• Title/Summary/Keyword: Irreversible reaction

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Synthesis of 1-Benzyl-4-Iodomethyl-2-Azetidinone and Electrochemical Reduction on the Iodo Group (1-Benzyl-4-Iodomethyl-2-Azetidinone의 합성과 Iodo기에 대한 전기화학적 환원반응)

  • Kim Il Kwang;Lee Young Haeng;Lee Chai Ho;Chai Kyu Yun;Kim Yoon Geun
    • Journal of the Korean Chemical Society
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    • v.35 no.1
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    • pp.70-77
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    • 1991
  • 1-Benzyl-4-iodomethyl-2-azetidinone(BIMA) was synthesized and its electrochemical reduction was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The irreversible two electron transfer on reductive dehalogenation of iodo group proceeded to form 1-benzyl-4-methyl-2-azetidinone by EEC electrode reaction mechanism at the first reduction step(-1.35 volts vs. Ag-AgCl). The polarographic reduction waves separated into two reduction steps due to anionic surfactant (sodium lauryl sulfate) effects, while the waves were shifted to the positive potential as the concentration of cationic surfactant (cetyltrimethylammonium bromide) increased. Upon the basis of results on the product analysis and interpretation of polarogram with pH variable, EEC electrochemical reaction mechanism was suggested.

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Electrochemical Behaviors for Cathodic Reaction of N'-aryl-N-alkyl-N-nitrosourea Drivatives (N'-aryl-N-alkyl-N-nitrosourea 유도체의 환원반응에 대한 전기화학적 거동)

  • Won, Mi Sook;Kim, Jack C.;Jeong, Euh Duck;Shim, Yoon-Bo
    • Journal of the Korean Chemical Society
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    • v.39 no.11
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    • pp.842-847
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    • 1995
  • The electrochemical reduction reactions of N '-aryl-N-alkyl-N-nitrosourea derivatives with a glassy carbon electrode were diffusion controlled and irreversible. The exchange kinetic constant ko values for reduction reaction of the N '-aryl-N-alkyl-N-nitrosoureas were at the range of $1.48{\times}10^{-6}{\sim}5.32{\times}10^{-7}\;cm/sec.$ The $k_0$ values for phenyl substituted on the aryl position were about 1.3∼2.8 times higher than that of other substituents. The same substituent for aryl groups on the both of N '-aryl-N-alkyl-N-nitrosourea and N '-aryl-N-(2-chloroethyl)-N-nitrosourea exhibited same value. The $E_p$ value was shifted to the negative direction as pH increased. The number of protons participated to the reduction was 4∼5, respectively. The substituent effect of aryl group on the reduction potential was not observed in this case.

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Electrochemical Properties of Oxygen Adducts Pentadentate Schiff Base Cobalt (Ⅱ) Complexes in Aprotic Solvents (비수용매에서 다섯 자리 Schiff Base Cobalt (Ⅱ) 착물들의 산소 첨가 생성물에 대한 전기화학적 성질)

  • Choe, Ju Hyeong;Jeong, Jin Sun;Choe, Yong Guk;Seo, Seong Seop
    • Journal of the Korean Chemical Society
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    • v.34 no.1
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    • pp.51-62
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    • 1990
  • Pentadentate Schiff base cobalt(II) complexes; Co(II)(Sal-DET) and Co(II)(Sal-DPT) were synthesized and these complexes were allowed to react with dry to form oxygen adducts of cobalt(II) complexes such as [Co(III)(Sal-DET)]$_2O_2$ and [Co(III)(DPT)]$_2O_2$ in aprotic solvents. These complexes have been identified by IR spectra, TGA, DSC, magnetic susceptibility measurements, and elemental analysis. It has been found that the oxygen adadduct complexes of $\mu$-peroxo type have hexaccordinated octahedral configuration with pentadentate schiff base cobalt(II) and oxygen, but the mole ratio of oxygen to cobalt(III) complexes of first step for oxygen adduct formation reaction of cobalt(II) complexes in aprotic solvents are 1:1. The redox reaction processes of Co(II)(Sal-DET), Co(II)(Sal-DPT), and oxygen adduct of cobalt(II) complexes were investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine. As a result the reduction reaction processes of Co(III)/Co(II) and Co(II)/Co(I) for cobalt(II) complexes and oxygen adducts of cobalt(II) complexes are two irreversible steps of one eletron process, and reaction processes of oxygen for oxygen adducts complexes were quasireversible and redox range of potential was $E_{pc}$ = -0.97V∼-0.86V and $E_{pa}$ = -0.87V ∼ 0.64V.

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Synthesis of Cobalt(II), Nickel(II) and Copper(II) Complexes with Tetradentate Schiff Base Ligand of o-BSDT $H_2$ and Electrochemical properties in DMSO (네자리 Schiff Base 리간드의 Cobalt(II), Nickel(II) 및 Copper(II) 착물의 합성과 DMSO용액에서 전기화학적 성질)

  • Ki-Hyung Chjo;Jong-Soon Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.509-519
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    • 1987
  • The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).

