CN1289774A - Ruthenium (II) polypyridine match for two-stage pH sensing and its preparing process - Google Patents
Ruthenium (II) polypyridine match for two-stage pH sensing and its preparing process Download PDFInfo
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- CN1289774A CN1289774A CN 99119645 CN99119645A CN1289774A CN 1289774 A CN1289774 A CN 1289774A CN 99119645 CN99119645 CN 99119645 CN 99119645 A CN99119645 A CN 99119645A CN 1289774 A CN1289774 A CN 1289774A
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Abstract
A process for preparing ruthenium (II) polypyridine match used for two-class pH sensor includes such steps as refluxing bis (2,2'-dipyridine)-dichloro-dihydrated ruthenium (II) and phenanthrolinimidazole derivative ligand in nole ratio of 1:1 in solvent for several hours, removing solvent, and chromatographing. The dependency of match emission to pH is realized by electron transfer in molecule and the protonation and deprotonation of nitrogen-contained donor are used to realize the different responses of its emission intersity to low pH value and high pH value.
Description
The invention belongs to the luminous field of sensing technologies of pH, particularly belong to the preparation of ruthenium (II) multi-pyridine ligand and have and distinguish the secondary pH luminescence sensor characteristic that holds your noise and answer in low pH value district and high pH value.
Transmitter or sensor (sensor) are exactly the molecule to some character or analyte generation response.Usually, a sensor is made up of a molecular recognition component and a response component, and the former has the ability that combines with specific species in mixture, and the latter then can produce a signal correspondingly immediately and change after combination.Be subjected to the enlightenment of natural complicated phenomenon in the bioprocess, chemists have successfully synthesized the organic molecule of many complexity, as crown ether, cryptand, ball alkane, and calixarene etc., these molecular energies and specific lewis' acid chelating, they are bases of molecular recognition.In general, crown ether and related compound thereof combine the back and itself can not produce the physical properties with identity and change with specific species, and this signal transmission and responsive basis just.In order to overcome this difficulty, the host molecule of a new generation is used to this field, and it mainly is based on the luminescence sensor of transition metal complex.This light-emitting inorganic ionization sensor is made up of three parts: (1) ion identification position (2) takes place to connect in conjunction with earth complex luminescent component (3) recognizing site and the chemistry between the earth complex luminescent component of response to analyte.
Although many light-emitting transition metal title complexs are arranged, have only Ru-polypyridine complex and rhodium three carbonyl alpha-diimine title complexs to be used for luminescence probe.This is because their thermostability, chemical stability, water-soluble, strong visible absorbance, effectively emission and long-life excited state.And because their excited state is polar, its excited state characteristic is as the emission quantum yield, and emission lifetime and oxidation-reduction potential etc. can be subjected to assistant ligand to a great extent, solvent polarity, and other Effect of Environmental.Measuring method commonly used is to absorb, launch or refraction spectrum in optical pickocff, and lift-off technology has the intrinsic highly sensitive.Because emission wavelength always is longer than incident wavelength, be possible with respect to zero or closely zero background read output signal like this, transmit for the disturbance of launching and can pass through intensity, forms such as strength ratio or life-span are come record.Transition metal complex has many potential advantages as emitting probe, comprises long lifetime of excited state and high emission quantum yield.With typical nanosecond the organic fluorescence probe compare, long lifetime of excited state makes them be easy to measure, and provides effective time difference to ubiquitous short-life organic luminescent substance.
