• Title/Summary/Keyword: Ring cleavage

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Density Functional Studies of Ring-Opening Reactions of Li+-(ethylene carbonate) and Li+-(vinylene carbonate)

  • Han, Young-Kyu;Lee, Sang-Uck
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.43-46
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    • 2005
  • Reaction energies were determined for reductive ring-opening reactions of Li$^+$-coordinated ethylene carbonate (EC) and vinylene carbonate (VC) by a density functional method. We have also explored the ring-opening of Li$^+$-EC and Li$^+$-VC by reaction with a nucleophile (CH$_3$O$^-$.) thermodynamically. Our thermodynamic calculations led us to conclude that the possible reaction products are CH$_3$OCH$_2$CH$_2$OCO$_2$Li (O$_2$-C$_3$ cleavage) for Li$^+$-EC +CH$_3$O$^-$., and CH$_3$OCHCHOCO$_2$Li (O$_2$-C$_3$ cleavage) and CH$_3$OCO$_2$CHCHOLi (C$_1$-O$_2$ cleavage) for Li$^+$-VC +CH$_3$O$^-$.. The opening of VC would occur at the C$_1$-O$_2$ side by a kinetic reason, although the opening at the O$_2$-C$_3$ side is more favorable thermodynamically.

Acid-Promoted Ring Cleavage Reactions of Silacyclohex-3-ene Derivatives

  • Myong Euy Lee;Jeong Hyun Kim;Chang Hwan Kim
    • Bulletin of the Korean Chemical Society
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    • v.15 no.9
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    • pp.729-732
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    • 1994
  • The acid-promoted cleavage of the E-and Z-isomers of 1-phenyl-6-neopentyl-1,3,4-trimethyl-1-silacyclohe x-3-ene(II) under various conditions gave clean and nearly quantitative formation of the ring-opened 2,3,7,7-tetramethyl-5-(X)silyl-1-octene products (X=OMe, Cl, OH). The possible mechanism for the formation of the ring-opened products was suggested that the initial protonation of II at C-4 would give a carbocation oriented so that they are ${\beta}$ to the silicon atom, and the subsequent nucleophilic attack at silicon would give rise to the observed products (VI, VII, VIII).

Cleavage Dependent Indirect Tensile Strength of Pocheon Granite Based on Experiments and DEM Simulation (포천화강암의 결에 따른 간접인장강도 특성에 대한 실험 및 개별요소 수치해석)

  • Zhuang, Li;Diaz, Melvin B.;Jung, Sung Gyu;Kim, Kwang Yeom
    • Tunnel and Underground Space
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    • v.26 no.4
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    • pp.316-326
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    • 2016
  • The purpose of this study is to investigate the influence of cleavages on indirect tensile strength (ITS) of the granite. Brazilian disc tests and ring tests with three different hole sizes were performed. 2D DEM (Discrete Element Method) simulation was employed to further understand the failure process during the tests and the mechanism behind. Results show that ITS decreases across hardway, grain and rift cleavage. Measured average ITS from ring tests is about 2.5 ~ 6.4 times of those measured from Brazilian disc tests, and it decreases with increasing ratio of diameters of inner hole and specimen. Failure pattern in ring tests is influenced by both hole size and relative positions of cleavages parallel and perpendicular to the loading direction.

Extradiol Cleavage of Two-ring Structures of Biphenyl and Indole Oxidation by Biphenyl Dioxygenase in Commamonas Acidovorans

  • On, Hwa-Young;Lee, Na-Ri;Kim, Young-Chang;Kim, Chi-Kyung;Kim, Young-Soo;Park, Yong-Keun;Ka, Jong-Ok;Lee, Ki-Sung;Min, Kyung-Hee
    • Journal of Microbiology and Biotechnology
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    • v.8 no.3
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    • pp.264-269
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    • 1998
  • Commamonas acidovorans SMN4 showed wide growth substrate spectra for various aromatic hydrocarbons. Strain SMN4 was able to grow on biphenyl producing a meta-cleavage compound, yellow 2-hydroxy-6-oxophenylhexa-2,4-dienoic acid with a spray of 2,3-dihydroxybiphenyl, while it also grew on catechol, developing yellow 2- hydroxymucoic semialdehyde with a spray of 100 mM catechol. Thus these results indicate that two-ring structures of biphenyl were cleaved by meta-mode in upper and lower pathways. Strain SMN4 metabolized various substituted biphenyl compounds and xylene to the corresponding benzoate derivatives through oxidation of the ring structures. It was clearly shown that biphenyl can be a common inducer in the oxidation of biphenyl and 2,3-dihydroxybiphenyl. Various compounds were examined for their suitability to serve as substrates for indole oxidation, indicating that biphenyl, benzoate, and succinate are quite good inducers of indigo production due to the activity of biphenyl dioxygenase. This results suggest that indigo formation is by means of the combined activities of biphenyl dioxygenase and tryptophanase.

