• Title/Summary/Keyword: Intermediate complex

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Adsorption of Macrocyclic Cobalt Complex on a Glassy Carbon Electrode for the Electrocatalytic Reduction of $O_2$

  • 강찬
    • Bulletin of the Korean Chemical Society
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    • v.19 no.7
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    • pp.754-760
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    • 1998
  • It was found that the adsorption of a cobalt(III) complex with a macrocyclic ligand, C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (hmc), was induced on a glassy carbon electrode by heavily oxidizing the electrode surface. Adsorption properties are discussed. The glassy carbon electrode with the adsorbed complex was employed to see the catalytic activities for the electro-reduction of O2. In the presence of oxygen, reduction of (hmc)Co3+ showed two cathodic waves in cyclic voltammetry. Compared to the edge plane graphite electrode at which two cathodic waves were also observed in a previous study, catalytic reduction of O2 occurred in the potential region of the first wave while it happened in the second wave region with the other electrode. A rotating disk electrode after the same treatment was employed to study the mechanism of the O2 reduction and two-electron reduction of O2 was observed. The difference from the previous results was explained by the different reactivity of the (hmc)CoOOH2+ intermediate, which is produced after the two electron reduction of (hmc)Co3+ in the presence of O2.

Mechanistic Studies on the Oxidation of Triphenylphosphine by $[(tpy)(bpy)Ru^{IV}=O]^{2+}$, Structure of the Parent Complex $[(tpy)(bpy)Ru^{II}-OH_2]^{2+}$

  • 석원경;김미영;Yoshinobu Yokomori;Derek J. Hodgson;Thomas J. Meyer
    • Bulletin of the Korean Chemical Society
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    • v.16 no.7
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    • pp.619-624
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    • 1995
  • Oxidation of triphenylphosphine to triphenylphosphine oxide by [(tpy)(bpy)Ru(O)]2+ (tpy is 2,2':6',2"-terpyridine and bpy is 2,2'-bipyridine) in CH3CN has been studied. Experiments with the 18O-labeled oxo complex show that transfer of oxygen from [(tpy)(bpy)RuⅣ=O]2+ to triphenylphosphine is quantitative within experimental error. The reaction is first order in each reactant with k (25.3 ℃)=1.25 × 106 M-1s-1. The inital product, [(tpy)(bpy)RuⅡ-OPPh3]2+, is formed as an observable intermediate and undergoes slow k (25 ℃)=6.7 × 10-5 s-1 solvolysis. Activation parameters for the oxidation step are ΔH≠=3.5 kcal/mol and ΔS≠=-23 eu. The geometry at ruthenium in the complex cation, [(tpy)(bpy)RuⅡ(OH2)]2+, is approximately octahedral with the ligating atoms being the three N atoms of the tpy ligand, the two N atoms of the bpy ligand, and the oxygen atom of the aqua ligand. The Ru-O bond length is 2.136(5) Å.

Photochemical Studies of Schiff Base Cu(II) Complex: (1) UV-Irradiation of N,$N^{\prime}$-bis(salicylidene)ethylenediamine copper(II)

  • An, Byeong Tae
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.202-204
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    • 1995
  • The ultraviolet photochemistry of N,N'-bis(salicylidene)ethylenediamine copper(II), Cu(sal)2en, was investigated with low pressure mercury lamp. Redution of Cu(Ⅱ) and formation of Cl- were shown on 254 nm irradiation both for aerated and deaerated chlorinated hydrocarbon solvent such as CH2Cl2, chloroform, and 1,2-dichloroethane. Relatively long lived $({\tau}=100{\mu}sec)$ intermediate was detected by flash photolysis. Overall photo-process can be described as the formation of Cl- and new copper complex, product(1) by chlorohydrocarbon mediation, photoinduced reduction by abstraction of halogen from solvent, followed by redox induced substitution of axial ligand with chlorine. Product(1) is possibly Cu(III) chlorosalicylaldeimido complex and cyclic -CH2CH2- moiety is absent in the structure. 247nm band of Cu(sal)2en should contain ligand to metal charge transfer character.

Stiffening evaluation of flat elements towards stiffened elements under axial compression

  • Manikandan, P.;Arun, N.
    • Advances in Computational Design
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    • v.3 no.1
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    • pp.71-86
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    • 2018
  • Thin-walled cross-sections can be optimized to enhance their resistance and progress their behaviour, leading to more competent and inexpensive structural system. The aim of this study is to afford a methodology that would facilitate progress of optimized cold formed steel (CFS) column section with maximum ultimate strength for practical applications. The proposed sections are designed to comply with the geometrical standards of pre-qualified column standards for CFS structures as well as with the number of industrialized and practical constraints. The stiffening evaluation process of CFS lipped channel columns, a five different cross section are considered. The experimental strength and behaviour of the proposed sections are verified by using the finite element analysis (FEA). A series comprehensive parametric study is carried out covering a wide range of section slenderness and overall slenderness ratio of the CFS column with and without intermediate web stiffeners. The ultimate strength of the sections is determined based on the Direct Strength Specification and other design equation available from the literature for CFS structures. A modified design method is proposed for the DSM specification. The results indicate that the CFS column with complex edge and intermediate web stiffeners provides an ultimate strength which is up to 78% higher than standard optimized shapes with the same amount of cross sectional area.

