• Title/Summary/Keyword: Semiquinone radical

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A Study on Generative Characteristics of Radicals in Aqueous Solutions of Humic Acids using Electron Spin Resonance (전자기공명기법을 이용한 Humic Acid 용액에서의 라디칼 발생 특성에 관한 연구)

  • Han, Sang-Kuk
    • Journal of Environmental Science International
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    • v.17 no.6
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    • pp.671-677
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    • 2008
  • We studied to determine quantitatively the radical species generated from humic acid (HA) solutions by irradiation(>400 mn). The formation of radical species from HA solutions was investigated with ESR spectroscopy. We gave ESR spectrum with g-value 2.0048 and line width 0.559mT, coincided with those of the semiquinone radical. 0.1 mg/L HA solution generated the radicals of $1.2{\times}10^{-6}M$, increased with increasing HA concentration. Also, pH and ionic strength effect of the amount of the semiquinone radical generate from HA solution. In this study, we have found that the singlet oxygen affects the semiquinone radicals generation in HA solution.

Time Resolved ESR Studies on Short-Lived Reaction Intermediates Produced by Laser Photolysis of Anthraquinone in Organic Solvents (유기용매에서 Anthraquinone의 광반응에서 생성하는 짧은 수명의 반응중간체에 관한 시간분해 ESR 연구)

  • Hong, Daeil;Yun, Young Hyoun;Sohn, Moo-Jeong;Kim, Kyung-Chan;Kuwata, Keiji
    • Journal of the Korean Chemical Society
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    • v.39 no.4
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    • pp.237-243
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    • 1995
  • The measurments of neutral semiquinone radicals, which were formed from the laser flash photolysis of anthraquinone (AQ) in the mixed solvents were carried out by the time resolved electron spin resonance (trESR) spectroscopy. The chemically induced dynamic electron polarization (CIDEP) spectra of the neutral semiquinone radical (AQH${\cdot}$) and semiquinone radical anion (AQ${\cdot}$-) were successively detected in the laser flash photolysis of AQ in the mixtures of 2-propanol (PrOH) and triethylamine (TEA). The neutral semiquinone radical was short-lived with the half-life of 0.8 ${\mu}sec$, whereas the semiquinone radical anion was relatively stable and then its cwESR could be observed. The rate constant of the spin-depolarization of semiquinone radical anion was $2.6{\times}10^5 sec^{-1}$ and the decay of the radical anion was the first order reaction with the rate constant of $3.0{\times}10^2\; sec^{-1}$. No CIDEP of semiquinone radical anion was observed in the mixture of PrOH and the lower concentration of TEA than 2 percent. The CIDEP spectrum of the neutral semiquinone radical was detected in the mixture of benzene and TEA with the half-life of 3.0 ${\mu}sec$. The neutral semiquinone radical could not be detected by cwESR. Neither CIDEP nor ESR absorption could be observed in PrOH, TEA or benzene only.

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Time Resolved Electron Spin Resonance Spectroscopy of Anthrasemiquinone Radical Produced by Pulse Laser Photolysis. A Study on Chemically Induced Dynamic Electron Polarization (광화학 반응에서 생성된 Anthrasemiquinone Radical의 시간분해 ESR ; CIDEP에 관한 연구)

  • Hong Daeil;Kuwata Keiji
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.404-412
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    • 1990
  • The time resolved electron spin resonance spectroscopy are used to two measurement methods of chemically induced dynamic electron polarization (CIDEP) and absorption ESR. The spectra of the semiquinone radical anion were successively detected in the laser flash photolysis of anthraquinone in the mixtures of 2-propanol and triethylamine. The semiquinone radical anion was fairly stable and its cw ESR could be observed. The rate constant (T1$^{-1}$) of the spin-depolarization of polarized semiquinone radical anion was 2.6 ${\times}\;1-^5$ sec$^{-1}$ and the decay of the radical anion was the first order with the rate constant (K$_1}$) of 300.0 sec$^{-1}$. The intensity of CIDEP spectra increased with the increasing the microwave power, but the Torrey wiggles appeared following with decay curves.

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The Electrochemical Reaction Mechanism and Applications of Quinones

  • Kim, R. Soyoung;Chung, Taek Dong
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3143-3155
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    • 2014
  • This tutorial review provides a general account of the electrochemical behavior of quinones and their various applications. Quinone electrochemistry has been investigated for a long time due to its complexity. A simple point of view is developed that considers the relative stability of the reduced quinone species and the values of the first and second reduction potentials. The 9-membered square scheme in buffered aqueous solutions is explained and semiquinone radical stability is discussed in this context. Quinone redox reaction has also been employed in various studies. Diverse examples are presented under three broad categories defined by the roles of quinone: molecular tool for physical chemistry, versatile electron mediator, and charge storage for energy conversion devices.

