• Title/Summary/Keyword: Radical chemistry

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Syntheses of Resveratrol and its Hydroxylated Derivatives as Radical Scavenger and Tyrosinase Inhibitor

  • Lee, Hyun-Suck;Lee, Byung-Won;Kim, Mi-Ran;Jun, Jong-Gab
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.971-975
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    • 2010
  • Eight hydroxylated stilbene derivatives including resveratrol, desoxyrhapontigenin and piceatannol as potential radical scavenger and tyrosinase inhibitor are synthesized using optimized Wittig-Horner reaction for excellent trans-selectivity in good yields. Antioxidant activity was tested against ABTS radical and tyrosinase inhibitory activity was performed with L-tyrosine as the substrate based on previous procedure with some modification. In general, catecholic stilbenes showed stronger activity against ABTS radical and resorcinolic moiety showed stronger tyrosinase inhibitory activity. Synthetic piceatannol which containing both catecholic and resorcinolic moieties showed the strongest activity in both as ABTS radical scavenger and tyrosinase inhibitor with $IC_{50}$ values of 4.1 and $8.6\;{\mu}M$, respectively.

Spectroscopic Evidence of Jet-Cooled p-Chloro-α-Methylbenzyl Radical in Corona Excitation

  • Huh, Chang-Soon;Yoon, Young-Wook;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • v.33 no.9
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    • pp.2943-2948
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    • 2012
  • We report the first spectroscopic evidence of the jet-cooled p-chloro-${\alpha}$-methylbenzyl radical. The visible vibronic emission spectrum was recorded from the corona discharge of precursor p-chloro-ethylbenzene seeded in a large amount of inert carrier gas helium using a pinhole-type glass nozzle coupled with a technique of corona excited supersonic expansion. From the comparison with the vibronic spectrum of the p-chlorobenzyl radical, we identified the evidence of formation of the jet-cooled p-chloro-${\alpha}$-methylbenzyl radical in the corona discharge of precursor p-chloro-ethylbenzene.

Rearrangement of Benzyl-type Radical in Corona Discharge of 2,6-Dichlorotoluene

  • Yoon, Young-Wook;Lee, Seung-Woon;Lee, Sang-Kuk
    • Bulletin of the Korean Chemical Society
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    • v.31 no.9
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    • pp.2479-2482
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    • 2010
  • Using a pinhole-type glass nozzle equipped for a corona-excited supersonic expansion (CESE), precursor 2,6-dichlorotoluene seeded in a large amount of inert carrier gas helium was discharged to produce jet-cooled but electronically excited benzyl-type radicals. The visible vibronic emission spectrum was recorded with a long-path monochromator to observe vibronic bands in the $D_1{\rightarrow}D_0$ electronic transition of benzyl-type radicals. The spectral analysis revealed the generation of not only the 2,6-dichlorobenzyl radical as a typical product, but also the o-chlorobenzyl radical as an unexpected species, which indicates the possible molecular rearrangement in eliminating a chlorine atom from the benzene ring. A possible mechanism is proposed for the formation of the o-chlorobenzyl radical from the precurs or in the gas phase.

CHEMILUMINESCENCE STUDIES ON THE BIOLOGICAl, INTERACTION BETWEEN SUPEROXIDE ANION RADICAL AND NITRIC OXIDE PRODUCED BY PHORBOI, ESTER-STIMULATED RAW264.7 MACROPHAGES

