• Title/Summary/Keyword: C-N bond formation

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Kinetics on the Reaction of 6-Chloroquinoline and p-Substituted Benzoylcholrides under High Pressures (고압하에서의 6-클로로퀴놀린과 p-치환 염화벤조일류의 반응에 관한 속도론적 연구)

  • Kim, Eung-Ryeol;Im, Jong-Wan;Kim, Se-Gyeong;Go, Yeong-Sin
    • Journal of the Korean Chemical Society
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    • v.46 no.3
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    • pp.187-193
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    • 2002
  • The reaction rates of substituted 6-chloroquinoline with p-substituted benzoyichorides $p-CH_3,$ p-H, $p-NO_2$ have been measured by conductometry in acetonitrile, and the constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ${\Delta}V^{\neq}$, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$, ${\Delta}G^{\neq}$) and the pressure dependence of Hammett p values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substiuents in substrate $(p-NO_2)$ with 6-chloroqinoline. When the activation volume and the activation entropy are all negative And the Hammett p values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical $S_N2$ reaction mechanism and "associative $S_N2$" in bond formation favored with increasing pressures.

Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures (압력변화에 따른 퀴놀린 유도체와 p-치환 염화벤조일류의 속도론적 연구)

  • Jong-Wan Lim;Se-Kyong Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.206-212
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    • 2003
  • The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

Poling Field Effect on Absorption and Luminescence of Disperse Red-19 and TiO2 Composites

  • Kim, Byoung-Ju;Hwang, Un-Jei;Jo, Dong-Hyun;Lim, Sae-Han;Kang, Kwang-Sun
    • Current Photovoltaic Research
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    • v.3 no.1
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    • pp.5-9
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    • 2015
  • Absorption and luminescence characteristics of disperse red-19 (DR-19) and $TiO_2$ composite have been investigated with various poling electric field strengths. Two step synthetic processes were employed to employ the DR-19 to the $TiO_2$ sol-gel. Firstly, urethane bond formation between DR-19 (-OH) and 3-isocyanatopropyl triethoxysilane (ICPTES, -N=C=O) performed (ICPDR) prior incorporation to the $TiO_2$ sol-gel. Secondary, the hydrolysis of the ethoxy group from the ICPTES and condensation reaction between silanol groups from ICPTES and $TiO_2$ sol-gel were performed. The ICPDR and $TiO_2$ sol-gel ($DRTiO_2$) were mixed and stirred for several days. The composite was coated to the ITO coated glass substrate. Corona poling were performed before drying the composite with various electric field strengths. The absorption intensity decreased with the increase of the poling field strength, which resulted in the increase of poling efficiency. The photoluminescence also decreased as the poling field strength increased. There is long luminescence tail for the poled $DRTiO_2$ film compared with unpoled $DRTiO_2$ film. The luminescence long tail indicates that the self-trapped excitons and polarons were generated when the $DRTiO_2$ film was poled with electric field.

Control of Graphene's Electrical Properties by Chemical Doping Methods

  • Lee, Seung-Hwan;Choi, Min-Sup;La, Chang-Ho;Yoo, Won-Jong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.119-119
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    • 2011
  • This study examined the synthesis of large area graphene and the change of its characteristics depending on the ratio of CH4/H2 by using the thermal CVD methods and performed the experiments to control the electron-hole conduction and Dirac-point of graphene by using chemical doping methods. Firstly, with regard to the characteristics of the large area graphene depending on the ratio of CH4/H2, hydrophobic characteristics of the graphene changed to hydrophilic characteristics as the ratio of CH4/H2 reduces. The angle of contact also increased to 78$^{\circ}$ from 58$^{\circ}$. According to the results of Raman spectroscopy showing the degree of defect, the ratio of I(D)/I(G) increases to 0.42% from 0.25% and the surface resistance also increased to 950 ${\Omega}$ from 750 ${\Omega}$/sq. As for the graphene synthesis at the high temperature of 1,000$^{\circ}$ by using CH4/H2 in a Cu-Foil, the possibility of graphene formation was determined as a function of the ratio of H2 included in the fixed quantity of CH4 as per specifications of every equipment. It was observed that the excessive amount of H2 prevented graphene from forming, as extra H-atoms and molecules activated the reaction to C-bond of graphene. Secondly, in the experiment for the electron-hole conduction and the Dirac-point of graphene using the chemical doping method, the shift of Dirac-point and the change in the electron-hole conduction were observed for both the N-type (PEI) and the P-type (Diazonium) dopings. The ID-VG results show that, for the N-type (PEI) doped graphene, Dirac-point shifted to the left (-voltage direction) by 90V at an hour and by 130 V at 2 hours respectively, compared to the pristine graphene. Carrier mobility was also reduced by 1,600 cm2/Vs (1 hour) and 1,100 cm2/Vs (2 hours), compared to the maximum hole mobility of the pristine graphene.