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Characterization of Benzoate Degradation via ortho-Cleavage by Streptomyces setonii

  • An, Hae-Reun;Park, Hyun-Joo;Kim, Eung-Soo
    • Journal of Microbiology and Biotechnology
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    • v.10 no.1
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    • pp.111-114
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    • 2000
  • Streptomyces are widespread in nature and play a very important role in the biosynthesis as well as biodegradation of natural and unnatural aromatic compounds. Both qualitatively and quantitatively through TLC and UV spectrophotometric assays, it was observed that the thermophilic soil bacteria S. setonii (ATCC 39116), which can utilize a benzoate as a sole carbon and energy source in a minimal liquid culture, was not very sensitive to the benzoate concentation and to the culture conditions such as the pH and temperature. The in vitro conversion of a catechol to a cis, cis-muconic acid by a crude S. setonii lysate implies that the aromatic ring cleavage by S. setonii is initiated by a thermostable catechol-1,2-dioxygenase, the key enzyme in the ortho-cleavage pathway of aromatic compound biodegradation. Unlike non-degrading S. lividans, S.setonii was also highly resistant to other similar hazardous aromatic compounds, exhibiting almost no adverse effect on its growth in a complex liquid culture.

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Mechanisms of Lignin Biodegradation by Ligninase, Phanerochaete Chrysosporium Burds

  • Hwang, Byung-Ho
    • Journal of Forest and Environmental Science
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    • v.6 no.1
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    • pp.45-60
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    • 1989
  • 리그닌 생분해의 분해경로 및 매카니즘에 관한 연구가 최근 Kirk와 Higuchi 등에 의하여 활발히 연구되고 있다. 특히, Phanerochaete chrysosporium이 생산해내는 Lignlnase를 이용하여 매우 가치있는 연구 결과를 얻고 있다. 본 총설에서는 Kirk와 Higuchi의 허가를 얻어서 그들의 논문을 중심으로 리그닌의 중요한 결합 양식 별로 즉, ${\beta}$-O-4, ${\beta}$-5, ${\beta}$-1, ${\beta}$-6, 5-5 등의 결합 모델 화합물들의 분해경로 및 매카니즘에 관하여 조사 정리하였다.

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Microbial Degradation of Monohydroxybenzoic Acids

  • Kim, Chi-Kyung;Tim
    • Journal of Microbiology
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    • v.38 no.2
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    • pp.53-61
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    • 2000
  • Hydroxybenzoic acids are the most important intermediates in the degradative pathways of various aromatic compounds. Microorganisms catabolize aromatic compounds by converting them to hydroxylated intermediates and then cleave the benzene nucleus with ring dioxygenases. Hydroxylation of the benzene nucleus of an aromatic compound is an essential step for the initiation and subsequent disintegration of the benzene ring. The incorporation of two hydroxyl groups is essential for the labilization of the benzene nucleus. Monohydroxybenzoic acids such as 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 4-hydrosybenzoic acid, opr pyrocattechuic acid that are susceptible for subsequent oxygenative cleavage of the benzene ring. These terminal aromatic intermediates are further degraded to cellular components through ortho-and/or meta-cleavage pathways and finally lead to the formation of constituents of the TCA cycle. Many groups of microorganisms have been isolated as degraders of hydroxybenzoic acids with diverse drgradative routes and specific enzymes involved in their metabolic pahtway. Various microorganisms carry out unusual non-oxidative decarboxylation of aromatic acids and convert them to respective phenols which have been documented. Futher, Pseudomonas and Bacillus spp. are the most ubiquitous microorganisms, being the principal components of microflora of most soil and water enviroments.

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Characterization of Petroleum Hydrocarbon Degradation by a Sphingomonas sp. 3Y Isolated from a Diesel-Contaminated Site. (디젤오염지역에서 분리한 세균 Sphingomonas sp. 3Y의 석유계 탄화수소분해특성)

  • Ahn, Yeong-Hee;Jung, Byung-Gil;Sung, Nak-Chang;Lee, Young-Ok
    • Journal of Life Science
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    • v.19 no.5
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    • pp.659-663
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    • 2009
  • Bacterial stain 3Y was isolated from a site that was contaminated with diesel for more than 15 years. The strain could grow on various petroleum using hydrocarbons as the sole carbon source. The strain grew not only on aliphatic hydrocarbons but also on aromatic hydrocarbons. 3Y grew on aliphatic petroleum hydrocarbons hexane or hexadecane, and aromatic petroleum hydrocarbons BTEX, phenol, biphenyl, or phenanthrene. The strain showed aromatic ring dioxygenase and meta-cleavage dioxygenase activities as determined by tests using indole and catechol. Aromatic ring dioxygenase is involved in the initial step of biodegradation of aromatic hydrocarbons while meta-cleavage dioxygenase catalyzes the cleavage of the benzene ring. Based on a nucleotide sequence analysis of its 16S rRNA gene, 3Y belongs to the genus Sphingomonas. A phylogenetic tress was constructed based on the nucleotide sequences of closest relatives of 3Y and petroleum hydrocarbon degrading sphingomonads. 3Y was in a cluster that was different from the cluster that contained well-known sphingomonads. The results of this study suggest that 3Y has the potential to cleanup oil-contaminated sites. Further investigation is warranted to optimize conditions to degrade petroleum hydrocarbons by the strain to develop a better bioremediation strategy.