• 제목/요약/키워드: Aldehyde or ketone

검색결과 18건 처리시간 0.02초

유기초음파화학·초음파가 $BaMnO_4$$KMnO_4-CuSO_4{\cdot}5H_2O$를 이용한 알코올의 산화반응에 미치는 영향 (The Effects of Sonic Waves on the Oxidation Reaction of Alcohols Using $BaMnO_4\;and\;KMnO_4-CuSO_4{\cdot}5H_2O$)

  • 유의상;신대현;한병희
    • 대한화학회지
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    • 제31권4호
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    • pp.359-363
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    • 1987
  • 초음파(50KHz)가 상온 상압하에서 $BaMnO_4$$KMnO_4-CuSO_4{\cdot}5H_2O$를 이용한 1차, 벤질, 2차 알코올의 알데히드 및 케톤 생성반응을 가속 완결시켰으며 고속교반이나 가열 환류반응보다 높은 산화율을 주었다.

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Inhibition of Proinflammatory Cytokine Generation in Lung Inflammation by the Leaves of Perilla frutescens and Its Constituents

  • Lim, Hun Jai;Woo, Kyeong Wan;Lee, Kang Ro;Lee, Sang Kook;Kim, Hyun Pyo
    • Biomolecules & Therapeutics
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    • 제22권1호
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    • pp.62-67
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    • 2014
  • This study was designed to find some potential natural products and/or constituents inhibiting proinflammatory cytokine generation in lung inflammation, since cytokines such as tumor necrosis factor-${\alpha}$ (TNF-${\alpha}$) and interleukin-6 (IL-6) are pivotal for provoking airway inflammation. In our preliminary screening procedure, the 70% ethanol extract of the leaves of Perilla frutescens (PFE) was found to clearly inhibit TNF-${\alpha}$ production in the lung at 100 mg/kg, after intranasal lipopolysaccharide treatment of mice. Based on this result, ten constituents including phenylpropanoids (allyltetramethoxybenzene, caffeic acid, dillapiole, elemicin, myristicin, nothoapiole, rosmarinic acid methyl ester, rosmarinic acid) and monoterpenes (perilla aldehyde and perilla ketone) were successfully isolated from the extract. Among them, elemicin and myristicin were found for the first time to concentration-dependently inhibit IL-$1{\beta}$-treated IL-6 production from lung alveolar epithelial cells (A549) at concentrations of $10-100{\mu}M$. These findings suggest that the phenylpropanoids including elemicin and myristicin have the potential to be new inhibitory agents against lung inflammation and they may contribute, at least in part, to the inhibitory activity of PFE on the lung inflammatory response.

Photoaddition Reactions of Silyl Ketene Acetals with Aromatic Carbonyl Compounds: A New Procedure for β-Hydroxyester Synthesis

  • Yoon, Ung-Chan;Kim, Moon-Jung;Moon, Jae-Joon;Oh, Sun-Wha;Kim, Hyun-Jin;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • 제23권9호
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    • pp.1218-1242
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    • 2002
  • Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.

Characterization on the Thermal Oxidation of Raw Natural Rubber Thin Film using Image and FT-IR Analysis

