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M.O. Studies of Configuration and Conformation (Part II) Configuration and Conformation of Ketimine isomers

  • Kim, Shi-Choon;Chun, Young-Gu;Lee, Ikchoon
    • Nuclear Engineering and Technology
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    • v.9 no.1
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    • pp.39-44
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    • 1977
  • The configuratior and conformation of N-methyl-C-phenylalkyl-ketimine isomers, Ph-CR=N$CH_3$ (R=H, $CH_3$, $CH_3$CH$_2$), have been studied from extended Huckel molecular orbital calculations. The result shows that the E-configuration of the C=N double bond is favored compared with that of the Z-configuration. The most preferable conformation of the phenyl ring rotamer in N-methyl-C-phenylaldimine and N-methyl-C-phenylmethylketimine are the coplanar forms with regard to the C=N plane, but the conformation of the $CH_3$CH$_2$-rotamer, in N-methyl-C-phenylethyl-ketimine, the gauche form (dihedral angle between C=N and $CH_3$CH$_2$- plane=90$^{\circ}$) is favored.

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The Reaction of Superoxide with Carbohydrate Sulphonates

  • Shin, Young-Sook;Nam Shin, Jeong E.
    • Bulletin of the Korean Chemical Society
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    • v.14 no.2
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    • pp.188-191
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    • 1993
  • The reaction between methyl 2,3-di-O-benzyl-4,6-di-O-mesyl-${\alpha}$-D-glucopyranoside (1b) and potassium superoxide resulted in hydrolysis, and gave methyl 2,3-di-O-benzyl-${\alpha}$-D-glucopyranoside (1) as a sole product. When the reaction was performed with a vicinal dimesylate, methyl 4,6-O-benzylidene-2,3-di-O-mesyl-${\alpha}$-D-altropyranoside (4b), again the hydrolysis product, methyl 4,6-O-benzylidene-${\alpha}$-D-altropyranoside (4) was obtained. However, the reaction of potassium superoxide with another vicinal dimesylate, methyl 4,6-O-benzylidene-2,3-di-O-mesyl-${\alpha}$-D-glucopyranoside (3b), nucleophilic displacement took place to afford methyl 4,6-O-benzylidene-${\alpha}$-D-altropyranoside (4). Apparently different results from two trans vicinal dimesylates, 3b and 4b are explained by the transient formation of epoxides, methyl 2,3-anhydro-4,6-O-benzylidene-${\alpha}$-D-allopyranoside (8) and methyl 2,3-anhydro-4,6-O-benzylidene-${\alpha}$-D-mannopyranoside (9) by $KO_2$. The reaction between the allo epoxide 8 and $KO_2$ gave altro 4. The manno epoxide 9 also afforded altro 4 as the major product. Facile epoxide formation by the reaction of a vicinal dimesylate and superoxide was also observed with 3-O-benzyl-1,2-O-isopropylidene-5,6-di-O-mesyl-${\alpha}$-D-glucofuranose: 5,6-anhydro-3-O-benzyl-1,2-O-isopropylidene-${\beta}$-L-idofuranose was obtained.

Teratogenicity of Food Residual Organophosphate in the Developing Chick Embryo (Chick embryo를 이용한 식품 잔류 농약의 기형성 연구)

  • 임윤규;최재준;이민웅;이영순
    • Journal of Food Hygiene and Safety
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    • v.5 no.4
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    • pp.171-178
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    • 1990
  • Potential teratogenicity of Azinphos-methyl and Carbaryl was investigated in developing chick embryos. $100\;\mu\textrm{l}$ of Azinphos-methyl and Carbaryl was injected into air sac on day 4 of incubation. Body weight changes and morphological changes were examined. The results obtained were summarized as follows; 1. Body length, limb lengths and claw length of groups treated with high dose of Azinphosmethyl and Carbaryl were significantly shortened compared to untreated of vehicle control and body weights of them were significantly lower than those of control groups. 2. Treatment of Azinphos-methyl and Carbaryl increased incidence ratios of dead embryo by dosage (Azinphos-methyl: 18%, 21%, 41%, Carbaryl: 26%, 50%). 3. One case of beak malformation occurred in Carbaryl treatment group.

