• 분석과학
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• 제8권4호
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• pp.481-486
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• 1995

Quenching experiments by photoinduced electron transfer between a charged donor and a neutral acceptor were carried out in acetonitrile, dichloromethane and mixed solvents of acetonitrile and dichloromethane. Tris(2, 2'-bipyridine) ruthenium(II) ($[Ru(bpy)_3]^{2+}$) which has 2+ charge and dicyanobis (2, 2'-bipyridine) ruthenium(II) ($Ru(bpy)_2(CN)_2$) which has no charge were used as electron donors, and a series of tris(${\beta}$-diketonato) ruthenium (III) was used as acceptor. In dichloromethane, $[Ru(bpy)_3]^{2+}$ and its counter ions ($ClO{_4}^-$) form ion pair. In the estimate of ${\Delta}G$ of electron transfer, the electrostatic potential between counter ions and product ion pair produced by electron transfer must be taken into account. A similar effect of counter ions was found in mixed solvents of 10, 30, 50, 70 and 90% acetonitrile ratio in volume. The effect of counter ion on ${\Delta}G$ became smaller with the increase in acetonitrile ratio. The result in mixed solvents suggests that $[Ru(bpy)_3]^{2+}$ and its counter ions form ion pair even in 90% acetonitrile solution.

• Bulletin of the Korean Chemical Society
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• 제9권5호
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• pp.317-322
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• 1988

Premicellar precipitation, resolubilization and luminescing behaviors of $RuL_3^{2+}$ (L = bpy, phen, $Me_2bpy$) in aqueous alkylsulfate and sulfonate solutions were studied. Addition of the anionic surfactants to $RuL_3\;^{2+}$ solutions caused initial precipitation which was redissolved by further addition of the surfactants. The apparent solubility products $K_{sp}$'s of the precipitates were evaluated assuming 1:2 salt formation. The values were smaller as the ligand is more hydrophobic and the length of hydrocarbon chain of the surfactant is longer. The $K_{sp}$ values for L = bpy were constant over wide surfactant concentration range. However, those for L = $Me_2bpy$ and also for phen, but to less extent, increased with the surfactant concentration. The resolubilization of 1:2 salts was followed by red-shift of emission band and extensive emission quenching above critical concentration of the surfactants. The critical concentration was lower for more hydrophobic surfactant. For L = $Me_2bpy$, the blue-shifted emission band with enhanced emission intensity was observed in intermediate surfactant concentration region. The high ionic strength of media prevented the precipitate formation, but facilitated the red-shift of the emission bands. The results support that the precipitate is dissolved by accretion of surfactant anions to the salts to form water-soluble surfactant-rich $RuL_3$-surfactant anionic species. These species appeared to aggregate cooperatively to produce large clusters which exhibited the red-shifted emission.

• Bulletin of the Korean Chemical Society
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• 제19권10호
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Bulletin of the Korean Chemical Society
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• 제27권1호
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• pp.99-105
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• 2006

Polyamine dendrimers functionalized with electrochemiluminescent (ECL) polypyridyl Ru(II) complexes, dend-$[CO-(CH_2)_3-mbpy{\cdot}Ru(L)_2]_3(PF_6)_6$ (dend: N$(CH_2CH_2NH)_3$-, L: bpy, o-phen, phen-Cl, DTDP), were synthesized through the complexation of dendritic polypyridyl ligands to Ru(II) complexes. Their electrochemical redox potentials, photoluminescence (PL), and relative ECL intensities were studied. The ECL emissions produced by the reaction between the electro-oxidized $Ru^{3+}$ species of polyamine dendrimers and tripropylamine as a coreactant were measured in a static system with potential cycles between 0.8 and 1.3 V or through flow injection analysis with a potential of +1.3 V, and were compared to that of $[Ru(o-phen)_3](PF_6)_2{\cdot}Dend-[CO-(CH_2)_3-mbpy{\cdot}Ru(bpy)_2]_3(PF_6)_6$ showed an ECL intensity that was two-fold greater than that of the reference complex $[Ru(o-phen)_3](PF_6)_2$.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.663-665
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• 2014

• Bulletin of the Korean Chemical Society
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• 제7권2호
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• pp.137-142
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• 1986

The luminescence spectra of $Ru(bpy)_3^{2+}$ in poly(methacrylic acid) (PMA) solutions varied sensitively with pH. At pH < 5.5, the emission intensity increased with pH up to 4 times, while it decreased with pH beyond the pH. The enhanced emission intensity was accompanied by blue-shift of the emission maxima as much as 15 nm. The enhancement of emission intensity was attributed to the restricted rotational mobility of ligand of the cation bound to densely coiled PMA molecules at pH < 5.5. The sharp decrease in emission intensity with increasing pH near pH 5.6 was accounted for conformational transition of the polymer to more extended structure, which was also revealed in viscosity measurement. The enhancement of emission intensity became higher as NaCl concentration of the solution increased. The binding constant of $Ru(bpy)_3^{2+}$ with two carboxylate groups of PMA was calculated as $2{\times}10^5\;M^{-1}$ in 0.1 M NaCl at pH 5.2. The pH dependence of luminescence quenching rate of $Ru(bpy)_3^{2+}$ by $Cu^{++}$ also showed maximum near pH 5, and the rate was more than $10^3$ times higher than that in water, whereas the maximum enhancement of quenching rate (about 20 times) in poly(acrylic acid) (PAA) solution occurred at pH 4.5. On the other hand, the pH dependence for neutral water soluble nitrobenzene (NB) exhibited opposite trend to that of $Cu^{++}$. The quenching constant vs pH curve for $MV^{++}$ was composite of those for $Cu^{++}$ and NB. The anomalous high quenching rate for $Cu^{++}$ in PMA solution at pH < 5.5 was attributed to the binding of $Ru(bpy)_3^{2+}$ and $Cu^{++}$ to the same region of PMA, when it conforms densely coiled structure in the pH range. The observation of mininium quenching rate for NB near pH 5.5 indicated that the $Ru(bpy)_3^{2+}$ bound to the densely coiled PMA is not accessible by NB, which is in bulk water phase. The composite nature of the pH dependence of quenching rate for $MV^{++}$ in PMA solution was attributed to the smaller binding affinity of the cation to PMA, compared to that of $Cu^{++}$. The sharp, cooperative conformational transition with pH observed in PMA was not revealed in PAA. But, the pH dependence of quenching rates in this polymer reflected increased charge density and, thus, binding of cations to the polymer, and expansion of the polymer chain with pH.

