The homobimetallic anion, $M^+({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5^-(M^+=Na^+,\;PPN^+)$was disrupted by CH2CHCH2Cl in THF at various temperatures ($20^{\circ}C~50^{\circ}C$) under the pseudo 1st order reaction conditions where excess of allyl chloride was employed under a nitrogen atmosphere. This homobimetallic anion seems to be involved in a concerted reaction mechanism in which a four-centered transition state is proposed. After undergoing the transition state, this reaction eventually leads to (MeCp)Mn$(CO)_3$ on addition of CO and $({\eta}^1-allyl)Mn(CO)_5$, respectively. However, in case of $Na^+$ analog, $Na^+$ may play a novel counter ion effect on the disruption reaction either by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$of the corresponding homobimetallic complex, eventually resulting in $({\eta}^5-MeCp)Mn(CO)_3$ or through the interaction between $Na^+$ and the leaving group (Cl) of allyl chloride. This reaction is of overall second order with respect to homobimetallic complex with the activation parameters (${\Delta}H^{\neq}=17.15{\pm}0.17kcal/mol,\;{\Delta}S^{\neq}=-9.63{\pm}0.10$ e.u. for $Na^+$ analog; ${\Delta}H^{\neq}=22.13{\pm}0.21 kcal/mol,\;{\Delta}S^{\neq}=9.74{\pm}0.19$ e.u. for $PPN^+$ analog reaction).
The atomic structures of silicate liquids at high pressure provide insights into the transport properties including thermal conductivities or elemental partitioning behavior between rocks and magmas in Earth's interior. Whereas the local electronic structure around silicon may vary with the arrangement of the nearby oxygens, the detailed nature of such relationship remains to be established. Here, we explored the atomic origin of the pressure-induced changes in the electronic structure around silicon by calculating the partial electronic density of states and L3-edge X-ray absorption spectra of SiO2 polymorphs. The result showed that the Si PDOS at the conduction band varies with the crystal structure and local atomic environments. Particularly, d-orbital showed the distinct features at 108 and 130 eV upon the changes in the coordination number of Si. Calculated Si XAS spectra showed features due to the s,d-orbitals at the conduction band and varied similarly with those observed in s,d-orbitals upon changes in the crystal structures. The calculated Si XAS spectrum for α-quartz was analogous to the experimental Si XRS spectrum for SiO2 glass, implying the overall similarities in the local atomic environments around the Si. The edge energies at the center of gravity of XAS spectra were closely related to the Si-O distance, thus showing the systematic changes upon densification. Current results suggest that the Si L2,3-edge XRS, sensitive probe of the Si-O distance, would be useful in unveiling the densification mechanism of silicate glasses and melts at high pressure.
Hyeroxyapatite(HAp) which has good biocompatibility was made by Wet Chemical Process. The surface of Ti-6Al-4V, coated with HAp by lon Beam Assisted Deposition (IBAD), was treated with 5ppm, 10ppm, 20ppm, and 100ppm of $AgNO_3$ solution. In this Ag impregnation process, $Ca^{2+}$ of HAp was substituted with $Ag^+$ of $AgNO_3$. In this study, the antimicrobial effect and biocompatibility of Ti-6Al-4V alloy which was coated with Ag-HAp were examined. The antimicrobial test was carried out with two kinds of bacteria(P. Aeruginosa, S. Epidermidis), which are highly infectious in a transplanting operation of implant materials. As a result of the test, it was observed that Ti-6Al-4V alloy which was treated by 20ppm of $AgNO_3$ solution has good biocompatibility. In order to observe the antimicrobial mechanism of $Ag^+$, E. coli which is the most common bacterium was treated by Ag-HAp. Then cell morphology of E. coli was observed by the transmission electron microscope(TEM). The destruction of cell wall and cytoplasm of E. coil were observed. A black spot appeared in the cytoplasm was analyzed by energy dispersive analysis X-ray (EDAX) and it showed a small amount of $Ag^+$. Thus, it was proved that $Ag^+$ destroys bacteria effectively and Ti-6Al-4V alloy which was impregnate with Ag ion show antimicrobial effect on infection bacteria.