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Influence of 3-(N-methyl-N-X(sub.)phenylaminooxoacetyl) group on the herbicidal activity of Imazethapyr derivatives (Imazethapyr 유도체의 제초활성에 미치는 3-(N-methyl-N-(X)-치환-phenylaminooxoacetyl) group의 영향)

  • Sung, N.D.;Kim, H.J.;Chang, H.S.;Kim, D.W.
    • Applied Biological Chemistry
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    • v.36 no.5
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    • pp.381-386
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    • 1993
  • New twenty five Imazethapyr derivatives, [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin -2-yl)-3-(N-methyl-N-X(sub.)-phenylaminooxoacetyl)-5-methylpyridine] were synthesized. and The quantitative structure activity relationships (QSARs) between their post-emergence herbicidal activity$(pI_{50})$ values in vivo against Barnyard grass (Echinochloa crus-galli) and physicochemical parameters of substituents(X) of 3-(N-methyl-N-X(sub.)-phenylaminooxoacetyl) group have been studied. From the basis on the findings, in case of post-emergence, the activities were dependent on the steric constant$(E_s<0)$ and electron donating $(\sigma<0)$ effect by subsitituents(X) of 3-(N-methyl-N-X(sub.)phenylaminooxoacetyl) group. Therefore, The most effective compound,15 (4-t-butyl group) and 20 (3,5-dimethyl group) were examined in this study. And the conditions on the compounds predicted to show higher herbicidal activity were also discussed.

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Effect of Certain Additives on Bread-Making Quality of Wheat-Purple Sweet Potato Flours (밀 및 자색고구마 가루의 제빵성에 대한 첨가제의 영향)

  • 김선영;유정희
    • Korean journal of food and cookery science
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    • v.13 no.4
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    • pp.492-499
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    • 1997
  • The effect of oxidants, gluten and gums on breadmaking quality of wheat-purple sweet potato(Ipomoea batatas) composite flour were studied. Alveograph tests of doughs showed that all additives increased the P, L and W values. Of these additives, L-Ascorbic acid, gluten, carboxy methyl cellulose have a significant effect on alveogram indexes. SEM showed that the dough added with additives changed some what in appearance when compared with the control. When oxidants was added, the doughs discontinuous gluten film were observed. No significant differences ,were evident in bread crumb color among the additives. And textural characteristics of bread crumb were influened by adding additives. Breads containing additives showed an increase in max weight, strength and hardness and a decrease in springness and cohesiveness. Average enthalpy values for all bread crumb after 7days increased with storage time. However, addition of additives decrease the rate of staling slightly more than that of the control. Addition of L-Ascorbic acid, L-Cystine, carboxy methyl cellulose and hydroxy propyl methyl cellulose increased the loaf volume significantly, and with except potassium bromate bread scores were acceptable.

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Plant growth promoting effect of 4-quinolinone metabolites from Pseudomonas cepacia and 4-quinolinone-3-carboxylate derivatives on red pepper plant (Capsicum annum) (Pseudomonas cepacia로부터 유래한 4-quinolinone 대사물질과 4-quinolinone-3-carboxylate 유도체의 고추(Capsicum annum)에서의 생장촉진 효과)

  • Moon, Surk-Sik;Myung, Eul-Jae;Cho, Soon-Chang;Park, Jae-Bum;Chung, Bong-Jin
    • The Korean Journal of Pesticide Science
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    • v.6 no.2
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    • pp.64-71
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    • 2002
  • Plant growth promoting activity of quinolinone metabolites, 2-(2-hepteny)-3-methyl-4-quinolinone (1), 2-heptyl-3-methyl-4-quinolinone, and 2-nonyl-3-methyl-4-quinolinone, produced by Pseudomonas cepacia and ethyl 2-methyl-3-alkyl-4-quinolinone carboxylates chemically synthesized were tested by using seed-germination assay, growth increments in plant height after foliar applications. Plant height increment, fresh weight, and the number of fruits were measured after seed-soaking and drench treatment. Compound 1 among the natural products showed a consistent growth promoting effect in seed-germination and plant height after a foliar application. After a seed-soaking and drench treatment, compound 1 and synthetic ethyl 2-methyl-4-quinolinone-3-carboxylate (5) showed a significant enhancement in fresh weight and the number of fruits after harvest. Compound 1 and 5 increased the number of fruits per plant by 44% and 84% over the control, respectively.

