• Bulletin of the Korean Chemical Society
• /
• v.27 no.8
• /
• pp.1099-1114
• /
• 2006

Our studies in the area of single electron transfer (SET) photochemistry have led to the discovery of efficient processes, in which regioselective formation of carbon-centered radicals takes place by nucleophile assisted desilylation of $\alpha$-trialkylsilyl substituted ether, thioether, amine and amide centered cation radicals. The rates of bimolecular desilylation of the intermediate cation radicals exceed those of other cation radical $\alpha$-fragmentation processes (e.g.,-deprotonation). This sereves as the basis for the design of highly regioselective, SET-induced photomacrocyclization reactions of polyether, polythioether, polyamide, and polypeptide linked phthalimides. Photocyclization reactions of trimethylsilyl-terminated substrates in these families are unique in that they produce polyfunctionalized macrocyclic substances in a highly efficient and regioselective manner. In addition, our studies in this area have led to important information about the factors that govern chemical and quantum efficiencies that should be applicable to a wide variety of redox processes promoted by SET from substrates containing more than one electron donor site.

• BMB Reports
• /
• v.33 no.1
• /
• pp.37-42
• /
• 2000

Based on the study by Leatham and Stabmann concerned with the rates (v) of amines and phenolic compounds oxidation catalyzed by laccase of basidiomycete Lentinus edodes (Berk.) Sing., as well as on the results of semiempirical quantum chemical computations using the PM3 method, the linear correlations of v and lnv values with first vertical ionization potentials of the substrates molecules and radicals derived from them, spin densities on N and O atoms of the above radicals, and with the radicals reorganization energies have been found.

• The Journal of Korean Medicine
• /
• v.26 no.3 s.63
• /
• pp.204-214
• /
• 2005

Objectives : The verity extract of the Gagam-Hyungbang-Gihwang-tang (GHG) was assessed to determine the mechanisms of its antioxidant activity. Methods : The fellowing effects were measured : GHG exhibited a concentration-treatment; scavenging ${\alpha},\;{\alpha}-diphenyl-\beta-picrylhydrazyl$ (DPPH) radical, linoleic acid oxidation in a thiocyanate assay system, and superoxide anion, hydroxyl radical-induced DNA nicking. We investigated mRNA levels such as superoxide-dismutase. Results : The GHG extract showed dose-dependent free radical scavenging activity, including DPPH radicals, hydroxyl radicals, and superoxide anion, using different systems. The GHG was also found to be effective in protecting plasmid DNA against the strand breakage induced by hydroxyl radicals in Fenton's reaction mixture. Furthermore, SOD-1 mRNA expression levels increased in tat hepatoma H4IIE cells Conclusions : We expect that GHG will to helpful to the development of antioxidant activity treatments.

• Toxicological Research
• /
• v.17 no.4
• /
• pp.249-253
• /
• 2001

Fumonisin B1, a mycotoxin, is thought to induce esophageal cancer in humans and apoptosis in animal cells by inhibiting ceramide synthase. Dumonisin Bl may also generate reactive oxygen species directly or indirectly, leading to DNA damage and lipid peroxidation. In this study, a DNA fragmentation assay, dichlorofluorescein (DCF) analysis, and single cell gel electrophoresis (SCGE) were used to investigate the involvement of cellular free radicals, specifically hydrogen peroxide, in the DNA damaging activity of fumonisin B1. From an in vitro DNA fragmentation assay, E. coli DNA, damage by fumonisin Bl was increased by the addition of superxide dismutase (SOD) and decreased by catalase. SCGE and DCF analysis in vivo showed that the nuclear DNA damage and intracellular free radicals in cultured rat hepatocytes treated with fumonisin B1 were increased with the concentration of fumonisin Bl . DNA damage and free radical generation were inhibited by the addition of catalase. Fumonisin Bl , in the presence of SOD, produces hydrogen peroxide causing oxidative DNA damage and protein malfunction, leading to genotoxicity and cytotoxicity of the toxin.

• Proceedings of the Korea Crystallographic Association Conference
• /
• 2002.11a
• /
• pp.53-53
• /
• 2002

Alkali-soluble random copolymer (ASR) was used as a functional resin in the emulsion polymerization of styrene to prepare structured nanoparticles. The calorimetric technique was applied to study the kinetics of emulsion polymerization of styrene using ASR and conventional ionic emulsifier, sodium dodecyl benzene sulfonate (SDBS). ASR could form aggregates like micelles and the solubilization ability of the aggregates was dependent on the neutralization degree of ASR. The rate of polymerization in ASR system was lower than that in SDBS system. This result can be explained by the creation of a hairy ASR layer around the particle surface, which decreases the diffusion rate of free radicals through this region. Although a decrease in particle size was observed, the rate of polymerization decreased with increasing ASR concentration. The higher the concentration of ASR is, the thicker and denser ASR layer may be, and the more difficult it would therefore be for radicals to reach the particle through this layer of ASR. The rate of polymerization decreased with increasing the neutralization degree of ASR. The aggregates with high neutralization of ASR are less efficient in solubilizing the monomer and capturing initiator radicals than that of the lower neutralization degree, which leads to decrease in rate of polymerization.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.10
• /
• pp.2783-2785
• /
• 2010

