• Title/Summary/Keyword: Acetyl radical

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Reactions of Acetyl Radical with Acetylene - A Computational Study

  • Tran, Tu Anh;Schiesser, Carl H.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.3
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    • pp.595-598
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    • 2010
  • Ab initio and DFT molecular orbital calculations predict that acetyl radical reacts with acetylene through interactions primarily involving the SOMO of the radical and the in-plane ${\pi}$-bond of acetylene. An energy barrier (${\Delta}E_1$) of 39.6 kJ $mol^{-1}$ is predicted for the preferred anti arrangement of reactants at the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory. NBO analysis reveals additional interactions between the radical SOMO and the nearby C-H ${\sigma}$-bond in acetylene worth about 10% of the total transition state interaction energy. This type of orbital interaction has not previously been observed in radical addition reactions involving C-C ${\pi}$-bonds.

Free-Radical Polymerization and Copolymerization of N-Acetyl ${\alpha}$-Aminoacrylic Acid (N-Acetyl ${\alpha}$-aminoacrylic Acid의 자유라디칼 중합 및 혼성중합)

  • Il Hyun Park;Chong Kwnag Lee;Jae Ho Choi;Jung-Il Jin
    • Journal of the Korean Chemical Society
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    • v.26 no.4
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    • pp.235-246
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    • 1982
  • The free radical polymerization and copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid were investigated. From the result of kinetic investigation of N-acetyl ${\alpha}$-aminoacrylic acid in DMF at $60^{\circ}C$, a rate equation of $R_p$ = $k_p[M]^{0.97}[I]^{0.59}$ was obtained. The overall activation energy for the polymerization was found to be 25.2 kcal/mole. Copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid with acrylic acid and styrene was carried out for the determination of monomer reactivity ratios. The monomer reactivity ratios for the monomer pairs determined at 70.0{\pm}0.1^{\circ}C$ using benzoyl peroxide as an initiator are; $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.49, $r_2$(acrylic acid) = 1.41, $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.44, $r_2$(styrene) = 0.91. The values of Alfrey-Price's Q and e parameters for N-acetyl ${\alpha}$-aminoacrylic acid were calculated to be 0.51 and 0.16 for the both systems. Differential thermal analysis and thermogravimetry showed that acrylic acid copolymers have poorer thermal stability as compared with the homopolymer of N-acetyl ${\alpha}$-aminoacrylic acid.

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Radical Scavenging Hydroxyphenyl Ethanoic Acid Derivatives from a Marine-Derived Fungus

  • Li Xifeng;Kim Se-Kwon;Kang Jung-Sook;Choi Hong-Dae;Son Byeng-Wha
    • Journal of Microbiology and Biotechnology
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    • v.16 no.4
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    • pp.637-638
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    • 2006
  • Bioassay-guided fractionation of an organic extract of the culture broth from an unidentified marine-derived fungus led to the isolation of a new metabolite, N-[2-(4-hydroxyphenyl) acetyl]formamide (1), along with four known polyketides, 4-hydroxyphenyl acetamide (2), 4-hydroxyphenyl acetic acid (3), 3,4-dihydroxyphenyl acetic acid (4), and N-[2-(4-hydroxyphenyl)ethenyl]formamide (5). The structures of 1-5 were elucidated by spectral data analyses. Among them, compounds 1, 4, and 5 exhibited significant radical scavenging activity against 1, 1-diphenyl-2-picrylhydrazyl (DPPH) with $IC_{50}$ values of 8.4, 11.9, and $0.2{\mu}M$, respectively.

Antioxidants and Acetyl-cholinesterase Inhibitory Activity of Solvent Fractions Extracts from Dendropanax morbiferus (황칠나무의 용매 분획별 추출물의 항산화 활성 및 Acetyl-cholinesterase 저해 활성비교)

  • Yu, Ji Min;Moon, Hyung In
    • Korean Journal of Plant Resources
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    • v.31 no.1
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    • pp.10-15
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    • 2018
  • The leaves and stems of Dendropanax morbiferus were separated from organic solvents with methanol. The organic solvent fractions were fractionated with dichloromethane, ethyl acetate and butanol according to the systematic fractionation method. Oxidation in the body induces aging, and antioxidant activity has attracted the attention of many people as a preventive component to suppress negative reactions in the body. To investigate the antioxidant activity of Dendropanax morbiferus were subjected to DPPH free radical assay. In addition, acetyl cholinesterase inhibitions were performed for Alzheimer's disease as an aging neurological disease. As a result, it was confirmed that the antioxidant effect of DPPH was generally good in the antioxidant test. The ethyl acetate fractions of Dendropanax morbiferus stems and leaves were $IC_{50}=30{\mu}g/m{\ell}$. Acetyl cholinesterase inhibition experiments were carried out at a concentration of $250{\mu}g/m{\ell}$. Dendropanax morbiferus stems fractions showed dichloromethane fraction of 57.68%, which significantly inhibited the activity of acetyl cholinesterase.