Ground Beam Structure Based Joint Stiffness Controlling Method for the Design of Compliant Mechanism (바닥 보 구조 기반 조인트 강성 조절법을 이용한 컴플라이언트 메커니즘의 설계)

  • Kim, Myung-Jin;Jang, Gang-Won;Kim, Yoon-Young
    • Proceedings of the Computational Structural Engineering Institute Conference
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    • 2007.04a
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    • pp.151-156
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    • 2007
  • Topology optimization has been widely used in many research areas due to its ability in providing intial designs for the problems with complex boundary conditions. This also has been useful in compliant mechanisms, but resulting layouts may not be immediately manufacturable because they usually consist of members with varying widths and shapes. Also, there occurs some numerical difficulties such as checkerboards or hinge patterns which result from 1-node connection, and intermediate values which make the manufacturing of the designed structure difficult. Though there are many remedies given to avoid this problems, they cannot be prevented. One may avoid this difficulty by employing uniform ground beams and explicit hinge joints. The proposed method is to connect uniform ground beams with elastic short-beam hinge joints. By choosing the widths of short beams as design variables, dominant deformations can occur mainly by flexible joints having intermediate widths. Unlike the conventional methods used for compliance minimization, intermediate widths must appear in compliant mechanism design problems. Also, the present approach does not encounter the problem of one-point hinges.

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Comparison of Electrical Conductivities in Complex Perovskites and Layered Perovskite for Cathode Materials of Intermediate Temperature-operating Solid Oxide Fuel Cell (중·저온형 고체산화물 연료전지 공기극 물질로 사용되는 이중층 페로브스카이트와 컴플렉스 페로브스카이트의 전기 전도도 비교)

  • Kim, Jung Hyun
    • Journal of the Korean Ceramic Society
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    • v.51 no.4
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    • pp.295-299
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    • 2014
  • Electrical conductivities of complex perovskites, layered perovskite and Sr doped layered perovskite oxides were measured and analyzed for cathode materials of Intermediate Temperature-operating Solid Oxide Fuel Cells (IT-SOFCs). The electrical conductivities of $Sm_{1-x}Sr_xCoO_{3-\delta}$ (x = 0.3 and 0.7) exhibit a metal-insulator transition (MIT) behavior as a function of temperature. However, $Sm_{0.5}Sr_{0.5}CoO_{3-\delta}$ (SSC55) shows metallic conductivity characteristics and the maximum electrical conductivity value compared to the values of $Pr_{0.5}Sr_{0.5}CoO_{3-\delta}$ (PSC55) and $Nd_{0.5}Sr_{0.5}CoO_{3-\delta}$ (NSC55). The electrical conductivity of $SmBaCo_2O_{5+\delta}$ (SBCO) exhibits a MIT at about $250^{\circ}C$. The maximum conductivity is 570 S/cm at $200^{\circ}C$ and its value is higher than 170 S/cm over the whole temperature range tested. $SmBa_{0.5}Sr_{0.5}Co_2O_{5+\delta}$ (SBSCO), 0.5 mol% Sr and Ba substituted at the layered perovskite shows a typically metallic conductivity that is very similar to the behavior of the SSC55 cathode, and the maximum and minimum electrical conductivity in the SBSCO are 1280 S/cm at $50^{\circ}C$ and 280 S/cm at $900^{\circ}C$.

Fast 2-D Complex Gabor Filter with Kernel Decomposition (커널 분해를 통한 고속 2-D 복합 Gabor 필터)

  • Lee, Hunsang;Um, Suhyuk;Kim, Jaeyoon;Min, Dongbo
    • Journal of Korea Multimedia Society
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    • v.20 no.8
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    • pp.1157-1165
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    • 2017
  • 2-D complex Gabor filtering has found numerous applications in the fields of computer vision and image processing. Especially, in some applications, it is often needed to compute 2-D complex Gabor filter bank consisting of the 2-D complex Gabor filtering outputs at multiple orientations and frequencies. Although several approaches for fast 2-D complex Gabor filtering have been proposed, they primarily focus on reducing the runtime of performing the 2-D complex Gabor filtering once at specific orientation and frequency. To obtain the 2-D complex Gabor filter bank output, existing methods are repeatedly applied with respect to multiple orientations and frequencies. In this paper, we propose a novel approach that efficiently computes the 2-D complex Gabor filter bank by reducing the computational redundancy that arises when performing the Gabor filtering at multiple orientations and frequencies. The proposed method first decomposes the Gabor basis kernels to allow a fast convolution with the Gaussian kernel in a separable manner. This enables reducing the runtime of the 2-D complex Gabor filter bank by reusing intermediate results of the 2-D complex Gabor filtering computed at a specific orientation. Experimental results demonstrate that our method runs faster than state-of-the-arts methods for fast 2-D complex Gabor filtering, while maintaining similar filtering quality.

