• Title/Summary/Keyword: 자유라디칼

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Homolytic Reactions of Isonitriles (이소니트릴의 자유라디칼반응)

  • Sung Soo Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.3
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    • pp.250-258
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    • 1980
  • Various radicals may add to isonitriles to give imidoyl radcals RN=CR'. This may be also generated via abstraction of imidoyl hydrogen from imine in the following manner: RN=CR' + R"${\cdot}{\rightarrow}$ RN=CR' + R"-H Imidoyl radicals would be stabilized via two pathways, ${\beta}$-cleavage and atom transfer reactions. ${\beta}$-Cleavage may occur in two directions depending upon structure of the radicals. Cyanide transfer and the "so-called" normal ${\beta}$-cleavage are the two modes of ${\beta}$-cleavage. Addition of t-butoxy radical to t-butyl isocyanide 7 generates an imidoyl radical t-Bu-N=C-O-Bu-t, which undergoes ${\beta}$-cleavage to give t-butyl isocyanate and t-butyl radical. Addition of phenyl radical to 7 forms the intermediate radical t-Bu-N=$C-C_6H_5$, which decomposes to give benzonitrile and t-butyl radical. The t-butyl radical generated from the ${\beta}$-cleavage adds to 7 giving the radical t-Bu-N=C-Bu-t, which cleaves only to pivalonitrile and t-butyl radical, inducing radical chain isomerization. Trimethylsilyl radical adds to 7 to give the intermediate t-Bu-N=$C-Si(CH_3)_3$, which collapses to $(CH_3)_3$SiCN and a t-butyl radical.

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Measurement of Atmospheric Nitrous Acid(HONO) using DNPH/HPLC in Seoul (DNPH/HPLC에 의한 서울시 대기 중의 Nitrous Acid 측정)

  • 정용국;홍상범;이재훈
    • Proceedings of the Korea Air Pollution Research Association Conference
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    • 2001.11a
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    • pp.325-326
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    • 2001
  • 오존은 태양광선의 존재 하에 질소산화물과 VOCs가 관련하여 발생하는 생성물이다. 대기중의 VOCs 는 히드록실 라디칼(hydroxyl radical, OHㆍ)과 같은 자유 라디칼(free radical)과 반응하여 하이드로퍼옥시 라디칼(hydroperoxy radical, HO$_2$ㆍ)과 알킬 퍼옥시 라디칼(alkyl peroxy radical, RO$_2$ㆍ)을 생성해 낸다. 이 퍼옥시 라디칼들은 NO를 NO$_2$ㆍ로 산화시키며 또한 히드록실 라디칼을 재생하며 이 히드록실 라디칼은 다시 VOCs와 반응한다. 그리고, 이때 산화된 NO$_2$는 햇빛에 의해 NO와 자유산소원자(free oxygen atom)로 광분해 되는데, 여기서 생성된 자유산소인자는 산소분자와 반응하여 오존을 생성한다. (중략)

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Curing and Coating Properties of Photo-Curable Self-Photoinitiating Acrylate (광경화형 자가광개시 아크릴레이트의 경화특성 및 도막물성)

  • Han, A-Ram;Hong, Jin-Who;Kim, Hyun-Kyoung
    • Journal of Adhesion and Interface
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    • v.15 no.1
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    • pp.22-30
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    • 2014
  • Self-photoinitiating acrylate (SPIA) which can undergo self-initiation under UV irradiation was synthesized by a Michael addition in the presence of a base catalyst. The SPIA polymerizations were investigated by photo-differential scanning calorimeter (photo-DSC) and surface physical properties such as pendulum hardness and pencil hardness. The results showed that the SPIA can cure upon UV irradiation by itself without a photoinitiator. But we found out that both the curing rate and the conversion were too low for the self-curing reaction of SPIA. In order to improve the SPIA curing properties, we introduced the SPIA/cationic hybrid system and observed the effects of the addition of commercial free radical type monomer and photoinitiator on the curing behaviors. SPIA/cationic hybrid system was the best suitable to improve the SPIA curing properties. The kinetic analysis indicated that the cationic monomer and photoinitiator apparently accelerated the cure reaction and rate of the hybrid SPIA system, mostly due to the synergistic effect of cationic monomer and photoinitiator increasing the mobility of active species and the generation of reactive species (free radical, cation) during the photopolymerization process. The physical properties showed that, unlike typical free radical system, the hybrid systems did not show oxygen inhibition effect because of cationic reaction on the coating surface.

