• Title/Summary/Keyword: Cyclic ketone

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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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    • v.55 no.1
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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.

Electrochemical Characteristics of all solid supercapacitor based on DAAQ(1,5-diaminoanthraquinone) and SPEEK(sulfonated polyether ether ketone) (DAAQ와 SPEEK를 이용한 전고상 슈퍼커패시터의 전기화학적 특성)

  • Kim, Jin-Yong;Kim, Hong-Il;Kim, Han-Joo;Park, Soo-Gil
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2005.07a
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    • pp.371-372
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    • 2005
  • Supercapacitors are promising devices for delivering high power density. Digital communications, electric vehicles and other devices that require electrical energy at high power levels in relatively short pulses have prompted considerable research on supercapacitors. In recent years, solid electrolytes have been investigated for supercapacitors. Solid electrolytes are advantageous over liquid electrolytes in respect of easy handling and reliability without electrolyte leakage. In this preliminary study, an electrochemical supercapacitor in all solid configuration has been fabricated using CNF-DAAQ and poly-vinylidenefluoride(PVdF). A new type of Supercapacitor was constructed by using carbon nanofibers(CNFs) and DAAQ(l,5-diaminoanthraquinone) monomer. DAAQ was deposited on the carbon nanofibers by chemical polymerization with $(NH_4)_2S_2O_8$ as oxidant in the 0.1M $H_2SO_4$. Dried SPEEK powder was mixed with N-methyl pyrrolidone to make 10 wt.% solution in an ultrasonic bath, the slurry was cast over a glass substrate heated to $70^{\circ}C$ for solvent evaporation. And then we used solid electrolyte of SPEEK. The unit cell consist of DAAQ-CNF/electrolyte/Pt. From the analysis, it is clear that surface of carbon nanofibers was quite uniformly coated with DAAQ. The performance characteristics of the supercapacitors have been evaluated using Cyclic Voltammetry.

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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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Characteristics of Non-biodegradable Substances in Landfill Leachate (매립장 침출수의 생물학적 난분해성물질 특성 규명)

  • Lim, Bong-Su;Park, Hye-Sook;Kim, Heung Rag
    • Journal of Korean Society on Water Environment
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    • v.21 no.5
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    • pp.484-489
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    • 2005
  • In order to determine the removal rate of non-biodegradable substances and the change of their structural properties, this study was carried out by an ozone-treatment experiment on leachate collected from the landfill area of D City in Chung chung nam-do and examined the change of the chemical properties of non-biodegradable substances. The main elements of non-biodegradable substances in landfill leachate were benzene, toluene, trichloroethane, trichloroethylene, xylene, etc. and the concentration of toluene was 15.7 mg/L on the average, benzene 7.2 mg/L, trichloroethane 1.1 mg/L, trichloroethylene 0.75 mg/L and xylene 0.5 mg/L. When leachate was treated with ozone for 10 min, 30 min and 60 min, UV absorbance was reduced with the increase of reaction time, and the reduction rate was 38.6% at 60 min. TOC was removed by 13.2% at 60 min. The low reduction rate of TOC may be because TOC reacts indirectly with OH radical produced from reaction with ozone while UV absorbance usually relies on direct reaction between organic matters and ozone molecules. Color was removed by up to 97%, which suggests that ozonation is highly effective in removing coloring elements in leachate. Sixteen kinds of non-biodegradable compounds were found in the leachate and most of them had the characteristic of aromatic hydrocarbon. Among them dibutyl phthalate was identical with a substance included in the list of US EPA, which is classified as a mutagen that may cause the mutation of genes and disorders in chromosomes. In addition, 2,5-Cyclohexadiene-1,4-dione, 1,2-Benzenedicarboxylic acid and butyl octyl ester were found to be similar to substances listed by USEPA. According to the result of analyzing structural changes before and after ozonation using GC-MS, cyclic compounds and aromatic compounds were observed in the original water and aliphatic compounds were newly observed after ozonation. In addition, through ozonation, humic substances of high molecular weight were oxidized and decomposed and produced low-molecular compounds such as aldehyde, ketone and carboxyl acid and highly biodegradable aliphatic carbon, which suggests the bio-degradability of non-biodegradable substances.