  • Lee, Hong;Pae, Hyun-Ock;Jun, Chang-Duk;Kwak, Hyun-Jeong;Park, Rae-Kil;Yoo, Ji-Chang;Lee, Seog-Jae;Kim, Myung-Sun;Kim, Hae-Song;Choi, Byung-Min;Chung, Hun-Taeg
    • Journal of Photoscience
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    • v.4 no.2
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    • pp.31-34
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    • 1997
  • The rapid and spontaneous interaction between superoxide anion radical and nitric oxide to yield the potent oxidants. peroxynitrite artion and peroxynitrous acid, was investigated in phorbol myristate acetate(PMA)-stimulated RAW264.7 macrophases by means of lucigenin- or luminol-enhanced chemiluminescence method. When RAW264.7 macrophages were stimulated by PMA. peroxynitrite-induced chemiluminescence was clearly observed. To prove observed chemiluminescencc due to the reaction between superoxide anion radical and nitric oxide produced by RAW264.7 macrophases, N-nitrosoglutathione (GSNO), a nitric oxide-releasing compound. superoxide dismutase(SOD), an enzyme removing superoxide anion radical by dismutating superoxide artion radical to hydrogen peroxide, and N-acethyl cysteine(NAC), a scarvenging reagent both superoxide artion radical and nitric oxide, were added in the cell system. Peroxynitrite- induced chemilumincscence was increased by exogenous addition of GSNO. whereas observed chemiluminescence was decreased by SOD and NAC. These results suggest that PMA-stimulated RAW264.7 macrophages produce both superoxide anion radical and nitric oxide to form peroxynitrite.

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Screening of antioxidant and antimicrobial activities of Caesalpinia bonducella Flem., leaves (Caesalpiniaceae)

  • Gupta, Malaya;Mazumdar, UK;Kumar, Ramanathan Sambath;Gomathi, Periyasamy;Rajeshwar, Y.;Kumar, T. Siva
    • Advances in Traditional Medicine
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    • v.4 no.3
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    • pp.197-209
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    • 2004
  • The study was aimed at evaluating the antioxidant and antimicrobial activities of methanol extract of Caesalpinia bonducella leaves (MECB) (Family: Caesalpiniaceae). The effect of MECB on antioxidant activity, reducing power, free radical scavenging (DPPH radical, nitric oxide radical, superoxide anion radical, hydroxyl radical and hydrogen peroxide radical scavenging), total phenolic content and antimicrobial activities were studied. The antioxidant activity of MECB increased in a dose dependent manner. About 50, 100, 250 and 500 g of MECB showed 53.4, 61.2, 69.1 and 76.2 % inhibition respectively on peroxidation of linoleic acid emulsion. Like antioxidant activity, the effect of MECB on reducing power increased in a dose dependent manner. The free radical scavenging activity of MECB was determined by DPPH radical scavenging method. The potency of this activity was increased with increased amount of extract. MECB was found to inhibit the nitric oxide radicals generated from sodium nitroprusside $(IC_{50}\;=\;102.8\;g/ml)$ whereas the $IC_{50}$ value of curcumin was 20.4 g/ml. Moreover, the MECB was found to scavenge the superoxide generated by photoreduction of Riboflavin. MECB was also found to inhibit the hydroxyl radical generated by Fenton reaction, where the $IC_{50}$ value is 104.17 g/ml compared with catechin 5 g/ml, which indicates the antioxidant activity of MECB. The MECB capable of scavenging hydrogen peroxide in a concentration-dependent manner. The amounts of total phenolic compounds were also determined. Antimicrobial activities of MECB were carried out using disc diffusion methods with five Gram positive, four Gram negative and four fungal species. The results obtained in the present study indicate that MECB leaves are potential source of natural antioxidant and antimicrobial agents.

Radical Additions of Arenethiols to Ynamides for the Selective Synthesis of N-[(Z)-2-(Arylsulfanyl)-1-alkenyl]amides

  • Sato, Akinori;Yorimitsu, Hideki;Oshima, Koichiro
    • Bulletin of the Korean Chemical Society
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    • v.31 no.3
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    • pp.570-576
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    • 2010
  • A variety of ynamides undergo highly regio- and stereoselective radical addition of arenethiols with the aid of triethylborane as a radical initiator. The products, N-[(Z)-2-arylsulfanyl-1-alkenyl]amides, can be reduced with triethylsilane in trifluoroacetic acid to yield N-[2-(arylsulfanyl)alkyl]amides.