Reaction Mechanism of Troleandomycin on the Activity of Human Liver Microsomal Cytochrome P450 3A4 (인체 간 조직의 Cytochrome P450 3A4의 활성에 대한 Troleandomycin의 작용기전)

  • 김복량;오현숙;김혜정
    • Toxicological Research
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    • v.11 no.2
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    • pp.329-335
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    • 1995
  • Incubation of aflatoxin $B_1$ $(AFB_1)$ with microsomes isolated from human liver number 110 yielded two metabolite peaks which were aflatoxin $Q_1$ $(AFQ_1)$ and $(AFB_1)$-exo-8, 9-epoxide (exo-epoxide) in high performance liquid chromatography. Production ratio of $AFQ_1$ to exo-epoxide was 2.43$\pm $0.04. Metabolism of $(AFB_1)$ to $(AFQ_1)$ and exo-epoxide was inhibited by troleandomycin in a same degree although troleandomycin was not activated as a mechanism-based inhibitor. The inhibitory effect was dependent upon either the incubation time with $(AFB_1)$ or the preincubation time before the addition of $(AFB_1)$. Incubation of troleandomycin and NADPH by the microsomes resulted in the formation of a cytochrome P 450 (P450)-metabollc intermediate (MI) complex and the level was approximately 80% of total P450 3A4 in the microsomes. This figure was similar to that of the inhibitory effect of troleandomycin on $AFB_1$ metabolism. Glutathione which was reported that it prevented the formation of MI complex in rat liver microsomes did not inhibit the formation of MI complex in human liver microsomes. These results suggested that the inhibitory effect of troleandomycin on $AFB_1$ metabolism is due to the formation of MI complex with P450 3A4. And the reaction mechanism of troleandomycin by human liver microsomes might be dlfferent from that one by rat liver microsomes.

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Structure and Properties of a Nonheme Pentacoordinate Iron(II) Complex with a Macrocyclic Triazapyridinophane Ligand

  • You, Minyoung;Seo, Mi Sook;Kim, Kwan Mook;Nam, Wonwoo;Kim, Jinheung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1140-1144
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    • 2006
  • A macrocyclic ligand, N,N',N'-tribenzyl-2,11,20-triaza[3,3,3](2,6)pyridinophane (BAPP), was used to prepare an iron(II) complex as a nonheme model complex, $[(BAPP)Fe]^{+2}$ (1). X-ray crystallography of a colorless crystal of 1 revealed that BAPP acted as a pentadentate ligand due to geometrical strain for the formation of a six-coordinate iron(II) complex by BAPP. As a result, the iron center revealed a significantly distorted square pyramidal geometry similar to that found in the active site of taurine dioxygenase (tauD). In the reaction of 1 with PhIO, no intermediate was observed in the UV-visible region of spectrometer at low temperatures. Catalytic oxidations of triphenyl phosphine with PhIO at ${-40^{\circ}C}$ revealed that 1 was able to convert triphenyl phosphine to triphenyl phosphine oxide.23; SSOCHKThioanisole was also oxidized to the corresponding methylphenyl sulfoxide under the same conditions.

Catalysis Reaction for the Formation of Hydrogen Cyanide from Metal Complex (금속착물로부터 HCN 생성에 대한 촉매반응연구)

  • 박흥재
    • Journal of Environmental Science International
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    • v.3 no.4
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    • pp.439-443
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    • 1994
  • In aqueous acid solution ${[Cr(CN)_6]}^{3-}$ aquates via a series of stepwise stereospecific reactions to give ${[Cr{(H_2O)}_6]}^{3+}$as the final product.Some of the intermediate cyanoaquo complexes in the sequence have been isolated.These complexes aquate by both acid independent and acid denpendent pathways, the latter involving protonation of the cyano ligands followed by aquation of the singly protonated species. The kinetic data for the aquation of {[CrCN{(H_2O)}_5]}^{2+}$ are consistent with the transition state structure ${[{(H_2O)}_4Cr(CN)-OH-Cr{(H_2O)}_5]}^{3+}$. Addition of $Cr^{2+}$ to solutions of cyanocobalt(III) complexes produces the metastable intermediate${[CrNC{(H_2O)}_5]}^{2+}$ This isomerizes to in a $Cr^{2+}$-catalyzed reaction which occurs by a ligand-bridged electron-change mechnism. From acid catalysis on these aquation reactions, it product HCN. Especially, $HSO_3$-ions do the role of catalyst in the formation of HCN from $CrCN^{3-}$

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