Ground state absorbs quantitative assay and the pH indicator that the material that changes with pH is used for pH already.But absorption spectrum generally is quite insensitive also difficult remote optical fiber and the little pH mensuration of being used for.The light emitting molecule that has the pH dependence on emmission spectrum can be used as sensitive pH indicator.Considerable biological phenomena all is to carry out under certain pH condition, and the pH in normal cell and the tumour cell has tangible difference.The rapid and accurate determination of pH value also is highly significant for diagnosing tumor in the cell, yet traditional pH meter is helpless.Have highly sensitive, volume is little, luminous pH transmitter that can telemetering should have potential in this respect and use.Although this luminous pH transmitter also is in early stage conceptual phase, bibliographical information is also rare, and its prospect is good.Lattice league (unit of length) in 1992 is (R.Grigg on the chemical communication of Englishize association will first, E.D.J.A.Norgert, J.Chem.Soc.Chem.Commun.1992,1300.) reported luminous pH transmitter based on the bipyridyl ruthenium title complex, they are that bipyridyl ruthenium links to each other with various amine by methylene radical, the emission that protonated and deprotonation by amine influences title complex produces the pH sensitivity, and the emission characteristic of title complex changes with the variation of pH.Lattice league (unit of length) in 1994 is again at the chemical communication (R.Grigg of Englishize association will, J.M.Holmes, S.K.Jones, E.D.J.A.Norgert, J.Chem.Soc.Chem.Commun.1994,185.) reported with the bipyridyl ruthenium to be luminescence unit, calixarene has been studied the characteristic of the emission of these compounds with the pH variation as the luminous pH transmitter of soda acid sensing unit.Although the emission characteristic of these molecules of report has the pH sensitivity characteristic, but the complex structure of compound, part calixarene 2,2 ＇-dipyridyl and 5,5 ＇-dimethyl dipyridyl is difficult for synthetic, and to pH is one-level sensitivity (promptly only responsive in a specific pH scope, as pH1-6 or pH7-11).
The objective of the invention is to overcome above-mentioned shortcoming, a kind of ruthenium simple in structure (II) multi-pyridine ligand is provided, its constructional feature is that nitrogenous electron donor(ED) covalent linkage is connected with ruthenium complexe, realized the dependence of the emission of title complex by the intramolecularly transfer transport to pH, and utilize nitrogenous protonated and deprotonation to realize that its emissive porwer responds respectively at low value and high value zone pH to body, make its characteristic, be used for highly sensitive diode luminescence pH transmitter with secondary sensitivity.And the part that has a soda acid sensitive group by the easiest obtain 5,6-phenanthroline diketone and one step of aldehyde obtain, and productive rate very high (70%-80%).The structural formula of ruthenium of the present invention (II) multi-pyridine ligand as shown in Figure 1.
The preparation method of Ru-polypyridine complex of the present invention carries out as follows:
With Ru (bpy)
2Cl
22H
2(1: 1, v/v) solvent refluxing 4-8 hour, cooled and filtered except that desolvating, added the saturated sodium perchlorate aqueous solution with filtrate, must precipitate with water-ethanol by 1: 1 mol ratio for O and phenanthroline imidazole ligands.This precipitation is used column chromatography after get purified product behind the recrystallization.Solvent is the mixed solvent of ethanol in water, and its volume ratio is 2: 1～5: 1.Column chromatography can be with silica gel or aluminium sesquioxide, and leacheate is the mixture of acetone and toluene, and volume ratio is 2: 1～5: 1.
Ru (bpy)
2Cl
22H
2The method for making of O is: with RuCl
33H
2O and 2,2 ＇-dipyridyl refluxed 3 hours in dimethyl formamide in 1: 1 in molar ratio, separated out the atropurpureus crystallization after concentrating, and filtered promptly.Synthesizing of phenanthroline imdazole derivatives part: with 5, the p-Aminobenzaldehyde of 6-phenanthroline diketone and replacement adds after 2.5 normal ammonium acetates refluxed 1 hour in Glacial acetic acid by 1: 1 mol ratio, cooling, neutralize with strong aqua, separate out yellow solid this moment, filter the back and obtain pure phenanthroline imdazole derivatives part with recrystallizing methanol.Wherein phenanthroline imdazole derivatives part is general formula Fig. 2:
The Ru-polypyridine complex of the present invention's preparation has strong absorption at visible region, in the aqueous solution of low pH, strong emission is arranged, weaken, when pH increases in the nitrogenous electron donor(ED) nitrogen-atoms deprotonation with the increase emission of pH, emissive porwer sharply weakens, and shows high pH susceptibility.When pH further was elevated to hydrogen atom ionization on the imidazoles secondary nitrogen-atoms, luminous intensity further weakened, and at this moment shows the second stage sensitivity to pH.Therefore title complex of the present invention can be used for the luminous pH transmitter of secondary sensitivity.
