• Title/Summary/Keyword: Electron transfer reaction

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Theoretical Studies of Transition Metal Carbene Complexes (Reactivities, Electronic Structures, and Diels-Alder Reaction) (전이금속의 Carbene 착물에 대한 이론적 연구 (반응성, 전자구조, Diels-Alder 반응))

  • Park Seong-Kyu;Kim IIl-Doo;Kim Joon Tae;Kim Sung-Hyun;Choi Chang-Jin;Cheun Young Gu
    • Journal of the Korean Chemical Society
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    • v.36 no.1
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    • pp.3-15
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    • 1992
  • Electronic structures and reactivities of the chromium, molybdenum, and tungsten carbene complexes, $(CO)_5Cr=CCHCH_2(XCH_3)\;,\;(CO)_5Mo=CCHCH_2(XCH_3)\;, and\;(CO)_5W=CCHCH_2(XCH_3)$, are studied by means of Extended Huckel calculations. The origin of the M=Ccarbene double bond is clarified from the diagram of the orbital correlation with the fragment orbitals. The ${\sigma}$ bond of the M=Ccarbene double bond is formed by the electron transfer interaction from the HOMO of the carbene to the LUMO of the $(CO)_5M$. The ${\pi}$ bond is formed through the back-transfer of electrons from one of the degenerated d${\pi}$ orbitals to the LUMO of the carbene. The polarization of charge of the M=Ccarbene bond is calculated to be M=Ccarbene for Mo, and W carbenes. The chemical and physical properties of these complexes are resulted from an appreciable positive charge on the carbene carbon. The electrophilic reactivity of the carbene carbon is not charge controlled, but is controlled by the frontier orbital, LUMO.

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Biological Dechlorination of Chlorinated Ethylenes by Using Bioelectrochemical System (생물전기화학시스템을 이용한 염화에틸렌의 생물학적 탈염소화)

  • Yu, Jaecheul;Park, Younghyun;Seon, Jiyun;Hong, Seongsuk;Cho, Sunja;Lee, Taeho
    • Journal of Korean Society of Environmental Engineers
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    • v.34 no.5
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    • pp.304-311
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    • 2012
  • Chlorinated ethylenes such as perchloroethylene (PCE) and trichloroethylene (TCE) are widely used as industrial solvents and degreasing agents. Because of improper handling, these highly toxic chlorinated ethylenes have been often detected from contaminated soils and groundwater. Biological PCE dechlorination activities were tested in bacterial cultures inoculated with 10 different environmental samples from sediments, sludges, soils, and groundwater. Of these, the sediment using culture (SE 2) was selected and used for establishing an efficient PCE dechlorinating enrichment culture since it showed the highest activity of dechlorination. The cathode chamber of bioelectrochemical system (BES) was inoculated with the enrichment culture and the system with a cathode polarized at -500 mV (Vs Ag/AgCl) was operated under fed-batch mode. PCE was dechlorinated to ethylene via TCE, cis-dichloroethylene, and vinyl chloride. Microbial community analysis with polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) showed that the microbial community in the enrichment culture was significantly changed during the bio-electrochemical PCE dechlorination in the BES. The communities of suspended-growth bacteria and attached-growth bacteria on the cathode surface are also quite different from each other, indicating that there were some differences in their mechanisms receiving electrons from electrode for PCE dechlorination. Further detailed research to investigate electron transfer mechanism would make the bioelctrochemical dechlorination technique greatly useful for bioremediation of soil and groundwater contaminated with chlorinated ethylenes.

Electrochemical Studies on the Lanthanides (란탄족 원소의 전기화학적 환원에 관한 연구 (제 1 보))

