• Title/Summary/Keyword: C-O bond

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Kinetic Studies on the Reaction of 4-Substituted-2,6-dinitrochlorobenzenes with Substituted Anilines in MeOH-MeCN Mixtures (MeOH-MeCN 혼합용매계에서 4-치환-2,6-이니트로 염화벤젠과 아닐린 치환체와의 반응에 대한 속도론적 연구)

  • Dae-Ho Kang;In-Sun Koo;Jong Gun Lee;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.565-574
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    • 1985
  • The rates of reaction between 4-substituted-2,6-dinitrochlorobenzenes with para-substituted anilines in methanol-acetonitrile mixtures were measured by conductometry. It was observed that the rate constant increases in the order of X = 4-$NO_2 {\gg}4-CN {\gg}4- CF_3$, where X is a substituent in the substrate. The rate constant also increases in the order of Y = p-O$CH_3{\gg}p- CH_3{\gg}H {\gg}p-Cl{\gg}m- NO_2$, where Y is a substituent in the aniline ring. Kinetic studies in the methanol-acetonitrile solvent system with various nucleophiles showed that the N-C bond forming step is making a great contribution to the overall second order rate constant. The electrophilic catalysis by methanol probably consists of the hydrogen bonding between alcoholic hydrogen and leaving chloride in the transition state. The nucleophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic oxygen and hydrogens of amines in the transition state. All these experimental facts are supporting the operation of $S_N$Ar machanism with the second step being the rate determining. This mechanism can be successfully fitted to the PES model.

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Microstructures and Hardness of Al-Si Coated 11%Cr Ferritic Stainless Steel, 409L GTA Welds (Al-Si 용융도금된 11%Cr 페라이트 스테인리스강, STS409L GTA 용접부의 미세조직과 경도)

  • Park, Tae-Jun;Kong, Jong-Pan;Na, Hye-Sung;Kang, Chung-Yun;Uhm, Sang-Ho;Kim, Jeong-Kil;Woo, In-Su;Lee, Jong-Sub
    • Journal of Welding and Joining
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    • v.28 no.3
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    • pp.92-98
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    • 2010
  • Ferritic stainless steels, which have relatively small thermal expansion coefficient and excellent corrosion resistance, are increasingly being used in vehicle manufacturing, in order to increase the lifetime of exhaust manifold parts. But, there are limits on use because of the problem related to cosmetic resistance, corrosions of condensation and high temperature salt etc. So, Aluminum-coated stainless steel instead of ferritic stainless steel are utilized in these parts due to the improved properties. In this investigation, Al-8wt% Si alloy coated 409L ferritic stainless steel was used as the base metal during Gas Tungsten Arc(GTA) welding. The effects of coated layer on the microstructure and hardness were investigated. Full penetration was obtained, when the welding current was higher than 90A and the welding speed was lower than 0.52m/min. Grain size was the largest in fusion zone and decreased from near HAZ to base metal. As welding speed increased, grain size of fusion zone decreased, and there was no big change in HAZ. Hardness had a peak value in the fusion zone and decreased from the bond line to the base metal. The highest hardness in the fusion zone resulted from the fine re-precipitation of the coarse TiN and Ti(C, N) existed in the base metal during melting and solidification process and the presence of fine $Al_2O_3$ and $SiO_2$ formed by the migration of the elements, Al and Si, from the melted coating layer into the fusion zone.

Optical Properties of SiNx Thin Films Grown by PECVD at 200℃ (200℃의 저온에서 PECVD 기법으로 성장한 SiNx 박막의 열처리에 따른 광학적 특성 변화 규명)

  • Lee, Kyung-Su;Kim, Eun-Kyeom;Son, Dae-Ho;Kim, Jeong-Ho;Yim, Tae-Kyung;An, Seung-Man;Park, Kyoung-Wan
    • Journal of the Korean Vacuum Society
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    • v.20 no.1
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    • pp.42-49
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    • 2011
  • We deposited $SiN_x$ thin films by using PECVD technique at $200^{\circ}C$ with various flow ratios of the $SiH_4/N_2$ gases. The photoluminescence measurements revealed that the maximum emission wavelength shifted to long wavelength as the ratio increased, however, positions of the several peak wavelengths, such as 1.9, 2.2, 2.4, and 3.1 eV, were independent on the ratio. Changes of the photoluminescence spectra were measured in the $N_{2}-$, $H_{2}-$, and $O_2$-annealed films. The luminescence intensities increased after the annealing process. In particular, the maximum emission wavelength shifted to short wavelength after $H_{2}-$ or $O_2$-annealing. But there were still several peaks on the spectra of all annealed films, several peak positions remained to be unchanged after the annealing. As for the light emission mechanism, we have considered the defect states of the Si- and N- dangling bonds in the $SiN_x$ energy gap, so that the energy transitions from/to the conduction/valence bands and the defect states in the gap were attributed to the light emission in the $SiN_x$ films. The experimental results point to the possibility of a Si-based light emission materials for flexible Si-based electro-optic devices.

Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 2016.05a
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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Computational Optimization of Bioanalytical Parameters for the Evaluation of the Toxicity of the Phytomarker 1,4 Napthoquinone and its Metabolite 1,2,4-trihydroxynapththalene

  • Gopal, Velmani;AL Rashid, Mohammad Harun;Majumder, Sayani;Maiti, Partha Pratim;Mandal, Subhash C
    • Journal of Pharmacopuncture
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    • v.18 no.2
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    • pp.7-18
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    • 2015
  • Objectives: Lawsone (1,4 naphthoquinone) is a non redox cycling compound that can be catalyzed by DT diaphorase (DTD) into 1,2,4-trihydroxynaphthalene (THN), which can generate reactive oxygen species by auto oxidation. The purpose of this study was to evaluate the toxicity of the phytomarker 1,4 naphthoquinone and its metabolite THN by using the molecular docking program AutoDock 4. Methods: The 3D structure of ligands such as hydrogen peroxide ($H_2O_2$), nitric oxide synthase (NOS), catalase (CAT), glutathione (GSH), glutathione reductase (GR), glucose 6-phosphate dehydrogenase (G6PDH) and nicotinamide adenine dinucleotide phosphate hydrogen (NADPH) were drawn using hyperchem drawing tools and minimizing the energy of all pdb files with the help of hyperchem by $MM^+$ followed by a semi-empirical (PM3) method. The docking process was studied with ligand molecules to identify suitable dockings at protein binding sites through annealing and genetic simulation algorithms. The program auto dock tools (ADT) was released as an extension suite to the python molecular viewer used to prepare proteins and ligands. Grids centered on active sites were obtained with spacings of $54{\times}55{\times}56$, and a grid spacing of 0.503 was calculated. Comparisons of Global and Local Search Methods in Drug Docking were adopted to determine parameters; a maximum number of 250,000 energy evaluations, a maximum number of generations of 27,000, and mutation and crossover rates of 0.02 and 0.8 were used. The number of docking runs was set to 10. Results: Lawsone and THN can be considered to efficiently bind with NOS, CAT, GSH, GR, G6PDH and NADPH, which has been confirmed through hydrogen bond affinity with the respective amino acids. Conclusion: Naphthoquinone derivatives of lawsone, which can be metabolized into THN by a catalyst DTD, were examined. Lawsone and THN were found to be identically potent molecules for their affinities for selected proteins.