• 분석과학
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• 제22권4호
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• pp.285-292
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• 2009

장기 저장된 탄약은 화공품의 노화에 따른 절심현상(연소 중단)으로 인해 불발 등의 악작용이 발생하게 된다. 탄약에 주로 사용되는 화공품은 초기 에너지를 부여하는 뇌관 화약과 뇌관 화약의 에너지를 받아 지연제를 점화시켜주는 점화제, 일정 시간 동안 연소를 지연시켜주는 지연제 등을 사용한다. 이러한 형태의 탄약에는 뇌관화약, 점화제, 지연제의 순으로 충전되는데 충전된 순서대로 에너지가 전달되어 기능을 발휘하게 된다. 탄약의 절심 현상은 점화제의 연소중단, 점화제로부터 지연제로의 불충분한 에너지 전달, 지연제의 연소 중단 등에 의해 발생하는데, 이러한 현상이 나타나는 요인으로는 각 구성 성분의 낮은 순도,부적절한 혼합비, 입자성 성분의 입자 크기 및 분포, 바인더의 종류, 각 구성 성분의 혼합방법, 장기저장시 흡입된 수분에 의한 구성성분의 가수분해 및 고온에 의한 구성 성분의 화학적 변화 등이 의심된다. 본 연구의 목적은 Zr-Ni계 지연관 결합체를 장기 보관했을 때 점화제 및 지연제에서 나타나는 연소중단현상의 원인을 규명하는 것이다. 이를 위해 본 연구에서는 현장에서 일어나는 절심현상과 일치하는 시험법을 개발하였고, 장-흐름 분획법(field-flow fractionation, FFF)을 이용하여 입자성 성분의 입자 크기와 분포를 조사하였으며, 장기보관에 의한 점화제와 지연제의 화학적인 변화 메커니즘을 조사하기 위하여 열분석(differential scanning calorimetry) 및 XRD, XPS (X-ray diffractometry, X-ray photoelectron Spectroscopy)분석을 수행하였다. XPS 와 XRD data 에 의하면, 점화제의 경우 산소의 1s 결합에너지 위치에서 M-O,M-OH 피크들이 관찰되었다. 이는 산화에 의한 새로운 생성물이 생성되었음을 의미한다. 즉 점화제의 산화에 의해 방출 열량이 감소하여 절심(연소 중단) 현상이 야기된다는 사실을 확인할 수 있었다.

• 한국지하수토양환경학회:학술대회논문집
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• 한국지하수토양환경학회 2004년도 총회 및 춘계학술발표회
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• pp.3-4
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• 2004

