• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1781-1786
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• 2007

Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

• Microbiology and Biotechnology Letters
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• v.49 no.2
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• pp.225-238
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• 2021

CH₄-oxidizing and N₂O-reducing bacterial consortia were enriched from the rhizosphere soils of maize (Zea mays) and tall fescue (Festuca arundinacea). Illumina MiSeq sequencing analysis was performed to comparatively analyze the bacterial communities of the consortia with those of the rhizosphere soils. Additionally, the effect of root exudate on CH₄ oxidation and N₂O reduction activities of the microbes was evaluated. Although the inoculum sources varied, the CH₄-oxidizing and N₂O-reducing consortia derived from maize and tall fescue were similar. The predominant methanotrophs in the CH₄-oxidizing consortia were Methylosarcina, Methylococcus, and Methylocystis. Among the N₂O-reducing consortia, the representative N₂O-reducing bacteria were Cloacibacterium, Azonexus, and Klebsiella. The N₂O reduction rate of the N₂O-reducing consortium from maize rhizosphere and tall fescue rhizosphere increased by 1.6 and 2.7 times with the addition of maize and tall fescue root exudates, respectively. The CH₄ oxidization activity of the CH₄-oxidizing consortia did not increase with the addition of root exudates. The CH₄-oxidizing and N₂O-reducing consortia can be used as promising bioresources to mitigate non-CO₂ greenhouse gas emissions during remediation of oil-contaminated soils.

• Journal of Korean Society for Atmospheric Environment
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• v.29 no.6
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• pp.789-800
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• 2013

$N_2O$ and $CH_4$, Greenhouse gas emission, Forest soil, Closed chamber technique, Soil uptake $N_2O$ and $CH_4$ are important greenhouse gases (GHG) along with $CO_2$ influencing greatly on climate change. Their soil emission rates are highly affected by bio-geo-chemical processes in C and N through the land-atmosphere interface. The forest ecosystems are generally considered to be net emission for $N_2O$; however, net sinks for $CH_4$ by soil uptake. Soil $N_2O$ and $CH_4$ emissions were measured at Mt. Taewha in Gwangju, Kyeonggi, Korea. Closed chamber technique was used for surface gas emissions from forest soil during period from May to October 2012. Gas emission measurement was conducted mostly on daytime (from 09:00 to 18:00 LST) during field experiment period (total 25 days). The gas samples collected from chamber for $N_2O$ and $CH_4$ were analyzed by gas chromatography. Soil parameters were also measured at the sampling plot. GHG averages emissions during the experimental period were $3.11{\pm}16.26{\mu}g m^{-2}hr^{-1}$ for $N_2O$, $-1.36{\pm}11.3{\mu}gm^{-2}hr^{-1}$ for $CH_4$, respectively. The results indicated that forest soil acted as a source of $N_2O$, while it acted like a sink of $CH_4$ on average. On monthly base, means of $N_2O$ and $CH_4$ flux during May (spring) were $8.38{\pm}48.7{\mu}gm^{-2}hr^{-1}$, and $-3.21{\pm}31.39{\mu}gm^{-2}hr^{-1}$, respectively. During August (summer) both GHG emissions were found to be positive (averages of $2.45{\pm}20.11{\mu}gm^{-2}hr^{-1}$ for $N_2O$ and $1.36{\pm}9.09{\mu}gm^{-2}hr^{-1}$ for $CH_4$); which they were generally released from soil. During September (fall) $N_2O$ and $CH_4$ soil uptakes were observed and their means were $-1.35{\pm}12.78{\mu}gm^{-2}hr^{-1}$ and $-2.56{\pm}11.73{\mu}gm^{-2}hr^{-1}$, respectively. $N_2O$ emission was relatively higher in spring rather than other seasons. This could be due to dry soil condition during spring experimental period. It seems that soil moisture and temperature mostly influence gas production and consumption, and then emission rate in subsoil environment. Other soil parameters like soil pH and chemical composition were also discussed with respect to GHG emissions.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.24 no.7
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• pp.589-593
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• 2011