Antioxidative flavonoids from the Leaves of Morus alba

  • Kim, Sun-Yeou;Gao, Jian Jun;Lee, Won-Chu;Ryu, Kang-Sun;Lee, Kang-Ro;Kim, Young-Choong
    • Archives of Pharmacal Research
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    • v.22 no.1
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    • pp.81-85
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    • 1999
  • Nine flavonoids (1-9) were isolated from the leaves of Morus alba (Moraceae). The structures of compounds were determined to be kaempferol-3-O-$\beta$-glucopyranoisde (astragalin, 1) kaempferol-3-O-(6"-O-acetyl)-$\beta$-D-glucopyranoside (2), quercetin-3-O-(6"-O-acetyl)-$\beta$-D-glucopyranoside (3), quercetin-3-O-$\beta$-D-glucopyranoside (4), kaempferol-3-O-$\alpha$-L-rhamnopyranosyl-(1 6)-$\beta$-D-glucopyranoside (5), quercetin-3-O-$\alpha$-L-rhamnopyranosyl-(1 6)-$\beta$-D-glucopyranoside (rutin, 6), quercetin-3-O-$\beta$-D-glucopyranosyl-(1 6)-$\beta$-D-glucopyranoside (7), quercetin-3,7-di-O-$\beta$-D-glucopyranoside (8) and quercetin (9) on th basis of spectroscopic and chemical studies. Compounds 7 and 9 exhibited significant radical scavenging effect on 1,1-diphenyl-2-picryl-hydrazyl radical.

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Quantitative Determination of Acetone formed in the Thermal and Photochemical Decompositions of Azobisisobutyronitrile

  • Yoon, Heung-Sick;Kim ,Kyong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.6 no.5
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    • pp.284-287
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    • 1985
  • Cyanoisopropyl radical derived from azobisisobutyronitrile (AIBN) by either thermolysis or photolysis reacts with oxygen to give cyanoisopropylperoxy radical which then was converted to acetone and cyano radical and/or acetyl cyanide and methyl radical. Of these products, acetone formed was quantitatively determined by the addition of thianthrene cation radical perchlorate to the reaction mixture. The results showed that 55.7 mmol, 16.9 mmol, and 16.0 mmol of acetone were formed for 7 hours from 1 mol of AIBN at $82{\pm}1^{\circ}C$ in acetonitrile, carbon tetrachloride, and benzene, respectively. However, 22.2 mmol of acetone was formed from photolysis of 1 mmol of AIBN in acetonitrile. The value decreased to 13.2 mmol by bubbling argon into the solvent prior to photolysis.

In Vitro Antioxidant Activity Profiles of ${\beta}$-Glucans Isolated from Yeast Saccharomyces cerevisiae and Mutant Saccharomyces cerevisiae IS2

  • Song, Hee-Sun;Moon, Ki-Young
    • Food Science and Biotechnology
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    • v.15 no.3
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    • pp.437-440
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    • 2006
  • To explore the possible usefulness of ${\beta}$-glucans as natural antioxidants, the antioxidant profiles of ${\beta}$-glucan, extracted from Saccharomyces cerevisiae KCTC 7911, and water soluble and insoluble mutant ${\beta}$-glucan, isolated from yeast mutant S. cerevisiae IS2, were examined by five different in vitro evaluation methods: lipid peroxidation value (POV), nitric oxide (NO), 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical, reducing power, and ${\beta}$-carotene diffusion assay. The antioxidant activities of all ${\beta}$-glucans evaluated in POV test were comparable to or better than that of the known antioxidant, vitamin C. Remarkably, the ${\beta}$-glucan and water insoluble mutant ${\beta}$-glucan possessed 2.5-fold more potent activity than vitamin C at a dosage of 2 mg. Although vitamin C showed 100-fold greater activity than all ${\beta}$-glucans in NO and DPPH tests for measuring the radical scavenging capacity, all ${\beta}$-glucans revealed higher radical scavenging activity than the known radical scavenger, N-acetyl-L-cysteine (NAC), in DPPH test. The water insoluble mutant ${\beta}$-glucan had 2.6- and 5-fold greater antioxidative activity than water soluble ${\beta}$-glucan in NO and DPPH tests, respectively, showing that all ${\beta}$-glucans were able to scavenge radicals such as NO or DPPH. While all ${\beta}$-glucans revealed lower antioxidant profiles than vitamin C in both reducing power activity and ${\beta}$-carotene agar diffusion assay, the ${\beta}$-glucan and water insoluble mutant ${\beta}$-glucan did show a marginal reducing power activity as well as a considerable ${\beta}$-carotene agar diffusion activity. These results confirmed the potential usefulness of these ${\beta}$-glucans as natural antioxidants.

