• Title/Summary/Keyword: pH dependence

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N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

  • Puttaswamy;Shubha, J.P.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1939-1945
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    • 2009
  • Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

Sorption of $UO^{2+}_2$ onto Goethite and Kaolinite: Mechanistic Modeling Approach

  • Jinho Jung;Lee, Jae-Kwang;Cho, Young-Hwan;Keum, Dong-Kwon;Hahn, Pil-Soo
    • Nuclear Engineering and Technology
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    • v.31 no.2
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    • pp.182-191
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    • 1999
  • The sorption of UO$_{2}$$^{2+}$ onto goethite and kaolinite under various experimental conditions was successfully interpreted using surface complexation modeling (SCM). The SCM approach used in this work is the triple-layer model (TLM) in which weakly bonded ions are modeled as outer-sphere (ion-pair) complexes and strongly bonded ions as inner-sphere (surface coordination) complexes. The change of ionic strength did not affect the U(VI) sorption onto goethite, thus the formation of inner-sphere surface complexes, (FeO)$_2$UO$_2$ and (FeO)$_2$(UO$_2$)$_3$OH$_{5}$ was assumed to simulate the effects of ionic strength and goethite concentration. On the other hand, the U(VI) sorption onto kaolinite showed ionic strength dependence, thus the formation of AlO-UO$_{2}$$^{2+}$(outer-sphere complex) and SiO(UO$_2$)$_3$OH$_{5}$ (inner-sphere complex) was assumed to simulate the experimental data. In the presence of carbonates, the sorption of U(VI) onto kaolinite decreased in the weakly alkaline pH range. This was well simulated assuming the formation of a outer-sphere surface complex, A1OH$^{2+}$- (UO$_2$)$_2$CO$_3$OH$_3$. Since SCM approach uses thermodynamic data such as surface complexation constants, it is more predictive than empirical modeling approach in which conditional values such as partition coefficient are used. used.

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Control of Dimethyl Sulfide Emissions Using Biofiltration

  • Kong, Sei-Hun;Kim, Jo-Chun;Allen, Eric R.;Park, Jong-Kil
    • Journal of Environmental Science International
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    • v.11 no.8
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    • pp.819-827
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    • 2002
  • Laboratory scale experiments were conducted to evaluate the performance of a biofilter for eliminating dimethyl sulfide(DMS). A commercial compost/pine bark nugget mixture served as the biofilter material for the experiments. The gas flow rate and DMS concentration entering the filter were varied to study their effect on the biofilter efficiency. The operating parameters, such as the residence time, inlet concentration, pH, water content, and temperature, were all monitored throughout the filter operation. The kinetic dependence of the DMS removal along the column length was also studied to obtain a quantitative description of the DMS elimination. High DMS removal efficiencies(>95%) were obtained using the compost filter material seeded with activated sludge. DMS pollutant loading rates of up to 5.2 and 5.5 g-DMS/m$^3$/hr were effectively handled by the upflow and downflow biofilter columns, respectively. The macrokinetics of the DMS removal were found to be fractional-order diffusion-limited over the 9 to 25 ppm range of inlet concentrations tested. The upflow column had an average macrokinetic coefficient(K$\_$f/) of 0.0789 $\pm$ 0.0178 ppm$\^$$\sfrac{1}{2}$//sec, while the downflow column had an average coefficient of 0.0935 $\pm$ 0.0200 ppm$\^$$\sfrac{1}{2}$//sec. Shorter residence times resulted in a lower mass transfer of the pollutant from the gas phase to the aqueous liquid phase, thereby decreasing the efficiency.

Advanced Transmittance and Surface-Morphology of CdS thin films prepared by chemical bath deposition using various complexing agents for solar cells (용액 증착법으로 증착된 CdS 박막의 제조와 고상과 액상 화합제에 따른 표면 특성 비교)

  • Yoo, Beom-Keun;Kim, Jin-Sang;Park, Yong-Wook;Choi, Doo-Jin;Yoon, Seok-Jin
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.456-456
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    • 2008
  • In the past few years, the deposition and characterization of cadmium sulfide semiconducting thin films has received a considerable amount of interest due to their potential application in the area of electronic and opto-electronic devices fabrications. Polycrystalline CdS thin films posses good optical transmittance, wide band-gap and electrical properties makes it as one of the ideal material for their application to solar cell fabrication. Cadmium sulfate thin films were deposited by the chemical bath deposition method using tartaric acid and triethanolamine as a complexing agent. Deposition parameters such as pH, temperature, deposition time and concentration of the reactant species were optimized so as to obtain reflecting, good adherent uniform thin films on the glass substrate. Reaction mechanism of the thin film formation is also reported. The crystallographic structure and the crystallite size were studied by the X-ray diffraction pattern. The optical band-gap of deposited film is identified by measuring the transmittance in the visible region. Temperature dependence of resistivity confirmed the semiconducting behavior of the film. Scanning electron micrographs (SEM) showed the presence of grain particles of size 50 nm.

