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Photosensitized Lysis of Egg Lecithin Liposomes by L-Tryptophan and N-Acetylphenylalanyl-L-Tryptophan

  • Cho, Dae-Won;Yoon, Min-Joong
    • Bulletin of the Korean Chemical Society
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    • v.7 no.1
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    • pp.78-81
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    • 1986
  • The photosensitized lysis of egg lecithin lipid membranes (liposomes) have been performed to UV-B light (270-320 nm) by L-tryptophan(L-Trp) and its peptide such as N-acetylphenylalanyl-L-tryptophan(NAPT) incorporated in the liposomes(ca. 0.1% by weight) or in the external buffer (0.1-0.3 mM). Requirement of oxygenation suggests that the lysis of liposomes is caused by the photosensitized oxidation of lipids. There was significant protection against lysis photosensitized by Trp in the external buffer by low concentration of ferricyanide (0.8 mM), but there was no effect on the lytic efficiency by $N_3^-$ which is singlet oxygen($^1O_2$) quencher, indicative of an electron transfer mechanism involved in the photosensitization. The small change of the lytic efficiency with increasing pH from 4 to 9 was interpreted by large target theory and subsequently indicates that superoxide($O_2^-$) may be an active intermediate for the oxidation. The efficiency of photosensitization of Trp was higher than that of NAPT under the same experimental condition. The weak lytic efficiency of liposomes photosensitized by NAPT was enhanced by incorporating NAPT in liposomes, but it was again quenched by ${\beta}$-carotene incorporated in the bilayer of liposomes. These results indicate that a portion of liposome lysis may be due to $^1O_2$ formation from the excited NAPT.

Photoisomerization of Symmetric Carbocyanines

  • 민형식;강유남;박정희
    • Bulletin of the Korean Chemical Society
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    • v.19 no.7
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    • pp.747-753
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    • 1998
  • The phoisomerization process of symmetric carbocyanine dyes such as 3,3'-diethyloxadicarbocyanine iodide (DODCI), 3,3'-diethylthiadicarbocyanine iodide (DfDCI), 1,1'-diethyl-2,2'-dicarbocyanine iodide (DDI), 1,1'-diethyl-2,2'-carbocyanine iodide (DCI), and cryptocyanine (1,1'-diethyl-4,4'-carbocyanine) iodide (CCI) have been studied by measuring the steady state and time resolved fluorescence spectra and the ground-state recovery profiles. The steady-state fluorescence spectrum of photoisomer as a function of concentration and excitation wavelength provides the evidence that the fluorescence of photoisomer is formed by the radiative energy transfer from the normal form and the quantum yield for the formation of photoisomer is increased by decreasing the excitation wavelength. The fluorescence decay profiles have been measured by using the time correlated single photon counting (TCSPC) technique, showing a strong dependence on the concentration and the detection wavelength, which is due to the formation of excited photoisomers produced either by the radiative energy transfer from the non-nal form or by absorbing the 590 nm laser pulse. We first report the fluorescence decay time of photoisomers for these cyanine dyes. The experimental results are explained by introducing the semiempirical calculations. The ground state recovery profiles of DTDCI, DDI, and CCI normal forms have been measured, showing that the recovery time from the singlet excited state is similar with the fluorescence decay time.

Unusual Fluorescence Spectroscopic Properties of 9-Anthrylethylene Derivatives : Photoisomerization

  • 최정권;Mahipal A. Reddy;윤민중
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.973-980
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    • 1998
  • The fluorescence spectroscopic properties of both trans and cis forms of 9-anthryiethylene derivatives such as 9-AnthCH=$CHCO_2CH_3$ [Ⅰ] and 9-AnthCH=CHCN [Ⅱ] as well as 9-AnthCH=>TEX>$CHCH_2O_2CCH_3$ [Ⅲ] and 9-AnthCH=$CHCH_2OH$ [Ⅳ] have been measured in various solvents. In nonpolar solvent, the trans-I and trans-Ⅱ show dual emission spectral bands at 340 nm and 460 nm when exciting with 270 nm while the other trans derivatives show single emission band at 430 or 460 nm. The dual emissions exhibit different excitation spectra, indicating that two emissive states are different from each other. It is interesting to note that the 340 nm emission of both trans-Ⅰ and trans-Ⅱ is enhanced at the expense of the drastic quenching of the 460 nm emission as the solvent polarity increases. The dual emissions are also observed for both cis-Ⅰ and cis-Ⅱ. The solvent dependence of the fluorescence decay times and quantum yields can be correlated with the solvent and excitation wavelength dependences of the trans→cis photoisomerization quantum yields. These results indicate that the 340 nm emission is originated from the $S_2$ state of the cis-form, and the $S_1$ state is the only singlet excited state presenting a large CT (charge transfer) character to facilitate the photoisomerization.

