• Title/Summary/Keyword: Bond mechanism

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Sensitivity of Ozone to NOx and VOCs in a Street Canyon (도로 협곡에서 NOx와 VOCs에 대한 오존의 민감도)

  • Lee, Kwang-Yeon;Kwak, Kyung-Hwan;Park, Seung-Bu;Baik, Jong-Jin
    • Journal of Korean Society for Atmospheric Environment
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    • v.29 no.3
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    • pp.307-316
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    • 2013
  • The sensitivity of ozone to $NO_x$ and volatile organic compounds (VOCs) emission rates under different ventilation rates and $NO_2-to-NO_x$ emission ratios in a street canyon is investigated using a chemistry box model. The carbon bond mechanism IV (CBM-IV) with 36 gaseous species and 93 chemical reactions is incorporated. $NO_x$ and VOCs emission rates considered range from 0.01 to $0.30ppb\;s^{-1}$ with intervals of $0.01ppb\;s^{-1}$. Three different ventilation rates and three different $NO_2-to-NO_x$ emission ratios are considered. The simulation results show that the ozone concentration decreases with increasing $NO_x$ emission rate but increases with increasing VOCs emission rate. When the emission ratio of VOCs to $NO_x$ is smaller than about 4, the ozone concentration is lower in the street canyon than in the background. On average, the magnitude of the sensitivity of ozone to $NO_x$ emission rate is significantly larger than that to VOCs emission rate. As the $NO_x$ emission rate increases, the magnitude of the sensitivity of ozone to $NO_x$ and VOCs emission rates decreases. Because the ozone concentration is lower in the street canyon than in the background, the increased ventilation rate enhances ozone inflow from the background. Therefore, the increase in ventilation rate results in the increase in ozone concentration and the decrease in the magnitude of the sensitivity of ozone to $NO_x$ and VOCs emission rates when the emission ratio of VOCs to $NO_x$ is smaller than about 4. On the other hand, the increase in $NO_2-to-NO_x$ emission ratio results in the increase in ozone concentration because the chemical ozone production due to the $NO_2$ photolysis is enhanced. In the present experimental setup, the contribution of the change in $NO_2-to-NO_x$ emission ratio to the change in the sensitivity of ozone to $NO_x$ emission rate is larger than that of the change in ventilation rate.

A Study on the Degradation Mechanism of Diazinon and the Acute Toxicity Assessment in Photolysis and Photocatalysis (광반응과 광촉매 반응을 이용한 Diazinon 농약의 분해 기전과 독성 평가에 관한 연구)

  • Oh, Ji-Yoon;Kim, Moon-Kyung;Son, Hyun-Seok;Zoh, Kyung-Duk
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.11
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    • pp.1087-1094
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    • 2008
  • Diazinon is a phosphorothiate insecticide widely used in the world including Korea. This study investigates the feasibility of photolysis and photocatalysis processes for the degradation of diazinon in water. Both photolysis and photocatalysis reactiosn were effective in degrdading diazinon, however lower TOC removals were achieved. In case of photocatalysis, approximately 40% of nitrogen from diazinon was recovered as NO$_3^-$, and less than 5% of phosphorus as PO$_4{^{3-}}$. However, the sulfur in diazinon molecule was completely recovered to SO$_4{^{2-}}$ from photocatalysis reaction, and the recovery from photolysis was 50%, indicating that P=S bond easily breaks first during photolysis and photocatalysis. The poor recoveries of ionic byproducts and TOC from photolysis and photocatalysis indicate the presence of other organic intermediates during reactions. The formation of organic intermediates were identified during reactions using GC/MS and LC/MS/MS, and the main degradation products were diazoxon, and 2-isopropyl-4-methyl-6-hydroxypyrimidine (IMP), respectively. Finally, the acute 48-hr toxicity test using Daphnia magna were employed to measure the toxicity reduction during photocatalysis of degradation. The results showed that the toxicity increased until 180 min of the photocatalysis reaction (from EC$_{50}$ (%) of 69.6 to 13.2%), however, acute toxicity completely disappeared (>100%) after 360 min. The toxicity results showed that the intermediates from photocatalysis such as diazoxon were more toxic than diazinon itself, however these intermediates can be degraded or mineralized with further reaction.

