• Title/Summary/Keyword: free radical formation

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Hydroxyl Radical-Generating Function of Horseradish Cu,Zn-Superoxide Dismutase

  • Eum, Won-Sik;Kwon, Oh-Bin;Kang, Jung Hoon
    • BMB Reports
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    • v.31 no.5
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    • pp.492-497
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    • 1998
  • Cu,Zn-superoxide dismutase (SOD) was purified from horseradish by using Mono Q and Superose 12 FPLC column chromatography. The native molecular mass of the purified enzyme was approximately 33 kDa, as determined by gel filtration. The subunit molecular weight, as estimated by SDS-PAGE, was 16 kDa. These results indicated that the native enzyme is a homodimer. We investigated the free radical-generating function of horseradish Cu,Zn-SOD by using a chromogen, 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulfonate) (ABTS) which reacts with ${\cdot}OH$ radicals to form $ABTS^{+{\cdot}}$ The formation of $ABTS^{+{\cdot}}$ was required for both active Cu, Zn-SOD and $H_2O_2$. The optimal pH for the free radical-generating activity of this enzyme was 6.0-8.0, and it retained about $40^{\circ}C$ of its maximum activity when exposed at $40^{\circ}C$ for 15 min. A neutral scavenger, ethanol, inhibited the $ABTS^{+{\cdot}}$ formation by horseradish Cu, Zn-SOD more effectively than that by the mammalian enzyme. These results suggest that the active channel of horseradish enzyme is slightly larger than that of the mammalian enzyme.

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Synthesis of Star-like Random Copolymers from Resorcinarene-Based Octa-Functional Alkoxyamine Initiator via Nitroxide Mediated Free Radical Polymerization

  • Abraham, Sinoj;Choi, Jae-Ho;Lee, Jin-Kyu;Ha, Chang-Sik;Kim, Il
    • Macromolecular Research
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    • v.15 no.4
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    • pp.324-329
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    • 2007
  • An octa-functional alkoxyamine initiator, with the 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO) free radical, was synthesized based on resorcinarene, with its efficiency to initiate the nitroxide-mediated free radical copolymerization of styrene and methyl methacrylate (MMA) described. A difunctional analogue of this initiator was also synthesized, using resorcinol as the core molecule. The structures of the resulting initiators were confirmed by homolysis studies based on electron spin resonance spectroscopy and molecular modeling. The polymerization behavior and characteristics of the polymers obtained using these two initiators were also compared. Well-defined star-shaped and linear random copolymers, with low polydispersities and controlled molecular weights, were prepared. The efficiencies of these initiators towards copolymerization, as well as the parameters permitting the formation of well-defined polymers, were also investigated. The reactivity ratios were $r_a=0.42(a=styrene)\;and\;r_b=0.33(b=MMA)$ for the octa-functional initiator system and $r_a=0.45\;and\;r_b=0.39$ for the difunctional initiator system.

Aromatic Formation from Vinyl Radical and Acetylene. A Mechanistic Study

  • Natalia, Debby;Indarto, Antonius
    • Bulletin of the Korean Chemical Society
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    • v.29 no.2
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    • pp.319-322
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    • 2008
  • The viability of acetylene addition in each step of aromatic formation initiated by vinyl radical and acetylene also with its competition with structure rearrangement is investigated by determining optimal geometries and barrier and reaction energies using quantum mechanical methods. In principle, the addition reaction has more difficult in term of free energy and enthalpy compared to geometry arrangement. Under combustion conditions, i.e. T = 1200 K, acetylene addition is unfavorable mechanism as the barrier energy values rise much higher than that of geometry arrangement. However, in longer chain hydrocarbon case, e.g. n-CxHx+1 where x ³ 8, C-C bond rotation is rather difficult and requires high energy to form a ring structure, elongation chain is preferable.