Photophysical Properties of 1,3-Dimethylnaphtho[1,2-e]uracil

  • Shim, Sang-Chul;Shin, Eun-Ju;Park, Seung-Ki;Kang, Ho-Kwon
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.196-200
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    • 1986
  • The solvent change and salt do not affect the fluorescence quantum yield of 1,3-dimethylnaphtho[1,2-e]uracil indicating the considerable energy gap between the lowest singlet $({\pi},\;{\pi}^{\ast})\;and\;(n,\;{\pi}^{\ast})$ states in the compound. The results are consistent with the strong quenching of fluorescence by ethyl iodide. Fluorescence quantum yield is nearly independent of temperature, probably due to the relatively inefficient internal conversion. Unusual spectral difference is observed in isopentane and ethanol at 77K. The temperature dependence of emission in isopentane and in ethanol suggests that the increase of charge transfer character by the conformational change in isopentane leads to the structureless and red-shifted fluorescence, while in ethanol the decrease of the charge transfer character by the hydrogen bonding interaction results in the structured and blue-shifted fluorescence along with phosphorescence at the low temperature. Temperature dependence of emission in poly(methylmethacrylate) matrix indicates that $T_1{\to}S_0$ radiationless decay is an important process responsible for the strong temperature dependence of phosphorescence.

Evaluation of peak-fitting software for magnesium quantification through k0-instrumental neutron activation analysis

  • Dasari, Kishore B.;Cho, Hana;Jacimovic, Radojko;Park, Byung-Gun;Sun, Gwang-Min
    • Nuclear Engineering and Technology
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    • v.54 no.2
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    • pp.462-468
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    • 2022
  • The selection and effective utilization of peak-fitting software for conventional gamma-ray spectrum analysis is significant for accurate determination of the mass fraction of elements, particularly in complex peak regions. Majority of the peak-fitting programs can derive similar peak characteristics for singlet peaks, but very few programs can deconvolute multi-peaks in a complex region. The deconvolution of multi-peaks requires special peak-fitting functions, such as left and right-skew distributions. In the this study, 843.76 keV (27Mg) peak area from the complex region (840 keV-850 keV) determined and compared using four different peak-fitting programs, namely, GammaVision, Genie2000, HyperLab, and HyperGam. The 843.76 keV peak interfered with 841.63 keV (152mEu) and 846.81 keV (56Mn). The total Mg concentration was determined through k0-instrumental neutron activation analysis by applying the isotopic interference correction factor 27Al(n,p)27Mg through the simultaneous determination of Al concentration. HyperLab and HyperGam peak-fitting programs reported consistent peak areas, and resultant concentrations agreed with the certified values of matrix-certified reference materials.

Quantitative Analysis of Coumarins from Angelica gigas Using $^1H$-NMR

  • Yoo, Jong-Su;Ahn, Eun-Mi;Song, Myoung-Chong;Bang, Myun-Ho;Kim, Dong-Hyun;Han, Min-Woo;Kwak, Ho-Young;Lee, Dae-Young;Lyu, Ha-Na;Baek, Nam-In
    • Food Science and Biotechnology
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    • v.17 no.3
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    • pp.573-577
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    • 2008
  • $^1H$-Nuclear magnetic resonance (NMR) spectrometry was applied to the quantitative analysis of coumarins in the roots of Angelica gigas without any chromatographic purification. The experiment was performed by the analysis of each singlet germinal methyl, which was well separated in the range of 1.0-2.0 ppm in the $^1H$-NMR spectrum. The quantity of the compounds was calculated by the ratio of the intensity of each compound to the known amount of internal standard (dimethyl terephthalate). These results were compared with the conventional gas chromatography (GC) method. The contents of decursin and decursinol angelate in A. gigas were determined $1.98{\pm}0.07$, $1.13{\pm}0.08%$ in quantitative $^1H$-NMR method and $2.06{\pm}0.24$, $1.17{\pm}0.24%$ in GC method, respectively. The advantages of quantitative $^1H$-NMR analysis are that can be analyzed to identify and quantify, and no reference compounds required for calibration curves. Besides, it allows rapid and simple quantification for coumarins with an analysis time for only 10 min without any preprocessing.

Photochemistry of Benzanilides (II). Photo-Fries Type Reaction of Benzanilides (벤즈아닐리드류의 광화학 (제2보). 벤즈아닐리드류의 Photo-Fries 형 반응)

  • Yong-Tae Park;Han-Chun Yun;Sang-Rok Do;Young-Du Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.4
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    • pp.441-447
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    • 1985
  • Several benzanilides were prepared by acylation of anilines with substituted benzoyl chlorides. While 2-chlorobenzanilides were photocyclized, 2-methylbenzanilide and 2'-methylbenzanilide were cleaved to give photo-Fries type products. 2-Nitrobenzanilide and 2'-nitrobenzanilide were inert in the above conditions due to lowering energy of the excited state by the nitro group. N, N-dibenzoylaniline and N, N-di-(2-chlorobenzoyl) aniline gave photo-Fries type reaction products effectively. In the benzanilide photo-Fries type reaction the excited singlet state was believed to be involved, since no oxygen effect was observed on the reaction rate. Quantum yield for 2-methylbenzanilide is higher in nonpolar and less viscous solvents than in polar and viscous solvents. The solvent cage radical pair is suggested in the photo-Fries type reaction of benzanilides.