Screening of Anti-Biofilm Compounds from Marine-Derived Fungi and the Effects of Secalonic Acid D on Staphylococcus aureus Biofilm

  • Wang, Jie;Nong, Xu-Hua;Zhang, Xiao-Yong;Xu, Xin-Ya;Amin, Muhammad;Qi, Shu-Hua
    • Journal of Microbiology and Biotechnology
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    • v.27 no.6
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    • pp.1078-1089
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    • 2017
  • Biofilm formation of Staphylococcus aureus is one of its mechanisms of drug resistance. Anti-biofilm screening of 106 compounds from marine-derived fungi displayed that 12 compounds inhibited S. aureus biofilm formation by >50% at the concentration of $100{\mu}g/ml$, and only secalonic acid D (SAD) and B inhibited by >90% at $6.25{\mu}g/ml$ without inhibiting cell growth after 24-h incubation. Meanwhile, it was found that the double bond between C-1 and C-10 of citrinin derivatives and the C-C connection position of two chromone monomers may be important for their anti-biofilm activities. Moreover, SAD slightly facilitated biofilm eradication and influenced its architecture. Furthermore, SAD slowed the cell growth rate in the preceding 18-h incubation and differentially regulated transcriptional expression of several genes, such as agr, isaA, icaA, and icaD, associated with biofilm formation in planktonic and biofilm cells, which may be the reason for the anti-biofilm activity of SAD. Finally, SAD acted synergistically against S. aureus growth and biofilm formation with other antibiotics. These findings indicated that various natural products from marine-derived fungi, such as SAD, could be used as a potential biofilm inhibitor against S. aureus.

Studies on the Quaternization of Tertiary Amines (I). Kinetics and Mechanism for the Reaction of Phenethyltosylate with Substituted Pyridines (3 차아민의 4 차화반응에 관한 연구 (제1보). Phenethyltosylate 와 치환 피리딘류의 반응에 관한 반응 속도론적 연구)

  • Kyung-A Lee;Kyu-Tag Howang;Soo-Dong Yoh
    • Journal of the Korean Chemical Society
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    • v.23 no.4
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    • pp.243-247
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    • 1979
  • Kinetics of the reaction of phenethyltosylate with substituted pyridines at 50, 60 and 70$^{\circ}C$ in acetonitrile were investigated by an electric conductivity method. The effects of substituents on the reaction of phenethyltosylate with pyridines were discussed. The rates of reaction were increased with electron donating power of substituents of pyridines. The isokinetic relationship was shown $E_{\alpha}$ and ${\Delta}S^{\neq}$, it's temperature was 240$^{\circ}$K. Bronsted plots were excellent linear except for 4-amino pyridine given by the following equation, logk=O. 22pKa-3.71 (r=O. 986). According to a plot of log k against Hammett substituent constants, the Iinearity was good except for bamino pyridine too, log k= -1.330${\sigma}$+0.08 (r= -0.987). In both cases, deviation of 4-amino pyridine from linearity was considered to solvent effect, resonance effect and ${\sigma}$ value itself. From all the above results, this reaction was found typical $S_N2$ reaction which the rates of reaction was determined by C…N bond formation at transition state.

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A Long Run Classical Model of Price Determination (한국(韓國)의 물가모형(物價模型))

  • Park, Woo-kyu;Kim, Se-jong
    • KDI Journal of Economic Policy
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    • v.14 no.4
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    • pp.3-26
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    • 1992
  • The pupose of this paper is to construct a price determination model of the Korean economy and to find out the propogation mechanism of monetary and fiscal policies. The model is a small-size macroeconometric model consisted of ten core equations : consumption, investment, exports, imports, consumer price index, wage rate, corporate bond rate, potential GNP, capital stock, and GNP identity. The model is a Keynesian model : consumer price index is determined by markup over costs, and wage rate is expressed by Phillipse curve ralation. Two features of the model, however, distinguish this model from other macroeconometric models of the Korean economy. First of all, the estimation of potential GNP and the capital stock is endogenized as suggested by Haque, Lahiri, and Montiel (1990). This allows us to calculate the level of excess demand, which is defined as the difference between the actual GNP and the potential GNP. Second, interest rate, inflation and wages are all estimated as endogenous variables. Moreover, all quantity variables include price variables as important determinants. For instance, interest rate is an important determinant of consumption and investment. Exports and imports are determined by the real effective exchange rate. These two features make the interactions between excess demand and prices the driving forces of this model. In the model, any shock which affects quantity variable(s) affects excess demand, which in turn affects prices. This strong interaction between prices and quantities makes the model look like a classical model over the long run. That is, increases in money supply, government expenditures, and exchange rate (the price of the U.S. dollar in terms of Korean won) all have expansionery effects on the real GNP in the short run, but prices, wage, and interest rate all increase as a result. Over the long run, higher prices have dampenning effects on output. Therefore the level of real GNP turns out to be not much different from the baseline level ; on the other hand, the rates of inflation, wage and interest rate remain at higher levels.