  • Park, Jong Min;Gang, Sam U;Do, Lee Mi;Han, Yang Su;Son, Byeong Chan
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.561-568
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    • 1990
  • Voltammetric behavior of some light lanthanide ions (La$^{3+}$, Pr$^{3+}$, Nd$^{3+}$, Sm$^{3+}$, and Eu$^{3+}$) in various supporting electrolytes has been investigated by several electrochemical techniques. The peak potentials and the peak currents, their dependency on the concentration, temperature and pH effects, the reversibility of the electrode reactions are described. The reduction of La$^{3+}$, Pr$^{3+}$ and Nd$^{3+}$ in 0.1 M lithium chloride proceeds by a three-electron change directly to the metallic state (Ln$^{3+}$ + 3e- → Ln$^0$) and charge transfer is totally irreversible. However, the reduction of Sm$^{3+}$ in 0.1 M tetramethylammonium iodide and Eu$^{3+}$ in 0.1 M lithium chloride proceeds in two stages (Ln$^{3+}$ + e- → Ln$^{2+}$ and Ln$^{2+}$ + 2e- → Ln$^0$). At pH values lower than ca.4 the hydrated lanthanide species (Ln(OH)$^{2+}$) reduced before the lanthanide ions (Ln$^{3+}$) due to the catalytic effect of hydrogen ions, and peak current increase with in the order Eu$^{3+}$ < Sm$^{3+}$ < Nd$^{3+}$ < Pr$^{3+}$ < La$^{3+}$ in differential pulse polarography. Some representative plots of $i_{pc}V^{-1/2} (proportional to current function) vs. V show considerable influence of hydrogen ion/lanthanide ion concentration in cyclic voltammetry. It is shown that a reaction of lanthanide ions with proton and/or water and catalytic reaction is enhanced at lower pH and at decreased lanthanide ion concentration.

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Synthesis of Diketo Copper(II) Complex and Its Binding toward Calf Thymus DNA (CTDNA) (이케토 구리(II) 착물의 합성 및 송아지 Thymus DNA(CTDNA)와의 상호작용)

  • Tak, Aijaz Ahmad;Arjmand, Farukh
    • Journal of the Korean Chemical Society
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    • v.55 no.2
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    • pp.177-182
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    • 2011
  • A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.

Electrochemical Behavior of Dissolved Hydrogen and Hydrogen Peroxide in Boric Acid Solution at the Elevated Temperature (붕산수용액 매질에서 용존수소와 과산화수소의 고온 전기화학 거동연구)

  • Yeon Jei-Won;Woo Seung-Kyun;Choi Young-Ku;Jung Yongju;Kim Won-Ho
    • Journal of the Korean Electrochemical Society
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    • v.7 no.1
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    • pp.21-25
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    • 2004
  • The electrochemical behaviors of dissolved hydrogen and hydrogen peroxide at a platinum disk electrode were investigated in boric acid solution by potentiostatic polarization method at the temperature of 25 and $200^{\circ}C$. The oxidation of dissolved hydrogen at $25^{\circ}C$ was kinetically controlled reaction, the rate of which depends upon the electron transfer on the electrode surface. As temperature was raised, however, the electrochemical characteristics of dissolved hydrogen were changed from a kinetically controlled reaction to a diffusion controlled one. One notable feature, with dissolved hydrogen at high temperature, is that an abnormal potential range was observed, where the oxidation rate of dissolved hydrogen rapidly decreased just before starting potential of water oxidation. We think it is caused by the deactivation of the electrode that results from the adsorption of hydroxyl ion on the surface of the platinum disk. On the contrary, a definite change with temperature was not identified in the case of the hydrogen peroxide except for the increase in current density that was due to the increasing diffusion coefcient with an increase of temperature.

Blue Light Photosensitization in Mitochondrial Membrane of Plant Cells (식물세포 미토콘드리아막에서 일어나는 청색광 Photosensitization)

  • Kim, Kyung-Hyun;Kim, Jong-Pyung;Jung, Jin
    • Korean Journal of Environmental Agriculture
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    • v.6 no.2
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    • pp.94-100
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    • 1987
  • Plant mitochondria, irradiated with blue-colored $sunlight(350{\sim}500nm)$ under aerobic and anaerobic conditions, were assayed as to the electron transfer activity of respiratory enzyme system, and compared with those irradiated with orange-colored light(white sunlight minus blue-colored light). The respiratory activity of mitochondria was most seriousely inhibited by illumination with blue-colored light under aerobic condition. Deaeration of mitochondrial suspension resulted in substantial decrease of the photoinhibition by blue-colored light. Meanwhile, orange-colored light demonstrated much less effectiveness-almost ineffectiveness-in causing the inhibition of mitochondrial respiration system. The results of enzymatic assay revealed a strong possibility that FMN in NDH and heme group at least in cytochrome c oxidase, but not FAD in SDH, are the photodynamic sensitizers in mitochondrial inner membrane. Also worthwhile to note is the significant difference from the others of SDH in its photoinhibitory response to the light quality of visible light; that the inhibition of SDH by irradiation was not affected by atmospheric condition and that orange-colored light gave rise to considerable extents of inhibition to the enzyme. This observation was tentatively interpreted in terms of photosensitized reaction not involving molecular oxygen possibly catalyzed by Fe-S centers in the enzyme. The superoxide production and the membrane peroxidation of mitochondria under various treatments also indicated that there was blue-light photodynamic reaction in mitochondria involving active oxygens.