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Characterization of the Interaction of Sulfiredoxin (Srx1) with a Vacoular Protein $\alpha$-Mannosidase (Ams1) in Saccharomyces cerevisiae (설피리독신과 알파-만노시다제 간의 단백질 결합 특성에 관한 고찰)

  • Barando, Karen P.;Kim, Il-Han
    • The Journal of Natural Sciences
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    • v.17 no.1
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    • pp.13-29
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    • 2006
  • Most redox-active proteins have thiol-bearing cysteine residues that are sensitive to oxidation. Cysteine thiols oxidized to sulfenic acid are generally unstable, either forming a disulfide with a nearby thiol or being further oxidized to a stable sulfinic acid, which have been viewed as an irreversible protein modification. However, recent studies showed that cysteine residues of certain thiol peroxidases (Prxs) undergo reversible oxidation to sulfinic acid and the reduction reaction is catalyzed by sulfiredoxin (Srx1). Specific Cys residues of various other proteins are also oxidized to sulfinic acid ($Cys-So_2H$). Srxl is considered one of the oxidant proteins with a role in signaling through catalytic reduction of oxidative modification like in the reduction of glutathionylation, a post-translational, oxidative modification that occurs on numerous proteins. In this study, the role of sulfiredoxin in cellular processes, was investigated by studying its interaction with other proteins. Through the yeast two-hybrid system (Y2HS) technique, we have found that Ams1 is a potential and novel interacting protein partner of Srxl. $\alpha$-mannosidase (Ams1) is a resident vacuolar hydrolase which aids in recycling macromolecular components of the cell through hydrolysis of terminal, non-reducing $\alpha$-D-mannose residues. It forms an oligomer in the cytoplasm and under nutrient rich condition and is delivered to the vacuole by the Cytoplasm to Vacuole (Cvt) pathway. Aside from the role of Srxl as a catalyst in the reduction of cysteine sulfenic acid groups, it may play a completely new function in the cellular process as indicated by its interaction with Ams1 of the yeast Saccharomyces cerevisiae.

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FIT OF FIXTURE/ABUTMENT/SCREW INTERFACES OF INTERNAL CONNECTION IMPLANT SYSTEM

  • Kim, Jin-Sup;Kim, Hee-Jung;Chung, Chae-Heon;Baek, Dae-Hwa
    • The Journal of Korean Academy of Prosthodontics
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    • v.43 no.3
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    • pp.338-351
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    • 2005
  • Statement of problem. Accurate fit between the implant components is important because the misfit of the implant components results in frequent screw loosening, irreversible screw fracture, plaque accumulation, poor soft tissue reaction, and destruction of osseointegration. Purpose. This study is to evaluate the machining accuracy and consistency of the implant fixture/ abutment/screw interfaces of the internal connection system by using a Stereoscopic Zoom microscope and FE-SEM(field emission scanning electron microscope) Materials and methods. The implant systems selected in this study were internal connection type implants from AVANA(Osstem^{\circledR}), Bioplant(Cowell-Medi^{\circledR}), Dio(DIO^{\circledR}), Neoplant(Neobiotech 􀋓), Implantium(Dentium􀋓)systems. Each group was acquired 2 fixtures at random. Two piece type abutment and one piece type abutment for use with each implant system were acquired. Screw were respectively used to hold a two piece type abutment to a implant fixture. The implant fixtures were perpendiculary mounted in acrylic resin block. Each two piece abutment was secured to the implant fixture by screw and one piece abutment also secured to the implant fixture. Abutment/fixture assembly were mounted in liquid unsaturated polyester. All samples were cross-sectioned with grinder-polisher unit. Finally all specimens were analysed the fit between implant fixture/abutment/screw interfaces Results and conclusions. 1. Implant fixture/abutment/screw connection interfaces of internal connection systems made in Korea were in good condition. 2. The results of the above study showed that materials and mechanical properties and quality of milling differed depending on their manufacturing companies.

Numerical Analysis of Enzyme Kinetics for Undergraduate Education in Engineering (공학분야 학부교육용 효소반응속도식의 수치해석)

  • Kim, Jae-Seok;Kim, Jae-Yoon;Lee, Jae-Heung
    • The Journal of Korean Institute for Practical Engineering Education
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    • v.2 no.1
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    • pp.35-41
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    • 2010
  • An enzyme-catalized reaction is usually characterized by a very large increase in the rate and high specificity. Kinetics of simple enzyme-catalized reactions are often referred to as Michelis-Menten kinetics. A chemical that interferes with an enzyme's activity is called inhibitor. There are two types of enzyme inhibitions (viz. reversible and irreversible). If an inhibitor attaches to the enzyme with weak bonds, such as hydrogen bonds, the inhibition is usually reversible. Many enzyme reactions are also inhibited reversibly by their corresponding products. The rate of substrate disappearance together with the rate of product formation may be written by nonlinear differential equations. In the present study, numerical analyses of simple enzyme kinetics and inhibited enzyme kinetics are reported for the purpose of undergraduate education in engineering.

