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

• Journal of the Korean Vacuum Society
• /
• v.7 no.3
• /
• pp.242-247
• /
• 1998

Hydrogenated amorphous carbon nitride[a-C:H(N)] films were deposited on p-type Si(100) at room temperature with bias voltage of 200 V by DC saddle-field plasma-enhanced chemical vapor deposition. Effects of the ratio of $N_2$ to $CH_4$($N_2/CH_4$), in the range of 0 and 4 on such properties as optical properties, microstucture, relative fraction of nitrogen and carbon, etc. of the films have been investigated. The thickness of the a-C:H(N) film was abruptly decreased with the addition of nitrogen, but at $N_2/CH_4$>0.5, the thickness of the film gradually decreased with the increase of the $N_2/CH_4$. The ratio of N to C(N/C) of the films was saturated at 0.25 with the increase of $N_2CH_4$. N-H, C≡N bonds of the films increased but C-H bond decreased with the increase of $N_2CH_4$.Optical band gap energy of the film decreased from 2.53 eV at the ratio of $N_2CH_4$=4.

• Journal of the Korean Chemical Society
• /
• v.28 no.6
• /
• pp.384-392
• /
• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Proceedings of the KIEE Conference
• /
• 1998.11c
• /
• pp.895-897
• /
• 1998

The optical spectra of microwave plasma by four kinds of gases($N_2$, $N_2-CH_4$, $H_{2}-CH_{4}$ and Air-$CH_4$) have been measured for investigating 388.4[nm] peak which has the same intensity as $H_{\alpha}$(656.4[nm]) peak. A 388.4[nm] peak by $N_2$ plasma, $N_{2}-CH_{4}$ plasma and Air-$CH_4$ plasma may be CN peak because it is with 337.1, 357.8 and 316.0[nm] peaks by $N_2$. And a 388.4[nm] peak by $H_{2}-CH_{4}$ plasma without by $N_2$ 337.1, 357.8 and 316.0[nm] peaks may be CH peak. In the investigation results for optical spectra by $H_{2}-CH_{4}$ plasma and $H_{2}-CH_{4}-O_{2}$ plasma, the density of hydrogen atom was increased because oxygen decompose hydrogen molecules in $H_{2}-CH_{4}$ plasma with oxygen. These hydrogen atom decompose $CH_4$ and increase CH radical. And the crystalline of deposited diamond was good and the growth rate increased.

• Bulletin of the Korean Chemical Society
• /
• v.7 no.6
• /
• pp.468-471
• /
• 1986

The isolated products from the reactions of $Rh(ClO_4)(CO)(PPh_3)_2$ (1) with CH_2$ = $CHCO_2C_2H_5$ (2) and trans-$CH_3CH$ = $CHCO_2C_2H_5$ (3) contain 80∼ 90% of $[Rh(CH_2 = CHCO_2C_2H_5)(CO)(PPh_3)_2]ClO_4$ (4) and [Rh(trans-$CH_3CH = CHCO_2C_2H_5(CO)(PPh_3)_2]ClO_4$ (5), respectively where 2 and 3 seem to be coordinated through the carbonyl oxygen. It has been found that complex 1 catalyzes the isomerization of $CH_2 = CH(CH_2)_8CO_2C_2H_5$ (6) to $CH_3(CH_2)_nCH = CH(CH_2)_{7-n}CO_2C_2H_5$ (n = 0∼7) under nitrogen at 25$^{\circ}C$. The isomerization of 6 is slower than that of $CH_2 = CH(CH_2)_9CH_3$ to $CH_3(CH_2)_nCH$ = $CH(CH_2)_{8-n}CH_3$ (n = 0∼8), which is understood in terms of the interactions between the carbonyl oxygen of 6 and the catalyst. It has been also observed that complex 1 catalyzes the hydrogenation of 2, 3, 6, trans-$C_6H_5CH = CHCO_2C_2H_5$ (7), $CH_3(CH_2)_7CH = CH(CH_2)_7CO_2C_2H_5$ (8) and $CH_2 = CH(CH_2)_9CH_3$ (9), and the isomerization (double bond migration) of 6 and 9 under hydrogen at 25$^{\circ}C$. The interactions between the carbonyl oxygen of the unsaturated esters and the catalyst affect the hydrogenation in such a way that the hydrogenation of the unsaturated esters becomes slower than that of simple olefins.

• Microbiology and Biotechnology Letters
• /
• v.49 no.2
• /
• pp.225-238
• /
• 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 the Korean Chemical Society
• /
• v.39 no.11
• /
• pp.856-862
• /
• 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
• /
• v.41 no.2
• /
• pp.88-97
• /
• 1997

The silyltriflates$(Ph_{3-n}SiH(OTf)_n)$have been produced by the reaction of triphenylsilane and triflic acid$(CF_3SO_3H)$at low temperature. These highly reactive compounds are a valuable reagent for the synthesis of numerous new functional substituted silane derivatives. The reaction of silyltriflates with alkenyl- and alkynylmagnesium bromide as well as organolithium compounds gave new silanes$Ph_2SiHR(R=\;C(CPh,\;CH=CH_2,\;CH_2CH=CH_2,\; (CH_2)_2CH=CH_2,\;(CH_2)_3CH=CH_2)$in high yields. The hydrosilation of prepared alkenyl- and alkynylsilanesPh_2SiHR$in the presence of a platinum catalyst(Pt/C) at high temperature$(200{\circ}C)$gave carbosilane polymers$((Ph_2SiCH=CPh)_n$and$(Ph_2Si(CH_2)m)n;\;m=2∼4, n{\ge}10)$along with five- and six-membered silaalkane ring compounds derived from intramolecular hydrosilation reactions. All of the prepared compounds are confirmed by NMR, UV, IR and mass spectroscopy as well as elemental analysis.

• Journal of Animal Environmental Science
• /
• v.18 no.3
• /
• pp.145-150
• /
• 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 Korean Society for Atmospheric Environment
• /
• v.29 no.6
• /
• pp.789-800
• /
• 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.