Synthesis of Dihydroxylated Chalcone Derivatives with Diverse Substitution Patterns and Their Radical Scavenging Ability toward DPPH Free Radicals

  • Kim, Beom-Tae;O, Kwang-Joong;Chun, Jae-Chul;Hwang, Ki-Jun
    • Bulletin of the Korean Chemical Society
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    • v.29 no.6
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    • pp.1125-1130
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    • 2008
  • A series of dihydroxylated chalcone derivatives with diverse substitution patterns on a phenyl ring B and the para-substituents on a phenyl ring A were prepared, and their radical scavenging activities were evaluated by simple DPPH test to determine quantitative structure-activity relationship in these series of compounds. The chalcone compounds with the ortho- (i.e. 2',3'- and 3',4'-) and para- (i.e. 2,5'-) substitution patterns show an excellent antioxidant activities (80-90% of control at the concentration of 50 $\mu$M) which are comparable to those of ascorbic acid and $\alpha$ -tocopherol as positive reference materials. On the contrary, the compounds with meta- (i.e. 2',4'-, 3',5'-) substitution pattern demonstrate very dramatic decrease in activities which are around 25% of the control even at the concentration of 200 $\mu$ M (IC50 > 200 $\mu$ M). These dramatic differences could be interpreted in terms of the ease formation of fairly stable semiquinone radicals from the ortho- and parasubstituted chalcone molecules through facilitating electron delocalization. Our results indicate that the substitution patterns of two hydroxyl groups on ring B are very important structural factors for their radical scavenging activity enhancement. Meanwhile, the substituents at para-position of the phenyl ring A of chalcones have no influence on the activity.

Photodecomposition Characteristics of Tetrabromobisphenol A (TBBPA) by Ultraviolet (UV-A) Irradiation (Ultraviolet-A (UV-A) 조사에 의한 Tetrabromobisphenol A (TBBPA)의 광분해 반응 특성)

  • Jang, Seok-Won;Han, Sang-Kuk
    • Journal of Korean Society of Environmental Engineers
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    • v.35 no.2
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    • pp.124-130
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    • 2013
  • Of all the brominated flame retardants (BFRs), TBBPA has the largest production volume (50% of the BFRs in current use). It is interest to investigate how they may degrade, because of it can pose an environmental hazard. By using UV-A (${\lambda}=352nm$ ), we have found that the UV-A irradiation increased the photodecomposition reaction rate of TBBPA in an intensity-dependent manner. We also observed 2,6-dibromo-p-benzosemiquinone radical ($a_{2H}=2.36G$, g = 2.0056) generated from TBBPA by reaction with singlet oxygen ($^1O_2$). On the other hand, when an aqueous preparation of HA was irradiated in the presence of TBBPA, the typical spectrum of semiquinone radical was detected by electron spin resonance (ESR). And then, we have found that the photodecomposition rate of TBBPA is decreased in depend on HA concentration. Radical formation and the reactive rate of TBBPA were inhibited by sodium azide used as a singlet oxygen quencher. Therefore we report that a similar $^1O_2$-induced oxidation can be initiate in aqueous solutions of TBBPA dissolved in humic acid (HA) by the UV-A irradiation (${\lambda}=352nm$). From these results, we suggest that the reaction rate of HA with $^1O_2$ is faster than that of TBBPA with $^1O_2$.

Application of Chemical Probes to Detect Superoxide Anion and Singlet Oxygen in Biological Systems during Gamma Irradiation

  • Lee, Min Hee;Cho, Eun Ju;Kim, Ji Hong;Kim, Ji Eun;Chung, Byung Yeoup;Cho, Jae-Young;Lee, Kang-Soo;Kim, Jin-Hong
    • Journal of Radiation Industry
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    • v.5 no.3
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    • pp.221-225
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    • 2011
  • To detect superoxide anion ($O_2{\cdot}^-$) or singlet oxygen ($^1O_2$) in biological systems during gamma irradiation, specific chemical probes, 4,5-dihydroxy-1,3-benzene disulfonic acid (Tiron) or 2,2,6,6-tetramethyl-piperidine (TEMP), were evaluated. Tiron or TEMP spin adducts was structurally stable in aqueous solution during gamma irradiation up to 500 or 1,000 Gy, respectively. The signal of Tiron semiquinone radical, a spin adduct of Tiron upon reaction with $O_2{\cdot}^-$, was slightly increased by gamma irradiation. This trend was dose-dependently manifested in $O_2$-saturated aqueous solution using nitro blue tetrazolium (NBT), a common probe for both hydrated electron ($e{^-}_{aq}$) and $O_2{\cdot}^-$. In contrast, a spin adduct of TEMP, was never inducible by gamma irradiation, while its signal was substantially enhanced by photosensitization of riboflavin. These results suggest that Tiron and NBT or TEMP could be utilized to detect $O_2{\cdot}^-$ or $^1O_2$ in biological systems during gamma irradiation, although $O_2{\cdot}^-$ or $^1O_2$ are not the main reactive oxygen species produced by water radiolysis.