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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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Study on the soluble exoression of recombinant human eoidermal growth factor using various fusion oartners in Escherichia coli (재조합 대장균에서 다양한 융합 파트너를 이용한 인간 상피세포성장인자의 발현 연구)

  • Kim, Byung-Lip;Baek, Jung-Eun;Kim, Chun-Sug;Lee, Hyeok-Weon;Ahn, Jung-Oh;Lee, Hong-Weon;Jung, Joon-Ki;Lee, Eun-Gyo;Kim, In-Ho
    • KSBB Journal
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    • v.23 no.3
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    • pp.205-212
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    • 2008
  • The efficient soluble expression of human epidermal growth factor (hEGF) was achieved by using functional fusion partners in cytoplasm and periplasm of Escherichia coli (E. coli). hEGF was over-expressed in inactive inclusion body form in cytoplasm of E. coli due to improper disulfide bond formation and hydrophobic interaction, yielding about 5.9 mg/L in flask culture. Six functional fusion partners were introduced by linking to N-terminal part of hEGF gene for the high-level expression of soluble and active hEGF in cytoplasm and peri plasm region. Three fusion partners for cytoplasmic expression such as acidic tail of synuclein (ATS), thioredoxin (Trx) and lipase, and three fusion partners for periplasmic expression such as periplasmic cystein oxidoreductases (DsbA and DsbC) and maltose binding protein (MBP) were investigated. hEGF fused with ATS and DsbA showed over 90% of solubility in cytoplasm and periplasm, respectively. Especially DsbA was found to be an efficient fusion partner for soluble and high-level expression of hEGF, yielding about 18.1 mg/L and three-fold higher level compared to that of insoluble non-fusion hEGF in cytoplasm. Thus, heterologous proteins containing complex disulfide bond and many hydrophobic amino acids can effectively be produced as an active form in E. coli by introducing a suitable peptide or protein.

유청단백질로 만들어진 식품포장재에 관한 연구

  • Kim, Seong-Ju
    • 한국유가공학회:학술대회논문집
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    • 2002.04a
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    • pp.59-60
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    • 2002
  • Edible films such as wax coatings, sugar and chocolate covers, and sausage casings, have been used in food applications for years$^{(1)}$ However, interest in edible films and biodegradable polymers has been renewed due to concerns about the environment, a need to reduce the quantity of disposable packaging, and demand by the consumer for higher quality food products. Edible films can function as secondary packaging materials to enhance food quality and reduce the amount of traditional packaging needed. For example, edible films can serve to enhance food quality by acting as moisture and gas barriers, thus, providing protection to a food product after the primary packaging is opened. Edible films are not meant to replace synthetic packaging materials; instead, they provide the potential as food packagings where traditional synthetic or biodegradable plastics cannot function. For instance, edible films can be used as convenient soluble pouches containing single-servings for products such as instant noodles and soup/seasoning combination. In the food industry, they can be used as ingredient delivery systems for delivering pre-measured ingredients during processing. Edible films also can provide the food processors with a variety of new opportunities for product development and processing. Depends on materials of edible films, they also can be sources of nutritional supplements. Especially, whey proteins have excellent amino acid balance while some edible films resources lack adequate amount of certain amino acids, for example, soy protein is low in methionine and wheat flour is low in lysine$^{(2)}$. Whey proteins have a surplus of the essential amino acid lysine, threonine, methionine and isoleucine. Thus, the idea of using whey protein-based films to individually pack cereal products, which often deficient in these amino acids, become very attractive$^{(3)}$. Whey is a by-product of cheese manufacturing and much of annual production is not utilized$^{(4)}$. Development of edible films from whey protein is one of the ways to recover whey from dairy industry waste. Whey proteins as raw materials of film production can be obtained at inexpensive cost. I hypothesize that it is possible to make whey protein-based edible films with improved moisture barrier properties without significantly altering other properties by producing whey protein/lipid emulsion films and these films will be suitable far food applications. The fellowing are the specific otjectives of this research: 1. Develop whey protein/lipid emulsion edible films and determine their microstructures, barrier (moisture and oxygen) and mechanical (tensile strength and elongation) properties. 2. Study the nature of interactions involved in the formation and stability of the films. 3. Investigate thermal properties, heat sealability, and sealing properties of the films. 4. Demonstrate suitability of their application in foods as packaging materials. Methodologies were developed to produce edible films from whey protein isolate (WPI) and concentrate (WPC), and film-forming procedure was optimized. Lipids, butter fat (BF) and candelilla wax (CW), were added into film-forming solutions to produce whey protein/lipid emulsion edible films. Significant reduction in water vapor and oxygen permeabilities of the films could be achieved upon addition of BF and CW. Mechanical properties were also influenced by the lipid type. Microstructures of the films accounted for the differences in their barrier and mechanical properties. Studies with bond-dissociating agents indicated that disulfide and hydrogen bonds, cooperatively, were the primary forces involved in the formation and stability of whey protein/lipid emulsion films. Contribution of hydrophobic interactions was secondary. Thermal properties of the films were studied using differential scanning calorimetry, and the results were used to optimize heat-sealing conditions for the films. Electron spectroscopy for chemical analysis (ESCA) was used to study the nature of the interfacial interaction of sealed films. All films were heat sealable and showed good seal strengths while the plasticizer type influenced optimum heat-sealing temperatures of the films, 130$^{\circ}$C for sorbitol-plasticized WPI films and 110$^{\circ}$C for glycerol-plasticized WPI films. ESCA spectra showed that the main interactions responsible for the heat-sealed joint of whey protein-based edible films were hydrogen bonds and covalent bonds involving C-0-H and N-C components. Finally, solubility in water, moisture contents, moisture sorption isotherms and sensory attributes (using a trained sensory panel) of the films were determined. Solubility was influenced primarily by the plasticizer in the films, and the higher the plasticizer content, the greater was the solubility of the films in water. Moisture contents of the films showed a strong relationship with moisture sorption isotherm properties of the films. Lower moisture content of the films resulted in lower equilibrium moisture contents at all aw levels. Sensory evaluation of the films revealed that no distinctive odor existed in WPI films. All films tested showed slight sweetness and adhesiveness. Films with lipids were scored as being opaque while films without lipids were scored to be clear. Whey protein/lipid emulsion edible films may be suitable for packaging of powder mix and should be suitable for packaging of non-hygroscopic foods$^{(5,6,7,8,)}$.