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A Study on the Etching Mechanism of $(Ba, Sr)TiO_3$ thin Film by High Density $BCl_3/Cl_2/Ar$ Plasma ($BCl_3/Cl_2/Ar$ 고밀도 플라즈마에 의한 $(Ba, Sr)TiO_3$ 박막의 식각 메커니즘 연구)

  • Kim, Seung-Bum;Kim, Chang-Il
    • Journal of the Institute of Electronics Engineers of Korea SD
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    • v.37 no.11
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    • pp.18-24
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    • 2000
  • (Ba,Sr)$TiO_3$ thin films have attracted great interest as new dielectric materials of capacitors for ultra-large-scale integrated dynamic random access memories (ULSI-DRAMs) such as 1 Gbit or 4 Gbit. In this study, inductively coupled $BCl_3/Cl_2/Ar$ plasmas was used to etch (Ba,Sr)$TiO_3$ thin films. RF power/dc bias voltage=600 W/-250 V and chamber pressure was 10 mTorr. The $Cl_2/(Cl_2+Ar)$ was fixed at 0.2 the (Ba,Sr)$TiO_3$ thin films were etched adding $BCl_3$. The highest (Ba,Sr)$TiO_3$ etch rate is $480{\AA}/min$ at 10 % $BCl_3$ to $Cl_2/Ar$. The change of Cl, B radical density measured by optical emission spectroscopy(OES) as a function of $BCl_3$ percentage in $Cl_2/Ar$. The highest Cl radical density was shown at the addition of 10% $BCl_3$ to $Cl_2/Ar$. To study on the surface reaction of (Ba, Sr)$TiO_3$ thin films was investigated by XPS analysis. Ion bombardment etching is necessary to break Ba-O bond and to remove $BaCl_2$. There is a little chemical reaction between Sr and Cl, but Sr is removed by physical sputtering. There is a chemical reaction between Ti and Cl, and $TiCl_4$ is removed with ease. The cross-sectional of (Ba,Sr)$TiO_3$ thin film was investigated by scanning electron microscopy (SEM), the etch slope is about 65~70$^{\circ}$.

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Kinetics on the Reaction of Substituted Quinolines and p-Substituted Benzoylchlorides under Various Pressures (압력변화에 따른 퀴놀린 유도체와 p-치환 염화벤조일류의 속도론적 연구)

  • Jong-Wan Lim;Se-Kyong Kim
    • Journal of the Korean Chemical Society
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    • v.47 no.3
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    • pp.206-212
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    • 2003
  • The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

Mutant Recombinant Hemoglobin (${\alpha}96Val{\rightarrow}Tyr$) Exhibits Low Oxygen Affinity and High Cooperativity

