• Title/Summary/Keyword: Ru Complex

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Comparative Study of Emission Quenching of Tris(${\alpha},{\alpha}'$-diimine)-Ruthenium(II) Complexes in Homogeneous and Sodium Dodecyl Sulfate Micellar Solutions

  • Park, Joon-Woo;Nam, Eun-Jin;Ahn, Byung-Tae
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.686-691
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    • 1991
  • Emission quenching of photoexcited tris(${\alpha},{\alpha} '$-diimine)-ruthenium(II) complex cations, $RuL_3^{2+}$ (L: 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine; 4,4'-diphenyl-2,2'-bipyridine; 1,10-phenanthroline; 5-methyl-1,10-phenanthroline; 5,6-dimethyl-1,10-phenanthroline or 4,7-diphenyl-1,10-phenanthroline) by $Cu^{2+}$, dimethylviologen $(MV^{2+})$, nitrobenzene (NB), and oxygen was studied in aqueous homogeneous and sodium dodecyl sulfate (SDS) micellar solutions. The apparent bimolecular quenching rate constants $k_q$ were determined from the quenching data and life-times of $^{\ast}RuL_3^{2+}$. In homogeneous media, the quenching rate was considerably slower than that for the diffusion-controlled reaction. The decreasing order of quenching activity of quenchers was $NB>O_2>MV^{2+}>Cu^{2+}$. The rate with $Cu^{2+}$ was faster as the reducing power of $^{\ast}RuL_3^{2+}$ is greater. On the other hand, the rates with NB and $O_2$ were faster as the ligand is more hydrophobic. This was attributed to the stabilization of encounter pair by van der Waals force. The presence of SDS enhanced the rate of quenching reactions with $Cu^{2+}$ and $MV^{2+}$, whereas it attenuated the quenching activity of NB and $O_2$ toward $RuL_3^{2+}$. The binding affinity of quenchers to SDS micelle and binding sites of the quenchers and $RuL_3^{2+}$ in micelle appear to be important factors controlling the micellar effect on the quenching reactions.

Decomposition Studies of DFP Using Transition Metal Catalysts (전이금속촉매를 사용한 DFP 분해 성능 연구)

  • Kye, Young-Sik;Jeong, Keunhong;Chung, Woo Young
    • Applied Chemistry for Engineering
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    • v.21 no.1
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    • pp.1-5
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    • 2010
  • Cu(II)-organic complexes were synthesized with Lewis base organic ligands including diamine, aminothiol, and dithiol to determine the reactivity for DFP hydrolysis. Results show that the aminothiol catalyst enhances the hydrolysis of DFP in three folds compared to diamine type because aminothiol has higher basicity than diamine. Due to low solubility of Cu(II)(1,2-ethane dithiol)$(NO_3)_2$, it is impossible to compare directly the rates in homogeneous condition. However, the rate of dithol complex is even 1.6 times faster than that of the diamine type. The reactivity of zeolite for DFP hydrolysis is also evaluated. NaY type does not promote the hydrolysis, but RuNaY shows relatively lower reactivity than those of Cu(II)-organic ligands complexes.

Synthesis and Characterization of 1-Transition Metal Complex Substituted-2,3,4,5-Tetraphenyl-1-Silacyclopentadienyl Complexes and Generation of Transition Metal Complex-Substituted Silylene

  • Paek Cheolki;Ko Jaejung;Kong Youngkun;Kim, Chang Hwan;Lee Myong Euy
    • Bulletin of the Korean Chemical Society
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    • v.15 no.6
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    • pp.460-465
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    • 1994
  • New silicon-monosubstituted (${\eta}^4$-2,3,4,5-tetraphenyl-l-silacyclopentadiene)transi tion metal complexes are described. (7-Alkyl-7-silanorbornadienyl)MLn(Alkyl=Methyl: MLn=CpRu$(CO)_2$: Alkyl=Methyl: MLn=CpNi(CO): Alkyl=Ethyl: MLn=CpNi(CO)) complexes were prepared from the corresponding silole-transition metal complexes with dimethylacetylenedicarboxylate. Cycloaddition products were obtained with 2,3-dimethyl-1,3-butadiene, 2,3-butanedione, and 1,4-benzoquinone through the ruthenium-substituted silylene. We have determined the crystal structure of (1-methyl-2,3,4,5-tetraphenyl-l-silacyclopentadien yl)cyclopentadienyldicarbonylruthenium by using graphite monochromated Mo-Ka radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a = 9.838(l), b = 15.972(3), c = 18.327(3) ${\AA}$, and ${\beta}= 94.28(l)^{circ}$. The ruthenium moiety CpRu$(CO)_2$ on silicon is in an axial position.

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.

Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects

  • Jo, Myeong-Ran;Seok, Won-K.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.3003-3008
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    • 2011
  • Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

Photoelectrochemical and Microscopic Studies in Hetero Type LB Films of Polypyridine Ru Complexes on ITO Electrodes (ITO전극위의 Hetero형 폴리피리딘Ru착체 LB막의 표면측정과 전기화학적 감광특성)

  • 최인희;박수길;임기조;이주성
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1995.11a
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    • pp.240-243
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    • 1995
  • The basic electrochemical and photochemical behavior of ultrathin mono- and hetero-type LB film of amphiphilic Ru bipyridine complex adsorbed on ITO electrode by the Langmuir- Blodgett(LB) method as monolayer and alternating multilayer state. With theoretical equation of cyclic voltammetry for redox species, the cyclic voltammogram were simulated successfully taking account the interaction parameters. We could fit almost all measured voltammograms with k$^{\circ}$=72s$\^$-1/, ${\alpha}$$\sub$a/=0.44, ${\alpha}$$\sub$c/=0.54, $\Gamma$$\sub$T/=1.4${\times}$10$\^$-10/, k=0.015s$\^$-1/ values. The AFM images of mono and hetero type LB film surfaces on ITO were also studied.