Free radical scavenging activity and characterization of the extrcts from Alpinia katsumadai and Areca catechu (초두구와 빈량 추출물의 자유라디칼 소거 활성 효과와 특성에 관한 연구)

  • 강순옥;이건국;최정도
    • Journal of the Society of Cosmetic Scientists of Korea
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    • v.27 no.1
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    • pp.133-150
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    • 2001
  • 자유라디칼은 반응성이 커서 세포의 구성 물질인 단백질, 지질, 당, DNA등과 반응하여 세포 및 조직을 손상시킴으로서 노화를 가져온다. 이러한 자유라디칼들은 자외선, 일반 대사, 스트레스, 질병, 흡연 등에 의해 생성되고 특히, 활성 산소 종인 hydroxyl radical, superoxide radical, lipid peroxide radical등은 피부 노화를 발생시키는 원인이 된다. 따라서 본 연구에서는 한방 식물로부터 유해한 활성 산소종을 소거하는 활성을 가진 물질을 기 위해 1차 스크리닝 하였고, 이중 육두구, 관중, 초두구, 빈랑, 금은화, 포공영, 우롱차, 황금, 녹차 추출물이 효과가 높게 나타났으며, 그중 초두구와 빈랑 90% 메탄올 추출물에서 가장 우수한 소거 활성을 나타냄으로써 이 추출물에 대하여 자유라디칼 소거 활성에 대하여 여러 가지 생물학적 활성을 조사하였다. 초두구와 빈랑추출물에 대한 hydroxyl radical, superoxide radical, lipid peroxide radical을 소거하는 활성을 핵산, 클로로포름, 에틸아세테이트, 물층으로 분획하여 조사한 결과 에틸아세테이트층에서 가장 우수한 활성을 보였다. 에틸아세테이트 분획에 대한 lipid peroxide radical 소거에 있어서 빈랑 추출물이 $IC_{50}$/ 값 50 $\mu\textrm{g}$/ml, 초두구 추출물은 $IC_{50}$/ 값 59 $\mu\textrm{g}$/ml로서 기준물질로 사용되는 vitamic C (120 $\mu\textrm{g}$/ml)나 butylated hydroxyl toluene (80 $\mu\textrm{g}$/ml) 보다 더 우수한 소거 효과를 보여주었고, hydroxyl radical을 소거하는 능력은 25 $\mu\textrm{g}$/ml와 150 $\mu\textrm{g}$/ml로 hydroxyl radical의 소거 능이 좋은 vitamin C (180 $\mu\textrm{g}$/ml) 보다 뛰어난 소거 활성을 나타내었다. Superoxide radical을 소거하는 효과는 초두구 추출물의 $IC_{50}$/ 값 10 $\mu\textrm{g}$/ml, 빈랑 추출물이 15 $\mu\textrm{g}$/ml을 나타냈고, 이는 기준 물질인 vitamin C (35 $\mu\textrm{g}$/ml)보다 좋은 소거 활성을 보여주었으며, gallic acid 9 $\mu\textrm{g}$/ml과 유사한 효과를 나타내었다. 사람 섬유아세포를 배양하여 hydroxyl radical과 superoxide radical를 발생시킨 후 초두구와 빈랑 추출물의 세포 보호 효과를 실험한 결과 25 $\mu\textrm{g}$/ml의 농도로 처리하였을 때 각각 85% 이상의 우수한 세포 보호 효과를 나타내었다. 초두구로부터는 자유라디칼 소거 활성이 있는 물질을 분리하기 위하여 분획한 후 가장 높은 소거 활성을 보인 에틸아세테이트 층에 대하여 silica column chromatography, preparative TLC를 수행하였다. 초두구로부터 분리된 물질은 HPLC를 이용한 분리에서 phenol성 물질인 gallic acid와 동일한 retention time을 보여줌으로써 초두구로부터 분리된 물질은 gallic acid와 유사한 phenol성 물질이거나 그의 유도체일 것으로 추측된다. 따라서, 초두구와 빈랑 추출물은 피부 노화의 주요인이 되고 있는 lipid radical, hydroxyl radical, superoxide radical을 소거하는 활성이 뛰어나 자유라디칼에 의하여 발생되는 피부노화를 방지할수 있는 물질로서의 효과가 기대된다.가 기대된다.

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Reaction of Thianthrene Cation Radical Perchlorate with Thioxanthene. Synthesis of Thioxanthene Derivatives (티안트렌 양이온 자유라디칼과 염소산염과 티오크잔틴의 반응. 티오크잔틴 유도체의 합성)

  • Kyongtae Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.34-43
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    • 1980
  • The reaction of thianthrene cation radical perchlorate with thioxanthene in acetonitrile gave thianthrene and dark reddish thioxanthylium ion instead of thioxanthene cation radical. Addition of aromatic nucleophiles such as anisole, aniline, N,N-diethylaniline, catechol, ethylbenzene, to the above mixture yielded the corresponding thioxanthenes with substituent at 9 position. Reactions with dibenzo-18-crown-6-ether, diphenylmercury, and triphenylphosphine gave similar products. However, reactions with aromatics with electron-withdrawing group were either too slow or inert to such a reaction.

