• Title/Summary/Keyword: $Ru(bpy)_3^{2+}$

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Enhanced Electrogenerated Chemiluminescence of Tris (2,2'-bipyridyl) Ruthenium (II)-$S_2O_8^{2-}$ System by Sodium Dodecyl Sulfate

  • Kang, Sung-Chul;Oh, Soo-Il;Kim, Kang-Jin
    • Bulletin of the Korean Chemical Society
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    • v.11 no.6
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    • pp.505-508
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    • 1990
  • The electrochemical reduction and electrogenerated chemiluminescence (ECL) of $Ru(bpy)_3^{2+}-S_2O_8^{2-}\;in\;CH_3CN-H_2O$ solution were studied in the presence of sodium dodecyl sulfate (SDS) as an anionic surfactant. SDS enhanced the ECL and the fluorescence intensities and lengthened the duration of ECL due to the solubilization of reactants and possibly to the stabilization of ECL intermediates in the SDS micellar environment.

DNA Dynamics: a Fluorescence Resonance Energy Transfer Study Using a Long-Lifetime Metal-Ligand Complex

  • Kang, Jung-Sook;Lakowicz, Joseph-R.;Piszczek, Grzegorz
    • Archives of Pharmacal Research
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    • v.25 no.2
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    • pp.143-150
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    • 2002
  • Fluorescent probes bound to DNA typically display nanosecond decay times and reveal only nanosecond motions. We extend the time range of measurable DNA dynamics using $[Ru(pby)_2(dppz)]^{2+}$ (bpy=2.2'-bipyridine, dppz=dipyrido[3,2-a2',3'-c]phenazine) (RuBD) which displays a mean lifetime near 90 ns. To test the usefulness of RuBD as a probe for diffusive processes in calf thymus DNA, we compared the efficiencies of fluorescence resonance energy transfer (FRET) using three donors which display lifetimes near 5 ns for acridine orange (AO), 22 ns for ethidum bromide (EB) and 92 ns for RuBD, with nile blue (NB) as the acceptor. The F rster distances for AO-NB, EB-NB and RuBD-NB donor-acceptor pairs were 42.3, 52.3, and $30.6{\;}{\AA}$, respectively. All three donors showed dramatic decreases in fluorescence intensities and more rapid intensity decays with increasing NB concentrations. The intensity decays of AO and EB in the presence of varying concentrations of NB were satisfactorily described by the one-dimensional FRET model without diffusion (Blumen and Manz, 1979). In the case of the long-lifetime donor RuBD, the experimental phase and modulation somewhat deviated from the recovered values computed from this model. The recovered NB concentrations and FRET efficiencies from the model were slightly larger than the expected values, however, the recovered and expected values did not show a significant difference. Thus, it is suggested that the lifetime of RuBD is too short to measure diffusive processes in calf thymus DNA.

Photoinduced Electron Tansfer of Microperoxidase-8

  • Su, Chien-Hua;Lin, Ren-Jay;Chang, I-Jy
    • Journal of Photoscience
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    • v.6 no.3
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    • pp.129-133
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    • 1999
  • Microperoxidase 8 (MP8) has been prepared by sequential hydrolysis of cytochrome C by pepsin and trypsin. This five-coordinated heme-octapetide fragment provides a uniques structure to evaluate the electronic coupling efficiency to the iron through axial position and porphyrin edge. At alkali pH, Ru(bpy)2(im)22+ is completely quenched in AcMP8Ru complex . Transient kinetics measurement showed the decay rate to be ~1 $\times$1012S-1. Ruthenium bipyridine complex with a carboxyl group substituted bipyridine has been prepared adn reacted with MR 8 to yield N-terminus bound RuMP8 complex. The luminescence decay rate has been measured as 1 $\times$109S-1. By using semiclassical electron transfer theory, we found the electron transfer efficiency through axial positioin of iron prophyrin is as good through prophyrin edge.