Modification and Inactivation of Human Ceruloplasmin by Oxidized DOPA

  • Kang, Jung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.625-628
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    • 2004
  • Ceruloplasmin (CP), the blue oxidase present in all vertebrates, is the major copper-containing protein of plasma. It has been proposed that oxidation of L-3,4-dihydroxyphenylalanine (DOPA) may contribute to the pathogenesis of neurodegenerative disorders. The effect of the oxidized products of DOPA on the modification of human CP was investigated. When CP was incubated with the oxidized L-DOPA, the protein was induced to be aggregated and ferroxidase activity was decreased in a time-dependent manner. Radical scavengers and catalase significantly inhibited the oxidized DOPA-mediated CP aggregation. Copper chelatrors, Diethylenetriaminepenta acetic acid (DTPA) and Diethyldithiocarbamic acid (DDC), also inhibited the oxidative modification of CP. The results suggested that DOPA oxidation led to the formation of free radical and induced the CP aggregation.

Naturally-Occurring Novel Anticatcinogens : Conjugated Dienoic Derivatives of Linoliec Acid (CLA) (새로이 분류된 천연 항암제 : Conjugated Dienoic Derivatives of Linoleic Acid (CLA))

  • 하영래;마이클파리자
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.20 no.4
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    • pp.401-407
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    • 1991
  • Anticarcinogenic conjugated dienoic derivatives of linoleic acid (CLA) is present in grilled beef, cheese, and related foods, CLA is generated via isomerization of linoleic acid in the cow's rumen by anaerobic bacteria and food proceessing as well. Another source of CLA is its endogenous generation via the carbon centered free radical oxdation of linoleic acid. We propose that the formation and generation of CLA in vivo represents a previously unrecognized in situ "defense mechanism" against membrane attack by oxygen free radicals. The cis, 9-trans, 11 CLS isomer is selectively incorporated into cellular phospholipid, which exhibits a potent antioxidant, reduces the activation of 2-amino-3-methylimidazo, [4,5-f] quinoline (IQ) for baxterial mutagenesis, and inhibits ornithine decarboxylase(ODC) activity induced by 12-0-tetradecanoylphorbol-13-acetate (TPA). We believe that at least these biological activities of CLA explain the anticarcinogenic activity of CLA.

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The Experimental Study of Glycyrrhiza uralensis on Wound Healing by Antioxidant Effect (감초 추출물의 항산화 효과에 의한 상처 치료 가능성 연구)

  • Lee, Yun Kyung;Roh, Seok Sun
    • Journal of Haehwa Medicine
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    • v.25 no.1
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    • pp.145-153
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    • 2016
  • Objectives : The purpose of this study is to evaluate the wound healing potential of Glycyrrhiza uralensis extract. Methods : Free radical scavenging activity tests for DPPH, peroxynitrite (ONOO) and hydroxyl radical (${\cdot}OH$) and total phenolic contents of Glycyrrhiza uralensis extract were conducted. Tube formation assay was performed using human umbilical vein endothelial cells (HUVECs). Results : The results showed that Glycyrrhiza uralensis extract exerted inhibitory effects on ONOO and ${\cdot}OH$. Tube formation in HUVEC was increase in a dose dependent manner. Conclusions : These results show the potential to promote the wound healing process by Glycyrrhiza uralensis extract.

Scavenging Property of Pyungwi-san Herbal-acupuncture Solution on ROS and RNS (평위산(平胃散) 약침액(藥鍼液)의 활성산소 및 활성질소 소거능)

  • Lee, Hyo-Seung;Moon, Jin-Young
    • Journal of Physiology & Pathology in Korean Medicine
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    • v.21 no.1
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    • pp.165-170
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    • 2007
  • Pyungwi-san(PWS) have been using as a basic prescription of digestive disorder in Korean traditional medicine. This study was performed to examine the in vitro antioxidant activity of the extract using different antioxidant tests including by 1,1-diphenyl-2-picryl-hydrazil (DPPH) radical scavenging, superoxide anion radical scavenging, metal chelating hydrogen peroxide scavenging, lipid peroxydation protective effect and scavenging effect of nitric oxide and peroxynitrite. Herbal-acupuncture solution of PWS(PWS-HS) exhibited a concentration-dependent inhibition of DPPH radical adduct formation and it showed dose-dependent free radical scavenging activity onto superoxide anions. In addition, the result of metal chelating hydrogen peroxide scavenging and ammonium thiocyanate experiments showed that PWS-HS was an active scavenger of hydroxyl radicals. Furthermore, it was also found to be effective in scavenging nitric oxide and peroxynitrite, well-known cytotoxic species that can oxidize several cellular components such as proteins, lipids and DNA.