This invention has utilized nitrogenous forceful electric power to physical efficiency these characteristics of emission of cancellation ruthenium (II) multi-pyridine ligand effectively, designed the target compound that nitrogenous strong electron donor(ED) covalent linkage is connected with ruthenium complexe, realized the dependence of the emission of target compound by the intramolecularly transfer transport to pH, and utilized the protonated and deprotonation of nitrogen-atoms and the character such as ionization of hydrogen atom to realize pH is changed the characteristic with secondary sensitivity, promptly in pH3-6 and two zones of pH9-11.Target compound is simple in structure, and preparation is easily gone, and molecule is stable, and emission is strong and to pH change sensitivity height.Can be used for highly sensitive diode luminescence pH transmitter.
Below in conjunction with embodiment in detail the present invention is described in detail
The preparation method 0.2mmol Ru (bpy) of embodiment 1 ruthenium (II) pyridine complex 1
2Cl
22H
2O, 0.2mmol, 0.2mmol phenanthroline imidazole ligands (structure is among Fig. 2, R=H), the 20ml alcohol-water (3: 1, v/v) refluxed 5 hours, solution becomes red-brown.Cooled and filtered boils off after ethanol adds the 5ml water dissolution, adds the saturated sodium perchlorate aqueous solution of 10ml again, separates out yellow mercury oxide immediately, filters, and uses silica gel column chromatography, and (2: 1, v/v) drip washing got product to acetone/toluene, productive rate 75%.The evaluation uv-absorbing of this compound: λ
Max(CH
3CN) 453.5nm (ε=1.661 * 10
4).Nucleus magnetic resonance:
1HNMR (CD
3CN): 8.98-8.95 (dd, 2H), 8.57-8.50 (q, 4H), 8.41 (s, 1H), 8.07 (ddd, 2H), and 7.99-7.96 (m, 4H), 7.84-7.82 (dd, 2H), 7.74-7.72 (q, 2H), 7.55-7.54 (m, 2H), 7.42 (m, 2H), 7.18 (m, 2H).Ultimate analysis: molecular formula Ru (C
33H
24N
8) 2ClO
43H
2O, theoretical value C, 44.71%, H, 3.41%, N, 12.64%, observed value: C, 45.24%, H, 3.52%, N, 12.93%.
When given pH, the absorbing wavelength of compound 1 and emission quantum yield are in table one, and its pKa value example is in table two.Wherein containing imidazoles and be weak acid is again weak base, so medium pH changes and can influence it and launch, compound 1 has following equilibrium relationship:
When pH was low, emission was main next in protonated title complex; When pH was high, emission mainly from the compound 1 of deprotonation, two significantly sudden changes occurred so launch between pH0.35-13.
Embodiment 2 Ru-polypyridine complexes 2 are (among structure such as Fig. 1
The preparation method is with compound 1, and used phenanthroline imidazole ligands is R=among Fig. 2
Productive rate, 58%.The evaluation of this compound: uv-absorbing: λ
Max(CH
3CN) 457.5nm (ε=2.40 * 10
4).Nucleus magnetic resonance:
1HNMR (CD
3CN): 8.88 (dd, 2H), 8.57-8.51 (t, 4H), 8.07 (t, 2H), 7.94-7.83 (m, 8H), 7.64-7.59 (m, 4H), 7.43 (t, 2H), 7.23 (t, 2H), 6.70-6.67 (d, 2H), 2.96 (s, 6H).Ultimate analysis: molecular formula Ru (C
41H
33N
9) 2ClO
42H
2O, theoretical value: C, 49.86%, H, 3.78%, N, 12.76%, observed value: C, 50.12%, H, 3.85%, N, 12.23%.The absorbing wavelength of compound 2 when given pH, emission wavelength and emission quantum yield example are in table 1, and its pKa value example is in table 2.For compound 2, the acid base equilibrium relation below existing:
When pH＜1, imidazoles and N, three N atoms on the accelerine are all by protonated, along with the increase imidazoles of pH and the N atom deprotonation in succession on the aniline, 2 emission has bigger weakening, so in low pH zone (pH＜6), weakening of this emission derives from the intramolecularly transfer transport of aniline to ruthenium complexe, when further raising, pH arrives the generation of the H on secondary N ionization on the imidazoles, at this moment 2 emission weakens and comes from aniline and to the transfer transport and the negative ion itself of title complex the emission of title complex thing is weakened, and susceptibility improves greatly.
