• Title/Summary/Keyword: methanol activation

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Solvent Effect in Nucleophilic Reactions of Substituted Benzoyl Chlorides with p-Nitroaniline (치환염 벤조일과 파라니트로아닐린과의 친핵반응에 미치는 용매효과에 관한 연구)

  • Kim, Wang Gi
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.251-258
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    • 1974
  • The rate constants for the nucleophilic substitution reactions of substituted benzoyl chlorides with p-nitroaniline in such solvents as acetone, acetonitrile, methanol, ethanol, etc. were conductometrically determined, and the activation thermodynamic parameters were also evaluated. In result, the reaction rates were faster in protic solvents than in aprotic solvent; in the solvents of similar property, the reaction rate in the solvent of the large dielectric constant was faster than that in the solvent of the small dielectric constant. Hammett plots in individual solvents showed the straight lines with positive slope; and we concluded that the reaction occurred via the addition-elimination mechanism.

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Transition-State Structures for Solvolysis of Methanesulfonyl Chloride

  • 양기열;강금덕;구인선;이익준
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1186-1191
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    • 1997
  • Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

Inhibition of Nitric Oxide Synthesis by Ergosterol Derivative from Phellinus pini in LPS-Activated RAW 264.7 Cells (낙엽송층버섯으로부터 Ergosterol 유도체의 분리 및 RAW 264.7 세포주의 Nitric Oxide 생성 저해활성)

  • Jang, Hyun-Jin;Yang, Ki-Sook
    • YAKHAK HOEJI
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    • v.50 no.6
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    • pp.367-371
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    • 2006
  • Phellinus pini (Hymenocaetaceae) has been used for the immunomodulating activity hypolipidemic effect, gastric cancer non-insulin dependant diabetes, diarrhea, and menstrual irregularity. From the screening of each fraction for the inhibitory activity of NO production in lipopolysaccaride (LPS) activated RAW 264.7 cells, methanol extract of Phellinus pini and hexane soluble fraction exhibited inhibition of NO production compared with LPS control without toxicity. The hexane soluble fraction showed dose dependent inhibition of NO production. According to activity guided fractionation, the active hexane fr. was repeatedly chromatographed over silica gel, ergosta-4,6,8(14),22- tetraen-3-one was isolated. The compound inhibited NOS activation (IC$_{50}$ = 29.7 uM) and NO production of activated macrophage at 30 uM.

Proton Magnetic Resonance Study of the Amino Group of Thioacetamide (TA) I. Quadrupole Relaxation Effects in NH$_2$ of Thioacetamide

  • Suhr, Jae-Ryun;Yoon, Chang-Ju;Ro, Seong-Gu;Choi, Young-Sang
    • Bulletin of the Korean Chemical Society
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    • v.8 no.4
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    • pp.230-232
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    • 1987
  • Nitrogen-14 quadrupolar relaxation has been observed in the amino proton nmr spectra of TA in acetone and methanol solutions over the temperature range $-83^{\circ}C\; to\;+35^{\circ}C.$ The proton nmr lineshapes were analyzed to yield a $^{14}N$ spin lattice relaxation time $(T_1)_N$ as a function of temperature. Activation energies and correlation times at $25^{\circ}C$ for the molecular reorientation in the two solution phases have been calculated and the results are discussed.

Antioxidant Activities and Induction of Apoptosis by Methanol Extracts from Avocado (아보카도 추출물의 Apoptosis 유도와 항산화 활성)

  • Lee, Sung-Gyu;Yu, Mi-Hee;Lee, Sam-Pin;Lee, In-Seon
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.37 no.3
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    • pp.269-275
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    • 2008
  • The avocado is a widely grown and consumed fruit that is high in nutrients and low in calories, sodium, and fats. In this study, antioxidant activities and induction of apoptosis by methanol extracts from sarcocarp, seed and peel of avocado were investigated in vitro. Contents of total polyphenols in methanol extracts from sarcocarp, seed and peel were 13.89, 137.12 and $223.45{\mu}g/mg$ respectively. Radical-scavenging activities of the methanol extracts were examined by using ${\alpha},{\alpha}$-diphenyl-${\beta}$-picrylhydrazyl (DPPH) radicals and 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) assay. The methanol extracts from the peel of avocado showed higher scavenging activities against DPPH, ABTS than those from sarcocarp and seed. Apoptosis in MDA-MB-231 cells mediated by the methanol extracts of avocado was associated with the increase of activation of caspase-3 and caspase-3 target protein, PARP. Therefore, with more researches on identification and action mechanism of active compounds, the methanol extracts from peel and seed of avocado is expected to be a natural source for the developments of functional food and medical agents to prevent human breast cancer.

