• 제목/요약/키워드: Double Rearrangement

검색결과 20건 처리시간 0.023초

Characteristics of the Intermediates in the Cyclization Reactions of Heterocycle-fused[1,4]oxazine Derivatives: Stepwise versus Concerted

  • Shin, Dong-Soo;Park, Jong-Keun
    • Bulletin of the Korean Chemical Society
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    • 제28권12호
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    • pp.2219-2225
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    • 2007
  • The reaction mechanisms for the cyclizations of N-methyl-2-(2-chloropyridin-3-yloxy)acetamide to 1-methylpyrido[ 3,2-b][1,4]oxazin-2-one and 1-methyl-pyrido[2,3-b][1,4]oxazin-2-one were investigated using ab initio Hartree-Fock, second-order Moller-Plesset perturbation, single point coupled cluster with both single and double substitution, and density functional theory methods. The 5-membered spiro intermediate (2) is optimized from the cyclization of the acyclic reactants through the proton-transfer reaction, and this intermediate proceeds continuously to the 6-membered intermediate through either a stepwise or a concerted reaction. In the stepwise reaction, an N-bridge-type intermediate as a stable structure is optimized, whereas, in the concerted reaction, the O-bridge-type intermediate is not optimized.

The Study of Molecular Structures for New Banana-shaped Liquid Crystals

  • Choi, S.;Huang, Y.M.;Jakli, A.;Lim, T.K.;Lee, C.K.;Shin, S.T.
    • 한국정보디스플레이학회:학술대회논문집
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    • 한국정보디스플레이학회 2003년도 International Meeting on Information Display
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    • pp.595-599
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    • 2003
  • We have studied the phase transition to look for molecular structure by using several different techniques for new banana-shaped liquid crystals shown in Fig. 1. Based on the similarities to recently observed fluro-contaning materials (switching involves layer structure rearrangement, increasing threshold with increasing temperature) for HC sample (where x is H), we assume that the phase C has a triclinic symmetry corresponding to the double tilted $smC_G$ Phase. The observation that the polarization peak appears at lower field ($E_o{\sim}15V/{\mu}m$) than the amplitude of the threshold ($E_{th}$) can be explained assuming a field induced $SmC_G$ - SmCP (or SmAP) transition at $E_{th}$

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발암물질인 아플라톡신 $G_1$의 탈독소화 반응에 관한 연구 (The Study on the Detoxification of Aflatoxin $G_1$ in Cancer Compound)

  • 장향동;김래현;이수경
    • 한국안전학회지
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    • 제11권4호
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    • pp.84-89
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    • 1996
  • The Oxidation of aflatoxin $G_1$ ($AFG_1$) with ozone in chloroform solvent gave the stable ozonide into ozonization of the double bond in the terminal furan ring, and this reaction have been carried out for 3hr at -78. 5$^{\circ}C$. The chloroform solvent was removed in a stream of nitrogen and the residue was separated by elution chromatography(EC). The structure of this compound have been identified by using MS, $^1H-NMR$, $^l3C-NMR$ and I. R spectroscopy, respectively. This compound was formed the normal stable AFG$_1$-ozonide into spontaneous rearrangement after unstable ozonide according to sigmatropic rearrange ment dependent upon cyclo addition by ozone.

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DNA 이중나선파손의 수복 과정과 이와 연관된 두경부암 발생 유전자 (PATHWAYS AND GENES OF DNA DOUBLE-STRAND BREAK REPAIR ASSOCIATED WITH HEAD AND NECK CANCER)

  • 오정환;이덕원;류동목
    • Journal of the Korean Association of Oral and Maxillofacial Surgeons
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    • 제35권1호
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    • pp.1-6
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    • 2009
  • DNA double-strand breaks (DSBs) occur commonly in the all living and in cycling cells. They constitute one of the most severe form of DNA damage, because they affect both strand of DNA. DSBs result in cell death or a genetic alterations including deletion, loss of heterozygosity, translocation, and chromosome loss. DSBs arise from endogenous sources like metabolic products and reactive oxygen, and also exogenous factors like ionizing radiation. Defective DNA DSBs can lead to toxicity and large scale sequence rearrangement that can cause cancer and promote premature aging. There are two major pathways for their repair: homologous recombination(HR) and non-homologous end-joining(NHEJ). The HR pathway is a known "error-free" repair mechanism, in which a homologous sister chromatid serves as a template. NHEJ, on the other hand, is a "error-prone" pathway, in which the two termini of the broken DNA molecule are used to form compatible ends that are directly ligated. This review aims to provide a fundamental understanding of how HR and NHEJ pathways operate, cause genome instability, and what kind of genes during the pathways are associated with head and neck cancer.