  • Kim, Ik-Sik;Cho, Hwanjeong;Sohn, Kyung-Suk;Choi, Hwa-Soon;Kim, Sung-Uk;Kim, Sinkon
    • Elastomers and Composites
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    • 제55권1호
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    • pp.51-58
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    • 2020
  • In this study, the thermal oxidation of raw natural rubber (NR) was investigated under controlled conditions by optical image and fourier transform infrared (FT-IR) analysis. The thermal oxidation was performed on a transparent thin film of raw NR coated on a KBr window in a dark chamber at 80℃ under low humidity conditions to completely exclude moisture and restrict light oxidation. Images of the thin film of raw NR were obtained before and after thermal oxidation. FT-IR absorption spectra were measured in the transmission mode at different thermal exposure times. The thermal oxidation of NR was examined by the changes in the absorption peaks at 3449, 1736, 1447, 1377, 1242, 1072, and 833 cm-1, which corresponded to a hydroxyl group (-OH), a carbonyl group (-C=O) from an aldehyde and a ketone, a methylene group (-CH2-), a methyl group (-CH3), a carbon-oxygen single bond (-C-O) from an epoxide, a carbon-oxygen bond (-C-O) from an ether, an alcohol, a peroxide, or a cyclic peroxide, and a cis-methine group (cis-CCH3=CH-), respectively. In the initial stage of thermal oxidation, two different types of free radicals were produced quickly and randomly by the homolytic cleavage of a double bond and allylic hydrogen abstraction. Aldehydes and ketones were formed from chain scissions of the double bonds and alcohols were produced from allylic hydrogen abstraction at the methylene or methyl groups. Two reactions seemed to proceed competitively with each other. At a later stage, oxidative crosslinks seemed to dominate through the combination of free radicals such as an allyl radical (CH=CHCH2·), alkoxy radical (RO·), and peroxy radical (ROO·) and the reaction of a hydroperoxide (-ROOH) with a double bond. The image obtained after thermal oxidation showed hardening without cracks. Based on these observations, a plausible two-step mechanism was suggested for chain hardening caused by the thermal oxidation.

식물성유를 첨가한 참기름 혼합유의 산화 안정성과 향기 성분 (Oxidative Stability and Flavor Compounds of Sesame Oils Blended with Vegetable Oils)

  • 주광지;김진주
    • 한국식품과학회지
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    • 제34권6호
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    • pp.984-991
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    • 2002
  • 순수 참기름과 채종유, 옥수수유, 대두유를 10%, 30%, 50%씩 첨가한 참기름 혼합유를 제조하여 $60^{\circ}C$의 incubator에서 8주간 저장하면서 혼합유의 산화 안정성과 향기 성분의 변화 그리고 관능 검사를 실시하였다. 모든 시료의 POV는 저장 6주에 최고값을 나타내었으며 채종유와 옥수수유 10%, 30%, 50%씩 그리고 대두유 10%를 첨가한 참기름 혼합유는 순수 참기름 보다 저장 기간 동안 과산화물 생성이 억제되어지는 효과가 있음을 나타났다. 산패 유도기간도 채종유와 옥수수유 10%, 30%, 50%씩 그리도 대두유 10%를 첨가한 참기름 혼합유에서는 대조구인 참기름 보다 그 기간이 더 연장되었다. 상대적 항산화 효과(Relative Antioxidant Effectiveness: RAE)는 10% 채종유를 첨가한 혼합유가 순수한 참기름 보다 6배의 효과가 있었다. 그리고 산가는 모든 혼합유 시료가 참기름 보다 더 낮은 결과를 나타내었으나 단일 식물성유 보다는 그 수치가 높았다. 혼합유의 향기 성분은 참기름에서 확인된 참기름의 독특한 방향을 나타내는 pyrazine류가 참기름 혼합유에서도 확인되었으며 저장 기간이 연장됨에 따라 모든 시료에서 산패의 지표가 되는 aldehyde, ketone, acid등의 carbonyl 화합물의 함량이 증가되었다. 관능평가에서는 10%의 채종유, 옥수수유, 대두유를 첨가한 참기름 혼합유 시료는 대조구인 순수 참기름과 유의적인 차이가 없는 것으로 밝혀졌다. 이와 같은 결과로 미루어 볼 때 참기름과 식물성유의 혼합은 매우 바람직하며 단일 식물성유보다 산화 안정성이 크게 증대되었을 뿐 아니라 관능적인 품질에도 차이가 없으므로 경제적인 면에서도 매우 유용할 것으로 생각된다.