DNA Cleavage Induced by the Reaction of Salsolinol with Cu,Zn-Superoxide Dismutase

  • Kang, Jung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2329-2332
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    • 2007
  • Salsolinol, endogenous neurotoxin, is known to be involved in the pathogenesis of Parkinson's disease (PD). In the present study, we have investigated the oxidative damage of DNA induced by the reaction of salsolinol with Cu,Zn-SOD. When plasmid DNA incubated with salsolinol and Cu,Zn-SOD, DNA cleavage was proportional to the concentrations of salsolinol and Cu,Zn-SOD. The salsolinol/Cu,Zn-SOD system-mediated DNA cleavage was significantly inhibited by radical scavengers such as mannitol, ethanol and thiourea. These results indicated that free radicals might participate in DNA cleavage by the salsolinol/Cu,Zn-SOD system. Spectrophotometric study using a thiobarbituric acid showed that hydroxyl radical formation was proportional to the concentration of salsolinol and was inhibited by radical scavengers. These results indicated that hydroxyl radical generated in the reaction of salsolinol with Cu,Zn-SOD was implicated in the DNA cleavage. Catalase and copper chelators inhibited DNA cleavage and the production of hydroxyl radicals. These results suggest that DNA cleavage is mediated in the reaction of salsolinol with Cu,Zn-SOD via the generation of hydroxyl radical by a combination of the oxidation reaction of salsolinol and Fenton-like reaction of free copper ions released from oxidatively damaged SOD.

Oxidative Modification of Neurofilament-L Induced by Endogenous Neurotoxin, Salsolinol

  • Kang, Jung-Hoon
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3421-3424
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    • 2011
  • The endogenous neurotoxin, 1-methyl-6,7-dihydroxy-1,2,3,4-tetrahydroisoquinoline (salsolinol), has been considered a potential causative factor for the pathogenesis of Parkinson's disease (PD). In this study, we examined oxidative modification of neurofilament-L (NF-L) induced by salsolinol. When disassembled NF-L was incubated with salsolinol, the aggregation of protein was increased with the concentration of sasolinol. The formation of carbonyl compound was obtained in salsolinol-mediated NF-L aggregates. This process was protected by free radical scavengers, such as N-acetyl-L-cysteine and glutathione. These results suggest that the aggregation of NF-L is mediated by salsolinol via the generation of free radicals. We also investigated the effects of copper ion on salsolinol-mediated NF-L modification. In the presence of copper ions, salsolinol enhanced the modification of NF-L. We suggest that salsolinol might be related to abnormal aggregation of NF-L which may be involved in the pathogenesis of neurodegenerative diseases and related disorders.

Acrolein, the toxic endogenous aldehyde, induces neurofilament-L aggregation

  • Jeong, Moon-Sik;Kang, Jung-Hoon
    • BMB Reports
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    • v.41 no.9
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    • pp.635-639
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    • 2008
  • Acrolein is a highly reactive by product of lipid peroxidation and individuals with neurodegenerative disorders have been shown to contain elevated concentrations of this molecule in the brain. In the present study, we examined the pattern of neurofilament-L (NF-L) modification elicited by acrolein. When NF-L was incubated with acrolein, protein aggregation occurred in a acrolein concentration-dependent manner. Exposure of NF-L to acrolein also led to the generation of protein carbonyl compounds. Through the addition of free radical scavengers we observed a significant decrease in acrolein-mediated NF-L aggregation. These results indicate that free radicals may be involved in the modification of NF-L by acrolein. In addition, dityrosine crosslink formation was observed in acrolein-mediated NF-L aggregates and these aggregates displayed thioflavin T reactivity, reminiscent of amyloid. This study suggests that acrolein-mediated NF-L aggregation might be closely related to oxidative reactions, thus these reactions may play a critical role in neuro-degenerative diseases.