결함 이중 Perovskite La1/3TaO3 단결정의 유전 및 전도특성 (Dielectric and conductivity properties of defect double Perovskite La1/3TaO3 single crystal)

  • 손정호
    • 한국결정성장학회지
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    • 제30권6호
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    • pp.215-219
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    • 2020
  • A-자리 결함 이중 Perovskite La1/3TaO3 단결정 시편을 제작하여 10~800 K 온도범위에서 유전특성을 조사하였다. 500 K 이하에서는 상유전성 거동이 나타났으며, 550 K 이상에서 유전이상과 유전상수의 열이력(thermal hysterisis)가 나타났다. 교류전도도 측정에 의한 활성화 에너지는 560 K 이하 영역에서 1.83 eV로 가장 크며, 560~690 K 영역에서 0.35 eV, 690 K 이상인 고온 영역에서 0.28 eV로 나타났다 이러한 결과로부터 500 K 이하 영역에서는 La3+-이온과 공공-자리가 무질서하게 배열하여 상유전상을 유지하며, 가장 높은 활성화 에너지를 나타낸 560 K 부근 영역에서는 La3+-이온이 공공-자리로의 전도 혹은 점프에 의한 재배열에 기인하여 유전이상이 나타난 것으로 판단된다.

DNA-dependent Protein Kinase Mediates V(D)J Recombination via RAG2 Phosphorylation

  • Hah, Young-Sool;Lee, Jung-Hwa;Kim, Deok-Ryong
    • BMB Reports
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    • 제40권3호
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    • pp.432-438
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    • 2007
  • V(D)J recombination, a site-specific gene rearrangement process occurring during the lymphocyte development, begins with DNA double strand breaks by two recombination activating gene products (RAG1/2) and finishes with the repair process by several proteins including DNA-dependent protein kinase (DNA-PK). In this report, we found that RAG2 was specifically phosphorylated by DNA-PK at the $365^{th}$ serine residue, and this phosphorylated RAG2 affected the V(D)J recombination activity in cells in the GFP expression-based assay. While the V(D)J recombination activity between wild-type RAG2 and mutant S365A RAG2 in the assay using a signal joint substrate was undistinguishable in DNA-PK deficient cells (M059J), the activity with wild-type RAG2 was largely increased in DNA-PK proficient cells (M059K) in comparison with mutant RAG2, suggesting that RAG2 phosphorylation by DNA-PK plays a crucial role in the signal joint formation during V(D)J recombination.

Transformation and Mutagenesis of the Nematode-trapping Fungus Monacrosporium sphaeroides by Restriction Enzyme-mediated Integration (REMI)

  • Xu Jin;Mo Ming-He;Zhou Wei;Huang Xiao-Wei;Zhang Ke-Qin
    • Journal of Microbiology
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    • 제43권5호
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    • pp.417-423
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    • 2005
  • In this study, the nematode-trapping fungus, Monacrosporium sphaeroides, was transformed with a plasmid harboring the hygromycin B phosphotransferase gene, via restriction enzyme-mediated integration (REMI). Frequencies of up to 94 transformants ${\mu}g^{-1}$ per linearized plasmid DNA were obtained by optimizing the PEG concentration, as well as the category and quantity of the added restriction enzyme. $90\%$ of the transformants were determined to be stable for drug resistance when 20 randomly selected transformants were tested. Southern analyses revealed that the transforming DNA was integrated into the M. sphaeroides genome either with or without rearrangement. Five mitotic stable mutant strains were obtained using this approach, all of which had been altered with regard to sporulation capacity and pathogenicity toward nematodes. Southern blot analyses of the five mutants revealed that foreign plasmid DNA had integrated into the genome. Three of the mutants, Tms2316, Tms3583 and Tms1536, exhibited integration at a single location, whereas the remaining two, Tms32 and Tms1913, manifested integration at double or multiple locations. Our results suggest that the transformation of M. sphaeroides via REMI will facilitate insertional mutagenesis, the functional analysis of a variety of genes, and the tagging or cloning of genes of interest.

