• Title/Summary/Keyword: $H_2O$-Type

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Kinetics and Mechanism of the Benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4304-4308
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    • 2011
  • Kinetic studies of the reactions of O,O-dimethyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots for substituent X variations in the nucleophiles are discrete with a break region between 4-Me and H, while the Hammett plots (log $k_2$ vs ${\sigma}_Z$) for substituent Z variations in the leaving groups are linear. The sign of the cross-interaction constant (${\rho}_{XZ}$) is positive for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ (= 2.54) value is observed with the weakly basic nucleophiles compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = 0.17). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a stepwise with a rate-limiting leaving group expulsion from the intermediate involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles.

Microstructure and Properties of Organic-Inorganic Hybrids(PDMS/SiO$_2$) Through Variations in Sol-Gel Processing (졸-겔공정의 변수조절을 통해 제조된 유기-무기복합체 (PDMS/SiO$_2$)의 미세구조와 특성)

  • Eun, Hui-Tae;Hwang, Jin-Myeong
    • Korean Journal of Materials Research
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    • v.11 no.2
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    • pp.94-103
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    • 2001
  • SiO$_2$ and PDMS/SiO$_2$ xerogels which are derived PDMS into TEOS have been synthesized by sol-gel process and controlled pore size and distribution through 2 step acid/base catalyzed processes using HCI and NH$_4$OH as a catalyst. In HCl catalyzed SiO$_2$ and PDMS/SiO$_2$ xerogels, pH and gellation time of xerogel were 2.3~2.5 and 12~13 days, respectively, and the shape of xerogel was identified to pellet type and column type. Under acidic condition of final reaction solution, the hydrolysis rate is accelerating, resulting in long gel times. The shape of xerogel is pellet type. In contrast, under less acidic condition, the condensation rate is accelerating, resulting in shorter gel times and the shape of xerogel is column type. The surface area and average Pore size were changed 400$\rightarrow$600($\m^2$/g) and 15$\rightarrow$28$\AA$, respectively, depending to the increase of the mole ratio of HCl/NH$_4$OH, and represented uniform pore size distribution. It is that all the alkoxide groups are hydrolyzed by HCl after the first step and the condensation rate is enhanced by NH$_4$OH. The regular backbone structures of silica are formed at low temperature and the uniform pores are produced by heat treatment.

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Environmental Isotope Characteristics of $CO_2$-rich Water in the Kangwon Province (강원도지역 탄산수의 환경동위원소적 특성)

  • 최현수;고용권;김천수;배대석;윤성택
    • Economic and Environmental Geology
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    • v.33 no.6
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    • pp.491-504
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    • 2000
  • Environmental isotope $^{18}O$, $^{2}H$, $^{3}H$,$^{13}C$, $^{34}S$and $^{87}Sr/^{86}Sr$) studies on ${CO_2}$-rich waters in the Kangwon Province were carried out to elucidate the origin, residence time, water-rock interaction and mixing process of their. ${\delta}^{18}O$ and ${\delta}D$ data indicate that ${CO_2}$-rich waters were derived from the local meteoric water. It also shows that each type of ${CO_2}$-rich water has distinct isotopic composition and Na-${HCO_3}$ type water (-10.8 to -12.1${\textperthousand}$, ${\delta}^{18}O$ ) is lighter than other type waters. These depleted isotopic values supposedly indicate that, considering the altitude effect of isotope in Korea, the recharge area of Na-${HCO_3}$ type water can be estimated to be relatively higher in elevation than those of Ca-${HCO_3}$ and Ca-Na-${HCO_3}$ type waters. Tritium contents close to zero are observed in the Na-${HCO_3}$ type water, confirming a long residence time and the possibility of a ${CO_2}$ inflow into the aquifer at great depth. These isotope data also show that the Ca-${HCO_3}$ type water has undergone mixing process with surface water during ascending at depth, whereas Na-${HCO_3}$ type water was less mixed with surface waters. The carbon isotope data (-8.8 to +0.8 ${\textperthousand}$ ${\delta}^{13}C$) indicate that dissolved carbon in the ${CO_2}$-rich waters was possibly derived from deep seated ${CO_2}$ gas. The high ${\delta}^{34}S$ values (up to 38.1${\textperthousand}$) of dissolved sulfates suggest that sulfate reduction by microbial activity had occurred at depth. Strontium isotopic data ($^{87}Sr/^{86}Sr$) of ${CO_2}$-rich waters indicate that the chemistry of the ${CO_2}$-rich waters is determined by water-rock (granite) interaction.

