II) multi-pyridine ligand, it is characterized in that: described ruthenium (II) multi-pyridine ligand is with two pyridines [3,2-a:2 ', 3 '-c] and azophenlyene-11,12-imidazoles is main part, using dipyridyl or phenanthroline as ruthenium (II) title complex of assistant ligand, and the chemical formula of this ruthenium (II) multi-pyridine ligand is [Ru (bpy)
2dppzi] (PF
6)
2or [Ru (phen)
2dppzi] (PF
6)
2, wherein, [Ru (bpy)
2dppzi] (PF
6)
2following (1) formula of structural formula shown in, [Ru (phen)
2dppzi] (PF
6)
2shown in following (2) formula of structural formula;
Bpy represents dipyridyl, and phen represents phenanthroline, and dppzi represents two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11,12-imidazoles.
2. the preparation method of ruthenium as claimed in claim 1 (II) multi-pyridine ligand, is characterized in that, comprises the following steps:
1) 5,6-dinitrobenzene benzo imidazoles synthetic
By 5-nitrobenzimidazole reacting by heating under the vitriol oil and nitrosonitric acid environment, cooling rear with sodium hydroxide neutralization, prepare 5,6-dinitrobenzene benzo imidazoles;
2) 5,6-diamino benzo imidazoles synthetic
By step 1) gained 5,6-dinitrobenzene benzo imidazoles is usingd palladium carbon as catalyzer, usings hydrazine hydrate as reductive agent, usings ethanol as solvent, under argon shield, reacts, and reaction product activated carbon decolorizing, filters, and prepares 5,6-diamino benzo imidazoles;
3) phenanthroline-5,6-diketone synthetic
With phenanthroline and Potassium Bromide, under the effect of vitriol oil concentrated nitric acid, prepare phenanthroline-5,6-diketone;
4) two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11, the main part of 12-imidazoles synthetic
By phenanthroline-5,6-diketone and 5,6-dinitrobenzene benzo imidazoles, with the mixed in molar ratio of 1:1, add methyl alcohol or ethanol as solvent, and reflux is prepared two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11, the main part of 12-imidazoles;
5) cis-[Ru (bpy)
2cl
2] 2H
2o's is synthetic
Use RuCl
3, dipyridyl and lithium chloride in DMF, reflux under argon shield, adds acetone after cooling, prepares cis-[Ru (bpy)
2cl
2] 2H
2o;
6) cis-[Ru (phen)
2cl
2] 3H
2o's is synthetic
Use RuCl
3, phenanthroline and lithium chloride in DMF, argon shield reflux, adds acetone after cooling, prepares cis-[Ru (phen)
2cl
2] 3H
2o;
7) [Ru (bpy)
2dppzi] (PF
6)
2synthetic
By cis-[Ru (bpy)
2cl
2] 2H
2o and two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11,12-imidazoles, with the mixed in molar ratio of 1:1, adds ethylene glycol, at argon shield and 120 ℃, reacts 6h, and cooling, thin up, adds NH
4pF
6saturated solution, obtains red precipitate, suction filtration, and water and ether washing precipitation, will precipitate and be dried, and with acetonitrile, dissolve, and use neutral alumina column chromatography for separation, by main red part under eluent wash-out, boil off solvent, obtain red powder for [Ru (bpy)
2dppzi] (PF
6)
2product;
8) [Ru (phen)
2dppzi] (PF
6)
2synthetic
By cis-[Ru (phen)
2cl
2] 3H
2o and two pyridines [3,2-a:2 ', 3 '-c] azophenlyene-11,12-imidazoles, with the mixed in molar ratio of 1:1, adds ethylene glycol, at argon shield and 120 ℃, reacts 6h, is chilled to room temperature, and thin up, adds NH
4pF
6saturated solution, obtains red precipitate, suction filtration, and water and ether washing precipitation, will precipitate and be dried, and with acetonitrile, dissolve, and use neutral alumina column chromatography for separation, by main red part under eluent wash-out, boil off solvent, obtain red powder for [Ru (phen)
2dppzi] (PF
6)
2product.
3. the preparation method of ruthenium as claimed in claim 2 (II) multi-pyridine ligand, is characterised in that: the concentration of the vitriol oil described in step 1) is 98%.
4. the preparation method of ruthenium as claimed in claim 2 (II) multi-pyridine ligand, is characterised in that: step 2) described in the weight percentage of Pd in palladium-carbon catalyst be 5%.
5. the preparation method of ruthenium as claimed in claim 2 (II) multi-pyridine ligand, is characterised in that: RuCl in step 5)
3with the mol ratio of dipyridyl be 1:2, RuCl in step 6)
3with the mol ratio of phenanthroline be 1:2.
6. the preparation method of ruthenium as claimed in claim 2 (II) multi-pyridine ligand, is characterised in that: the eluent described in step 7) and step 8) is mixed and forms by the volume ratio of 1:3 by toluene and acetonitrile.
7. the application of ruthenium as claimed in claim 1 (II) multi-pyridine ligand in preparing telomere G-tetra-serobila DNA molecular photoswitches.
8. the application of ruthenium as claimed in claim 7 (II) multi-pyridine ligand, is characterised in that: the telomere G-tetra-serobila DNA that described telomere G-tetra-serobila DNA are people.
9. the application of ruthenium as claimed in claim 8 (II) multi-pyridine ligand, is characterised in that: described telomere G-tetra-serobila DNA contain 22 Nucleotide.
10. the application of ruthenium as claimed in claim 7 (II) multi-pyridine ligand, is characterised in that: the nucleotides sequence of described telomere G-tetra-serobila DNA is classified 5 '-AGGGTTAGGGTTAGGGTTAGGG-3 ' as.
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| CN102731577B (en) * | 2012-06-18 | 2014-12-24 | 广东药学院 | Synthetic method for ruthenium metal complex |
| CN102924525B (en) * | 2012-06-18 | 2015-01-07 | 广东药学院 | Synthesis method for novel ruthenium (II) polypyridyl complex |
| CN103145760B (en) * | 2012-12-27 | 2015-06-17 | 中国科学院上海硅酸盐研究所 | Post-processing method of ruthenium complex reaction liquid and obtained ruthenium complex crude products |
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