Toxicological Studies on the Essential Oil of Eugenia caryophyllata Buds

  • Park, Hee-Juhn
    • Natural Product Sciences
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    • v.12 no.2
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    • pp.94-100
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    • 2006
  • The essential oil (EC-oil) obtained from the buds of Eugenia caryophyllata (Myrtaceae) was examined for its free radical-scavenging activity, cytotoxicity, and in vivo toxicity. To find the xenobiotic properties of EC-oil, serum thiobarbituric acid reactive substances (TBARS) level and hepatic drug-metabolizing enzyme activities were measured. It was found that EC-oil displayed xenobiotic properties like bromobenzene. The cytotoxicities of eugenol and of the EC-oil were greatly attenuated by the sulfhydryl-containing N-acetyl-L-cysteine (NAC), suggesting that eugenol was susceptible to nucleophilic sulfhydryl. In addition, eugenol also showed potent free radical-scavenging activity in the 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay. Moreover, methyleugenol considerably exhibited less cytotoxicity and less potent free radical-scavenging activity than eugenol, and the cell viability of the methyleugenol was more increased with NAC treatment than the eugenol. These results indicate that the phenolic OH in eugenol may play a crucial role in both cytotoxicity and free radical-scavenging activity. The fashion on oxidative stress and hepatic drug-metabolizing enzyme activities of eugenol resembled those of bromobenznene.

A Study on the Glucose-regulating Enzymes and Antioxidant Activities of Water Extracts from Medicinal Herbs (한약재의 물 추출물이 당대사 관련 효소와 항산화 활성에 관한 연구)

  • Choe, Myeon;Kim, Dae-Jung;Lee, Hyeon-Ju;You, Jin-Kyoun;Seo, Dong-Joo;Lee, Joon-Hee;Chung, Mi-Ja
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.37 no.5
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    • pp.542-547
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    • 2008
  • The anti-diabetic effects of water extracts (WE) from medicinal herbs on hepatic glucose-regulating enzymes, such as glucokinase (GCK), pyruvate dehydrogenase (PDH), acetyl-CoA carboxylase (ACC) and ${\alpha}$-glucosidase, were studied using the cytosol fraction in liver and mitochondia fraction in heart of a type II diabetic animal (GK rat, Goto-Kakizaki). The free radical scavenging activity of water extracts by DPPH method was also tested. We found that free radical scavenging activity was strong in Corni fructu (CF), Mokdan Bark (MDB), Chenhwabon (CHB) and Sanyack (SY), while that of Backbocreng (BBR), Shuckgihwang (SGH) and Taecsa (TS) was lower. For GCK activity in cytosol of liver, CF and CHB had a more effective activity than other extracts. PDH activity in mitochondria fraction of heart was higher in all of the extracts, expect for the TS extract, than in the control. ACC activity in cytosol fraction of liver was significantly higher in the CF, CHB, SGH, TS and SY extracts than in the control. CF, BBR and MDB led to a decrease in the ${\alpha}$-glucosidase activity. Therefore, these results suggest that all of the extracts may be used as functional material in the development as anti-diabetic functional food and medicine.

Antioxident components from Aralia continentalis

  • Kim, Ju-Sun;Kang, Sam-Sik;Park, Jae-Sue
    • Proceedings of the Korean Society of Applied Pharmacology
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    • 1998.11a
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    • pp.182-182
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    • 1998
  • The root of Aralia continentalis Kitagawa(Araliaceae) have been used as an analgesic and fever remedy, and for treatment of rheumatism in Chinese medicine, whereas the young leaves are used for salad. An antioxidant activity of the young leaves of A continentalis was determined by measuring lipid peroxide produced when a mouse liver homogenate was exposed to the air at 37$^{\circ}C$, using 2-thiobarbituric acid(TBA) and by evaluation the radical scavenging activity on 1,l-diphenyl-2 picrylhydrazyl (DPPH) radical. Bioassay guided fractionation of MeOH extract isolated six flavonoid compounds as active components from EtOAc fraction. Adenosine and two saponins were isolated from the weak active BuOH fraction. The antioxidant effect by DPPH radical scavenging activity showed that quercetin was the most active among these compounds. Hyperoside and kaempferol were also active, while 6"-O-acetyl astragalin, astragalin, trifolin, adenosine, oleanolic acid 28-O-glucosyl ester and salsoloside C methyl ester were almost inactive. All the compounds were identified by spectroscopic methods.

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