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Mesothermal Gold Vein Mineralization of the Seolhwa Mine: Fluid Inclusion and Sulfur Isotope Studies (설화 광산의 중열수 금광화작용: 유체포유물 및 황동위원소 연구)

  • Yun, Seong-Taek;So, Chil-Sup;Choi, Seon-Gyu;Choi, Sang-Hoon;Heo, Chul-Heo
    • Journal of the Korean earth science society
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    • v.22 no.4
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    • pp.278-291
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    • 2001
  • Mesothermal gold vein minerals of the Seolhwa mine were deposited in a single stage of massive quartz veins which filled the mainly NE-trending fault shear zones exclusively in the granitoid of the Gyeonggi Massif. The Seolhwa mesothermal gold mineralization is spatially associated with the Jurassic granitoid of 161 Ma. The vein quartz contains three main types of fluid inclusions at 25$^{\circ}$C: 1) low-salinity (< 5 wt.% NaCl), liquid CO$_{2}$-bearing, type IV inclusion; 2) gas-rich (> 70 vol.%), aqueous type II inclusions; 3) aqueous type I inclusions (0${\sim}$15 wt.% NaCl) containing small amounts of CO$_{2}$. The H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl inclusions represent immiscible fluids trapped earlier along the solvurs curve at temperatures from 430$^{\circ}$ to 250$^{\circ}$C and pressures of 1 kbars. Detailed fluid inclusion chronologies may suggest a progressive decrease in pressure during the auriferous mineralization. The aqueous inclusion fluids represent either later fluids evelved through extensive fluid unmixing (CO$_{2}-CH$_{4}$ effervescence) from a homogeneous H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl fluid due to decreases in temperature and pressure, or the influence of deep circulated meteoric waters possibly related to uplift and unloading of the mineralizing suites. The initial fluids were homogeneous containing H$_{2}$O-CO$_{2}-CH$_{4}$-N$_{2}$-NaCl components and the following properties: the initital temperature of >250$^{\circ}$ to 430$^{\circ}$C, X$_{CO}\;_{2}$ of 0.16 to 0.62, 5 to 14 mole% CH$_{4}$, 0.06 to 0.3 mole% N$_{2}$ and salinities of 0.4 to 4.9 wt.% NaCl. The T-X data for the Seolhwa gold mine may suggest that the Seolhwa auriferous hydrothermal system has been probably originated from adjacent granitic melt which facilitated the CH$_{4}$ formation and resulted in a reduced fluid state evidenced by the predominance of pyrrhotite. The dominance of negative ${\delta}\;^{34}$S values of sulfides (-0.6 to 1.4$%_o$o) are consistent with their deep igneous source.

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Simultaneous Catalytic Reduction of NO and N2O over Pd-Rh Supported Mixed Metal Oxide Honeycomb Catalysts - Use of H2 or CO as a Reductant (혼합금속산화물에 담지된 Pd-Rh의 허니컴 촉매에서 NO와 N2O의 동시 환원 - H2 또는 CO 환원제의 사용)