General characteristics of groundwater contamination by As were reviewed with several recent researches, and its occurrence in groundwater of Korea was investigated based on a ffw previous studies and a groundwater quality survey in Nonsan and Geumsan areas. In Bangladesh, which has been known as the most serious arsenic calamity country, about $28\%$ of the shallow groundwaters exceeded the Bangladesh drinking water standard, $50{\mu}g/L$, and it was estimated that about 28 million people were exposed to concentrations greater than the standard. Groundwater was characterized by circum-neutral pH with a moderate to strong reducing conditions. Low concentrations of $SO_4^{2-}$ and $NO_3^-$, and high contents of dissolved organic carbon (DOC) and $NH_4^+$ were typical chemical characteristics. Total As concentrations were enriched in the Holocene alluvial aquifers with a dominance of As(III) species. It was generally agreed that reductive dissolution of Fe oxyhydroxides was the main mechanism for the release of As into groundwater coupling with the presence of organic matters and microbial activities as principal factors. A new model has also been suggested to explain how arsenic can naturally contaminate groundwaters far from the ultimate source with transport of As by active tectonic uplift and glaciatiion during Pleistocene, chemical weathering and deposition, and microbial reaction processes. In Korea, it has not been reported to be so serious As contamination, and from the national groundwater quality monitoring survey, only about $1\%$ of grounwaters have concentrations higher than $10{\mu}g/:L.$ However, it was revealed that $19.3\%$ of mineral waters, and $7\%$ of tube-well waters from Nonsan and Geumsan areas contained As concentrations above $10{\mu}g/:L.$. Also, percentages exceeding this value during detailed groundwater quality surveys were $36\%\;and\;22\%$ from Jeonnam and Ulsan areas, respectively, indicating As enrichment possibly by geological factors and local mineralization. Further systematic researches need to proceed in areas potential to As contamination such as mineralized, metasedimentary rock-based, alluvial, and acid sulfate soil areas. Prior to that, it is required to understand various geochemical and microbial processes, and groundwater flow characteristics affecting the behavior of As.
Background: To clarify the effect of hypoxia on vascular contractility, we tried to show whether hypoxia induced the release of endothelium-derived relaxing factor (EDRF) and the nature of the underlying mechanism for this release. Material and Method: Isometric contractions were observed in rabbit aorta, and the released EDRF from the rabbit aorta was bioassayed by using rabbit denuded carotid artery. The intracellular $Ca^{2+}$ concentration ($[Ca^{2+}]_i$) in the cultured rabbit aortic endothelial cells was recorded by a microfluorimeter with using Fura-2/AM. Hypoxia was evoked to the blood vessels or endothelial cells by eliminating the $O_2$ in the aerating gases in the external solution. Chemical hypoxia was evoked by applying deoxyglucose or $CN^-$. Result: Hypoxia relaxed the precontracted rabbit thoracic aorta that had its endothelium, and the magnitude of the relaxation was gradually increased by repetitive bouts of hypoxia. In contrast, hypoxia-induced relaxation was not evoked in the aorta that was denuded of endothelium. In a bioassay experiment, hypoxia released endothelium-derived relaxing factor (EDRF) and the release was inhibited by L-NAME or the $K^+$ channel blocker tetraethylammonium (TEA). In the cultured endothelial cells, hypoxia augmented the ATP-induced increase of the intracellular $Ca^{2+}$ concentration ($[Ca^{2+}]_i$) and this increase was inhibited by TEA. Furthermore, chemical hypoxia also increased the $Ca^{2+}$ influx. Conclusion: From these results, it can be concluded that hypoxia might induce the release of NO from rabbit aortic endothelial cells by increasing $[[Ca^{2+}]_i$.
