• Title/Summary/Keyword: nitroxide

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Orientational Control of Nano Structures from Block Copolymer Using Homo-Polymer Nano Interface (단일 성분 고분자 나노 계면의 도입을 통한 블락 고분자 박막의 나노 구조 배향 조절)

  • In, Insik
    • Journal of Adhesion and Interface
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    • v.9 no.4
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    • pp.30-33
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    • 2008
  • Two polymeric interfaces with single component homo-polymers were prepared to control the orientation of block copolymer thin-film nanostructures. Poly(4-acetoxy styrene) (OH-PAS) and poly(4-methoxy styrene) (OH-PMS) which have the average chemical composition of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) were precisely synthesized through nitroxide-mediated radical polymerization. After dehydration reactions between above polymers and SiOx layers of silicon wafers, the polymer-modified interface induced partial (30%) vertical orientation of PS-b-PMMA thin film in the case of OH-PMS and wholly parallel orientation in the case of OH-PAS. Chemical compositions of polymeric interface layers are regarded as the key parameter to control the orientation of nanostructures of block copolymer thin film.

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The hyperfine interaction in water-solvent system (물-용매계에서의 초미세 상호작용)

  • Lee, Mi-Nyeong;Kim, Tae-Kwan;Lee, Sung-Ki;Park, Yoon-Chang
    • Analytical Science and Technology
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    • v.18 no.3
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    • pp.194-200
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    • 2005
  • The N hyperfine coupling constants ($a_N$) of di-t-butyl nitroxide (DTBN) radicals in water-solvent system were measured with EPR spectroscopy. Various kinds of the solvents with different polarity such as acetone, dimethylsulfoxide (DMSO), methanol, ethanol and 1-propanol were applied and studied. Equilibrium constants for the solvation equilibrium and the solvent parameters ($E_T$, molar transition energy) of various water-solvent system were obtained from the experimental results and are presented. The $a_N$ values were plotted as a function of mole fraction of the solvent. In case of water-DMSO, water-ethanol and water-1-propanol system, slight negative deviations from the straight line were observed. In water-acetone system, the absorption wavelength (${\lambda}$) due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition increased linearly with the increase of mole fraction of acetone. The relationship between $a_N$ of DTBN and ${\lambda}$ due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition in water-acetone and water-DMSO system was examined. It was found that the electronic structure of the nitroxide radicals is stablized from the fact that the N hyperfine coupling constants of DTBN radicals are greatly unaffected in the environment of water-solvent system.

Nitridation of Thin $SiO_2$ Film ($SiO_2$薄膜의 熱的 窒化)

  • Lee, Yong-Soo;Lee, Yong-Hyun;Sohn, Byung-Ki
    • Journal of the Korean Institute of Telematics and Electronics
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    • v.25 no.11
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    • pp.1323-1328
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    • 1988
  • Thermally grown $SiO_2$ films on silicon have been thermally nitrided in the $NH_3$ gas ambient and their properties have been investigated by analyzing the AES data and the results of the I-V and the C-V measurements. The Auger depth profile show that the nitrogen-rich layers are formed at the nitrided oxide film surface and near the $SiO_2$-Si interface. The higher the nitridation temperature is, the larger the refractive index of nitroxide film is. And the thinner the oxide film to be nitrided for the same nitridation temperature is, the larger the refractive index of nitroxide film is. When thin $SiO_2$ film is thermally nitrided, the I-V characteristics show the Fowler-Nordheim conduction fashion. Flatband voltages of $SiO_2$ films are shifted by nitridation, due to the fixed charge formation.

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SFRP Synthesis of Acenaphthylene Oligomers and Block Copolymers. Potential Light Harvesting Structures

  • Ali, Dildar;Ahmed, Zaheer;Dust, Julian M.;Kazmaier, Peter M.;Buncel, Erwin
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2377-2384
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    • 2011
  • Azo-acenaphthylene oligomers with repeating acenaphthylene units "n" up to 4, 5, 7, 17 and 19 have been prepared successfully using nitroxide mediated Stable Free Radical Polymerization (SFRP). Azo-acenaphthylene oligomers, reversibly end-capped by the stable nitroxide 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO), were further reacted via radical addition to 4-(naphthalenemethoxy)styrene monomer for diblock co-polymer formation. Characterization of the oligomers and diblock co-polymers was accomplished using MALDI-MS supported by GPC (Gel Permeation Chromatography) and $^1H$ NMR spectrometry. MALDI-MS afforded definitive results by providing an inter-peak interval of 152 (m/z), corresponding to acenaphthylene monomer, and inter-peak interval of 260 (m/z) for the naphthalenemethoxystyrene monomer unit in block copolymers. Our study opens the way to control the number of repeat units in the oligomers. Further these oligomers can be tailored with various monomers for the formation of block copolymers.