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Effect of Teaching Program for Model Ignorance on the Perception and Teaching Practice of Pre-service Chemistry Teachers (모델 이그노런스 교수프로그램이 예비화학교사의 인식 및 교수 실행에 미치는 효과)

  • Jeon, Eunsun;Paik, Seoung-Hey
    • Journal of the Korean Chemical Society
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    • v.66 no.3
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    • pp.228-242
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    • 2022
  • In this study, the educational effect was investigated by providing a teaching program so that pre-service chemistry teachers could apply model ignorance education to teacher training practice. The teaching program was constructed in consideration of the sensemaking concept proposed in the study of Odden & Russ and the process of teacher sensemaking proposed by Asli et al. The subjects of this study were 23 pre-service teachers in the 4th year of chemistry education department at a teacher training university in the central region of Korea. In order to form a sensemaking for the model's ignorance education, the teaching program consisted of four stages; the initial idea generation stage, cognition of model's ignorance stage in a inconsistent situation, the lesson strategy construction stage for model ignorance education, and lesson plan & practice stage during teacher training practice. In the first stage of this program, pre-service teachers' initial ideas about the Arrhenius model and Bronsted-Lowry model of acid-base reaction, and the electron transfer model of the oxidation-reduction reaction were investigated. In the second stage, inconsistant situation that cannot be explained by the knowledge of model was presented to recognize the ignorance of the model. The third stage was to develop the teaching ability of model's ignorance through textbook analysis and lesson strategy composition activities. As a final stage, during the teacher training practice, the pre-service teachers were asked to plan and practice the implementation of the model's ignorance education. Through the teaching program to form a sensemaking for ignorance education of the models, pre-service teachers had come to recognize the ignorance of the model, acquired ability to organize and execute lesson strategies reflecting model ignorance, and acquired recognition of the educational value and necessity of teaching the ignorance of models.

The Assessment of Photochemical Index of Nursery Seedlings of Cucumber and Tomato under Drought Stress (건조스트레스에 의한 오이와 토마토 공정육묘의 광화학적 지표 해석)

  • Ham, Hyun Don;Kim, Tae Seong;Lee, Mi Hyun;Park, Ki Bae;An, Jae-Ho;Kang, Dong Hyeon;Kim, Tae Wan
    • Korean Journal of Environmental Biology
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    • v.36 no.4
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    • pp.479-487
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    • 2018
  • The purpose of this study is to analyze photochemical activity of nursery seedlings under drought stress, using chlorophyll fluorescence reaction analysis. Young nursery seedlings of tomato (Lycopersicon esculentum Mill.) and cucumber (Cucumis sativa L.), were grown under drought stress for 8 days. Analysis of chlorophyll fluorescence reaction (OJIP) and parameters, were performed to evaluate photochemical fluctuation in nursery seedlings under drought stress. Chlorophyll fluorescence reaction analysis showed maximal recorded fluorescence (P) decreased from the 5 day after treatment in tomato seedlings, while an amount of chlorophyll fluorescence increased at the J-I step. Thus, physiological activity was reduced. In cucumber seedlings, maximal recorded fluorescence (P) and maximal variable fluorescence ($F_V$) lowered from the 4 day after treatment, and chlorophyll fluorescence intensity of J-I step increased. Chlorophyll fluorescence parameter analysis showed electron transfer efficiency of PSII and PSI were significantly inhibited with decreasing $ET2_O/RC$ and $RE1_O/RC$ from the 5 day after treatment, in tomato seedlings and from the 4 day after treatment, in cucumber seedlings. $ET2_O/RC$ and $PI_{ABS}$ significantly changed. In conclusion, 6 indices such as $F_V/F_M$, $DI_O/RC$, $ET2_O/RC$, $RE1_O/RC$, $PI_{ABS}$ and $PI_{TOTAL}ABS$ were selected for determining drought stress in nursery seedlings. Drought stress factor index (DFI) was used to evaluate whether the crop was healthy or not, under drought stress. Cucumber seedlings were less resistant to drought stress than tomato seedlings, in the process of drought stress.

