CN1289775A - Ruthenium (II) polypyridine match and its preparing process - Google Patents
Ruthenium (II) polypyridine match and its preparing process Download PDFInfo
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- CN1289775A CN1289775A CN 99119648 CN99119648A CN1289775A CN 1289775 A CN1289775 A CN 1289775A CN 99119648 CN99119648 CN 99119648 CN 99119648 A CN99119648 A CN 99119648A CN 1289775 A CN1289775 A CN 1289775A
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- ruthenium
- emission
- match
- polypyridine
- pyridine ligand
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Abstract
A ruthenium (II) polypyridine match used as high-senstivity luminous pH sensor is prepared through refluxing the bis (2,2'-dipyridine)-dichloro-dihydrated ruthenium II (Ru (bpy)2Cl2.2H2O) and phenolhydroxyl-contained phenanthrolinimidazole derivative ligand in mole ratio of 1:1 in water-alcohol solvent for 5 hours, removing solvent and chromatographying. The dependency of match emission to pH is realized by electron transfer in molecule. The emission of said compound has high sensitivity to pH change.
Description
The invention belongs to highly sensitive pH field of sensing technologies, particularly belong to preparation of ruthenium (II) multi-pyridine ligand and the luminous sensitive response of height thereof pH.
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 produced the organic molecule that has successfully synthesized 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 heat and 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.This ion (comprises H
+) control emission is not only meaningful but also significant equally for making up molecular electronic device to the ion-sensitive in the life science.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.The pH luminescence sensor of high-sensitivity miniature energy telemetering should have potential in this respect and use.Although this pH luminescence sensor 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 Englishize association will first, E.D.J.A.Norgert, J.Chem.Soc.Chem.Communication.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.The lattice league (unit of length) was again at the will (R.Grigg of Englishize association in 1994, J.M.Holmes, S.K.Jones, E.D.J.A.Norgert, J.Chem.Soc.Chem.Communication.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, the degree of its pH sensitivity also is not very high, and the emissive porwer in its pH sensitive range changes about 4-5 doubly.And the synthetic complexity of compound, particularly the part calixarene 2,2 '-dipyridyl and 5,5 '-dimethyl dipyridyl is difficult for synthetic.
The objective of the invention is to overcome above-mentioned shortcoming, a kind of ruthenium simple in structure (II) multi-pyridine ligand and preparation method thereof is provided.The structural formula of ruthenium of the present invention (II) multi-pyridine ligand is as follows:
The preparation method of Ru-polypyridine complex of the present invention carries out as follows: with Ru (bpy)
2Cl
22H
2O and phenanthroline imidazole ligands by 1: 1 mol ratio water-ethanol (1: 1, v/v) in the solvent backflow 4-8 hour, cooled and filtered will be steamed filtrate going out and be desolvated, add the saturated sodium perchlorate aqueous solution, must precipitate. this precipitation is settled out with adding the saturated sodium perchlorate aqueous solution behind the column chromatography again.Behind recrystallization, get purified product.Ru (bpy)
2Cl
22H
2The method for making of O is: with RuCl
3.3H
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 5,6-phenanthroline diketone and phenolic aldehyde add 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, its structural formula is:
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.
The Ru-polypyridine complex of the present invention's preparation has strong absorption at visible region, strong emission is arranged in the aqueous solution of acetonitrile and low pH, increase emission with pH weakens, when pH reaches the hydroxyl deprotonation of alkoxyl group phenol, emissive porwer sharply weakens, show the pH susceptibility of height, the emissive porwer in its pH sensitive area changes about 50 times, can be used for high-sensitive luminous pH transmitter.
It is forceful electric power to physical efficiency these characteristics of emission of cancellation ruthenium (II) multi-pyridine ligand effectively that this invention utilizes phenol oxygen base negative ion, o-alkoxyl phenol covalent linkage is linked to each other with ruthenium complexe, realized the dependence of the emission of target compound by the intramolecularly transfer transport, the characteristic of utilizing the good photophysical property of ruthenium complexe and changing with pH to pH.The emission of title complex of the present invention is very responsive to the variation of pH.In the pH5-11 scope, about 50 times of luminous intensity variations can be used for highly sensitive luminous pH transmitter.
Below in conjunction with embodiment in detail the present invention is described in detail
Embodiment
The preparation method is as follows for compound of the present invention (structural formula as previously mentioned): 0.2mmol Ru (bpy)
2Cl
22H
2O, 0.2mmol, 0.2mmol 4-hydroxyl-3-methoxyl group-phenanthroline imidazole ligands, 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, separate out yellow mercury oxide immediately, filter, use silica gel column chromatography, acetone/toluene (2: 1, v/v) drip washing gets product, productive rate 75%.The evaluation uv-absorbing of this compound: λ
Max(CH
3CN) 459.5nm (ε=2.18 * 10
4). nucleus magnetic resonance:
1HNMR (CD
3CN): 8.90-8.88 (d, 2H), 8.57-8.50 (t, 4H), 8.08-8.07 (td, 2H), 7.97-7.74 (m, 8H), 7.65-7.60 (m, 4H), 7.46-7.42 (td, 2H), 7.25-7.23 (t, 2H), 6.83 (d, 1H), 3.85 (s, 3H).Ultimate analysis: molecular formula Ru (C
40H
30N
8) 2ClO
43H
2O, theoretical value: C, 47.72%, H, 3.60%, N, 11.13%, observed value: C, 47.61%, H, 3.72%, N, 10.91%.yield, 73%.
