Phosphorescence characteristics of ruthenium complex as an optical transducer for biosensors (original) (raw)
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Developing Red-Emissive Ruthenium(II) Complex-Based Luminescent Probes for Cellular Imaging
Ruthenium(II) complexes have rich photophysical attributes, which enable novel design of responsive luminescence probes to selectively quantify biochemical analytes. In this work, we developed a systematic series of Ru(II)-bipyrindine complex derivatives, [Ru(bpy)3-n(DNP-bpy)n](PF6)2 (n = 1, 2, 3; bpy, 2,2′-bipyridine; DNP-bpy, 4-(4-(2,4-dinitrophenoxy)phenyl)-2,2′-bipyridine), as luminescent probes for highly selective and sensitive detection of thiophenol in aqueous solutions. The specific reaction between the probes and thiophenol triggers the cleavage of the electron acceptor group, 2,4-dinitrophenyl, eliminating the photoinduced electron transfer (PET) process, so that the luminescence of on-state complexes, [Ru(bpy)3-n(HP-bpy)n]2+ (n = 1, 2, 3; HP-bpy, 4-(4-hydroxyphenyl)-2,2′-bipyridine), is turned on. We found that the complex [Ru(bpy)(DNP-bpy)2]2+ remarkably enhanced the on-to-off contrast ratio compared to the other two (37.8 compared to 21 and 18.7). This reveals a new strategy to obtain the best Ru(II) complex luminescence probe via the most asymmetric structure. Moreover, we demonstrated the practical utility of the complex as a cell-membrane permeable probe for quantitative luminescence imaging of the dynamic intracellular process of thiophenol in living cells. The results suggest that the new probe could be a very useful tool for luminescence imaging analysis of the toxic thiophenol in intact cells.
Sensors and Actuators B: Chemical, 2000
A range of fluorescent ruthenium II polypyridyl complexes have been employed in an optical sensor device for pH analysis. The dye materials were immobilised in a sol-gel glass matrix and characterised upon exposure to aqueous buffer solutions. Changes of below 0.1 pH units were detectable using these dye-doped glass films, and linear ranges as large as pH 3-9 were observed. Sol-gel immobilisation effectively enhanced the operating range of these materials compared to solution. Interference from fluorescence quenching due to molecular oxygen was found to place important restrictions on the nature of dyes suitable for this application. q 2000 Elsevier Science S.A. All rights reserved.
Development of a Ruthenium(II) Complex-Based Luminescent Probe for Hypochlorous Acid in Living Cells
A unique ruthenium(II) complex, [Ru(bpy)2(DNPS-bpy)](PF6)2 (bpy: 2,2′-bipyridine, DNPS-bpy: 4-(2,4-dinitrophenylthio)methylene-4′-methyl-2,2′-bipyridine), has been designed and synthesized as a highly sensitive and selective luminescence probe for the recognition and detection of hypochlorous acid (HOCl) in living cell samples. The probe can rapidly and specifically react with HOCl to afford a highly luminescent bipyridine-Ru(II) complex derivative, [Ru(bpy)2(COOH-bpy)](PF6)2 (COOH-bpy: 4′-methyl-2,2′-bipyridyl-4-carboxylic acid), accompanied by the remarkable luminescence enhancement.
A Highly Sensitive Fluorescent Chemosensor for Ruthenium: Oxidation Plays a Triple Role
Chemistry - A European Journal, 2013
A Highly Sensitive Fluorescent Chemosensor for Ruthenium: Oxidation Plays a Triple Role Ruthenium comes to its senses: Determining how effectively ruthenium residues are removed from olefin metathesis reactions calls for an alternative evaluation method to ICP-MS. A fluorescent chemosensor for ruthenium has been developed based on an alkene oxidation reaction (see figure). This fluorescence method has a good selectivity as well as an excellent sensitivity and a 0.32 ppb detection limit. Its streamlined and high-throughput character is demonstrated by sensing residual Ru in samples containing functionalized organic compounds.
The Analyst, 1993
A simple, low-cost technique for the fabrication of optical sensors for oxygen is described and preliminary results obtained using these sensors are reported. The technique is based on coating a declad portion of an optical fibre with a microporous glass film prepared by the sol-gel process. A ruthenium complex [Rut'-tris-(2,2'-bipyridine) or Ru~~-tris(4,7-diphenyl-l,1O-phenanthroline)] is trapped in the nanometre-scale cage-like structure of the porous film. In this sensor configuration the complex is excited by the evanescent field of the 488 nm radiation guided by the optical fibre. The luminescence from such complexes is known t o be quenched by oxygen and the sensors exhibit repeatable quenching behaviour when exposed t o various concentrations of oxygen. The ratio R = lo/lloo where lo and llo0 represent the detected signals from a sensor exposed t o 100% nitrogen and 100% oxygen, respectively, is used as a measure of the sensitivity of the sensor. Sensors based on the diphenylphenanthroline complex exhibit greater sensitivity than those based o n the bipyridine complex, in accordance with theoretical predictions. More importantly, however, the design potential of the sol-gel process for sensor fabrication is demonstrated by the achievement of a substantial increase in R when the process parameters are adjusted t o increase the pore volume.