느타리버섯의 향기(香氣) 성분(成分)에 관한 연구(硏究) (Studies on the Volatile Aroma Components of Pleurotus ostreatus)

  • 홍재식;이지열;김영회;김명곤;정기태;이극로
    • 한국균학회지
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    • 제14권1호
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    • pp.31-36
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    • 1986
  • Pleurotus ostreatus로 부터 휘발성 향기 성분을 분리한 다음 GC 및 GC/MS를 이용하여 성분을 화인하고, 마쇄 후 시간 경과에 따른 휘발성 향기 성분 및 지방산 변화를 조사한 결과를 요약하면 다음과 같다. 1. 분리된 향기 성분은 버섯 고유의 향(香)을 지니고 있었고 수율(收率)은 123 ppm이었다. 2. 분리 확인된 27종의 성분 중 비교적 많이 함유된 성분은 약 67%의 1-octen-3-ol을 포함하여 3-octanone, 3-octanol, 2-octenol 및 2, 4-decadienal이었으며 $C_8$화합물이 전체량의 약 80%를 차지하였다. 3. 버섯을 마쇄 후 시간 경과에 따라 n-hexanol, 3-octanol, 1-octen-3-ol 등의 alcohol 류는 증가하였으나 n-hexanal, 1-octen-3-one 등의 aldehyde 및 ketone 류는 감소하였으며 전체 지방산에 대한 불포화 지방산의 비율도 감소하는 경향이었다. 4. 버섯에 linoleic acid와 linolenic acid를 각각 첨가하여 마쇄했을 때 향기 성분 중에서 $C_6{\sim}C_{10}$화합물이 차지하는 비율도 증가하였는데 linolenic acid보다는 linoleic acid를 첨가했을 때 더 많이 증가하였다.

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동충하초 균사체로 발효시킨 백련잎차의 품질특성 (Quality Properties of White Lotus Leaf Fermented by Mycelial Paecilomyces japonica)

  • 김종숙;왕수빈;강성구;조영숙;박석규
    • 한국식품영양과학회지
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    • 제38권5호
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    • pp.594-600
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    • 2009
  • 눈꽃 동충하초 균사체를 이용한 백련잎 발효차와 비발효차의 열수와 에탄올 추출물에 대한 품질특성을 평가하기 위하여, 추출수율, 갈변도, 유리당, 유기산, 유리아미노산, 무기질의 함량을 조사하였고, 또한 수증기 증류법으로 백련잎차의 휘발성 성분을 동정하였다. 추출수율은 발효 및 비발효차 모두 열수 추출물이 에탄올 추출물보다 높았으며, 백련잎 발효차의 열수 추출용매에서 유의적으로 가장 높은 26.55%를 나타내었고(p<0.05), 갈변도는 흡광도로서 열수 추출물이 에탄올 추출물에 비하여 1.6배 이상으로 높은 값을 나타내었다. 총 유리당은 백련잎 발효차의 열수 추출물에서 43.4%로 가장 높은 함량을 나타내었으며, glucose 함량은 발효차의 열수 및 에탄올 추출물에서 각각 5.6배, 3.7배 유의적으로 증가되었다(p<0.05). 총 유기산은 $861.9{\sim}4,704.8\;mg%$ 범위로서 발효 백련잎차의 에탄올 추출물이 가장 높았으며, 그 중에는 succinic acid가 에탄올 추출물에서 유의적으로 가장 높았고(p<0.05), 백련잎 발효차는 비발효차의 경우와는 달리 acetic acid, malic acid, tartaric acid가 확인되었다. 총 유리아미노산은 건물 당 $346.4{\sim}1,480.8\;mg%$ 범위 로서, 비발효 백련잎차의 열수 추출물이 가장 높은 함량을 나타내었다(p<0.05). 백련잎 발효차는 비발효차에 비하여 총 유리아미노산 함량이 감소하는 경향이었으며, 용매별로는 열수 추출물이 에탄올 추출물에 비하여 2.9배 유의적으로 높았고(p<0.05). 총 무기질은 비발효 및 발효차의 열수 추출물이 에탄올 추출물에 비하여 각각 2.1배, 1.7배 높았으며, 그 중에서는 발효차의 열수 추출물이 유의적으로 가장 높은 함량을 나타내었다(p<0.05). 휘발성 성분은 aldehyde류 11종, alcohol류 14종, ketone류 11종, hydrocarbone류 11종, acid류 12종으로 총 59개를 동정할 수가 있었으며, 특히 비발 효차는 alcohol류, 발효차는 aldehyde류와 ketone류에서 서로 다른 휘발성분들이 확인되었다.

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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