• Title/Summary/Keyword: intermediates

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Porous silica ceramics prepared by sol-gel process-Effect of $H_2O/TEOS$ molar ratio- (솔-젤법에 의한 다공성 실리카 세라믹스의 제조-$H_2O/TEOS$ 몰비의 영향-)

  • Lee, Jin-Hui;Kim, Wha-Jung;Lee, Joon
    • Journal of the Korean Ceramic Society
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    • v.34 no.2
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    • pp.216-224
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    • 1997
  • Porous silica ceramics were prepared(with HCI catalyst) using H2O/TEOS molar ratios of 2.6~59.0, with the EtOH/TEOS ratio fixed. After preparing 9 kinds of sol, the followings were investigated; measurement of the gelation time, thermal analyses by TG/DTA, property analyses of the intermediates by FT-IR and X-ray diffractometry with dried samples, analyses of SiO2 polymer by FT-IR, the investigation of specific sur-face area and pore size distribution by N2-adsorption isotherm, and structural change of SiO2 polymer and pore morphology by TEM observation, with samples heat-treated to 50$0^{\circ}C$. In the concentrations of in-vestigated compositions and catalyst, gelation time showed a minimum at ca. 11 moles of water per one mole of TEOS, the highest degree of polymerization at ca. 8-18 moles, and the largest specific surface area at ca. 11 moles, which means that the polymerization proceeded fastest at ca. 11 moles of water. In con-clusion, the more water used, the faster the polymerization reaction up to ca. 11 moles, but more than ca. 11 moles of water caused retardation of gelation and resultant reduction of specific surface area.

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Determination of Adsorption Isotherms of Hydroxide ata Platinum Electrode Interface Using the Phase-Shift Method and Correlation Constants

  • Chun, Jin-Y.;Chun, Jang-H.
    • Journal of the Korean Electrochemical Society
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    • v.10 no.3
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    • pp.219-228
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    • 2007
  • The phase-shift method and correlation constants, i.e., the electrochemical impedance spectroscopy (EIS) techniques for studying linear relationships between the behaviors (${\varphi}\;vs.\;E$) of the phase shift ($0^{\circ}{\leq}-{\varphi}{\leq}90^{\circ}$) for the optimum intermediate frequency and those (${\theta}\;vs.\;E$) of the fractional surface coverage ($1{\geq}{\theta}{\geq}0$), have been proposed and verified to determine the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$) of H for the cathodic $H_2$ evolution reaction (HER) at noble and transition-metal/aqueous solution interfaces. At the Pt/0.1 MKOH aqueous solution interface, the Langmuir, Frumkin, and Temkin adsorption isotherms (${\theta}\;vs.\;E$), equilibrium constants ($K=5.6{\times}10^{-10}\;mol^{-1}\;at\;0{\leq}{\theta}<0.81$, $K=5.6{\times}10^{-9}{\exp}(-4.6{\theta})\;mol^{-1}\;at\;0.2<{\theta}<0.8$, and $K=5.6{\times}10^{-10}{\exp}(-12{\theta})\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$, interaction parameters (g = 4.6 for the Temkin and g = 12 for the Frumkin adsorption isotherm), rates of change of the standard free energy ($r=11.4\;kJ\;mol^{-1}$ for g=4.6 and $r=29.8\;kJ\;mol^{-1}$ for g=12), and standard free energies (${\Delta}G_{ads}^0=52.8\;kJ\;mol^{-1}\;at\;0{\leq}{\theta}<0.81,\;49.4<{\Delta}G_{\theta}^0<56.2\;kJ\;mol^{-1}\;at\;0.2<{\theta}<0.8$ and $80.1<{\Delta}_{\theta}^0{\leq}82.5\;kJ\;mol^{-1}\;at\;0.919<{\theta}{\leq}1$) of OH for the anodic $O_2$ evolution reaction (OER) are also determined using the phase-shift method and correlation constants. The adsorption of OH transits from the Langmuir to the Frumkin adsorption isotherm (${\theta}\;vs.E$), and vice versa, depending on the electrode potential (E) or the fractional surface coverage (${\theta}$). At the intermediate values of ${\theta}$, i.e., $0.2<{\theta}<0.8$, the Temkin adsorption isotherm (${\theta}\;vs.\;E$) correlating with the Langmuir or the Frumkin adsorption isotherm (${\theta}\;vs.\;E$), and vice versa, is readily determined using the correlation constants. The phase-shift method and correlation constants are accurate and reliable techniques to determine the adsorption isotherms and related electrode kinetic and thermodynamic parameters. They are useful and effective ways to study the adsorptions of intermediates (H, OH) for the sequential reactions (HER, OER) at the interfaces.