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Development of Active thin Film Optical Waveguide $C^{2+}$ -ion Sensor (능동형 박막 광도파로 칼슘 이온 센서의 개발)

  • Lee, Su-Mi;Gang, Sin-Won
    • Journal of the Institute of Electronics Engineers of Korea SC
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    • v.37 no.4
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    • pp.49-54
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    • 2000
  • A new functional organic thin film optical waveguide ion sensor is designed, which can select a specific ion, i.e., $Ca^{2+}$ -ion. The sensing membrane was composed of PVC-PVAC-PVA copolymer matrix based on anionic cation-selective chromoionophor(ETH5294), neutral ionophore(K23El), anionic site and plasticizer and it was coated on the etched glass substrate as embeded type optical waveguide itself. The sensor sensitivity dependence on waveguide length and thickness, contence of chromoionophore, and each mode was investigated. And this sensor could detect $Ca^{2+}$ ion in concentrations ranging from 1$\times$10­6~1M(with 0.05M tris-HCI buffer solution of pH7.4) by measuring the absorbance change at 514nm of light. Utilizing thin film membrane, the fast response time and high sensitivity are obtained. Also, it is expected that this sensor can be applied to various biochemical important ions.ons.

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Nonstoichiometry of the Yttrium Oxide and the Holmium Oxide (산화이트륨 및 산화홀뮴의 비화학양론)

  • Chang, Soon-Ho;Yo, Chul-Hyun;Choi, Jae-Shi;Pyun, Mu-Sil
    • Journal of the Korean Chemical Society
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    • v.28 no.4
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    • pp.231-237
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    • 1984
  • The x-values in the nonstoichiometric chemical formulas $YO_{1.5+x}\;and\;HoO_{1.5+x}$, have been measured in the temperature range from 700$^{\circ}$C to 1000$^{\circ}$C under oxygen pressures from $2{\times}l0^{-1}\;to\;1{\times}10^{-6}$ atm by gravimetric method. The observed x-values increase with increasing temperature and oxygen pressure. The enthalpies of formation of excess oxygen in yttrium oxide and holmium oxide decrease with decreasing oxygen pressure and are all positive values representing an endothermic process. The 1/n values calculated from the slopes of the plots of log x vs. log $P_{O2}$ increase with temperature and are positive values which means the higher oxygen pressure dependence at higher temperature. We have examined the nonstoichiometric defect and conduction mechanism from x-values and thermodynamic data.

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Fabrication Thermal Responsive Tunable ZnO-stimuli Responsive Polymer Hybrid Nanostructure

  • Lee, Jin-Su;Nam, Sang-Hun;Yu, Jung-Hun;Hwang, Ki-Hwan;Ju, Dong-Woo;Jeon, So-Hyoun;Seo, Hyeon-Jin;Yun, Sang-Ho;Boo, Jin-Hyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.429.2-429.2
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    • 2014
  • ZnO nanowire is known as synthesizable and good mechanical properties. And, stimuli-responsive polymer is widely used in the application of tunable sensing device. So, we combined these characteristics to make precise tunable sensing devise. In this work, we investigate the dependence of ZnO nanowire alignment and morphology on si substrate using nanosphere template with various conditions via hydrothermal process. Also, pH-temperature dependant tuning ability of nanostructure was studied. The brief experimental scheme is as follow. First, Zno seed layer was coated on a si wafer ($20{\times}20mm$) by spin coater. And then $1.15{\mu}m$ sized close-packed PS nanospheres were formed on a cleaned si substrate by using gas-liquid-solid interfacial self-assembly method. After that, zinc oxide nanowires were synthesized using hydrothermal method. Before the wire growth, to specify the growth site, heat treatment was performed. Finally, NIPAM(N-Isopropylacrylamide) was coated onto as-fabricated nanostructure and irradiated by UV light to form the PNIPAM network. The morphology, structures and optical properties are investigated by FE-SEM(Field Emission Scanning electron Microscopy), XRD(X-ray diffraction), OM(Optical microscopy), and WCA(water contact angle).