  • Choi, Jong-Whan;Yeh, Byung-Il;Han, Dong-Pyou;Lee, Hyean-Woo;Sohn, Joon Hyung;Jung, Seun-Ho;Kim, Hyun-Won
    • BMB Reports
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    • v.31 no.6
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    • pp.595-599
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    • 1998
  • To investigate conformational information of a low oxygen affinity recombinant hemoglobin (rHb) containing $96Val{\rightarrow}Trp$ mutation at the ${\alpha}96$ position, we ave produced rHb (${\alpha}96Val{\rightarrow}Phe$) and rHb (${\alpha}96Val{\rightarrow}Tyr$), using the Escherichia coli expression system and site-directed mutagenesis. The oxygen affinity of rHb (${\alpha}96Val{\rightarrow}Phe$) is similar to that of human normal adult hemoglobin (Hb A). However, the oxygen affinity of rHb (${\alpha}96Val{\rightarrow}Tyr$) showed much lower oxygen affinity than Hb A which is similar to that of rHb (${\alpha}96Val{\rightarrow}Tyr$), providing an opportunity as a potential candidate for a hemoglobin-based blood substitute. Both rHb (${\alpha}96Val{\rightarrow}Phe$) and rHb (${\alpha}96Val{\rightarrow}Tyr)$ showed high cooperativity in oxygen binding. IH-NMR spectroscopy shows that both rHb (${\alpha}96Val{\rightarrow}Phe$) and rHb (${\alpha}96Val{\rightarrow}Tyr$) have very similar tertiary structure around the heme pockets and uaternary structure in the ${\alpha}_1/{\beta}_2$ subunit interface ompared to Hb A. The low oxygen affinity of rHb (${\alpha}96Val{\rightarrow}Tyr$) has been suggested to be due to a hydrogen bond caused by an extra hydroxyl group not present in rHb (${\alpha}96Val{\rightarrow}Phe$). However, investigation of the carbonmonoxy form of rHb (${\alpha}96Val{\rightarrow}Phe$) and (${\alpha}96Val{\rightarrow}Try$) in the presence of inositol hexaphosphate at low temperature suggests that low oxygen affinity of (${\alpha}96Val{\rightarrow}Try$) may arise from a mechanism different to that of rHb (${\alpha}96Val{\rightarrow}Trp$).

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Kinetics of the Reaction of Phenacyl Bromide with Anilines in Methanol and Dimethylformamide (Phenacyl Bromide와 置換아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Soo-Dong Yoh;Doo-Jung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.376-382
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    • 1981
  • The rates and the activation parameters for the reaction of phenacyl bromide with substituted anilines in methanol and dimethylformamide were measured. The effects of substituted anilines were discussed. The rate of the reaction was increased with the electron donating power of substituent and showed larger value in DMF than in MeOH. The isokinetic relationship was shown between ${\delta}H^{\neq}$ and ${\delta}S^{\neq}$, isokinetic temperature was 539 and $400^{\circ}C$ in MeOH and DMF respectively, but p-nitro aniline was deviated from linearity in both solvents caused by solvent effects. The excellent linear relationship between log k and p$K_a$ of substituted anilines was observed by following equation. log k = 0.57p$K_a$-1.28 (r = 0.996) in MeOH at $45^{\circ}C$, log k = 0.65p$K_a$-0.88 (r = 0.970) in DMF at $45^{\circ}C$. From the Hammett plot, this reaction was a nucleophilic displacement of aniline to phenacyl bromide and the following equation was obtained at $45^{\circ}C$. log k/$k_0$ = -2.00${\sigma}$ + 0.06 (r = 0.985) in MeOH; log k/$k_0$ = -2.22${\sigma}$ + 0.08 (r = 0.995) in DMF. Large deviation of p-nitro aniline in DMF is resulted from solvent effects too. From above results, the substituent effect of this reaction can be described as $S_N2$ mechanism and bond formation more proceeds in DMF relative to MeOH.

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Kinetic Studies on the Reaction of 4-Substituted-2,6-dinitrochlorobenzenes with Substituted Anilines in MeOH-MeCN Mixtures (MeOH-MeCN 혼합용매계에서 4-치환-2,6-이니트로 염화벤젠과 아닐린 치환체와의 반응에 대한 속도론적 연구)

  • Dae-Ho Kang;In-Sun Koo;Jong Gun Lee;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.6
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    • pp.565-574
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    • 1985
  • The rates of reaction between 4-substituted-2,6-dinitrochlorobenzenes with para-substituted anilines in methanol-acetonitrile mixtures were measured by conductometry. It was observed that the rate constant increases in the order of X = 4-$NO_2 {\gg}4-CN {\gg}4- CF_3$, where X is a substituent in the substrate. The rate constant also increases in the order of Y = p-O$CH_3{\gg}p- CH_3{\gg}H {\gg}p-Cl{\gg}m- NO_2$, where Y is a substituent in the aniline ring. Kinetic studies in the methanol-acetonitrile solvent system with various nucleophiles showed that the N-C bond forming step is making a great contribution to the overall second order rate constant. The electrophilic catalysis by methanol probably consists of the hydrogen bonding between alcoholic hydrogen and leaving chloride in the transition state. The nucleophilic catalysis by methanol may be ascribed to the formation of hydrogen bonds between alcoholic oxygen and hydrogens of amines in the transition state. All these experimental facts are supporting the operation of $S_N$Ar machanism with the second step being the rate determining. This mechanism can be successfully fitted to the PES model.

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