The pKa value example of above-claimed cpd is in table 1 and following equilibrium relationship is arranged:
When hanging down pH, three grades of N atoms on the imidazoles are protonated, and with the rising deprotonation of pH, emissive porwer reduces.When pH sharply descends in 5 ~ 11 emissive porwers, its variation approximately is 50 times, this mainly be since O-methoxy phenol negative ion to due to the transfer transport cancellation of ruthenium complexe.This compound absorbing wavelength, emission wavelength, the emission quantum yield with the variation of pH in as table 2.
Table 1: the pk of title complex
aValue *
pk
a1????pk
a2????pk
a3????pk
a1 *????pk
a2 *??????pk
a3 *
1．97???8．5????10．61????／?????6．71????????／
Pk
a: obtain pk by absorbing titration curve
a *: obtain by the emission titration curve.All mensuration is all carried out in phosphate buffer solution, pH scope 0.55-12.6, pKa and pKa
*By the Henderson-Hasselbalch formula: (1) .log[(A
Max-A)/(A-A
Min)]=pKa (abs)-pH, and log[(φ
Max-φ)/(φ-φ
Min)]=pKa (1um)-pH estimation obtains.
Absorbing wavelength, emission wavelength and the emission quantum yield of the described compound of table 2. when given pH
| ????pH | ??λ em max(nm) | ????λ abs max(nm) | ????φ×10 3 |
| ????1 ????3 ????7 ????12 | ????635 ????632 ????620 ????630 | ????436 ????458 ????460 ????462 | ????49.0 ????46.0 ????10.5 ????0.51 |
Claims (2)
1. a ruthenium (II) multi-pyridine ligand is characterized in that the general formula of described ruthenium (II) multi-pyridine ligand is as follows:
2. the method for making of a kind of according to claim 1 ruthenium (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 5 hours in volume ratio is 3: 1 alcohol-water, remove and desolvate, carrying out silica gel column chromatography, is 2: 1 acetone/toluene leacheate drip washing with volume ratio.The structure of described phenanthroline imdazole derivatives part is:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119648A CN1087744C (en) | 1999-09-24 | 1999-09-24 | Ruthenium (II) polypyridine match and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119648A CN1087744C (en) | 1999-09-24 | 1999-09-24 | Ruthenium (II) polypyridine match and its preparing process |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101891627A (en) * | 2009-05-22 | 2010-11-24 | 中国科学院化学研究所 | Ruthenium-containing coordination compound and preparation method 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 |
| CN102465171A (en) * | 2010-11-05 | 2012-05-23 | 同济大学 | Application of polypyridyl ruthenium complex [Ru(bpy)2(dppzi)]<2+>, and application method thereof |
| CN102464676A (en) * | 2010-11-05 | 2012-05-23 | 同济大学 | Ruthenium (II)-polypyridine complex, and preparation method and application 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 |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112266402A (en) * | 2020-08-19 | 2021-01-26 | 深圳大学 | Polypyridine ruthenium complex and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9217811D0 (en) * | 1992-08-21 | 1992-10-07 | Graetzel Michael | Organic compounds |
-
1999
- 1999-09-24 CN CN99119648A patent/CN1087744C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8394815B2 (en) | 2002-08-19 | 2013-03-12 | Lorus Therapeutics Inc. | 2,4,5-trisubstituted imidazoles and their use as anti-microbial agents |
| US8969372B2 (en) | 2003-11-14 | 2015-03-03 | Aptose Boisciences Inc. | Aryl imidazoles and their use as anti-cancer agents |
| 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 |
| 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 |
| CN101891627A (en) * | 2009-05-22 | 2010-11-24 | 中国科学院化学研究所 | Ruthenium-containing coordination compound and preparation method thereof |
| CN101891627B (en) * | 2009-05-22 | 2015-04-29 | 中国科学院化学研究所 | Ruthenium-containing coordination compound and preparation method thereof |
| CN102464676B (en) * | 2010-11-05 | 2014-03-05 | 同济大学 | Ruthenium (II)-polypyridine complex, and preparation method and application thereof |
| CN102464676A (en) * | 2010-11-05 | 2012-05-23 | 同济大学 | Ruthenium (II)-polypyridine complex, and preparation method and application thereof |
| CN102465171A (en) * | 2010-11-05 | 2012-05-23 | 同济大学 | Application of polypyridyl ruthenium complex [Ru(bpy)2(dppzi)]<2+>, and application 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 |
| US11149047B2 (en) | 2017-10-30 | 2021-10-19 | Aptose Biosciences, Inc. | Aryl imidazoles for treatment of cancer |
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|---|---|
| CN1087744C (en) | 2002-07-17 |
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