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The study of electrochemi-luminescence device fabrication (전기화학형 발광소자의 제작에 관한 연구)

  • Kwon, Hyuk-Moon;Kwak, Dong-Joo;Sung, Youl-Moon;Song, Jae-Eun
    • Proceedings of the KIEE Conference
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    • 2009.07a
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    • pp.1326_1327
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    • 2009
  • In this study, used simplest sandwich cells containing $Ru2^+$ liquid electrolytes in order to clarify the role of nanoporous $TiO_2$ electrodes. And, the cell structure is as follow: F:$SnO_2$ glass/nanoporous $TiO_2$/ tris(2,2'-bipyridy)ruthenium(II) colplex [$Ru(bpy)_3(PF_6)_2$] in acetonitrile/ F:$SnO_2$ glass. The result, we found that ECL intensities increased rapidly by use of cathodes with nanoporous $TiO_2$ layers. And, porous $TiO_2$ electrodes were confirmed to be efficient for ECL devices as well as solar cell devices. It is thought that the increases in the ECL intensities may be associated with both formation of $Ru^+$ in porous $TiO_2$ electrodes and the process taking place after reduction of $Ru^+$ which occurs in the nanoporous electrodes.

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Unidirectional Photo-induced Charge Separation and Thermal Charge Recombination of Cofacially Aligned Donor-Acceptor System Probed by Ultrafast Visible-Pump/Mid-IR-Probe Spectroscopy

  • Kim, Hyeong-Mook;Park, Jaeheung;Noh, Hee Chang;Lim, Manho;Chung, Young Keun;Kang, Youn K.
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.587-596
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    • 2014
  • A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

Fabrication of ZnO Nanorod-based Electrochemical Luminescence Cells and Fundamental Luminescence Properties (산화아연 나노로드 전극을 이용한 전기화학발광 셀의 제작 및 발광특성 고찰)

  • Oh, Hyung-Suk;Sung, Youl-Moon
    • The Transactions of The Korean Institute of Electrical Engineers
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    • v.63 no.1
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    • pp.76-79
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    • 2014
  • We report Zinc oxide (ZnO) nanorods synthesis and electrochemical luminescence (ECL) cell fabrication. The ECL cell was fabricated using the electrode of ZnO nanorods and Ru(II) complex ($Ru(bpy)_3{^{2+}}$) as a luminescence materials. The fabricated ECL cell is composed of F-doped $SnO_2$ (FTO) glass/ Ru(II)/ZnO nanorods/FTO glass. The highest intensity of the emitting light was obtained at the wavelength of ~620 nm which corresponds to dark-orange color. At a bias voltage of 3V, the measured ECL efficiencies were 5 $cd/m^2$ for cell without ZnO nanorod, 145 $cd/m^2$ for ZnO nanorods-$5{\mu}m$, 208 $cd/m^2$ for ZnO nanorods-$8{\mu}m$ and 275 $cd/m^2$ for ZnO nanorods-$10{\mu}m$, respectively. At a bias voltage of 3.5V, the use of ZnO nanorods increases ECL intensities by about 3 times compared to the typical ECL cell without the use of ZnO nanorods.

Method for the Measurement of Dissolved Oxygen in a Cell Culture Microchannel Using Oxygen-Sensitive Luminescence (산소 민감 발광 염료를 이용한 마이크로 채널 내에서 배양되는 세포 주변의 산소 농도 측정)

  • Lee, Seung-Youl;Jin, Song-Wan
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.36 no.5
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    • pp.533-538
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    • 2012
  • In this study, we used an $O_2$-sensitive luminescent dye to measure the $O_2$ concentration of culture media around HeLa cells cultured in a microchannel. $[Ru(bpy)_3]^{2+}$, which dissolves easily in water and which has no phototoxic effect, was used as the $O_2$-sensitive dye. The ratiometric sensing method was applied by introducing calcein as the $O_2$-insensitive dye, in order to overcome the disadvantages of intensity-based sensing. By performing calibration with an amperometric $O_2$ sensor, we could calculate the exact concentration of $O_2$ in the culture media. We applied this technique to measure the $O_2$ concentration around the cultured cells in the microchannel. As expected, the $O_2$ concentration gradually decreased as the cells moved farther away from the channel. This method is expected to be applicable to the investigation of hypoxia, which occurs commonly in scaffolds.