In vivo ESR measurement of free radical reaction in living mice

  • Han, Jin-Yi;Hideo Utsumi
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 2000.04a
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    • pp.6-7
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    • 2000
  • Recently, free radicals such as active oxygen species, nitric oxide, etc are believed to be one of the key substances in physiological and pathological, toxicological phenomena, and oxidative damages, and all organism have defencing system against such as free radicals. Formation and extinction of free radicals may be regulated through bio-redox system, in which various enzymes and compounds should be involved in very complicated manner. Thus, direct and non-invasive measurement of in vivo free radical reactions with living animals must be essential to understand the role of free radicals in pathophysiological phenomena. Electron spin resonance spectroscopy (ESR) is very selective and sensitive technique to detect free radicals, but a conventional ESR spectrometer has large detect in application to living animals, since high frequent microwave is absorbed with water, resulting in generation of high fever in living body. In order to estimate in vivo free radical reactions in living whole animals, we develop in vivo ESR-CT technique using nitroxide radicals as spin probes. Nitroxide radicals and their reduced forms, hydroxylamines, are known to interact with various redox systems. We found that! ! the signal decay due to reduction of nitroxyl radicals is influenced by aging, inspired oxygen concentration, ischemia-referfusion injury, radiation, etc. In the present paper, I will introduce in vivo ESR technique and my laboratory recent results concerning non-invasive evaluation of free radical reactions in living mice.

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Preparation of Copolymers by Controlled Radical Polymerization and their Applications

  • Choi, Kil-Yeong;Kim, Yong-Seok;Han, Seung-San;Lee, Jae-Heung
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.95-96
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    • 2006
  • Surface modification of clay minerals has become increasingly important for improving the practical applications of clays such as polymeric nanocomposites. We used the copolymer as modifiers having phenyl components, and successfully developed a route for the preparation of amine functionalized polymer based on oligostyrene and its block copolymers. The oligo(St-co-VBC)s with controlled molecular weight were synthesized via nitroxide mediated polymerization method. We also successfully prepared organophilic layered silicates whose surface is covered with styrenic copolymers. Through the analysis of chemical structure and morphology, we concluded that copolymers were very effective organic modifiers to change the surface characteristics of layered silicates.

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Polystyrene Microgel with Maltohexaose. Synthesis and Potential Application for Fullerene-Coating on Hydrophilic Surface

  • Narumi, Atsushi
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.318-318
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    • 2006
  • 4-Vinylbenzyl maltohexaoside peracetate, 1, was copolymerized with divinylbenzene using the initiator for nitroxide-mediated living radical polymerization, 2, to afford the polystyrene microgel with acetyl maltohexaose, 3. The deacetylation of 3 was achieved by treatment with sodium methoxide in dry 1,4-dioxane to produce the polystyrene microgel with maltohexaose, 4. A good coating property of the polystyrene microgel was combined with an excellent hydrophilic property derived from maltohexaose. In addition, 4 showed the ability to solubilize fullerene in aqueous solution. Therefore, 4 has a potential application as a special coating using functional but incompatible compounds such as fullerene on the surface of various hydrophilic materials.

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Fabrication of counter electrodes for dye-sensitized solar cells by using surface modified and dispersion controlled multi-walled carbon nanotubes (표면개질 및 분산제어된 다중벽 탄소나노튜브를 이용한 염료감응태양전지 대전극의 제조)

  • Choi, Hee-Jung;Lee, Gi-Won;Park, Nam-Kyu;Kim, Kyung-Kon;Hong, Sung-Chul
    • 한국신재생에너지학회:학술대회논문집
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    • 2008.05a
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    • pp.445-447
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    • 2008
  • 본 연구에서는 다중벽 탄소나노튜브용 표면개질제를 리빙라디칼중합법을 통하여 제조하고, 이를 이용하여 표면개질되고 분산제어된 다중벽탄소나노튜브를 제조하고 염료감응형 태양전지의 대전극 재료로 사용하였다. 우선 리빙라디칼중합법 중 nitroxide mediated polymerization (NMP) 기술을 이용하여 poly(maleic anhydride-co-p-acetoxystyrene)-block-poly(p-acetoxystyrene)를 합성하고, 공중합체중의 maleic anhydride기에 이미드화 반응을 통하여 pyrene기를 도입하였다. 공중합체 중의 p-acetoxystyrene 반복단위들은 가수분해 반응을 통하여 p-hydroxystyrene 반복단위로 변환하였으며, 제조된 공중합체의 구조와 열 특성 등을 GPC, GC, $^1H$-NMR, TGA을 통하여 분석하였다. 제조된 공중합체를 이용하여 다중벽 탄소나노튜브의 표면을 polymer wrapping법으로 처리하였고, 표면개질된 탄소나노튜브의 분산성을 다양한 용매에서 비교분석하였다. 표면이 개질되고 페이스트 내에의 분산성이 향상된 다중벽탄소나노튜브를 염료감응태양전지의 대전극 제조에 응용하였으며, 표면처리 및 분산제어 여부에 따른 제작 특성 및 동작특성 등을 평가하였다.

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