The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
/
v.5
no.1
/
pp.16-26
/
2000
Physical characteristics and nutrient distributions in seawater were investigated to understand the mechanism of red tide outbreak in coastal waters off Kohung area. To identify any physical and chemical differences before, during and after the red tide outbreaks, 6 times of field observations have been carried out from May to October, 1997. We found that major environmental properties of the seawater in the study area were determined not by the local meteoric conditions or nearby-land influences, but by the intrusion of seawater from offshore. In particular, extreme environmental variations in seawater were found during the period of red tide outbreak from August to September. Before the red tide outbreak, high concentrations of DIN(Dissolved Inorganic Nitrogen)were found in seawater, but they decreased during the outbreak. Whereas no significant variations of DIP(Dissolved Inorganic Phosphate) were found. For the water mass in the semienclosed northern part of the study area, local nutrient sources originated from nearby-lands were estimated to cover 70% of total DIN input, but the rest part of the water mass in the study area, sporadic intrusion of offshore water mass could account for the major source of DIN supply. An offshore water mass influenced by Yangtze river effluent was suggested as one of the candidates with its high nitrate contents, high seawater temperature and low salinity. A red tide related phytoplankton, Gyrodinium impudicum, was found in seawater on the 21th day of August and, on the same day, a unique water mass with high temperature and extremely low salinity suddenly appeared in the study area. On the 22th day of September, after one and half month duration of red tide we found that red tide had disappeared simultaneously with the intrusion of new water mass with different characteristics.
The behavior of rare earth compounds such as $La_{2}O_{3}$, $CeO_{2}$, and $Ca(OH)_{2}$ on the removal of fluoride and heavy metals in the steel wastewater has been investigated. The removal mechanism of fluoride by rare earth elements has been known to be the formation of insoluble compounds between $F^{-}$ and cations such as $La^{3+}$ and $Ce^{4+}$ produced by the dissociation of rare earth compounds (To reduce the running cost of the fluoride wastewater treatment facility, their fluoride removal efficiencies were compared with those of inexpensive rare earth minerals such as natural lanthanide and cerium compound used as a glass polishing agent). All of the rare earth oxides used in this study showed a higher removal efficiency of fluoride than $Ca(OH)_{2}$ in the wastewater. In the case of artificial HF solution, the removal efficiency of fluoride showed in the order: $CeO_{2}$-mineral < $CeO_{2}$ < $Ca(OH)_{2}$ < $La_{2}O_{3}$-mineral < $La_{2}O_{3}$. However, the removal efficiency of fluoride in the wastewater increased in the following order: $Ca(OH)_{2}$ < $CeO_{2}$ mineral < $CeO_{2}$ < $La_{2}O_{3}$ mineral < $La_{2}O_{3}$. All agents showed high efficiencies for the removal of Mn and total Cr in the rare earth compounds. In the case of $Ca(OH)_{2}$, fluoride removal decreased with increasing pH while. However, the rare earth compounds showed a higher fluoride removal in higher pH condition, the optimum pH condition seemed to be around 7 considering both water quality and fluoride removal. Under the pH 7 condition, the $Ca(OH)_{2}$ was superior to rare earth compounds in Mn removal and the lanthanide was superior to others in total Cr removal.