Biosynthetic pathway of shikimate and aromatic amino acid and its metabolic engineering in plants (식물에서 shikimate 및 방향족 아미노산 생합성 경로와 이의 대사공학적 응용)

  • Lim, Sun-Hyung;Park, Sang Kyu;Ha, Sun-Hwa;Choi, Min Ji;Kim, Da-Hye;Lee, Jong-Yeol;Kim, Young-Mi
    • Journal of Plant Biotechnology
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    • v.42 no.3
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    • pp.135-153
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    • 2015
  • The aromatic amino acids, which are composed of $\small{L}$-phenylalanine, $\small{L}$-tyrosine and $\small{L}$-tryptophan, are general components of protein synthesis as well as precursors for a wide range of secondary metabolites. These aromatic amino acids-derived compounds play important roles as ingredients of diverse phenolics including pigments and cell walls, and hormones like auxin and salicylic acid in plants. Moreover, they also serve as the natural products of alkaloids and glucosinolates, which have a high potential to promote human health and nutrition. The biosynthetic pathways of aromatic amino acids share a chorismate, the common intermediate, which is originated from shikimate pathway. Then, tryptophan is synthesized via anthranilate and the other phenylalanine and tyrosine are synthesized via prephenate, as intermediates. This review reports recent studies about all the enzymatic steps involved in aromatic amino acid biosynthetic pathways and their gene regulation on transcriptional/post-transcriptional levels. Furthermore, results of metabolic engineering are introduced as efforts to improve the production of the aromatic amino acids-derived secondary metabolites in plants.

Supported Metal Nanoparticles: Their Catalytic Applications to Selective Alcohol Oxidation (금속 나노 촉매를 활용한 선택적 알코올 산화 반응)

  • Hussain, Muhammad Asif;Joseph, Nyanzi;Kang, Onyu;Cho, Young-Hun;Um, Byung-Hun;Kim, Jung Won
    • Applied Chemistry for Engineering
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    • v.27 no.3
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    • pp.227-238
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    • 2016
  • This review article highlights different types of nano-sized catalysts for the selective alcohol oxidation to form aldehydes (or ketones) with supported or immobilized metal nanoparticles. Metal nanoparticle catalysts are obtained through dispersing metal nanoparticles over a solid support with a large surface area. The nanocatalysts have wide technological applications to industrial and academic fields such as organic synthesis, fuel cells, biodiesel production, oil cracking, energy conversion and storage, medicine, water treatment, solid rocket propellants, chemicals and dyes. One of main reactions for the nanocatalyst is an aerobic oxidation of alcohols to produce important intermediates for various applications. The oxidation of alcohols by supported nanocatalysts including gold, palladium, ruthenium, and vanadium is very economical, green and environmentally benign reaction leading to decrease byproducts and reduce the cost of reagents as opposed to stoichiometric reactions. In addition, the room temperature alcohol oxidation using nanocatalysts is introduced.

Computational Chemistry Study of CO2 Fixation and Cyclic Carbonate Synthesis Using Various Catalysts (촉매를 이용한 이산화탄소 고정화 및 고리형 카보네이트 합성반응에 대한 계산화학적 해석)

  • An, Hye Young;Kim, Min-Kyung;Jeong, Hui Cheol;Eom, Ki Heon;Won, Yong Sun
    • Clean Technology
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    • v.22 no.1
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    • pp.35-44
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    • 2016
  • In this study, a computational chemistry methodology called as molecular modeling was been applied to explain several experiment results mechanistically. The reaction chosen for this study was to remove carbon dioxide, known as a primary greenhouse gas, by an epoxide via the carbon dioxide fixation to produce carbonates. This reaction inherently needs the use of catalysts because it has a significantly high activation barrier (55~59 kcal/mol). Among various types of catalysts, we studied in zeolitic imidazolate framework 90 (ZIF-90)/ionic liquid immobilized ZIF-90 (IL-ZIF-90), polystyrene-supported quaternized ammonium salt, KI/KI-glycine, and dimethylethanolamine (DMEA). First, probable reaction pathways were proposed based on calculated energetics by computational chemistry. The energetics was then used for the thermodynamic interpretation on the activity of catalysts. In the case of ZIF-90/IL-ZIF-90 and KI/KI-glycine, IL-ZIF-90 and KI-glycine showed better yields compared to their counterparts. The calculation proposed interesting results that it is not from the lowering of activation energy but from the unstable intermediates of ZIF-90 and KI-glycine. For DMEA, the calculated activation energy was ~42 kcal/mol, much lower than that of the non-catalytic reaction. A possible reaction pathway was located to confirm the interaction between −NH group from ammonium and oxygen from epoxide for polystyrene-supported quaternized ammonium salt.

Comparison of In Vitro Antioxidant Activity and Cyclooxygenase-2 Promoter Inhibitory Activity in Harmonia axyridis Pallas and Coccinella septempunctata $Linn\dot{e}$ (약용곤충 무당벌레류 추출물의 항산화활성과 Cyclooxygenase-2 Promoter 억제활성 비교)

  • Heo Jin-Chul;Park Ja-Young;Hwang Jae-Sam;Park Hae-Cheol;Kang Seok-Woo;Hwang Seok-Jo;Yun Chi-Young;Kwon Taeg-Kyu;Lee Sang-Han
    • Food Science and Preservation
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    • v.13 no.4
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    • pp.513-518
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    • 2006
  • Insect resources have been widely recognized that seven millions of insects exhibit it own biological activity by whole body or its metabolic intermediates. In order to investigate antioxidant activity and compare the cyclooxygenase-2 promoter activity from insect extract, we tested in vitro antioxidant assays and cyclooxygenase-2 promoter assay in Coccinella septempunctata Linne and Harmonia axyridis extracts have the anti-oxidant and cyclooxygenase-2 inhibition activities, we examined the anti-oxidant assays including DPPH, FRAP and linoleic acid, ana inhibition of cyclooxygenase-2 expression using a cyclooxygenase-2 promoter-inserted stable cell line. We found that Harmonia axyridis Pallas extract had potentials to anti-oxidant activity and inhibited about 25% of cyclooxygenase-2 transcription activity. These findings indicate that Coccinella septempunctata Linne and Harmonia axyridis Pallas extracts could be an useful insect resource for agrobiotechnological purposes.