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Are Bound Residues a Solution for Soil Decontamination\ulcorner

  • Bollag, Jean-Marc
    • Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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    • 2003.10a
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    • pp.111-124
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    • 2003
  • Processes that cause immobilization of contaminants in soil are of great environmental importance because they may lead to a considerable reduction in the bioavailability of contaminants and they may restrict their leaching into groundwater. Previous investigations demonstrated that pollutants can be bound to soil constituents by either chemical or physical interactions. From an environmental point of view, chemical interactions are preferred, because they frequently lead to the formation of strong covalent bonds that are difficult to disrupt by microbial activity or chemical treatments. Humic substances resulting from lignin decomposition appear to be the major binding ligands involved in the incorporation of contaminants into the soil matrix through stable chemical linkages. Chemical bonds may be formed through oxidative coupling reactions catalyzed either biologically by polyphenol oxidases and peroxidases, or abiotically by certain clays and metal oxides. These naturally occurring processes are believed to result in the detoxification of contaminants. While indigenous enzymes are usually not likely to provide satisfactory decontamination of polluted sites, amending soil with enzymes derived from specific microbial cultures or plant materials may enhance incorporation processes. The catalytic effect of enzymes was evaluated by determining the extent of contaminants binding to humic material, and - whenever possible - by structural analyses of the resulting complexes. Previous research on xenobiotic immobilization was mostly based on the application of $^{14}$ C-labeled contaminants and radiocounting. Several recent studies demonstrated, however, that the evaluation of binding can be better achieved by applying $^{13}$ C-, $^{15}$ N- or $^{19}$ F-labeled xenobiotics in combination with $^{13}$ C-, $^{15}$ N- or $^{19}$ F-NMR spectroscopy. The rationale behind the NMR approach was that any binding-related modification in the initial arrangement of the labeled atoms automatically induced changes in the position of the corresponding signals in the NMR spectra. The delocalization of the signals exhibited a high degree of specificity, indicating whether or not covalent binding had occurred and, if so, what type of covalent bond had been formed. The results obtained confirmed the view that binding of contaminants to soil organic matter has important environmental consequences. In particular, now it is more evident than ever that as a result of binding, (a) the amount of contaminants available to interact with the biota is reduced; (b) the complexed products are less toxic than their parent compounds; and (c) groundwater pollution is reduced because of restricted contaminant mobility.

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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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