  • Lee, Seung Jae;Moon, Seung Hyun
    • Korean Chemical Engineering Research
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    • v.47 no.1
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    • pp.96-104
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    • 2009
  • In order to lower a reaction temperature with high conversions for simultaneous catalytic reduction of NO and $N_2O$ over Pd-Rh supported mixed metal oxide honeycomb catalysts, $H_2$ or CO was utilized as a reductant. When using the reductants, the effects of reaction conditions were examined in NO and $N_2O$ conversions, where reaction temperatures, concentrations of the reductants and oxygen and the concentration ratio of $N_2O$ to NO were varied. In using $H_2$ reductant, larger than 50% of NO and $N_2O$ conversions was observed at the temperatures below $200^{\circ}C$ in absence of $O_2$. In using CO reductant, NO and $N_2O$ conversions increased from the temperatures higher than $200^{\circ}C$ and $300^{\circ}C$, respectively. However, in use of both reductants, NO and $N_2O$ conversions decreased with increasing oxygen concentration. As a result, $H_2$ reductant could reduce simultaneously NO and $N_2O$ at relatively lower reaction temperature than CO. Also, NO and $N_2O$ conversions were less influenced by using $H_2$ reductant than CO one. Concentration ratio between NO and $N_2O$ did not affect their conversions regardless the type of reductants. Pretreatment of the catalyst in $H_2$ was more effective in simultaneous reduction of NO and $N_2O$ at low reaction temperature than that in $O_2$.

A Novel Hydrogen-reduced P-type Amorphous Silicon Oxide Buffer Layer for Highly Efficient Amorphous Silicon Thin Film Solar Cells (고효율 실리콘 박막태양전지를 위한 신규 수소저감형 비정질실리콘 산화막 버퍼층 개발)

  • Kang, Dong-Won
    • The Transactions of The Korean Institute of Electrical Engineers
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    • v.65 no.10
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    • pp.1702-1705
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    • 2016
  • We propose a novel hydrogen-reduced p-type amorphous silicon oxide buffer layer between $TiO_2$ antireflection layer and p-type silicon window layer of silicon thin film solar cells. This new buffer layer can protect underlying the $TiO_2$ by suppressing hydrogen plasma, which could be made by excluding $H_2$ gas introduction during plasma deposition. Amorphous silicon oxide thin film solar cells with employing the new buffer layer exhibited better conversion efficiency (8.10 %) compared with the standard cell (7.88 %) without the buffer layer. This new buffer layer can be processed in the same p-chamber with in-situ mode before depositing main p-type amorphous silicon oxide window layer. Comparing with state-of-the-art buffer layer of AZO/p-nc-SiOx:H, our new buffer layer can be processed with cost-effective, much simple process based on similar device performances.

Production of Biosurfactant by Tsukamurella sp. 26A (Tsukamurella sp. 26A에 의한 생물계면활성제의 생산)

  • 최경숙;김순한;정영기;장경립;이태호
    • Korean Journal of Microbiology
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    • v.33 no.3
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    • pp.187-192
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    • 1997
  • The strain producing biosurfactant was isolated from soil. The isolated strain was identified as the genus Tsukamurella through its morphological, cultural, physiological, menaquinone type, fatty acid composition characteristics. The highest biosurfactant production by Tsukamurella sp. 26A was observed after 4 days cultivation in the culture medium containing n-hexadecane 7%, $NaNO_{3}$ 0.2%, $K_2HPO_4$ 0.001%, $MgSO_{4}$ center dot $7H_{2}O$ 0.02%, $CaCl_2$ center dot $2H_{2}O$ 0.02%, yeast extract 0.02%(pH 6.8-7.0, 30^{\circ}C.$ The surface and interfacial tension of an aqueous solution reached 30 mNim and 1.5 mNim, respectively. The biosurfactant stabilized oil-in-water emulsion with a variety of hydrocarbons, edible oils and petroleum oils.

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A Study on the Humidity Sensitive Characteristics of Perovskite-type Oxides Containing Alkaline Earth Ions (알칼리토족 이온을 함유한 페로브스카이트형 산화물의 감습특성에 관한 연구)

  • Yuk, J.H.;Lee, N.H.;Kang, D.H.;Han, S.O.;Park, K.H.;Lee, D.C.
    • Proceedings of the KIEE Conference
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    • 1992.07b
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    • pp.737-739
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    • 1992
  • The microstructure and humidity sensitive characteristics of $V_2O_5$ doped $CaTiO_3$ were studied. Sensing elements were prepared in bulk form. This element exhibits a porous structure. The grain grows and electrical conductivity increases as doping amount of $V_2O_5$ increases. The change of impedance and capacitance under different r.h is remarkable, and the conduction carriers of this element were ions.