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Changes of Western Men′s Underclothes - in the First Half of the 20C - (서양 남성 속옷의 변천에 관한 고찰 - 20세기 전기 -)

  • 김주애
    • Journal of the Korean Society of Costume
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    • v.50 no.5
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    • pp.53-64
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    • 2000
  • The purpose of this study was to investigate the historical changes of western men's underclothes in the first half of the 20C and analyze functions and features of men's underclothes. This study was to utilize many literatures in the analysis of historical changes of western men's underclothes. In the 1900's, the attached collar was giving place to the detachable, and the coloured shirt for day wear was becoming accepted. The correct wear fur various occasions was given. Double collar was the favourite for day wear. The dress-shirt protector worn over the dress-shirt front. Men preferred to vest and pants in one as a combined garment. In the 1910's, underclothes were permitting freer movement, but what was still more significant was the glowing inclination to reduce the layers which covered the body. The new conception of decency which was beginning to appear continued to characterize underclothing the symbols of social rank, expect for formal occasion, were declining. For day the white shirt was being displaced by the soft-fronted shirt. In the 1927-1930's, Underclothes were reduced in number, extent and thickness. Underclothing had lost two of its original function : it no longer preserved the warmth of the body, nor did it disguise its essential shape. Both sexes discarded the use of white underwear, In the 1930's, men saw an increasing preference for the coloured shirt. Combinations became increasingly popular and the singlet were displacing the under-vest in the 1930's. All undergarments were very commonly in natural colours. In the 1940's, for evening dress. shirt was plain linen front and square cuffs. Short trunks reached to mid-thigh, had a front waist yoke with three button fastening. Underclothes were pursued ease and activity.

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Vascular Cell Responses against Oxidative Stress and its Application

  • Ryoo, Sung-Woo;Lee, Sang-Ki;Kim, Cuk-Seong;Jeon, Byeong-Hwa
    • International Journal of Vascular Biomedical Engineering
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    • v.2 no.2
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    • pp.1-9
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    • 2004
  • The history of studies in biology regarding reactive oxygen species (ROS) is approximately 40 years. During the initial 30 years, it appeared that these studies were mainly focused on the toxicity of ROS. However, recent studies have identified another action regarding oxidative signaling, other than toxicity of ROS. Basically, it is suggested that ROS are reactive, and degenerate to biomolecules such as DNA and proteins, leading to deterioration of cellular functions as an oxidative stress. On the other hand, recent studies have shown that ROS act as oxidative signaling in cells, resulting in various gene expressions. Recently ROS emerged as critical signaling molecules in cardiovascular research. Several studies over the past decade have shown that physiological effects of vasoactive factors are mediated by these reactive species and, conversely, that altered redox mechanisms are implicated in the occurrence of metabolic and cardiovascular diseases ROS is a collective term often used by scientist to include not only the oxygen radicals($O2^{-{\cdot}},\;{^{\cdot}}OH$), but also some non-radical derivatives of oxygen. These include hydrogen peroxide, hypochlorous acid (HOCl) and ozone (O3). The superoxide anion ($O2^{-{\cdot}}$) is formed by the univalent reduction of triplet-state molecular oxygen ($^3O_2$). Superoxide dismutase (SOD)s convert superoxide enzymically into hydrogen peroxide. In biological tissues superoxide can also be converted nonenzymically into the nonradical species hydrogen peroxide and singlet oxygen ($^1O_2$). In the presence of reduced transition metals (e.g., ferrous or cuprous ions), hydrogen peroxide can be converted into the highly reactive hydroxyl radical (${^{\cdot}}OH$). Alternatively, hydrogen peroxide may be converted into water by the enzymes catalase or glutathione peroxidase. In the glutathione peroxidase reaction glutathione is oxidized to glutathione disulfide, which can be converted back to glutathione by glutathione reductase in an NADPH-consuming process.

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Energy Transfer and Device Performance in Polymer Based Electrophosphorescent Light Emitting Diodes and Effect of Ligand Modification in the Optical and Electrical Properties of Phosphorescent Dyes (고분자 전기인광소자에서의 에너지 전이, 소자 특성 및 인광염료의 리간드 변화에 따른 광학적, 전기적 특성 변화)

  • Lee Chang-Lyoul;Das R. R.;Noh Young-Yong;Kim Jang-Joo
    • Polymer(Korea)
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    • v.29 no.2
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    • pp.107-121
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    • 2005
  • Electrophosphorescent light emitting diodes (LEDs) using phosphorescent dyes as triplet emitter, which incorporate a heavy metal atom to mix singlet and triplet states by the strong spin-orbit coupling, can achieve the theoretically $100\%$ internal quantum efficiency. In this paper, we report on the performance and the energy transfer mechanism of polymer based highly efficient electrophosphorescent LEDs. The effect of phase separation and aggregation to the energy transfer between polymer hosts and phosphorescent guests and performance of polymer electrophosphorescent LEDs were investigated. Finally, the effect of introducing substitute group and ligand modification of phosphorescent dyes on optical and electrical properties are reported.