Absorbing wavelength, emission wavelength and the emission quantum yield of table 1. compound 1,2 when given pH
Table 2.1,2 pk
aValue
A: obtain b through the MLCT curve: the absorption variation through ultraviolet obtains.
Claims (4)
1. a ruthenium (II) multi-pyridine ligand is characterized in that nitrogenous electron donor(ED) covalent linkage is connected with ruthenium (II) title complex, and its general formula is:
2. according to the method for making of the described a kind of ruthenium of claim 1 (II) multi-pyridine ligand, it is characterized in that carrying out as follows: with two (2,2 ＇-dipyridyl)-two chloro-two hydration rutheniums (II) and phenanthroline imdazole derivatives 1: 1 in molar ratio refluxed for 5 a few hours in volume ratio is 2: 1～5: 1 alcohol-water, remove and desolvate, carry out silica gel column chromatography, do leacheate drip washing with 1: 1～4: 1 acetone/toluene solution.The structure of described phenanthroline imdazole derivatives part is a general formula:
3. the method for making of a kind of ruthenium as claimed in claim 2 (II) multi-pyridine ligand is characterized in that described solvent is the mixture of ethanol and water, and its volume ratio is 3: 1.
4. the method for making of a kind of ruthenium as claimed in claim 2 (II) multi-pyridine ligand. it is characterized in that described chromatography processing, can be silica gel or alumina chromatographic column, its leacheate is the mixture of acetone and toluene, and volume ratio can be 2: 1.
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| JP2007511504A (en) * | 2003-11-14 | 2007-05-10 | ローラス セラピューティクス インコーポレーテッド | Arylimidazoles and their use as anticancer agents |
| CN100412080C (en) * | 2005-04-06 | 2008-08-20 | 友达光电股份有限公司 | Organo-metallic complex and organic LED and display containing the complex |
| US7989089B2 (en) | 2003-04-17 | 2011-08-02 | Lg Display Co., Ltd. | Organic luminescent compounds and methods of making and using same |
| CN102188998A (en) * | 2011-03-25 | 2011-09-21 | 大连理工大学 | Water oxidation catalyst containing ruthenium as well as preparation and application thereof |
| US8148392B2 (en) | 2005-05-25 | 2012-04-03 | Lorus Therapeutics Inc. | 2-indolyl imidazo [4,5-d] phenanthroline derivatives and their use in the treatment of cancer |
| CN102755909A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Catalyst for preparing cyclohexane by benzene hydrogenation and preparation method thereof |
| US8394815B2 (en) | 2002-08-19 | 2013-03-12 | Lorus Therapeutics Inc. | 2,4,5-trisubstituted imidazoles and their use as anti-microbial agents |
| US9309247B2 (en) | 2013-03-20 | 2016-04-12 | Lorus Therapeutics Inc. | 2-substituted imidazo[4,5-D]phenanthroline derivatives and their use in the treatment of cancer |
| CN106750194A (en) * | 2016-12-20 | 2017-05-31 | 湘潭大学 | One class benzimidazole derivative containing Phen closes polymer-metal complex of Cd (II) and its production and use |
| CN109456365A (en) * | 2018-12-05 | 2019-03-12 | 湖南文理学院 | A kind of ruthenium complex fluorescence probe, preparation method and purposes |
| US11104957B2 (en) | 2013-10-04 | 2021-08-31 | Aptose Biosciences, Inc. | Compositions and methods for treating cancers |
