• Title/Summary/Keyword: Ru complex

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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.

Synthesis and Supramolecular Assembly of Ru(II)-Terpyridine Complexes linked with β-Cyclodextrin or Adamantyl Group (β-CD 또는 아다만탄이 결합된 루테늄(II)-터피리딘 착화합물의 제조와 초분자 조립)

  • Park, Dae-Rim;Chung, Yong-Chae;Choi, Kyung-Ho;Kim, Hyung-Jin
    • Journal of the Korean Chemical Society
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    • v.51 no.6
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    • pp.526-535
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    • 2007
  • Ru(II)-terpyridine complexes (8, 9, 11) linked with adamantyl or β-cyclodextrin moieties were synthesized and characterized based on their 1H and 13C NMR spectra as well as MS spectra. Ru(II)-terpyridine complexes (8, 11) linked with adamantyl moiety were readily dissolved in aqueous solution via encapsulation by β-cyclodextrin when they were mixed with an equimolar amount of β-cyclodextrin. In the similar way, the adamantane guest of the Ru(II)-terpyridine complexes (8, 11) were encapsulated by β-cyclodextrin moiety of the ruthenium complex 9 to afford supramolecular assemblies in aqueous environment. Formation of assemblies was corroborated by 1H NMR spectroscopy.

Ru-NiOx nanohybrids on TiO2 support prepared by impregnation-reduction method for efficient hydrogenation of lactose to lactitol

  • Mishra, Dinesh Kumar;Dabbawala, Aasif A.;Truong, Cong Chien;Alhassan, Saeed M.;Jegal, Jonggeon;Hwang, Jin Soo
    • Journal of Industrial and Engineering Chemistry
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    • v.68
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    • pp.325-334
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    • 2018
  • Lactose is a reducing disaccharide consisting of two different monosaccharides such as galactose and glucose. The hydrogenation of lactose to lactitol is a formidable challenge because it is a complex process and several side products are formed. In this work, we synthesized Ru-Ni bimetallic nanohybrids as efficient catalysts for selective lactose hydrogenation to give selective lactitol. Ru-Ni bimetallic nanohybrids with $Ru-NiO_x$ (x = 1, 5, and 10 wt%) are prepared by impregnating Ru and Ni salts precursors with $TiO_2$ used as support material. Ru-Ni bimetallic nanohybrids (represented as $5Ru-5NiO/TiO_2$) catalyst is found to exhibit the remarkably high selectivity of lactitol (99.4%) and turnover frequency i.e. ($374h^{-1}$). In contrast, monometallic $Ru/TiO_2$ catalyst shows poor performance with ($TOF=251h^{-1}$). The detailed characterizations confirmed a strong interaction between Ru and NiO species, demonstrating a synergistic effect on the improvement on lactitol selectivity. The impregnation-reduction method for the preparation of bimetallic $Ru-NiO/TiO_2$ catalyst promoted Ru nanoparticles dispersed on NiO and intensified the interaction between Ru and NiO species. $Ru-NiO/TiO_2$ efficiently catalyzed the hydrogenation of lactose to lactitol with high yield/selectivity at almost complete conversion of lactose at $120^{\circ}C$ and 55 bar of hydrogen ($H_2$) pressure. Moreover, $Ru-NiO/TiO_2$ catalyst could also be easily recovered and reused up to four runs without notable change in original activity.

Synthesis of Novel Electrochemiluminescent Polyamine Dendrimers Functionalized with Polypyridyl Ru(II) Complexes and Their Electrochemical Properties

  • Lee, Do-Nam;Park, Hee-Sang;Kim, Eun-Hwa;Jun, Young-Moo;Lee, Ja-Young;Lee, Won-Yong;Kim, Byeong-Hyo
    • Bulletin of the Korean Chemical Society
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    • v.27 no.1
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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 $[Ru(o-phen)_3](PF_6)_2$.