Development of a functional ruthenium (II) complex for probing hypochlorous acid in living cells
A functional ruthenium(II) complex, [Ru(bpy)2(AN-bpy)](PF6)2 (bpy: 2,2′-bipyridine, AN-bpy: 4-methyl-4′-(4-amino-3-nitro-phenoxy-methylene)-2,2′-bipyridine), has been designed and synthesized as a turn-on luminescent probe for the imaging of hypochlorous acid (HOCl) in living cells. Due to the intramolecular photoinduced electron transfer (PET), the ruthenium(II) complex itself is almost non-luminescent. However, it can specifically and rapidly react with HOCl in aqueous media to afford a highly luminescent derivative, [Ru(bpy)2(HM-bpy)](PF6)2 (HM-bpy: 4-hydroxymethyl-4′-methyl-2,2′-bipyridine), accompanied by a 110-fold luminescence enhancement. Taking advantage of high specificity and sensitivity, and excellent photophysical properties of the ruthenium(II) complex probe, [Ru(bpy)2(AN-bpy)](PF6)2 was successfully applied to the luminescence imaging of the exogenous HOCl in living HeLa cells and the endogenous HOCl in porcine neutrophils. The results corroborate that indeed [Ru(bpy)2(AN-bpy)](PF6)2 is a useful luminescent probe for the monitoring of HOCl in biological systems.
Designing photoreactive Ruthenium(II) complexes for biomedical applications
2012
The development of therapeutic agents represents one of the main research objectives in the fight against cancer. In this context, the “laboratoire de Chimie Organique et Photochimie” focuses its interest in the design of photoreactive Ruthenium II complexes. The interesting photoreactivity is mainly due to the photooxidizing properties of complexes bearing deficient ligands. It has been demonstrated that a photo-induced electron transfer (PET) is indeed possible between a DNA guanine moiety and a Ru II complex containing at least two accepting ligands. This primary PET process can lead to the formation of a photoadduct, in which a covalent link is formed between the Ru II complex and a DNA strand. This covalent binding allows the development of gene silencing strategies where two complementary oligonucleotides (ODNs) are irreversibly photocrosslinked. The present work concerns the preparation and a first photophysical study of new Ru II
Journal of Fluorescence, 2008
Photophysical constants of three novel ruthenium dyes derived from tridentate pyridinediimine (pydim) ligands has been declared and their photoluminescent properties were investigated in solvents of dichloromethane (DCM), tetrahydrofuran (THF) and ethanol (EtOH) by UV-Visible absorption, emission and excitation spectra. The quantum yield, fluorescence decay time, molar extinction coefficient and Stoke's shift values of the novel ruthenium complexes were determined. The perfluoro compound (PFC) nonadecafluorodecanoic acid which is also known as medical gas carrier has been used for the first time together with newly synthesized Ruthenium complexes in ethyl alcohol. The utilities of oxygen sensing materials were investigated in EtOH in presence of chemically and biochemically inert PFC.
Talanta, 1994
A flow injection analysis system for a reduced form of nicotinamide adenine dinucleotide (NADH) was constructed by the electrogenerated chemiluminescence using ruthenium tris(2,2'-bipyridine) complex, and this technique was applied to the determination of ethanol concentration by using an immobilized alcohol dehydrogenase (ADH). The NADH determination was optimum under the following conditions. The flow rate was 1.5 to 2.0 ml/mitt, and the applied voltage was 1.6 V. The NADH calibration plot showed the linear correlation in the concentration range 10 to 250rM, and the lower detection limit was 10pM. Ethanol was successfully measured in the concentration range 10 ppm to 5% by using ADH-immobilized glass beads.
Nitric oxide (NO) is one of the most important intercellular signaling molecules, and plays important roles in various biological systems. In this work, a unique RuII complex, tris[(5-(4-methylamino-3-aminobenzylamino)-1,10-phenanthroline)] ruthenium(II) hexafluorophosphate [Ru(MAA-phen)3][PF6]2, has been designed and synthesized as a luminescent probe for the detection of NO in aqueous media. The complex itself is almost non-luminescent, but can specifically react with NO under the aerobic conditions to afford its highly luminescent triazole derivative in aqueous media, [Ru(MTA-phen)3]2+ (MTA-phen: methyl-trazolebenzylamino-1,10-phenanthroline), accompanied by a 302-fold increase in luminescence intensity at 598 nm with a 130 nm Stokes shift. The luminescence response of [Ru(MAA-phen)3]2+ to NO is rapid, highly specific without interferences of other reactive oxygen/nitrogen species, and highly stable against the pH changes in the range of pH 4.5–9.5. These features enable [Ru(MAA-phen)3]2+ to be used as a probe for the highly selective and sensitive luminescence detection of NO in weakly acidic, neutral, and weakly basic media.