[ $SnO_2$ ]nano powders were prepared by solution reduction method using tin chloride($SnCl_2{\cdot}2H_2O$), hydrazine($N_2H_4$) and NaOH. The $SnO_2$ thick films for gas sensors were fabricated by screen printing method on alumina substrates and annealed at $300^{\circ}C$ in air, respectively. XRD patterns of the $SnO_2$ nano powders showed the tetragonal structure with (110) dominant orientation. The particle size of $SnO_2$ nano powders at the ratio of $SnCl_2:N_2H_4$+NaOH= 1:6 was about 60 nm. The sensing characteristics were investigated by measuring the electrical resistance of each sensor in a test box. Sensitivity of $SnO_2$ gas sensor to 5 ppm $CH_4$gas and 5 ppm $CH_3CH_2CH_3$ gas was investigated for various $SnCl_2:N_2H_4$+NaOH proportion. The highest sensitivity to $CH_4$ gas and $CH_3CH_2CH_3$ gas of $SnO_2$ sensors was observed at the $SnCl_2:N_2H_4$+NaOH= 1:8 and $SnCl_2:N_2H_4$+NaOH= 1:6, respectively. Response and recovery times of $SnO_2$ gas sensors prepared by $SnCl_2:N_2H_4$+NaOH= 1:6 was about 40 s and 30 s, respectively.

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2517-2522
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• 2012

New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

• Journal of Animal Environmental Science
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• v.18 no.3
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• pp.145-150
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• 2012

This study was conducted to measure methane ($CH_4$) and nitrous oxide ($N_2O$) emissions from the 6 month old litter stockpile used for korean native cattle (Hanwoo) from August 3, 2007 to October 4, 2007. Daily mean $CH_4$ emissions was peaked to 273.013 ${\mu}g\;m^{-2}\;s^{-1}$ (SE : ${\pm}1.047{\mu}g\;m^{-2}\;s^{-1}$) on first day and then gradually decreased to 2.309 ${\mu}g\;m^{-2}\;s^{-1}$ (SE : ${\pm}0.061{\mu}g\;m^{-2}\;s^{-1}$) at the end of this experiment. Daily mean $N_2O$ emissions was as little as 0.269 ${\mu}g\;m^{-2}\;s^{-1}$ (SE : ${\pm}0.018{\mu}g\;m^{-2}\;s^{-1}$) on first day, but exponentially increased up to 3.569 ${\mu}g\;m^{-2}\;s^{-1}$ (SE : ${\pm}0.454{\mu}g\;m^{-2}\;s^{-1}$) on 43rd day and then slowly decreased to 1.888 ${\mu}g\;m^{-2}\;s^{-1}$ (SE : ${\pm}0.012{\mu}g\;m^{-2}\;s^{-1}$) at the end of this experiment. Carbon dioxide equivalent ($CO_2$-eq), calculated by global warming potentials of $CH_4$ or $N_2O$, of $CH_4$ on first day occupied approximately 99% of sum of $CO_2$-eq of $CH_4$ and $N_2O$. Methane emissions decreased and $N_2O$ emissions increased so that $CO_2$-eq ratio of $CH_4$ to $N_2O$ was 50:50 on 34th day. The effect of $N_2O$ on the ratio was increase thereafter. The ratio of daily mean $CH_4$ and $N_2O$ emissions to daily error of the mean was calculated to find daily fluctuation of $CH_4$ and $N_2O$ emissions. The ratio of $CH_4$ was less than 1.0% till 11th day but increased to 10.9% on 57th day. The ratio of $N_2O$ (0.4%~51.0%) was higher than that of $CH_4$, showing high in early stage and then gradually decrease, which was different from the pattern of $CH_4$. The ratio of daily mean emissions to daily error of the mean was little in case of active $CH_4$ or $N_2O$ generation period, which would be caused by the temporal and spatial heterogeneity of composting process. Hence more air supply on early stage to decrease $CH_4$ generation and proper turning to reduce spatial heterogeneity are needed to mitigate greenhouse gas emissions.

• Journal of the Korean Chemical Society
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• v.39 no.11
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• pp.856-862
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• 1995

The tungsten oxo-nitrosyl complexes (n-Bu4N)2[W5O12(NO)2{RC(NH2)NHO}2{RC(NH)NO}2] (R=(CH3)2CH, CH3CH2CH2, CH3SCH2) have been synthesized by the reactions of polyoxotungsten complex (n-Bu4N)2[W6O19] and tungsten dinitrosyl monomeric complex [W(NO)2(acac)(CH3CN)2](BF4) with butylamidoxime derivatives. The prepared complexes have been characterized by elemental analysis, infrared, UV-visible, 1H NMR and 13C NMR spectroscopy. The pentanuclear species was formed by the interaction of the electron-withdrawing {W(NO)2}2+ unit between the two dinuclear tungsten {W2O5}2+ cores. We can estimate to exist large proton interactions viewed from the four doublet in 1H NMR spectrum of (n-Bu4N)2[W5O12(NO)2{(CH3)2CHC(NH2)NHO}2{(CH3)2CHC(NH)NO}2]. We also drew informations of the two different coordination mode and symmetry of the complexes because two ligands appear in 13C NMR spectra instead of four. The {W(NO)2}2+ unit has been cis-form and C2v symmetry in geometric structure.