Cellular growth and fatty acid content of Arctic chlamydomonadalean

  • Jung, Woongsic;Kim, Eun Jae;Lim, Suyoun;Sim, Hyunji;Han, Se Jong;Kim, Sanghee;Kang, Sung-Ho;Choi, Han-Gu
    • ALGAE
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    • v.31 no.1
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    • pp.61-72
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    • 2016
  • Arctic microalgae thrive and support primary production in extremely cold environment. Three Arctic green microalgal strains collected from freshwater near Dasan Station in Ny-Alesund, Svalbard, Arctic, were analyzed to evaluate the optimal growth conditions and contents of fatty acids. The optimal growth temperature for KNF0022, KNF0024, and KNF0032 was between 4 and 8℃. Among the three microalgal strains, KNF0032 showed the maximal cell number of 1.6 × 107 cells mL-1 at 4℃. The contents of fatty acids in microalgae biomass of KNF0022, KNF0024, and KNF0032 cultured for 75 days were 37.34, 73.25, and 144.35 mg g-1 dry cell weight, respectively. The common fatty acid methyl esters (FAMEs) analyzed from Arctic green microalgae consisted of palmitic acid methyl ester (C16:0), 5,8,11-heptadecatrienoic acid methyl ester (C17:3), oleic acid methyl ester (C18:1), linoleic acid methyl ester (C18:2), and α-linolenic acid methyl ester (C18:3). KNF0022 had high levels of heptadecanoic acid methyl ester (26.58%) and heptadecatrienoic acid methyl ester (22.17% of the total FAMEs). In KNF0024 and KNF0032, more than 72.09% of the total FAMEs consisted of mono- and polyunsaturated fatty acids. Oleic acid methyl ester from KNF0032 was detected at a high level of 20.13% of the FAMEs. Arctic freshwater microalgae are able to increase the levels of polyunsaturated fatty acids under a wide range of growth temperatures and can also be used to produce valuable industrial materials.

Toxicity Evaluation of Agricultural Insecticides on Workers of Pharaoh Ant, Monomorium pharaonis (Hyme-noptera : Formicidae) (애집개미 (Monomorium pharaonis) 일개미에 대한 농업용 살충제의 독성평가)

  • Kang, Shin-Ho;Han, Jong-Been;Park, Shin-Sub;Kim, Gil-Hah
    • The Korean Journal of Pesticide Science
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    • v.10 no.3
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    • pp.218-224
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    • 2006
  • Toxicities of 34 agricultural insecticides was tested against Monomorium pharaonis workers by diet dipping method. Ten insecticides among them, bifenthrin, chlorpyrifos, chlorpyrifos-methyl, cypermethrin, dichlorvos, fenthion, fenitrothion, methidathion, pirimifos-methyl, and phenthoate showed 100% rapid mortality. $LC_{50}$ (ppm) values of selected insecticides were appeared on the order of pirimifos-methyl (0.33), chlorpyrifos-methyl (0.76), phenthoate (1.70), bifenthrin (1.78), dichlorvos (2.50), cypermethrin (9.92), chlorpyrifos (22.21), fenitrothion (36.58), fenthion (40.96), and methidathion (64.34). $LT_{50}$ (day) values by diet dipping method showed that dichlorvos, benfuracarb and cypermethrin acted more rapid than boric acid and hydramethylnon. The values of the former three were 0.25, 0.38 and 0.27 days, and those of the latter two were 3.4 and 2.6 days, respectively. In persistance effect tests, chlorpyrifos-methyl, fenthion and methidathion showed over 90% insecticidal activity for 13 days.