| US11149047B2 (en) | 2017-10-30 | 2021-10-19 | Aptose Biosciences, Inc. | Aryl imidazoles for treatment of cancer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9217811D0 (en) * | 1992-08-21 | 1992-10-07 | Graetzel Michael | Organic compounds |
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- 1999-09-24 CN CN99119645A patent/CN1088713C/en not_active Expired - Fee Related
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| US8987305B2 (en) | 2002-08-19 | 2015-03-24 | Aptose Biosciences Inc. | 2,4,5-trisubstituted imidazoles and their use as anti-microbial agents |
| US8394815B2 (en) | 2002-08-19 | 2013-03-12 | Lorus Therapeutics Inc. | 2,4,5-trisubstituted imidazoles and their use as anti-microbial agents |
| US7989089B2 (en) | 2003-04-17 | 2011-08-02 | Lg Display Co., Ltd. | Organic luminescent compounds and methods of making and using same |
| US10080739B2 (en) | 2003-11-14 | 2018-09-25 | Aptose Biosciences Inc. | Aryl imidazoles and their use as anti-cancer agents |
| JP2007511504A (en) * | 2003-11-14 | 2007-05-10 | ローラス セラピューティクス インコーポレーテッド | Arylimidazoles and their use as anticancer agents |
| US8969372B2 (en) | 2003-11-14 | 2015-03-03 | Aptose Boisciences Inc. | Aryl imidazoles and their use as anti-cancer agents |
| CN100412080C (en) * | 2005-04-06 | 2008-08-20 | 友达光电股份有限公司 | Organo-metallic complex and organic LED and display containing the complex |
| US8148392B2 (en) | 2005-05-25 | 2012-04-03 | Lorus Therapeutics Inc. | 2-indolyl imidazo [4,5-d] phenanthroline derivatives and their use in the treatment of cancer |
| CN102188998A (en) * | 2011-03-25 | 2011-09-21 | 大连理工大学 | Water oxidation catalyst containing ruthenium as well as preparation and application thereof |
| CN102188998B (en) * | 2011-03-25 | 2012-11-14 | 大连理工大学 | Water oxidation catalyst containing ruthenium as well as preparation and application thereof |
| CN102755909B (en) * | 2011-04-28 | 2014-08-06 | 中国石油天然气股份有限公司 | Catalyst for preparing cyclohexane by benzene hydrogenation and preparation method thereof |
| CN102755909A (en) * | 2011-04-28 | 2012-10-31 | 中国石油天然气股份有限公司 | Catalyst for preparing cyclohexane by benzene hydrogenation and preparation method thereof |
| US9309247B2 (en) | 2013-03-20 | 2016-04-12 | Lorus Therapeutics Inc. | 2-substituted imidazo[4,5-D]phenanthroline derivatives and their use in the treatment of cancer |
| US11104957B2 (en) | 2013-10-04 | 2021-08-31 | Aptose Biosciences, Inc. | Compositions and methods for treating cancers |
| CN106750194A (en) * | 2016-12-20 | 2017-05-31 | 湘潭大学 | One class benzimidazole derivative containing Phen closes polymer-metal complex of Cd (II) and its production and use |
| CN106750194B (en) * | 2016-12-20 | 2020-05-22 | 湘潭大学 | Polymeric metal complex containing phenanthroline imidazole derivative and Cd (II), and preparation method and application thereof |
| US11149047B2 (en) | 2017-10-30 | 2021-10-19 | Aptose Biosciences, Inc. | Aryl imidazoles for treatment of cancer |
| CN109456365A (en) * | 2018-12-05 | 2019-03-12 | 湖南文理学院 | A kind of ruthenium complex fluorescence probe, preparation method and purposes |
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