Synthesis and Reactions of Organoruthenium(Ⅲ) Complexes (새로운 3가 유기루테늄 착물의 합성과 반응)

  • Lee Dong-Hwan;Kim Hag-Gu;Seo Dae-Ryong;Kim Byung-Soon
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.98-104
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    • 1993
  • The paramagnetic organoruthenium(III) complexes $({\eta}^5-C_5Me_5)RuCl_2(PR_3) (PR_3 = PMe_3,\;PEt_3,\;PiPr_3,\;PCy_3,\;PMe_2Ph,\;PMePh_2,\;PPh_3,\;P(p-C_6H_4CH_3)_3$, DPPE, DPPB, Py) (2a∼2k) were synthesized by the reaction of $[({\eta}^5-C_5Me_5)RuCl_2]_2$ (1) with 1 equivalent of the corresponding phosphines $(PR_3)$. The effective magnetic moment ((${\mu}_{eff} = 1.65∼2.07 B.M.$)) derived from the magnetic susceptibility measurements of the complexes (2a∼2k) were consistent with the presence of a "single" unpaired electron in the molecule. Treatment of dichlororuthenium (III) complex ({\eta}^5-C_5Me_5)RuCl_2(PR_3)$ (2) (i) with KBr in acetone afforded the dibromoruthenium (III) complex $({\eta}^5-C_5Me_5)RuBr_2(PR_3) (PR_3 = PPh_3)$, (ii) with sodium amalgam in diethylether led to the bis(phosphine) derivatives $({eta}^5-C_5Me_5)RuCl(PR_3)_2 (PR_3 = PMe_3,\;PMePh_2)$, and (iii) with carbonmonoxide gave to the carbonyl derivatives $({\eta}^5-C_5Me_5)RuCl(PR_3)(CO) (PR_3 = PMe_3,\;PPh_3)$.

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Magnetism in α-RuCl3 : Dependence on Coulomb Interaction and Hund's Coupling

  • Gong, Hoshin;Kim, Kyoo;Ji, Sungdae;Kim, Bongjae;Min, B.I.
    • Journal of the Korean Physical Society
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    • v.73 no.11
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    • pp.1691-1697
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    • 2018
  • Employing the density functional theory, we have investigated the roles of Coulomb and Hund's interactions in the electronic and magnetic properties of newly discovered ${\alpha}-RuCl_3$ having the $R{\overline{3}}$ symmetry, which is in close proximity of the Kitaev system. We show that both the size and the direction of local magnetic moment are highly dependent on Coulomb and Hund's interactions, and the spin and orbital parts show different behaviors. The validity of the so-called $j^{eff}$ picture is accessed upon interaction parameters, and the explicit roles of Hund's interaction in the local electronic structures and magnetic properties are discussed.

The Comparative Study in the Oxygen Atom Transfer Reaction by Ruthenium Mono-Oxo Complexes

  • Seok, Won K.;Son, Yung J.;Moon, Sung W.;Lee, Heung N.
    • Bulletin of the Korean Chemical Society
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    • v.19 no.10
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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.

Synthesis, Characterizations, and Intramolecular Quenching Behavior of an Axially-Linked Trinuclear Molecular Wire Containing Ruthenium(II) Porphycenes

  • Abe, Masaaki;Ashigara, Shiho;Okawara, Toru;Hisaeda, Yoshio
    • Rapid Communication in Photoscience
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    • v.4 no.1
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    • pp.22-24
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    • 2015
  • A new trinuclear complex $[Ru(TPrPc)(CO)]_2[Ru(pytpy)_2](PF_6)_2$ (TPrPc = 2,7,12,17-tetra-n-propylporphycenato dianion and pytpy = 4'-(4-pyridyl)-2,2':6',2"-terpyridine) has been synthesized and characterized as the first example of a discrete molecular wire containing metalloporohycenes as a building block. The trinuclear complex shows multiple-step redox behavior in 0.1 M n-$Bu_4NPF_6$-dichloromethane. The mononuclear $[Ru(pytpy)_2]^{2+}$ precursor shows emission at 640 nm (deaerated acetone, 298 K) upon illumination at the metal-to-ligand charge transfer (MLCT) band at 495 nm, but the trinuclear molecular wire is found to be non-emissive upon photoexcitation at the central $[Ru(pytpy)_2]^{2+}$ entity, indicating an efficient quenching ability of the axially-linked, ruthenium(II)-porphycene chromophores in an intramolecular fashion.