• 통합자연과학논문집
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• 제2권1호
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• pp.24-27
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• 2009

Electrochemistry of 1.0 mM tris(2,2'-bipyridyl)ruthenium(II) ($Ru(bpy)_3{^{2+}}$) in 300 mM $H_2SO_4$ solution with and without sodium dodecyl sulfate (SDS) is studied. In the presence of SDS, $E_{pa}$ of $Ru(bpy)_3{^{2+}}$ shifts to positive direction compared to the SDS free case. The intersection of two lines on ${\Delta}E_p$ vs. -log[SDS] plot is measured as a critical micelle concentration (CMC), which is 3.67 mM SDS.

• Journal of Photoscience
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• 제7권4호
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• pp.155-159
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• 2000

[Ru(bpy)$_2$(dppz)]$^2$$^{+}$ (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine)(RuBD), a long-lifetime metal-ligand complex displays photophysical properties including long lifetime, polarized emission, and very little background fluorescence. To further show the usefulness of this luminophore(RuBD) for probing nucleic acid dynamics, its intensity and anisotropy decays when bound to tRN $A^{val}$ were examined using frequency-domain fluorometry with a blue light-emitting diode(LED)as the modulated light source. Unexpectedly much longer mean lifetime was obtained at 4$^{\circ}C$(<$\tau$>=178.3 ns) as compared to at $25^{\circ}C$(<$\tau$>=117.0 ns), suggesting more favorable conformation of tRN $A^{val}$ for RuBD when intercalated at 4$^{\circ}C$. The anisotropy decay data showed longer rotational correlation times at 4$^{\circ}C$(52.7 and 13.0 ns) than at $25^{\circ}C$ (32.9 and 10.3 ns). The presence of two rotational correlation times suggests that RuBD reveals both local and overall rotational motion of tRN $A^{val}$. Due to long lifetime of RuBD and small size of tRN $A^{val}$, very low steady-state anisotropy values were observed, 0.048 and 0.036 at 4 and $25^{\circ}C$, respectively. However, a clear difference in the modulated anisotropy values was seen between 4 and $25^{\circ}C$. These results indicate that RuBD can be useful for studying hydrodynamics of small nucleic acids such as tRN $A^{val}$.^{val}$.>.$.>.

• Bulletin of the Korean Chemical Society
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• 제11권6호
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• pp.552-557
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• 1990

Luminescence quenching reactions of photoexcited tris(2,2'-bipyridine)ruthenium (Ⅱ) complex cation, $Ru(bpy)_3\;^{2+}$, by dialkylviologens (dimethyl, dioctyl, dibenzyl, methyloctyl, methyldodecyl, and methylbenzyl) were studied in sodium dodecylsulfate (SDS), poly(styrenesulfonate) (PSS), and poly(vinylsulfonate) (PVS) solutions. The relative quenching rate varies widely with the microheterogeneous media employed: the highest quenching rate is observed for methyldodecylviologen in homogeneous aqueous medium, dibenzylviologen in SDS and PVS solutions, and dimethylviologen in PSS solution; the lowest rate is found for dimethylviologen in homogeneous medium and SDS solution, methyldodecylviologen in PSS and PVS solutions. These results were interpreted in terms of reduction potential of viologens, affinity of $Ru(bpy)_3\;^{2+}$ and viologens to the microparticles, and the structures of the viologen-colloid complexes.

• Bulletin of the Korean Chemical Society
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• 제25권8호
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• pp.1177-1181
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• 2004

The determination of uric acid in urine samples was studied by a chemiluminescence measurement using tris (2,2'-bipyridine)ruthenium(II)-octylphenylpolyglycolether [Ru$(bpy)_3^{2+}$ -OPE] system. The oxidized uric acid by Ce(IV) excited Ru$(bpy)_3^{2+}$ to emit a chemiluminescence in this system so that the intensity was stoichio-metrically dependent upon the concentration of uric acid. In a reaction cell, a luminescent reagent, oxidant, surfactant and sulfuric acid were flowed into and mixed with a taken sample. Experimental conditions were optimized to obtain the maximum intensity of chemiluminescence. Each reactant solution of more than the following concentration gave a good result: $2\;{\times}\;10^{?4}$ M Ru$(bpy)_3^{2+}$ , 0.01 M Ce(IV), 6% OPE, and 0.33 M $H_2SO_4$. Any interferences were not shown in this process by the investigation of concomitant constitutes such as albumin, creatine, lactic acid, glucose, urea, $Cl^?,\; Mg^{2+},\;Ca^{2+}$ and so on. The linearity of a calibration curve was good with r = 0.998, the relative standard deviation of the slope was 3.3% and the detection limit was 5.6ng/mL. The recoveries of 80 to 91% were obtained from the standard spiked samples. The values were little bit low, but this procedure could be considered to be reliable for the determination of trace uric acid in urine samples.