Charge-Directed Peptide Backbone Dissociations of o-TEMPO-Bz-C(O)-Peptides

  • Jeon, Aeran;Lee, Ji Hye;Kwon, Hyuk Su;Park, Hyung Soon;Moon, Bong Jin;Oh, Han Bin
    • Mass Spectrometry Letters
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    • v.4 no.4
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    • pp.71-74
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    • 2013
  • In the present study, we report that the charge-directed (assisted) peptide dissociation products, such as b- and y-type peptide backbone fragments, were the major products in MS/MS and $MS^3$ applications of some o-TEMPO-Bz-C(O)-peptide ions, while radical-driven dissociation products, such as a/x and c/z-type fragments, were previously shown to be the major products in the free radical initiated peptide sequencing mass spectrometry (FRIPS MS). Those o-TEMPO-Bz-C(O)-peptides share a common feature in their sequences, that is, the peptides do not include an arginine residue that has the highest proton affinity among free amino acids. The appearance of b- and y-type fragments as major products in FRIPS MS can be understood in terms of the so-called "mobile-proton model". When the proton is highly mobilized by the absence of arginine, the chare-directed peptide dissociation pathways appear to be more competitive than the radical-driven dissociation pathways, in our FRIPS experiments.

Screening of the Tyrosinase Inhibition and Hyaluronidase Inhibition Activities, and Radical Scavenging Effects Using Plants in Cheju (제주산 식물을 이용한 Tyrosinase 억제 활성, Hyaluronidase 억제 활성, 라디칼 소거 활성 검색)

  • Lee, Sun-Joo;Jung, Deok-Sang;Bu, Hee-Jeong;Yang, Hong-Chul;Riu, Key-Zung;Lee, Nam-Ho
    • Korean Journal of Pharmacognosy
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    • v.32 no.3 s.126
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    • pp.175-180
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    • 2001
  • Solvent extracts of 17 plants collected in Cheju Island were investigated for their biological properties related to cosmeceuticals such as tyrosinase and hyaluronidase inhibition and also radical scavenging effects. The chloroform fraction of Phytolacca esculenta root exhibited strong inhibition against tyrosinase activity. No fraction showed significant hyaluronidase inhibition. Some solvent extracts of plants such as Achyranthes japonica and Artemisia princeps showed considerable radical scavenging activities.

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Antioxidative Effects of Polyozellin and Thelephoric Acid Isolated from Polyozellus multiflex (까치버섯(Polyozellus multiplex)으로부터 분리한 polyozellin과 thelephoric acid의 항산화 활성)

  • Chung, Shin-Kyo;Jeon, So-Young;Lee, Hee-Ju;Kim, Suk-Kyung;Kim, Sang-In;Kim, Geum-Soog;Kwon, Soon-Ho;Kim, Ja-Young;Song, Kyung-Sik
    • Applied Biological Chemistry
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    • v.47 no.2
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    • pp.283-286
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    • 2004
  • In the course of screening for reactive oxygen species scavengers from natural products, two antioxidants were isolated from the edible mushroom Polyozellus multiflex and identified as polyozellin and thelephoric acid. Thelephoric acid inhibited 45.7% of the super oxide anion radical, 74.6% of the hydroxyl radical, and 44.0% of the DPPH radical at 0.1 mM, while the positive control ${\alpha}-tocopherol$ did 22.1%, 75.6%, and 26.5% of each radical, respectively. Polyozellin, the reductive acetylated form of thelephoric acid, showed almost same scavenging activity against above mentioned radicals. The isolated compounds showed scavenging activity on the superoxide anion radical in the ESR method ($IC_{50}$ of polyozellin and thelephoric acid were $218.0\;{\mu}M$ and $21.1\;{\mu}M$, respenctively). However, they showed no significant activity on the hydrogen peroxide radical.