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Effects of propofol-induced autophagy against oxidative stress in human osteoblasts

  • Kim, Eun-Jung;Choi, In-Seok;Yoon, Ji-Young;Park, Bong-Soo;Yoon, Ji-Uk;Kim, Cheul-Hong
    • Journal of Dental Anesthesia and Pain Medicine
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    • v.16 no.1
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    • pp.39-47
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    • 2016
  • Background: Oxidative stress occurs during the aging process and other conditions such as bone fracture, bone diseases, and osteoporosis, but the role of oxidative stress in bone remodeling is unknown. Propofol exerts antioxidant effects, but the mechanisms of propofol preconditioning on oxidative stress have not been fully explained. Therefore, the aim of this study was to evaluate the protective effects of propofol against $H_2O_2$-induced oxidative stress on a human fetal osteoblast (hFOB) cell line via activation of autophagy. Methods: Cells were randomly divided into the following groups: control cells were incubated in normoxia (5% $CO_2$, 21% $O_2$, and 74% $N_2$) without propofol. Hydrogen peroxide ($H_2O_2$) group cells were exposed to $H_2O_2\;(200{\mu}M)$ for 2 h, propofol preconditioning (PPC)/$H_2O_2$ group cells were pretreated with propofol then exposed to $H_2O_2$, 3-methyladenine (3-MA)/PPC/$H_2O_2$ cells were pretreated with 3-MA (1 mM) and propofol, then were exposed to $H_2O_2$. Cell viability and apoptosis were evaluated. Osteoblast maturation was determined by assaying bone nodular mineralization. Expression levels of bone related proteins were determined by western blot. Results: Cell viability and bone nodular mineralization were decreased significantly by $H_2O_2$, and this effect was rescued by propofol preconditioning. Propofol preconditioning effectively decreased $H_2O_2$-induced hFOB cell apoptosis. However, pretreatment with 3-MA inhibited the protective effect of propofol. In western blot analysis, propofol preconditioning increased protein levels of collagen type I, BMP-2, osterix, and TGF-${\beta}1$. Conclusions: This study suggests that propofol preconditioning has a protective effect on $H_2O_2$-induced hFOB cell death, which is mediated by autophagy activation.

Effects of Open or Closed Suctioning on Lung Dynamics and Hypoxemia in Mechanically Ventilated Patients (기관 내 흡인 유형이 인공호흡기 대상자의 폐기능과 저산소혈증에 미치는 효과)

  • Lee, Eun Young;Kim, Su Hyun
    • Journal of Korean Academy of Nursing
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    • v.44 no.2
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    • pp.149-158
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    • 2014
  • Purpose: This study was conducted to compare effects of open and closed suctioning methods on lung dynamics (dynamic compliance, tidal volume, and airway resistance) and hypoxemia (oxygen saturation and heart rate) in mechanically ventilated patients. Methods: This study was a cross-over repeated design. Participants were 21 adult patients being treated with endotracheal intubation using a pressure-controlled ventilator below Fraction of Inspired Oxygen ($FiO_2$) 60% and PEEP $8cmH_2O$. Data were collected at baseline and 1, 2, 3, 4, 5, and 10 minutes after suctioning. Data were analyzed using two-factor ANOVA with repeated measures on time and suctioning type. Results: Effects of the interaction between suction type and time were significant for oxygen saturation and heart rate but not significant for dynamic compliance, tidal volume, or airway resistance. Prior to performance of suctioning, tidal volume and oxygen saturation were significantly lower, but airway pressure and heart rate were significantly higher using the closed suctioning method as compared with the open suctioning method. Conclusion: For patients on ventilator therapy below $FiO_2$ 60% and PEEP $8cmH_2O$, open suctioning performed after delivery of 100% $FiO_2$ using a mechanical ventilator may not have as much negative impact on lung dynamics and hypoxemia as closed suctioning.