Anti-oxidative and anti-inflammatory effect of Do-Ki-Tang methanol extract in mouse macrophage cells (마우스 대식세포에서 도기탕 (導氣湯) 메탄올 추출물의 항산화 및 항염증 효과)

  • Kim, Dong-Wan;Yun, Hyun-Jeong;Heo, Jun-Young;Kim, Tae-Hoon;Cho, Hyun-Jin;Park, Sun-Dong
    • The Korea Journal of Herbology
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    • v.25 no.4
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    • pp.103-112
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    • 2010
  • Objective : The aim of this study was to determine whether methanol extract of Do-Ki-Tang (DKT) inhibit free radical generation and production of nitrite an index of NO, $PGE_2$, iNOS, COX-2 and pro-inflammatory cytokines such as TNF-${\alpha}$, IL-$1{\beta}$, IL-6 and MCP-1 in lipopolysaccharide (LPS)-stimulated RAW 264.7 macrophages. Methods : Cytotoxic activity of extract on RAW 264.7 cells was measured using 5-(3-caroboxymeth-oxyphenyl)-2H-tetra-zolium inner salt (MTS) assay. The expression level of inflammatory response-related proteins was confirmed by western blot. The production of proinflammatory cytokines was measured by ELISA. Results : Our results indicated that DKT scavenged DPPH radical and nitric oxide in vitro. Moreover, DKT significantly inhibited the LPS-induced NO, $PGE_2$ production and iNOS, COX-2 expression accompanied by an attenuation of TNF-${\alpha}$, IL-$1{\beta}$, IL-6 and MCP-1 formation in macrophages. Furthermore, DKT treatment also blocked LPS-induced intracellular ROS production and the activation of NF-${\kappa}B$ and MAPKs. Conclusion : Our data suggest that the anti-inflammatory effect of DKT is mediated through down-modulation of pro-inflammatory mediators and cytokines by blocking the signaling pathways of NF-${\kappa}B$ and MAPKs. These inhibitory effects by DKT represent a potential therapeutic approach to the treatment of inflammatory diseases.

Studies on the Antioxidation and Antimicrobial Effect of Smilacis Glabrae Rhizoma (토복령의 항산화작용 및 항균 효과에 대한 연구)

  • 양기호
    • The Journal of Korean Medicine
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    • v.25 no.2
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    • pp.1-8
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    • 2004
  • Objectives : This study was performed to investigate the effects of Smilacis GlabraeRhizoma on antioxidation and antimicrobial activity. Methods : In this study, we investigated the effects of peroxide radicals on hydrogen donating activity and linoleic acid, and the MDA contents on the hepatic lipids of rats, via methanol extractions and subfractions of Smilacis Glabrae Rhizoma. Results : 1. Hydrogen donating activity was very great for the radical scavenging effects, depending on the additional concentration at the fraction level of chloroform and ethyl acetate. 2. The peroxide radicals in linoleic acid were lower depending on the additional concentration, at the fraction level of ethyl acetate, than the controls. We concluded that both had significant anti-oxidation effects. 3. MDA contents of the hepatic lipid had also inhibition effects on lipid radicals, in proportion to the concentration of n-hexane, chloroform, and ethyl acetate fraction level. 4. After extracting Smilads Glabrae Rhizoma with 80% methanol, we experimented with the extracts the antibiosis each concentration, for 5 bacilli, Bacilus subtilis, staphylococcus aureus, Escherichia coli, Salmonela typhimurium, and Alcaligenes faecalis. While the effects showed differentiations by concentration, they had usually the significant inhibition effect for the multiplication at 37.5~75ug/ml. To identify the effective constituents, we identified the antibiosis of the fractions assaying cyclically hexane, chloroform, ethyl acetate, and butanol. The result showed that antimicrobial activation of both Gram-positive and Gram-negative bacillus except for E. coli was measured highest at the fraction level of BuOH and water. Conclusions : This result suggest that the extractions of Smilacis Glabrae Rhizoma, at ethyl acetate fraction, had significant anti-oxidation effects and at BuOH and water fraction had relatively strong antimicrobial activity against Bacilus subtilis, staphylococcus aureus, Salmonela typhimurium, and Alcaligenes faecalis.