Methyl p-Hydroxycinnamate Suppresses Lipopolysaccharide-Induced Inflammatory Responses through Akt Phosphorylation in RAW264.7 Cells

  • Vo, Van Anh;Lee, Jae-Won;Shin, Seung-Yeon;Kwon, Jae-Hyun;Lee, Hee Jae;Kim, Sung-Soo;Kwon, Yong-Soo;Chun, Wanjoo
    • Biomolecules & Therapeutics
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    • v.22 no.1
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    • pp.10-16
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    • 2014
  • Derivatives of caffeic acid have been reported to possess diverse pharmacological properties such as anti-inflammatory, anti-tumor, and neuroprotective effects. However, the biological activity of methyl p-hydroxycinnamate, an ester derivative of caffeic acid, has not been clearly demonstrated. This study aimed to elucidate the anti-inflammatory mechanism of methyl p-hydroxycinnamate in lipopolysaccharide (LPS)-stimulated RAW 264.7 macrophage cells. Methyl p-hydroxycinnamate significantly inhibited LPS-induced excessive production of pro-inflammatory mediators such as nitric oxide (NO) and $PGE_2$ and the protein expression of iNOS and COX-2. Methyl p-hydroxycinnamate also suppressed LPS-induced overproduction of pro-inflammatory cytokines such as IL-$1{\beta}$ and TNF-${\alpha}$. In addition, methyl p-hydroxycinnamate significantly suppressed LPS-induced degradation of $I{\kappa}B$, which retains NF-${\kappa}B$ in the cytoplasm, consequently inhibiting the transcription of pro-inflammatory genes by NF-${\kappa}B$ in the nucleus. Methyl p-hydroxycinnamate exhibited significantly increased Akt phosphorylation in a concentration-dependent manner. Furthermore, inhibition of Akt signaling pathway with wortmaninn abolished methyl p-hydroxycinnamate-induced Akt phosphorylation. Taken together, the present study clearly demonstrates that methyl p-hydroxycinnamate exhibits anti-inflammatory activity through the activation of Akt signaling pathway in LPS-stimulated RAW264.7 macrophage cells.

FUNGAL EXTRACELLULAR POLYSACCHARIDES INVOLVED IN RECYCLING OF METABOLITES AND OSMOTOLERANCE OF PENICILLIUM FELLUTANUM : APPLICATION OF $^{13}$ C-NMR SPECTROSCOPY FOR THE STUDY ON FUNGAL PHYSIOLOGY AND METABOLISM

  • Park, Yong-Il;Gander, John.-E.
    • Proceedings of the Korean Society for Applied Microbiology Conference
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    • 2000.04a
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    • pp.208-213
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    • 2000
  • Penicillium fellutanum produces a phosphorylated, choline-containing extracellular peptido-polysaccharide, peptidophosphogalactomannan (pPxGM) (8). The $\^$13/C-methyl labeled pPxGM ([methyl-$\^$13/C]pPxGM) was prepared from the cultures supplemented with L-[methyl-$\^$13/C]methionine or [2-$\^$13/C]glycine and was used as a probe to monitor the fate of phosphocholine in this polymer. Addition of purified [methyl-$\^$l3/C]pPxGM to growing cultures in low phosphate medium resulted in the disappearance of [methyl-$\^$13/C]phosphocholine and -N,N'-dimethyl-phosphoethanolamine from the added [methyl-$\^$13/C]pPxGM. Two $\^$l3/C-methyl-enriched cytoplasmic solutes, choline-O-sulfate and glycine betaine, were found in mycelial extracts, suggesting that phosphocholine-containing extracellular pPxGM of P.fellutanum is a precursor of intracellular choline-O-sulfate and glycine betaine and thus of phosphatydilcholine (l0). $\^$13/C-Methyl-labeled cells grown in 3 M NaCl-containing medium showed 2.6- and 22-fold more accumulation of $\^$13/C-methyl labeled choline-O-sulfate and glycine betaine, respectively, originated from the extracellular [$\^$13/C-methyl]pPxGM than those grown without added NaCl. The results suggest that, in addition to glycerol and erythritol, glycine betaine and choline-O-sulfate and thus choline are also osmoprotectants and hence that pPxGM is involved in osmotolerance of this fungus (11). Taken collectively, the $\^$l3/C- and $\^$31/P-NMR analyses of cytosolic solute pools and structural modulation of extracellular pPxGM corresponding to environmental stimuli in P. fellutanum, provided evidence that pPxGM is involved in cellular choline metabolism, osmotolerance, and recycling of metabolites.

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