• Title/Summary/Keyword: Nitrogen conversion

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Difference in Chemical Composition of PM2.5 and Investigation of its Causing Factors between 2013 and 2015 in Air Pollution Intensive Monitoring Stations (대기오염집중측정소별 2013~2015년 사이의 PM2.5 화학적 특성 차이 및 유발인자 조사)

  • Yu, Geun Hye;Park, Seung Shik;Ghim, Young Sung;Shin, Hye Jung;Lim, Cheol Soo;Ban, Soo Jin;Yu, Jeong Ah;Kang, Hyun Jung;Seo, Young Kyo;Kang, Kyeong Sik;Jo, Mi Ra;Jung, Sun A;Lee, Min Hee;Hwang, Tae Kyung;Kang, Byung Chul;Kim, Hyo Sun
    • Journal of Korean Society for Atmospheric Environment
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    • v.34 no.1
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    • pp.16-37
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    • 2018
  • In this study, difference in chemical composition of $PM_{2.5}$ observed between the year 2013 and 2015 at six air quality intensive monitoring stations (Bangryenogdo (BR), Seoul (SL), Daejeon (DJ), Gwangju (GJ), Ulsan (US), and Jeju (JJ)) was investigated and the possible factors causing their difference were also discussed. $PM_{2.5}$, organic and elemental carbon (OC and EC), and water-soluble ionic species concentrations were observed on a hourly basis in the six stations. The difference in chemical composition by regions was examined based on emissions of gaseous criteria pollutants (CO, $SO_2$, and $NO_2$), meteorological parameters (wind speed, temperature, and relative humidity), and origins and transport pathways of air masses. For the years 2013 and 2014, annual average $PM_{2.5}$ was in the order of SL ($${\sim_=}DJ$$)>GJ>BR>US>JJ, but the highest concentration in 2015 was found at DJ, following by GJ ($${\sim_=}SJ$$)>BR>US>JJ. Similar patterns were found in $SO{_4}^{2-}$, $NO_3{^-}$, and $NH_4{^+}$. Lower $PM_{2.5}$ at SL than at DJ and GJ was resulted from low concentrations of secondary ionic species. Annual average concentrations of OC and EC by regions had no big difference among the years, but their patterns were distinct from the $PM_{2.5}$, $SO{_4}^{2-}$, $NO_3{^-}$, and $NH_4{^+}$ concentrations by regions. 4-day air mass backward trajectory calculations indicated that in the event of daily average $PM_{2.5}$ exceeding the monthly average values, >70% of the air masses reaching the all stations were coming from northeastern Chinese polluted regions, indicating the long-range transportation (LTP) was an important contributor to $PM_{2.5}$ and its chemical composition at the stations. Lower concentrations of secondary ionic species and $PM_{2.5}$ at SL in 2015 than those at DJ and GJ sites were due to the decrease in impact by LTP from polluted Chinese regions, rather than the difference in local emissions of criteria gas pollutants ($SO_2$, $NO_2$, and $NH_3$) among the SL, DJ, and GJ sites. The difference in annual average $SO{_4}^{2-}$ by regions was resulted from combination of the difference in local $SO_2$ emissions and chemical conversion of $SO_2$ to $SO{_4}^{2-}$, and LTP from China. However, the $SO{_4}^{2-}$ at the sites were more influenced by LTP than the formation by chemical transformation of locally emitted $SO_2$. The $NO_3{^-}$ increase was closely associated with the increase in local emissions of nitrogen oxides at four urban sites except for the BR and JJ, as well as the LTP with a small contribution. Among the meterological parameters (wind speed, temperature, and relative humidity), the ambient temperature was most important factor to control the variation of $PM_{2.5}$ and its major chemical components concentrations. In other words, as the average temperature increases, the $PM_{2.5}$, OC, EC, and $NO_3{^-}$ concentrations showed a decreasing tendency, especially with a prominent feature in $NO_3{^-}$. Results from a case study that examined the $PM_{2.5}$ and its major chemical data observed between February 19 and March 2, 2014 at the all stations suggest that ambient $SO{_4}^{2-}$ and $NO_3{^-}$ concentrations are not necessarily proportional to the concentrations of their precursor emissions because the rates at which they form and their gas/particle partitioning may be controlled by factors (e.g., long range transportation) other than the concentration of the precursor gases.

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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