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Noncovalently Linked Zinc Porphyrin-Ru(bpy)3 Dyad Assembled via Axial Coordination

  • Kim, Dol;Shin, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.24 no.10
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    • pp.1490-1494
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    • 2003
  • Noncovalently linked electron donor-acceptor dyad consisting of zinc tetratolylporphyrin and pyridine appended ruthenium trisbipyridine comlex was prepared, via axial coordination of pyridine moiety in ruthenium trisbipyridine complex on zinc tetratolylporphyrin. For the purpose of comparison, axial coordination of pyridine-appended 2,2'-bipyridine on zinc tetratolylporphyrin was also investigated. The Kvalues were detemined based on absorption of fluorescence studies. The fluorescence of zinc teratolylporphrin was efficiently quenched upon axial coordination of pyridine moiety, prbably due to the photoinduced electron transfer from zinc tetrtolylporphyrin to ruthenium trisbipyridine, supported by free enegy estimation.

Determination of Mercury at Electrodes Modified with Poly-$[Ru(v-bpy)_3]^{2+}$ Incorporating Amino Acids (몇 가지 아미노산으로 변성한 $[Ru(v-bpy)_3]^{2+}$ 고분자 피막 전극을 이용한 수은의 정량)

  • Cha, Seong Keuk
    • Journal of the Korean Chemical Society
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    • v.40 no.8
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    • pp.542-548
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    • 1996
  • Electrodes modified with threonine, methionine and serine as ligands, which are incorporated by ion exchange into a polycationic film of electropolymerized $[Ru(v-bpy)_3]^{2+}$, have been employed in the determination of mercury in solution. The redox response of the surface-immobilized mercury/ligand complex was used as the analytical signal. When the polymeric film was electropolymerized, the supporting electrolytes were TBAP and $KPF_6$ to compare the morphology and anodic stripping of resulted polymer electrodes. At the case of the latter, the film had high porosity to give an easy incorporation of dopant anions into polymeric film matrix and a high sensitivity in determination of mercury ion. Especially, this polymer modified electrode exhibited possibility of multiple use in mercury determination over ten times. In all cases, calibration curves which were plotted by log of the surface coverage-normalized redox response vs. log[Hg] exhibited an excellent correlation (r=0.99) for mercury concentrations ranging from 1.0{\times}10^{-8}{\sim}1.0{\times}10^{-2}M$. At these curves relative standard deviation was 5∼8% and saturation response was not observed at high concentration region. Serine of the employed ligands had the best sensitivity in analytical application, which had greater stability constant in forming a complex with mercury than others as $pK_{Hg}=8.54$. The formation constants of threonine and methionine were respectively 7.04 and 7.80.

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Studies on Electrocardiogram of the Normal Korean Native Goat II. Waveforms and Amplitudes of the Unipolar Precordial Chest Leads (정상적인 한국 흑염소의 심전도에 관한 연구 II. 담부단극유도의 파형과 전위)

  • 최인혁;김기주;윤여백;서석열;김남수
    • Journal of Veterinary Clinics
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    • v.14 no.2
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    • pp.338-348
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    • 1997
  • The electrocardiographic (ECG) parameters on unipolar precordial chest leads in the normal Korean native goat of 343 heads as to CV$_{6}$LU, CV$_{6}$LL CV$_{6}$RU, CV$_{6}$RL and V10 have been measured with a 3-channel Elertrocardiograph and computed, analysed. All wave types as positive, negatives biphasic and flatting in the P and T waves appeared in all leads but any special wave type was not shown more than 60%. Average amplitudes with the highest frequent rate in P wave were 81.4$\pm$32.0 $\mu $V (52.3%), 59.6$\pm $ 27.5 $\mu $V (50.5 %) of Positive type in leads CV$_{6}$LU and CV$_{6}$LL, and -5fl.5$\pm $22.6 $\mu $V (44.0%) of negative type in leads VIO, and 51.3% and 44% of flatting type in leads CV$_{6}$RU and CV$_{6}$RL, but flatting type of clinic form appeared frequent rate between 53% and 77% in all leads. In T wave, average amplitudes with the highest frequent rate were 265.0$\pm $97.1 $\mu $V (54.0%) and 212.2$\pm $90.7 $\mu $V (57.0%) of positive type in leads CV$_{6}$LL and CV$_{6}$RL, and -252.8$\pm $90.7 $\mu $V (56.6%) of negative in lead V10, but amplitudes of T waves that positive and negative type appeared similarity frequent ra蛇 ware 208.7$\pm $99.7 $\mu $V (42.1%), -159.0$\pm $81.6 (43.8%) in lead CV$_{6}$LU and 153.2$\pm $139.0 $\mu $V (47.3%), -130.0$\pm $81.4 (43.2%) in lead CV$_{6}$RU, Amplitudes of QRS complex wave forms showed the highest frequent rate were 218.2$\pm $96.4 $\mu $V (47.8%), 308.3$\pm $135.2 $\mu $V (46.8 %), 232.8$\pm $126.5 $\mu $V (58.5%) and 225.3$\pm $89.6 $\mu $V (54.9%) of R type in the leeds CV$_{6}$LU, CV$_{6}$LL, CV$_{6}$RU and CV$_{6}$RL, and were -92.5$\pm $79.1 $\mu $V,479.0 $\pm $116.6 $\mu $V (33.2%) and 212.1 $\pm $86.7 $\mu $V (32.8%) of QR and 05 type in the lead V10. These results in the V10, CV$_{6}$RU, CV$_{6}$RL, CV$_{6}$LU, CV$_{6}$LL. may be not starve to purpose of unipolar precordial chest leads.

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