Quantitative Analysis of Ergosterol as a Biomarker of Mold-contaminated Foods Using the Enzyme Biosensor (효소 바이오센서를 이용한 식품의 곰팡이 오염 지표물질인 Ergosterol 정량분석)

  • Kim, Mi-Kyeong;Kim, Jong-Won;Kim, Mee-Ra
    • Korean journal of food and cookery science
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    • v.25 no.2
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    • pp.252-259
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    • 2009
  • Ergosterol is the significant component of the cell wall of fungi. Its presence is regarded as evidence of fungi contamination in grain and other foods. Many studies on ergosterol detection have been carried out using chemical methods, but those methods required complicated pre-treatments and long analysis times. In this study, an amperometric biosensor was developed for fast and precise ergosterol detection. The biosensor system used the electron transfer of hydrogen peroxide produced from the reaction of ergosterol with cholesterol oxidase. The biosensor system consisted of a peristaltic pump, a syringe loading sample injector, an enzyme reactor, a fabricated flow-through cell containing a working electrode, a reference electrode and a counter electrode, and a potentiostat/recorder. The working electrode was prepared by coating modified multi-wall carbon nanotube (MWNT) on glassy carbon electrode. The $MWNT-NH_2$ coated glassy carbon electrode linearly responded to hydrogen peroxide in the range of $1{\times}10^{-5}{\sim}8{\times}10^{-5}$ M with a detection limit of $10^{-7}$ M in the basic performance test. The currents produced from the ergosterol biosensor showed the linearity in a range from $1.0{\times}10^{-6}$ M to $1.0{\times}10^{-5}$ M ergosterol.

Electricity Generation and De-contamination Effect for Characteristic Electrode Material in a Microbial Fuel Cell System Using Bay Sediment (MFC의 금속 및 탄소전극에 의한 전기생산 특성과 오염저감 효과)

  • Kwon, Sung-Hyun;Song, Hyung-Jin;Lee, Eun-Mi;Cho, Dae-Chul;Rhee, In-Hyoung
    • Journal of Environmental Science International
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    • v.19 no.8
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    • pp.951-960
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    • 2010
  • Sediment works as a resource for electric cells. This paper was designed in order to verify how sediment cells work with anodic material such as metal and carbon fiber. As known quite well, sediment under sea, rivers or streams provides a furbished environment for generating electrons via some electron transfer mechanism within specific microbial population or corrosive oxidation on the metal surfaces in the presence of oxygen or water molecules. We experimented with one type of sediment cell using different anodic material so as to attain prolonged, maximum electric power. Iron, Zinc, aluminum, copper, zinc/copper, and graphite felt were tested for anodes. Also, combined type of anodes-metal embedded in the graphite fiber matrix-was experimented for better performances. The results show that the combined type of anodes exhibited sustainable electricity production for ca. 600 h with max. $0.57\;W/m^2$ Al/Graphite. Meanwhile, graphite-only electrodes produced max. $0.11\;W/m^2$ along with quite stationary electric output, and for a zinc electrode, in which the electricity generated was not stable with time, therefore resulting in relatively sharp drop in that after 100 h or so, the maximum power density was $0.64\;W/m^2$. It was observed that the corrosive reaction rates in the metal electrodes might be varied, so that strength and stability in the electric performances(voltage and current density) could be affected by them. In addition to that, COD(chemical oxygen demand) of the sediment of the cell system was reduced by 17.5~36.7% in 600 h, which implied that the organic matter in the sediment would be partially converted into non-COD substances, that is, would suggest a way for decontamination of the aged, anaerobic sediment as well. The pH reduction for all electrodes could be a sign of organic acid production due to complicated chemical changes in the sediment.