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Computational Study on Unsteady Mechanism of Spinning Detonations

  • Matsuo, Akiko;Sugiyama, Yuta
    • 한국전산유체공학회:학술대회논문집
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    • 2008.03a
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    • pp.367-373
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    • 2008
  • Spinning detonations propagating in a circular tube were numerically investigated with a one-step irreversible reaction model governed by Arrhenius kinetics. Activation energy is used as parameter as 10, 20, 27 and 35, and the specific heat ratio and the heat release are fixed as 1.2 and 50. The time evolution of the simulation results was utilized to reveal the propagation mechanism of single-headed spinning detonation. The track angle of soot record on the tube wall was numerically reproduced with various levels of activation energy, and the simulated unique angle was the same as that of the previous reports. The maximum pressure histories of the shock front on the tube wall showed stable pitch at Ea=10, periodical unstable pitch at Ea=20 and 27 and unstable pitch consisting of stable, periodical unstable and weak modes at Ea=35, respectively. In the weak mode, there is no Mach leg on the shock front, where the pressure level is much lower than the other modes. The shock front shapes and the pressure profiles on the tube wall clarified the mechanisms of these stable and unstable modes. In the stable pitch at Ea=10, the maximum pressure history on the tube wall remained nearly constant, and the steady single Mach leg on the shock front rotated at a constant speed. The high and low frequency pressure oscillations appeared in the periodical unstable pitch at Ea=20 and 27 of the maximum pressure history. The high frequency was one cycle of a self-induced oscillation by generation and decay in complex Mach interaction due to the variation in intensity of the transverse wave behind the shock front. Eventually, sequential high frequency oscillations formed the low frequency behavior because the frequency behavior was not always the same for each cycle. In unstable pitch at Ea=35, there are stable, periodical unstable and weak modes in one cycle of the low frequency oscillation in the maximum pressure history, and the pressure amplitude of low frequency was much larger than the others. The pressure peak appeared after weak mode, and the stable, periodical unstable and weak modes were sequentially observed with pressure decay. A series of simulations of spinning detonations clarified that the unsteady mechanism behind the shock front depending on the activation energy.

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Computational Study on Unsteady Mechanism of Spinning Detonations

  • Matsuo, Akiko;Sugiyama, Yuta
    • 한국전산유체공학회:학술대회논문집
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    • 2008.10a
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    • pp.367-373
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    • 2008
  • Spinning detonations propagating in a circular tube were numerically investigated with a one-step irreversible reaction model governed by Arrhenius kinetics. Activation energy is used as parameter as 10, 20, 27 and 35, and the specific heat ratio and the heat release are fixed as 1.2 and 50. The time evolution of the simulation results was utilized to reveal the propagation mechanism of single-headed spinning detonation. The track angle of soot record on the tube wall was numerically reproduced with various levels of activation energy, and the simulated unique angle was the same as that of the previous reports. The maximum pressure histories of the shock front on the tube wall showed stable pitch at Ea=10, periodical unstable pitch at Ea=20 and 27 and unstable pitch consisting of stable, periodical unstable and weak modes at Ea=35, respectively. In the weak mode, there is no Mach leg on the shock front, where the pressure level is much lower than the other modes. The shock front shapes and the pressure profiles on the tube wall clarified the mechanisms of these stable and unstable modes. In the stable pitch at Ea=10, the maximum pressure history on the tube wall remained nearly constant, and the steady single Mach leg on the shock front rotated at a constant speed. The high and low frequency pressure oscillations appeared in the periodical unstable pitch at Ea=20 and 27 of the maximum pressure history. The high frequency was one cycle of a self-induced oscillation by generation and decay in complex Mach interaction due to the variation in intensity of the transverse wave behind the shock front. Eventually, sequential high frequency oscillations formed the low frequency behavior because the frequency behavior was not always the same for each cycle. In unstable pitch at Ea=35, there are stable, periodical unstable and weak modes in one cycle of the low frequency oscillation in the maximum pressure history, and the pressure amplitude of low frequency was much larger than the others. The pressure peak appeared after weak mode, and the stable, periodical unstable and weak modes were sequentially observed with pressure decay. A series of simulations of spinning detonations clarified that the unsteady mechanism behind the shock front depending on the activation energy.

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Electrochemical Study on Rancidity of a Soybean Oil (콩기름의 산패에 대한 전기화학적 연구)

  • Hong, Kang Hee;Kim, Hee Cheol;Park, Byung Ho;Lee, Sang Mi;Jeong, Byeong Goo;Kim, Kyung Nam;Ko, Young Chun
    • Analytical Science and Technology
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    • v.15 no.4
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    • pp.388-391
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    • 2002
  • Rancidity of a soybean oil is investigated by an electrochmical method. The redox process of the soybean oil is totally irreversible and diffusion-controlled reaction. As scan rates are faster, the anodic peak potential of the soybean oil is shifted to the positive potential and the anodic current is increased. The anodic peak potentials of the soybean oil is not rarely changed up to open-42 days in the both atmosphere and room temperature. After the open times, the anodic peak potential is largely shifted to a negative direction. This indicates the oxidation of the soybean oil becomes easier. The anodic peak current of the soybean oil is decreased gradually up to open-42 days. But after the open times, the anodic peak current increases suddenly. It must be due to the formation of a carbonyl group owing to rancidity of the soybean oil.