내포지역 읍성 원형과 읍치경관의 근대적 변형 -읍성취락의 사회공간적 재편과 근대화 - (Original Form of Castle Town and Modern Transformation of Eupchi(county seat) Landscape in Naepo Area, Korea)

  • 전종한
    • 대한지리학회지
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    • 제39권3호
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    • pp.321-343
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    • 2004
  • 이 글은 내포지역의 읍성 연구를 사례로 음성취락의 사회공간적 재편과 근대화에 접근한 것이다. 한반도의 서 남해안 일대는 방어상의 이유와 넓은 하안 충적평야, 해안 저지대의 농경제적 가치 때문에 다른 지역에 비해 우선적으로 읍성 축조가 이루어졌다. 내포지역은 그러한 대표적인 공간이다. 내포지역의 읍치경관 원형은 방위와 길흉의 연관성에 대한 전통적 관념이나 권력의 자연화 전략을 반영하며 일정한 원칙 하에 조형되면서도 국지적 단위의 시 공간성을 반영하고 있었다. 조선시대동안 초기 읍성이 지닌 공간성은 군사적 공간으로부터 점차 정치 행정적 중심지로 변화하여 갔다. 일제강점기가 되면, 전통시기의 읍치가 통치 행정 치소로서의 기능을 넘어 자본 축적의 중심, 경제와 교육의 거점, 촌락 공간의 중심지로 변모하기 시작한다. 내포지역에는 개항지가 설치되지 않았음에도 불구하고 일본인의 읍성안 토지 장악은 주요 개항지의 그것보다 훨씬 더 전면적이었다. 더욱이 읍성 공간을 천한 공간으로 여기던 전통적 인식은 조선인들의 신속한 읍성 이탈을 부추긴 반면, 읍성 공간이 갖는 정치, 경제, 사회적 중심성과 서비스업에 종사함으로써 얻은 풍부한 자본력은 일본인들의 광범위한 토지 점유를 가속화한 흡입 요인으로 작용하였다. 이미 1920년대부터 구읍성 일대는 통치 기능 외에 금융, 상업, 교육, 교통 기능의 중심지이자 새로운 도시 문제의 발원지로서 이전과는 다른 새로운 공간성을 갖게 된다. 이와 같이 일제강점기 동안의 경관 변형은 기존 거주민(조선인)에 의해서가 아닌 대체 거주민(일본인)을 통해 주도되었고, 결과적으로 그것은 형태와 기능상의 변혁이었음은 물론이고 매우 급격한 사회공간적 재편이었다.

개질된 NR/IR 블랜드의 가황 반응에서 나타나는 전기적 특성 안정화의 주파수 의존성 (Frequency Dependency of Electrical Property Stabilization during Vulcanization of Modified NR/IR Blends)

  • 안원술
    • Elastomers and Composites
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    • 제39권3호
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    • pp.179-185
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    • 2004
  • 이소프렌 고무(IR)와 천연고무(NR)가 중량비로 25/75로 혼합된 베이스 고무수지에 카본블랙(CB) 및 가교조제가 섞인 고무복합계의 가황반응 도중의 전기적 성질 변화를 in-situ로 측정하였다. 130, 140, 150, 및 $160^{\circ}C$로 정해진 각각의 가황 반응 온도에서 반응시작 전과 반응도 중의 각각 정해진 시간에서 1Hz에서 10kHz까지의 인가주파수 변화에 따른 체적고유저항 값(P)의 변화를 측정하였다. 가황 반응이 시작되기 전의 초기 P값은 낮은 인가주파수에서는 약 $9.0{\times}10^7\;{\Omega}-cm$의 높은 값으로부터 인가주파수가 높아짐에 따라 급격히 떨어지는 현상을 보이다가 점점 안정화되어 약 $1.0{\times}10^7\;{\Omega}-cm$으로 감쇠되어가는 이중 안정화 패턴의 형태를 보였다. 그러나 초기 P 값의 반응온도에 따른 변화는 온도가 낮아짐에 따라 반응 전보다 반응 후에 1/3 이하로 현저히 낮아지는 현상이 관찰되었고 이와 함께 안정화에 걸리는 주파수 의존도 역시 상대적으로 적어지는 것이 관찰되었다. 관찰된 현상과 해석으로부터 전기적 특성 안정화에 따르는 주파수 의존성은 도체인 전극과 샘플의 계면에서 일어나는 전하의 충-방전 현상과 가황에 따른 샘플 내의 구조변화와 CB의 재배열 등에 의한 전기전도성의 변화로 해석되었다.

Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 한국균학회 2016년도 춘계학술대회 및 임시총회
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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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