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Effect of Substituent of Chain Transfer agent in the Free Radical Polymerization (자유 라디칼 중합반응에서 사슬이동제의 치환기 효과)

  • Chung, I.
    • Elastomers and Composites
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    • v.40 no.1
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    • pp.53-58
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    • 2005
  • Carbon tetrachloride is very reactive chain transfer agent due to the resonance stability of the trichlorocarbon radicals after breaking of C-Cl bond. Effect of benzylic radical comparing to trichlorocarbon radicals in the chain tranrfer reactions was investigated. From the structural point of view, cumyl chloride is a good candidate because it has the C-Cl bond with benzylic radicals after displacement of C-Ci bond. The reactivity of free radical polymerization of styrene in the presence of cumyl chloride was compared with that of carbon tetrachloride by calculating chain transfer constants. Results show that the cumyl chloride acts as a stronger chain transfer agent than carbon tetrachloride. The calculated chain transfer constant of cumyl chloride shows higher value (0.0463) than that of carbon tetrachloride (0.0011) in the styrene polymerization. High reactivity of cumyl chloride comparing to that of carbon tetrachloride is probably due to the higher resonance stability or benzylic radical than that or trichlorocarbon radicals after breaking of C-Cl bond. Monte Carlo simulation method is applied for characterizing the validity of kinetic constants according to the ratio of chain transfer agent to monomer.

Isolation and Structure Elucidation of Radical Scavengers from Chrysanthemum boreale Makino (산국(山菊)의 자유라디칼 소거 물질 분리 및 동정)

  • Han, Wan-Soo
    • Korean Journal of Medicinal Crop Science
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    • v.11 no.1
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    • pp.1-4
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    • 2003
  • Two antioxidative compounds in Chrysanthemum boreale were isolated by a bioassay using a 2, 2-diphenyl-1-picrydrazyl(DPPH) free radical. They were identified as apigenin, linarin(acacetin-7-O-rutinoside) on the basis of $^1H\;and\;^{13}C-NMR$ and MS data. The DPPH radical scavenging activity$(RC_{50}:\;13.3{\mu}g)$ of apigenin was similar to that of ${\alpha}-tocopherol\;(12.1{\mu}g)$ and L-ascorbic acid$(13.1{\mu}g)$

Free Radical Polymerization Algorithm for a Thermoplastic Polymer Matrix : A Molecular Dynamics Study (무정형 열가소성 고분자의 자유 라디칼 중합 분자동역학 시뮬레이션 알고리즘)

  • Jung, Ji-Won;Park, Chan-Wook;Yun, Gun-Jin
    • Composites Research
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    • v.32 no.3
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    • pp.163-169
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    • 2019
  • In this paper, we constructed a molecular dynamics (MD) polymer model of PMMA with 95% of conversion by using dynamic polymerization algorithm of a thermoplastic polymer based on free radical polymerization. In this algorithm, we introduced a united-atom level coarse-grained force field that combines the non-bonded terms from the TraPPE-UA force field and the bonded terms from the PCFF force field to alleviate the computation efforts. The molecular weight distribution and the average molecular weight of the polymer were calculated by investigating each chain generated from the free radical polymerization simulation. The molecular weight of the polymer was controlled by the number of initiator radicals presented in the initial state and molecular weight effect to the density, the glass transition temperature, and the mechanical properties were studied.

Antioxidative and Free Radical Scavenging Effects of Rhus javanica Linne (오배자의 항산화 및 자유라디칼 소거효과)

  • Cha, Bae-Cheon;Lee, Sung-Bae
    • Korean Journal of Medicinal Crop Science
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    • v.6 no.3
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    • pp.181-187
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    • 1998
  • This study was carried out to investigate the antioxidative activities of medicinal plants. Through the examination of methanol extracts from 30 species for radical scavenging effects using DPPH method, the extracts from Rhus javanica Linne, Smilax china Linne and Polygonum cuspidatum Siebold et Zucarinii showed strong antioxidative activity. Because of its highest antioxidative activity among 30 medicinal plants, radical scavenging effects of 4 different extract compartments (n- Hexane, EtOAc, BuOH and $H_2O$ extracts) from Galla Rhois MeOH extract of Rhus javanica Linne were examined by DPPH method and antioxidant effects on the 4 different extract compartments were tested by Ferric-Thiocyanate method. Antioxidative activities of n- Hexane, EtOAc and BuOH extracts were similar or even higher than that of natural (tocopherol) or synthetic antioxidants (BHA), suggesting that major fractions for the antioxidative activity of Rhus javanica Linne were the n- Hexane, EtOAc and BuOH extract compartments.

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Photochemical Synthesis of Aspartylphenylalanyl Methyl Ester (광 알킬화 반응에 의한 Aspartylphenylalanyl Methyl Ester의 합성)

  • Sang Chul Shim;Kyu Ho Chae
    • Journal of the Korean Chemical Society
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    • v.19 no.5
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    • pp.367-374
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    • 1975
  • Glycine residue in N-X-glycylphenylalanine methyl ester(X = trifluoroacetyl or acetyl) was converted into aspartic acid derivative by a photoalkylation reaction. The reaction was induced with 350 nm lamp using a combination of diacetyl/di-t-butyl peroxide (DBP) as the photoinitiator, and acetic anhydride as the alkylating agent. In the thermal reaction with DBP and acetic anhydride, the same alkylation reaction of the dipeptide was observed. From this thermal alkylation reaction the photoalkylation reaction is also thought to undergo via free radical mechanism.

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