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Low cost, highly sensitive and selective electrochemical detection of arsenic (III) using silane grafted based nanocomposite

  • Lalmalsawmi, Jongte;Zirlianngura, Zirlianngura;Tiwari, Diwakar;Lee, Seung-Mok
    • Environmental Engineering Research
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    • v.25 no.4
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    • pp.579-587
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    • 2020
  • Novel silane grafted bentonite was obtained using the natural bentonite as precursor material. The material which is termed as nanocomposite was characterized by the Fourier Transform Infra-red (FT-IR) and X-ray diffraction (XRD) methods. The surface imaging and elemental mapping was performed using Scanning Electron Microscopic (SEM/EDX) technique. The electroanalytical studies were performed using the nanocomposite electrode. The electroactive surface area of nanocomposite electrode was significantly increased than the pristine bentonite or bare carbon paste based working electrode. The impedance spectroscopic studies were conducted to simulate the equivalent circuit and Nyquist plots were drawn for the carbon paste electrode and nanocomposite electrodes. A single step oxidation/reduction process occurred for As(III) having ΔE value 0.36 V at pH 2.0. The anodic stripping voltammetry was performed for concentration dependence studies of As(III) (0.5 to 20.0 ㎍/L) and reasonably a good linear relationship was obtained. The detection limit of the As(III) detection was calculated as 0.00360±0.00002 ㎍/L having with observed relative standard deviations (RSD) less than 4%. The presence of several cations and anions has not affected the detection of As(III) however, the presence of Cu(II) and Mn(II) affected the detection of As(III). The selectivity of As(III) was achieved using the Tlawng river water sample spiked with As(III).

Biochemical and Genetic Characterization of Arazyme, an Extracellular Metalloprotease Produced from Serratia proteamaculans HY-3

  • Kwak, Jang-Yul;Lee, Ki-Eun;Shin, Dong-Ha;Maeng, Jin-Soo;Park, Doo-Sang;Oh, Hyun-Woo;Son, Kwang-Hee;Bae, Kyung-Sook;Park, Ho-Yong
    • Journal of Microbiology and Biotechnology
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    • v.17 no.5
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    • pp.761-768
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    • 2007
  • Serratia proteamaculans HY-3 isolated from the digestive tract of a spider produces an extracellular protease named arazyme, with an estimated molecular mass of 51.5 kDa. The purified enzyme was characterized as having high activities at wide pH and temperature ranges. We further characterized biochemical features of the enzymatic reactions under various reaction conditions. The protease efficiently hydrolyzed a broad range of protein substrates including albumin, keratin, and collagen. The dependence of enzymatic activities on the presence of metal ions such as calcium and zinc indicated that the enzyme is a metalloprotease, together with the previous observation that the proteolytic activity of the enzyme was not inhibited by aspartate, cysteine, or serine protease inhibitors, but strongly inhibited by 1,10-phenanthroline and EDTA. The araA gene encoding the exoprotease was isolated as a 5.6 kb BamHI fragment after PCR amplification using degenerate primers and subsequent Southern hybridization. The nucleotide sequence revealed that the deduced amino acid sequences shared extensive similarity with those of the serralysin family of metalloproteases from other enteric bacteria. A gene(inh) encoding a putative protease inhibitor was also identified immediately adjacent to the araA structural gene.

Carbon Dioxide Production and Quality Changes in Korean Fermented Soybean Paste and Hot Pepper-Soybean Paste (포장된 전통 된장 및 고추장의 저장 중 $CO_2$ 발생과 특성변화)

  • Kim, Gi-Tae;Hwang, Yong-Il;Lim, Seong-Il;Lee, Dong-Sun
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.29 no.5
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    • pp.807-813
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    • 2000
  • One hundred fifty grams of Korean fermented soybean paste and hot pepper-soybean paste were packaged in glass jar of 232 mL and Sotred at 5, 13, 22 and 30℃. During the storage, the changes in their microbial flora and quality attributes were monitored. Carbon dioxide production rate from the stored pastes were also determined from initial change of CO₂concentration in headspace of the pack. Hot pepper-soybean pate showed much higher CO₂ production rate higher dependence of CO₂ production on temperature compared to soybean paste. Total aerobic bacteria count and lactic acid bacteria count did not change significantly through the storage. Yeast count in soybean paste decreased slowly after initial uprise while that of hot pepper-soybean paste steadily decreased. Surface color of hot pepper paste changed to dark red with slight decrease in 'L' value and slight increase in 'a' and 'b' values, whereas any significant color change was not observed in soy paste. Titratable acidity increased with time with higher increase in soybean paste, but pH stayed at constant level for both pastes. All the rates of quality change were higher with higher temperature. Pressure buildup due to CO₂ production needs to be considered first in designing the packages of the fermented pastes before their color changes and other chemical quality changes.

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