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Mutagenicity of N-Nitrosodimethylamine in Salmonella / Microsome Assay and the Effect of Vitamin C on the Formation of N-Nitrosodimethylamine (Salmonella / Microsome Assay 에서의 N-nitrosodimethylamine의 돌연변이 유발성과 N-nitrosodimethylamine의 생성에 대한 비타민 C의 영향)

  • 김소희;박건영;서명자
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.20 no.3
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    • pp.260-265
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    • 1991
  • The effective method to detect the mutagenicity of N-nitrosodimethylamineI (NDMA) by using Salmonella/microsome assay was studied. The Effect of vitamin C on the mutagenicity of the formed NDMA and during the formation of NDMA from nitrite and secondary amine was also investigated. Aroclor 1254-induced hamster S9 mix was more effective in activation NDMA than rat S9 mix induced by Aroclor 1254 or phenobarbital. Dimethyl sulfoxide and ethanol suppressed the mutagenic effect of NDMA, however, phosphate butter (pH 7.4), distilled water, 95% methanol and Tween 80 + water (1 : 4) were the appropriate dissolving system in the mutagenicity test of NDMA. Vitamin C did not show any inhibitory effect on the mutagenicity of the formed NDMA. However, the revertants of Salmonella typhinutrium TA 100 were significntly reduced (p<0.05) when vitamin C was added to the reaction mixture of nitrite and dimethylamine during the formation of NDMA. The amount of the formed NDMA was analyzed using HPLC and the level was decreased by about 95%. Thus it was concluded that vitamin C inhibited greatly the formation of NDMA from nitrite and dimethylamine.

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Anti-inflammatory effect of methanol extract from Erigeron Canadensis L. may be involved with upregulation of heme oxygenase-1 expression and suppression of $NF{\kappa}B$ and MAPKs activation in macrophages

  • Sung, Jeehye;Sung, Misun;Kim, Younghwa;Ham, Hyeonmi;Jeong, Heon-Sang;Lee, Junsoo
    • Nutrition Research and Practice
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    • v.8 no.4
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    • pp.352-359
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    • 2014
  • BACKGROUND/OBJECTIVES: In this study, we determined the anti-inflammatory activities and the underlying molecular mechanisms of the methanol extract from Erigeron Canadensis L. (ECM) in LPS-stimulated RAW264.7 macrophage cells. MATERIALS/METHODS: The potential anti-inflammatory properties of ECM were investigated by using RAW264.7 macrophages. We used western blot assays and real time quantitative polymerase chain reaction to detect protein and mRNA expression, respectively. Luciferase assays were performed to determine the transactivity of transcription factors. RESULTS: ECM significantly inhibited inducible nitric oxide synthase (iNOS)-derived NO and cyclooxygenase-2 (COX-2) derived PGE2 production in LPS-stimulated RAW264.7 macrophages. These inhibitory effects of ECM were accompanied by decreases in LPS-induced nuclear translocations and transactivities of $NF{\kappa}B$. Moreover, phosphorylation of mitogen-activated protein kinase (MAPKs) including extracellular signal-related kinase (ERK1/2), p38, and c-jun N-terminal kinase (JNK) was significantly suppressed by ECM in LPS-stimulated RAW264.7 macrophages. Further studies demonstrated that ECM by itself induced heme oxygenase-1 (HO-1) protein expression at the protein levels in dose-dependent manner. However, zinc protoporphyrin (ZnPP), a selective HO-1 inhibitor, abolished the ECM-induced suppression of NO production. CONCLUSIONS: These results suggested that ECM-induced HO-1 expression was partly responsible for the resulting anti-inflammatory effects. These findings suggest that ECM exerts anti-inflammatory actions and help to elucidate the mechanisms underlying the potential therapeutic values of Erigeron Canadensis L.

Nucleophilic Displacement at Sulfur Center (XVII). Solvolysis of 2-Anthracenesulfonyl Chloride (황의 친핵성 치환반응 (제17보) 2-염화안트라센 술포닐의 가용매 분해반응)

  • Hyong Tae Kim;Soo Dong Yoh;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.167-177
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    • 1983
  • The kinetics of 2-anthracenesulfonyl chloride in methanol-water, ethanol-water, acetone-water and acetonitrile-water has been studied by electroconductometric method. For media in which water has the same mole fraction, the rate was greater in protic solvent than in dipolar aprotic solvent and it was greater consistently in methanol-water than in ethanol-water over the whole range of solvent composition investigated, while the two rates in acetone-water and acetonitrile-water inverted at about 0.9 of mole fraction of water. Both m value, susceptibility of rate to the ionizing power and n value, solvent participation number in the transition state were much smaller in protic solvent. These values and the activation parameters show that solvolysis of 2-anthracenesulfonyl chloride proceeds by $ S_N2$ mechanism.

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