Properties of Sodium Dodecyl Sulfate / Triton X-100 Mixed Micelle

  • Park, Joon-Woo;Chung, Myung-Ae;Choi, Kyung-Moon
    • Bulletin of the Korean Chemical Society
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    • v.10 no.5
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    • pp.437-442
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    • 1989
  • The cmc's of sodium dodecyl sulfate (SDS)/Triton X-100 surfactant mixtures were determined by surface tension measurement at various surfactant compositions. The cmc values were lower than those predicted from ideal mixture. The regular solution theory was applied to calculate the interaction parameter, micellar composition, and the activity coefficients of surfactants in the mixed micelle. The interaction parameter (${\beta}$) was - 2.1. The nonideality arised largely from decreased activity of SDS in the mixed micelle. The mean aggregation numbers (${\bar{n}}$) and micropolarity of hydrocarbon region of the mixed micelles were determined by luminescence probe techniques. The total aggregation number (${\bar{n}}_{SDS}+{\bar{n}}_{TX}$) in mixed micelles showed little dependency on the composition of the micelle. The apparent dielectric constant of the hydrocarbon region of the micelle vs micellar composition plot showed positive deviation from linearity. Emission and emission quenching of excited tris(2,2'-bipyridine)ruthenium(Ⅱ) cation, $(Ru(bpy)_3^{2+})$, by methylviologen ($MV^{2+}$) were also investigated in the mixed micellar solutions. The quenching rate was lowest when the mole fraction of SDS in the surfactant mixtures (${\alpha}_{SDS}$) is about 0.25 and highest at ${\alpha}_{SDS}$ = 0.85. This was explained in terms of combined effects of binding of the cations with the micelle and mobility of the bound cations on the surface of the micelles.

Synthesis of Self-Assembled Peptide Nanoparticles Based on Dityrosine Covalent Bonds (다이타이로신 공유결합으로 자기조립된 펩타이드 나노입자의 합성)

  • Hur, Yun-Mi;Min, Kyoung-Ik
    • Korean Chemical Engineering Research
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    • v.59 no.1
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    • pp.112-117
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    • 2021
  • In this study, a method of self-assembly of peptides based on irreversible covalent bonds was studied by mimicking a biological covalent bond, dityrosine bond. A tyrosine-rich short peptide monomer having the sequence of Tyr-Tyr-Leu-Tyr-Tyr (YYLYY) was selected to achieve a high-density of dityrosine bond. The peptide nanoparticles covalently self-assembled with dityrosine bonds were synthesized by one-step photo-crosslinking of a peptide using a ruthenium catalyst under visible light. The effect of the concentration of each component for the size of the peptide nanoparticle was studied using dynamic light scattering, UV-Vis spectroscopy, and transmission electron microscopy. As a result, the synthesis conditions for size of the peptide nanoparticles ranging from 130 nm to 350 nm were optimized.

Dependence of Molecular Recognition for a Specific Cation on the Change of the Oxidation State of the Metal Catalyst Component in the Hydrogel Network

  • Basavaraja, Chitragara;Park, Do-Young;Choe, Young-Min;Park, Hyun-Tae;Zhao, Yan Shuang;Yamaguchi, Tomohiko;Huh, Do-Sung
    • Bulletin of the Korean Chemical Society
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    • v.28 no.5
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    • pp.805-810
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    • 2007
  • Molecular recognition for a specific cation depending on the change of the oxidation state of the metal catalyst component contained in the hydrogel network has been studied in a self-oscillating hydrogel. The selfoscillating hydrogels are synthesized by the copolymerization of N-isopropylacrylamide (NIPAAm), lead methacrylic acid (Pb(MAA)2), and Ru(bpy)3 2+ monomer as a metal catalyst component. The recognition for a specific cation (in this study, Ca2+ has been used) is characterized by the adsorbed amount of Ca2+ into the gel. The recognition of the gels for Ca2+ is higher at the temperature below the LCST, and also higher at the oxidized state than at reduced state of the metal catalyst component which corresponds to a more swollen state. Moreover, a propagating wave induced by a periodic change of the oxidation state with the diffusion phenomena in the oscillating hydrogel shows a possibility for temporal and site-specific molecular recognition due to the local swelling of the gel.