Results will be presented from two field studies that evaluated the in-situ treatment of chlorinated aliphatic hydrocarbons (CAHs) using aerobic cometabolism. In the first study, a cometabolic air sparging (CAS) demonstration was conducted at McClellan Air Force Base (AFB), California, to treat chlorinated aliphatic hydrocarbons (CAHs) in groundwater using propane as the cometabolic substrate. A propane-biostimulated zone was sparged with a propane/air mixture and a control zone was sparged with air alone. Propane-utilizers were effectively stimulated in the saturated zone with repeated intermediate sparging of propane and air. Propane delivery, however, was not uniform, with propane mainly observed in down-gradient observation wells. Trichloroethene (TCE), cis-1, 2-dichloroethene (c-DCE), and dissolved oxygen (DO) concentration levels decreased in proportion with propane usage, with c-DCE decreasing more rapidly than TCE. The more rapid removal of c-DCE indicated biotransformation and not just physical removal by stripping. Propane utilization rates and rates of CAH removal slowed after three to four months of repeated propane additions, which coincided with tile depletion of nitrogen (as nitrate). Ammonia was then added to the propane/air mixture as a nitrogen source. After a six-month period between propane additions, rapid propane-utilization was observed. Nitrate was present due to groundwater flow into the treatment zone and/or by the oxidation of tile previously injected ammonia. In the propane-stimulated zone, c-DCE concentrations decreased below tile detection limit (1 $\mu$g/L), and TCE concentrations ranged from less than 5 $\mu$g/L to 30 $\mu$g/L, representing removals of 90 to 97%. In the air sparged control zone, TCE was removed at only two monitoring locations nearest the sparge-well, to concentrations of 15 $\mu$g/L and 60 $\mu$g/L. The responses indicate that stripping as well as biological treatment were responsible for the removal of contaminants in the biostimulated zone, with biostimulation enhancing removals to lower contaminant levels. As part of that study bacterial population shifts that occurred in the groundwater during CAS and air sparging control were evaluated by length heterogeneity polymerase chain reaction (LH-PCR) fragment analysis. The results showed that an organism(5) that had a fragment size of 385 base pairs (385 bp) was positively correlated with propane removal rates. The 385 bp fragment consisted of up to 83% of the total fragments in the analysis when propane removal rates peaked. A 16S rRNA clone library made from the bacteria sampled in propane sparged groundwater included clones of a TM7 division bacterium that had a 385bp LH-PCR fragment; no other bacterial species with this fragment size were detected. Both propane removal rates and the 385bp LH-PCR fragment decreased as nitrate levels in the groundwater decreased. In the second study the potential for bioaugmentation of a butane culture was evaluated in a series of field tests conducted at the Moffett Field Air Station in California. A butane-utilizing mixed culture that was effective in transforming 1, 1-dichloroethene (1, 1-DCE), 1, 1, 1-trichloroethane (1, 1, 1-TCA), and 1, 1-dichloroethane (1, 1-DCA) was added to the saturated zone at the test site. This mixture of contaminants was evaluated since they are often present as together as the result of 1, 1, 1-TCA contamination and the abiotic and biotic transformation of 1, 1, 1-TCA to 1, 1-DCE and 1, 1-DCA. Model simulations were performed prior to the initiation of the field study. The simulations were performed with a transport code that included processes for in-situ cometabolism, including microbial growth and decay, substrate and oxygen utilization, and the cometabolism of dual contaminants (1, 1-DCE and 1, 1, 1-TCA). Based on the results of detailed kinetic studies with the culture, cometabolic transformation kinetics were incorporated that butane mixed-inhibition on 1, 1-DCE and 1, 1, 1-TCA transformation, and competitive inhibition of 1, 1-DCE and 1, 1, 1-TCA on butane utilization. A transformation capacity term was also included in the model formation that results in cell loss due to contaminant transformation. Parameters for the model simulations were determined independently in kinetic studies with the butane-utilizing culture and through batch microcosm tests with groundwater and aquifer solids from the field test zone with the butane-utilizing culture added. In microcosm tests, the model simulated well the repetitive utilization of butane and cometabolism of 1.1, 1-TCA and 1, 1-DCE, as well as the transformation of 1, 1-DCE as it was repeatedly transformed at increased aqueous concentrations. Model simulations were then performed under the transport conditions of the field test to explore the effects of the bioaugmentation dose and the response of the system to tile biostimulation with alternating pulses of dissolved butane and oxygen in the presence of 1, 1-DCE (50 $\mu$g/L) and 1, 1, 1-TCA (250 $\mu$g/L). A uniform aquifer bioaugmentation dose of 0.5 mg/L of cells resulted in complete utilization of the butane 2-meters downgradient of the injection well within 200-hrs of bioaugmentation and butane addition. 1, 1-DCE was much more rapidly transformed than 1, 1, 1-TCA, and efficient 1, 1, 1-TCA removal occurred only after 1, 1-DCE and butane were decreased in concentration. The simulations demonstrated the strong inhibition of both 1, 1-DCE and butane on 1, 1, 1-TCA transformation, and the more rapid 1, 1-DCE transformation kinetics. Results of tile field demonstration indicated that bioaugmentation was successfully implemented; however it was difficult to maintain effective treatment for long periods of time (50 days or more). The demonstration showed that the bioaugmented experimental leg effectively transformed 1, 1-DCE and 1, 1-DCA, and was somewhat effective in transforming 1, 1, 1-TCA. The indigenous experimental leg treated in the same way as the bioaugmented leg was much less effective in treating the contaminant mixture. The best operating performance was achieved in the bioaugmented leg with about over 90%, 80%, 60 % removal for 1, 1-DCE, 1, 1-DCA, and 1, 1, 1-TCA, respectively. Molecular methods were used to track and enumerate the bioaugmented culture in the test zone. Real Time PCR analysis was used to on enumerate the bioaugmented culture. The results show higher numbers of the bioaugmented microorganisms were present in the treatment zone groundwater when the contaminants were being effective transformed. A decrease in these numbers was associated with a reduction in treatment performance. The results of the field tests indicated that although bioaugmentation can be successfully implemented, competition for the growth substrate (butane) by the indigenous microorganisms likely lead to the decrease in long-term performance.