Ki-Kyung Chjo;Yong-Kook Choi;Sang-Bock Kim;Jong-Ki Park;Dong-Hwa Park
Journal of the Korean Chemical Society
/
v.36
no.6
/
pp.894-905
/
1992
Dioxygen binding and homogeneous catalytic oxidation of hydrazobenzene were investigated by employing tetradentate Schiff base Cobalt(II) complexes such as Co(II)(SED)$(Py)_2$, Co(II)(SOPD)$(Py)_2$ and Co(II)(SND)$(Py)_2$ in saturated oxygen methanol solvent. The major product of hydrazobenzene ($H_2$AB) oxidation by catalysts of superoxo type [Co(III)(SED)(Py)$O_2$] and [Co(III)(SOPD)(Py)$O_2$] complexes are trans-azobenzene (t-AB) and rate constants k for oxidation reaction was 7.692 ${\times}$$10^{-2}$ M/sec for [Co(III)(SED)(Py)$O_2$] and 5.076 ${\times}$$10^{-2}$ M/sec for [Co(III)(SOPD)(Py)$O_2$]. But cis-azobenzene (c-AB) are obtained as a major product with ${\mu}$-peroxo type [Co(III)(SED)(Py)]$_2O_2$ catalyst, and rate constant k is 1.266 ${\times}$$10^{-2}$ M/sec. The rate constants of oxidation reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a intermediate activated complexes of catalyst, hydrazobenzene and oxygen has been proposed. $H_2$AB + Co(II)(Schiff base)$(Py)_2$ + $O_2$${\rightleftharpoons}_{MeOH}^K$ Co(III)(Schiff base)(Py)$O_2$${\cdot}$$H_2$AB + Py $\longrightarrow^k$ Co(II)(Schiff base)$(Py)_2$ + t-AB + $H_2O_2$(Scchiff base : SED and SOPD). $H_2$AB + 2Co(II)(SND)$(Py)_2$ + $O_2$${\rightleftharpoons}_{MeOH}^K$ [Co(III)(SND)(Py)]$_2O_2$${\cdot}$H_2$AB + 2Py ${\longrightarrow}^k$ (Co(II)(SND)$(Py)_2$ + c-AB + $H_2O_2$.
This paper was performed to study the nature of varietal resistance of some Korean-new rice cultivars to the brown planthopper (BPH), Nilaparvata lugens ($ST{\AA}L$). The rice cultivars tested were Cheongcheong, Gaya, Hangangchal, Samgang, Nampoong and Yeongpoong which have been reported as having resistant genes for the BPH. The check varieties were Jinheung, Sangpoong and Chucheong for susceptible and IR-36 for resistant. The factors studied were referred to the seedling responses, preference in feeding and oviposition of BPH, antibiosis (nymphal development, adult emergence and sex ratio, adult body weight, population build-up, feeding amount and amylase activity), and chemical composition (inorganic components, chlorophyll contents, cell wall components, amino acids and esterase isozymes) of leaf- sheath and/or roots of rice plants. In conclusion, the natures of varietal resistance of rice cultivars to the BPH were not only correlated with the resistant reaction of rice plant, but also they were related with the non preference in feeding and oviposition and those resistant cultivars had the antibiotic effects to the insects. Their antibiotic effects of rice cultivars to the BPH would be related with some of the chemical components of rice plants, such as the contents of magnesium oxide (MgO), and chlorophyll and the different esterase isozymes.
Background: The leaves and roots of Panax ginseng are rich in ginsenosides. However, the chemical compositions of the leaves and roots of P. ginseng differ, resulting in different medicinal functions. In recent years, the aerial parts of members of the Panax genus have received great attention from natural product chemists as producers of bioactive ginsenosides. The aim of this study was the isolation and structural elucidation of novel, minor ginsenosides in the leaves of P. ginseng and evaluation of their antiinflammatory activity in vitro. Methods: Various chromatographic techniques were applied to obtain pure individual compounds, and their structures were determined by nuclear magnetic resonance and high-resolution mass spectrometry, as well as chemical methods. The antiinflammatory effect of the new compounds was evaluated on lipopolysaccharide-stimulated RAW 264.7 cells. Results and conclusions: Two novel, minor triterpenoid saponins, ginsenoside $LS_1$ (1) and 5,6-didehydroginsenoside $Rg_3$ (2), were isolated from the leaves of P. ginseng. The isolated compounds 1 and 2 were assayed for their inhibitory effect on nitric oxide production in LPS-stimulated RAW 264.7 cells, and Compound 2 showed a significant inhibitory effect with $IC_{50}$ of $37.38{\mu}M$ compared with that of NG-monomethyl-L-arginine ($IC_{50}=90.76{\mu}M$). Moreover, Compound 2 significantly decreased secretion of cytokines such as prostaglandin $E_2$ and tumor necrosis factor-${\alpha}$. In addition, Compound 2 significantly suppressed protein expression of inducible nitric oxide synthase and cyclooxygenase-2. These results suggested that Compound 2 could be used as a valuable candidate for medicinal use or functional food, and the mechanism is warranted for further exploration.
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