• Journal of the Korean Chemical Society
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• v.40 no.1
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• pp.28-36
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• 1996

The pentanuclear complexes have been obtained by the reactions of molybdenum(VI) and tungsten(VI) polynuclear complexes with molybdenum(O) and tungsten(O) dinitrosyl mononuclear complexes, and methylthioamidoxime. The prepared complexes (n-Bu4N)2[Mo4O12Mo(NO)2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2](1), (n-Bu4N)2[W4O12Mo(NO)2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2](2), (n-Bu4N)2[Mo4O12W (NO)2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2] (3) have been characterized by elemental analysis, infrared, UV-visible and 1H NMR spectra. The complexes are elucidated the cis-{M(NO)2}2+(M = Mo, W) unit and a slight delocalization by spectroscopy. The structure of (n-Bu4N)2[W4O12Mo(NO) 2{CH3SCH2C(NH2)NHO}2{CH3SCH2C(NH)NO}2] was determined by X-ray single crystal diffraction. Crystal data are follows: Monoclinic, $P21}a$, a = 22.14(2) $\AA$, b = 14.93(1) $\AA$, c = 23.20(1) $\AA$, $\beta$ = 111.08(6) $\AA$, V = 7155(9) $\AA$, Z = 4, final R = 0.072 for 6191(I > $3\sigma(I)).$ The structure of complex forms two dinuclear [W2O5{CH3SCH2C(NH2)NHO}{CH3SCH2C(NH)NO}] and a central {Mo(NO)2} 2+ core. The geometric structure of the {Mo(NO)2} 2+unit is the formally cistype and C2v symmetry.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.26 no.5
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• pp.742-749
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• 2002

Numerical Study with detailed chemistry has been conducted to investigate the flame structure and NOx formation characteristics in oxygen -enhanced(CH$_4$/O$_2$-$N_2$) and oxygen-enhanced-EGR(CH$_4$/O$_2$-$CO_2$) counter diffusion flame with various strain rates. A small amount of $N_2$is included in oxygen-enhanced-EGR combustion, in order to consider the inevitable $N_2$contamination by $O_2$production process or air infiltration. The results are as follows : In CH$_4$/O$_2$-$CO_2$flame it is very important to adopt a radiation effect precisely because the effect of radiation changes flame structure significantly. In CH$_4$/O$_2$-$N_2$flame special strategy to minimize NO emission is needed because it is very sensitive to a small amount of $N_2$. Special attention is needed on CO emission by flame quenching, because of increased CO concentration. Spatial NO production rate of oxygen-enhanced combustion is different from that of air and oxygen-enhanced-EGR combustion in that thermal mechanism plays a role of destruction as well as production. In case CH$_4$/O$_2$-$CO_2$flame contains more than 40% $CO_2$it is possible to maintain the same EINO as that of CH$_4$/Air flame with accomplishing higher temperature than that of CH$_4$/Air flame. EINO decreases with increasing strain rate, and those effects are augmented in CH$_4$/O$_2$flame.

• Proceedings of the KSME Conference
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• 2001.11b
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• pp.185-190
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• 2001

Numerical Study with detailed chemistry has been conducted to investigate the flame structure and NOx formation characteristics in oxygen-enhanced$(CH_4/O_2-N_2)$ and oxygen-enhanced-EGR$(CH_4/O_2-CO_2)$ counter diffusion flame with various strain rates. A small amount of $N_2$ is included in oxygen-enhanced-EGR combustion, in order to consider the inevitable $N_2$ contamination by $O_2$ production process or air infiltration. The results are as follows : In $CH_4/O_2-CO_2$ flame it is very important to adopt a radiation effect precisely because the effect of radiation changes flame structure significantly. In $CH_4/O_2-N_2$ flame special strategy to minimize NO emission is needed because it is very sensitive to a small amount of $N_2$. Special attention is needed on CO emission by flame quenching, because of increased CO concentration. Spatial NO production rate of oxygen-enhanced combustion is different from that of air and oxygen-enhanced-EGR combustion in that thermal mechanism plays a role of destruction as well as production. In case $CH_4/O_2-CO_2$ flame contains more than 40% $CO_2$ it is possible to maintain the same EINO as that of $CH_4/Air$ flame with accomplishing higher temperature than that of $CH_4/Air$ flame. EINO decreases with increasing strain rate, and those effects are augmented in $CH_4/O_2$ flame. Complementary study is needed with extending the range of strain rate variation.