Searching for new molecular radicals which are believed to play an important role as reaction intermediates in aromatic chain reactions, we have applied the technique of corona excited supersonic expansion employing a pinhole-type glass nozzle to obtain the vibronic spectrum from the corona discharge of precursor 3,5-difluorotoluene with a large amount of inert carrier gas helium. An analysis of the observed spectrum revealed that many vibronic bands are from other isomeric difluorobenzyl radicals generated in the jet by migration of the fluorine atom or methylene group to the adjacent position in the 3,5-difluorobenzyl radical. A possible mechanism was proposed for the formation of other isomers by using a bridged cyclic intermediate structure.

• Preventive Nutrition and Food Science
• /
• v.12 no.1
• /
• pp.7-10
• /
• 2007

Theaflavins (TF) and thearubigins (TR) were separated from Korean microbially fermented tea leaves. Contents of TF (74.4 $\mu$M/g) and TR (37.2%) were higher than reported for black tea fermented by oxidase. Antioxidant activities of TF, TR and EGCG were analyzed and protective effects of COS-7 cells against copper and cadmium-induced toxicity were investigated. TF and TR exhibited good inhibition rates of about 85$\sim$90% for antioxidant and scavenging activities of free radicals and protected COS-7 cells against apoptosis or damage caused by stress, such as cadmium and copper-oxidative injury, free radicals etc. These results indicate that TF, TR and EGCG have antioxidant and scavenging activities against free radicals and protect COS-7 cells from Cu, Cd induced injury.

• Archives of Pharmacal Research
• /
• v.19 no.2
• /
• pp.132-136
• /
• 1996

Exogenously applied oxygen free radical generating agent, pyrogallol, highly elevated extracellular glutamate accumulation and augmented N-methyl-D-aspartate (NMDA)-induced glutamate accumulation in cerebellar granule neuronal cells, but did not in astrocytes. Superoxide dismutase remarkably decreased the pyrogallol-induced glutamate accumulation, but either NMDA or kainate antagonists did not. In addition, pyrogallol did not affect the NMDAinduced intracellular calcium elevation. Pyrogallol partially blocked glutamate uptake into astrocytes. These results suggest that oxygen free radicals elevate extracellular glutamate accumulation by stimulating the release of glutamate as well as blocking the glutamate uptake.

• Korean Journal of Microbiology
• /
• v.26 no.1
• /
• pp.44-51
• /
• 1988

The intracellular free radicals produced at different stages of cell cycle of Saccharomyces cerevisiae ATCC 24858 were investigated by means of electron spin resonance(ESR) spectroscopy. The synchronized cells by repeated starvation and refeeding revealed different ESR spectral pattern compared to that of asynchronized cells. Each spectrum centered at g=2.005, which indicates free radicals. The relative spin concentration was maximat at the end of DNA increase. The variation of the relative spin concentration at each distinct stage of the cell cycle was evaluated in relation to ascorbate concentration, L-galactonolactone oxidase activity, and ascorbate oxidase activity. The highest activities of L-galactonolactone oxidase and ascorbate oxidase were detected just before and at the maximum of relative spin concentration, respectively. And ascorbate concentration fluctuated through each stage of cell cycle with the changes of relative spin concentration, L-galactonolactone oxidase activity, and ascorbate oxidase activity. Thus it is suggested that intracellular free radicals should be related to cell cycle, interacted with ascorbate, and may play an important role in the cell cycle of Saccharomyces cerevisiae.

• Journal of the Korean Vacuum Society
• /
• v.9 no.1
• /
• pp.76-80
• /
• 2000

CF & $CF_2$ radicals in a $C_4F_8$ inductively coupled plasma were observed with laser induced fluorescence. 251.9nm UV laser was used for the $CF_2$ excitation and 265.3nm UV emitted light for the detection which has the maximum intensity among many induced fluorescence lights. In the case of CF radical detection, 232.9nm UV laser was used for the excitation and 247.6nm for the detection. $CF_2$ radical density increased toward substrate, while CF radical had its maximum at about 10nm away from the substrate. The atomic fluorine density which was studied by the actinometry increased as the position moves away from the substrate. This phenomena was thought to have a close relation with the polymer growth on the wafer. When the bias voltage increased, $CF_2$ , CF radicals decreased while the atomic fluorine increased tio some extent and then decreased, which was thought to be due to the change in the ionization and dissociation.