• Tuberculosis and Respiratory Diseases
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• 제45권4호
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• pp.723-735
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• 1998

배 경: 비타민 C가 동물실험에서 기도 과민성을 감소시키는 역할을 하는 것으로 보고되고 있는데 이는 비타민 C가 히스타민 분해를 촉진하고, cyclooxygenase 통로를 $PGF_{2\alpha}$에서 $PGE_2$로 이동시키며 평활근 수축을 감소시키고, 산화물의 환원제로 작용하는 사실에 기인한다고 한다. 또한 비흡연자에 비하여 흡연자에서 혈중 비타민 C 농도가 감소하는데 이는 비타민 C가 흡연시 생성되는 산화물의 환원제로 소모되며, 니코틴에 의해 분비되는 catecholamine, serotonin의 합성에 관여하며, 결핍된 식이로 인한 것으로 알려져있다. 연구자들은 기도 과민성이 있는 흡연자와 대조군인 비흡연지를 대상으로 비타민 C의 기도 과민반응에 대한 효과를 알아보고 비타민 C의 기도 과민성에 대한 역할을 알아보고자 본 연구를 시행하였다. 방 법: 17명의 흡연자와 8명의 비흡연자에서 기도 과민반응에 대한 비타민 C의 급성 효과를 알아보기 위하여 혈중 비타민 C 농도 측정을 위한 채혈과 폐기능 검사와 메타콜린 기관지 유발검사를 시행하고 비타민 C 3 g 투여 후 1시간 뒤에 상기 검사들을 다시 시행하였고 1주 후 기도 과민반응에 대한 비타민 C의 만성 효과를 알아보기 위하여 17명의 흡연자에서 1주 동안 매일 비타민 1 g 투여 후 혈중 비타민 C 농도 측정을 위한 채혈과 폐기능 검사와 메타콜린 기관지 유발검사를 시행하였다. 또한 기도 과민성에 대한 비타민 C 의 역할을 알아보기 위하여 l주 후 메타콜린에 반응하는 15명중 12명의 흡연자에서 비타민 C 3 g과 cyclooxygenase 억제제인 indomethacin 100 mg을 동시 투여 후 폐기능 검사와 메타콜린 기관지 유발검사를, 1 주 후 메타콜린에 반응하는 12명의 흡연자에서 indomethacin 100 mg만 단독 투여 후 폐기능 검사와 메타콜린 기관지 유발 검사를 시행하였다. 결 과: 전혈 비타민 C 농도를 측정한 결과 흡연자, 비흡연자 각각 $1.17{\pm}:0.22$ mg/dL, $1.14{\pm}:0.19$ mg/dL로 유의한 차이는 없었다(p>0.05). 흡연자 17명중 15명(88.2%)이 메타콜린 기관지 유발검사 양성이었고 이중 10명은 $PC_{20}FEV_1$이 8mg/mL 이하였고, 비흡연자군 8명중 7명(87.5%)이 기관지 유발검사 음성이었다. 기관지 유발집사 양성인 15명의 흡연자중 13명에서 비타민 C 3 g 복용 1 시간 후 기관지 반응이 유의하게 감소하였고 l일 비타민 C 1 g 씩 1 주간 복용 후에도 기관지 반응의 감소가 계속 유지되었다. 흡연자의 $PC_{20}FEV_1$과 전혈 비타민 C 농도 사이에는 유의한 상관관계는 없었다. 비타민 C 3 g 투여 후 흡연자에서 관찰할 수 있었던 기관지 반응의 유의한 감소가 indomethacin 100 mg 첨가 후 소실되었다(p>0.05). 결 론: 이상의 결과로 볼 때 혈중 비타민 C 농도는 흡연자군, 비흡연자군에 있어서 유의한 차이가 없지만 흡연자군은 비흡연자군에 비하여 기도 과민성이 유의하게 증가되어 있었으며, 비타민 C 투여에 의해 증가된 기도 과민성이 유의하게 감소하고 indomethacin 첨가 후 비타민 C의 이러한 효과가 소실됨으로 보아 비타민 C가 arachidonic acid 대사작용에 관여함으로 기도 과민성이 감소되리라 사료된다.

• 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.