Prediction of Retention Indices of Various Compounds in Gas-Liquid Chromatography (기체-액체 크로마토그래피에서 화합물의 머무름 지표의 예측에 관한 연구)

  • Cha, Gi Won;Lee, Deok Jae
    • Journal of the Korean Chemical Society
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    • v.38 no.2
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    • pp.108-121
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    • 1994
  • The retention indices of branched-chain alkane, benzene ring, alcohol, amine, ketone, aldehyde and cyclic compounds were measured at 150, 180 and $210^{\circ}C$ on OV-1701 and OV-1 capillary columns. The group retention factors (GRF) of the substituents and the st` ructure retention factors (SRF) of the molecular structure change are derived from the retention indices of reference compounds and series of homologues. The $GRF_f$ equation of `f'th substituent is $GRF_f\;=\;I_{obs}-(100Z + \sum\limits_{i{\neq}f}GRF_i$ + {\sum}$SRF_i$)and the SRFf equation of `f'th molecular structure group is $SRF_f\;=\;I_{obs}-(100Z + {\sum}GRFi + \sum\limits_{i{\neq}f}SRF_i$). The predicted retention indices for those compound were in agreement, within the error of $\pm2$ and $\pm3%$, with the observed values that were obtained using the OV-1701 and OV-1 capillary column, respectively. The $\Delta$ xi of the substituents and $\Delta$ yi of the molecular structure change according to temperature change are derived from the $\Delta'/^{\circ}C$ of reference compounds and series of homologues. The $\Delta$ xi equation of the `f'th substituent is ${\Delta}x_f = {$\Delta}'/^{\circ}C+ \sum\limits_{i{\neq}f}\Delta$ xi + {\sum}{\Delta}yi\;and\;{\Delta}yi$ equation of the `f'th molecular structure group is ${\Delta}y_f$ = {\Delta}'/^{\circ}C+{\sum}{\Delta}xi +\sum\limits_{i{\neq}f}{\Delta}yi$. The predicted $\Delta'/^{\circ}C$ for these compounds were in agreement, within the error of ${\pm}18%$ and 17%, with the observed values that were obtained using the OV-1701 and OV-1 capillary column, respectively.

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Volatile Flavor Components in Chinese Quince Fruits, Chaenomeles sinensis koehne (모과의 휘발성 Flavor 성분에 관한 연구)

  • Chung, Tae-Young;Cho, Dae-Sun;Song, Jae-Chul
    • Korean Journal of Food Science and Technology
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    • v.20 no.2
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    • pp.176-187
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    • 1988
  • Volatile flavor components in the Chinese quince fruits were trapped by simultaneous steam distillation-extraction method, and these were fractionated into the neutral, the basic, the phenolic and the acidic fraction. In the identification of carboxylic acids, the acidic fraction was methylated with diazomethane. Volatile flavor components in these fractions were analyzed by the high-resolution GC and GC-MS equipped with a fused silica capillary column. The total of one hundred and forty-five compounds from the steam volatile concentrate of the Chinese quince fruits were identified: they were 3 aliphatic hydrocarbons, 1 cyclic hydrocarbon, 4 aromatic hydrocarbons, 9 terpene hydrocarbons, 17 alcohols, 3 terpene alcohols, 6 phenols, 21 aldehydes, 7 ketones, 28 esters, 27 acids, 3 furans, 2 thiazoles, 2 acetals, 3 lactones and 9 miscellaneous ones. The greater part of the components except for carboxylic acids were identified from the neutral fraction. The neutral fraction gave a much higher yield than others and was assumed to be indispensable for the reproduction of the aroma of the Chinese quince fruits in a sensory evaluation. According to the results of the GC-sniff evaluation, 1-hexanal, cis-3-hexenal, trans-2-hexenal, 2-methyl-2-hepten-6-one, 1-hexanol, cis-3-hexenol, trans, trans-2, 4-hexadienal and trans-2-hexenol were considered to be the key compounds of grassy odor. On the other hand, esters seemed to be the main constituents of a fruity aroma in the Chinese quince fruits.

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