Thermal Decomposition of A New Insecticide KH-502 [O, O-Diethyl O-(1-phenyl -3-trifluoromethy-5-pyrazoyl) thiophosphoric acid ester] (신규(新規) 살충제(殺蟲劑)인 O, O, O-Diethyl-O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl) thiophosphoric acid ester의 열(熱)에 의한 분해성(分解性))

  • Cho, Boo-Yeon;Han, Dae-Sung
    • Korean Journal of Environmental Agriculture
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    • v.11 no.3
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    • pp.225-234
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    • 1992
  • Thermal decomposition was conducted to investigate the influence of the various factors on stability of a new insecticide, [O, O-Diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl) thiophosphoric acid ester : KH-502], in view of those informations applicable for industrial exploitation. In the thermal decomposition experiment, KH-502 was, after mixing with Fe, Cu and adjustment of moisture and pH conditions, subjected to three temperatures, 25, 50, and $100^{\circ}C$. Results for stability, and degradation pattern of KH-502 from the above experiment can be summarized as follows: 1. Main products of the thermal decomposition when this was conducted in the closed system were identified as following five compounds:O, O, O-Triethylthiophosphoric acid(TEPA), 1-Phenyl-3-trifluoromethyl-5-ethoxypyrazole(PTMEP), 1-Phenyl-2-ethyl-3-trifluoromethyl-5-hydroxypyrazole(PETMHP), O, O-Diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phosphoric acid ester(KH-502 oxo form), O, S-Diethyl O-(1-phenyl-3-trifluoromethyl-5-pyrazoyl)phospho rothiolate(S-ethyl KH-502). However, compounds such as oxo form and S-ethyl KH-502 were not identified when the thermal decomposition was proceeded in the open system. 2. KH-502 was stable at 25 and 50$^{\circ}C$, but it was decomposed at 100$^{\circ}C$ following the first-order kinetics at the early stages of decomposition. 3. Rate constants for the thermal decomposition of KH-502 at 100$^{\circ}C$ were in the orders of Cu powder addition 0.344>Cu plate addition 0.21>moisture addition 0.05>closed system=open system=iron addition=pH 5.5 adjustment 0.04>pH 8.5 adjustment 0.027 day$^{-1}$, representing KH-502 was decomposed fast at Cu powder treatment and slow at pH 8.5 adjustment. 4. Half-life for the thermal decomposition of KH-502 at 100$^{\circ}C$ was in the orders of Cu powder addition 2.02

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Diversity and Phylogenetic Analysis of Fluorescent Pseudomonads Isolated from Soil-Root System of Red Pepper in Greenhouse (비닐하우스 고추재배지의 토양과 근계로부터 분리된 형광성 Pseudomonads의 계통 분류 및 다양성)

  • Kwon, Soon-Wo;Kim, Jong-Shik;Song, Jae-Kyeong;Ryu, Jin-Chang
    • Korean Journal of Soil Science and Fertilizer
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    • v.33 no.4
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    • pp.275-282
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    • 2000
  • Among the fluorescent pseudomonad isolates from soil- root system of red pepper in Chinju, Kyunsangnam-Do, the phylogenetic analysis for 35 isolates were conducted. The partial 16S ribosomal DNA sequences were used as taxonomic key for phylogenetic analyses, and these sequences were enabled to identification of the fluorescent pseudomonad isolates on the species level. The 17 isolates among them were classified into Pseudomonas putida group, and consisted of the strains isolated mainly from soil. This group were subdivided into 4 subgroups (I, II, III, and IV). The subgroup I and IV were unique ones which were relatively remotely related with subgroup II and III including the type strain of P. putida. The 15 isolates among 35 isolates were grouped along with the type strain of Pseudomonas fluorescens, and 3 isolate were characterized as intermediates of P. fluorescens and Pseudomonas chlororaphis. Most of strain isolateds from the rhizosphere soil and rhizoplane of red pepper were identified as P. fluorescens and closely related with each other. In this study, root of red pepper was supposed to be colonized by a specific strain or strains of P. fluorescens.

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Inhibitory Effects of Copper on the Anaerobic Degradation of Propionate (프로피온산의 혐기성 분해시 구리의 저해 효과)

  • Shin, Hang-sik;Lee, Chae-young
    • Journal of the Korea Organic Resources Recycling Association
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    • v.7 no.2
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    • pp.25-34
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    • 1999
  • The effects of copper on the anaerobic degradation of propionate were studied using anaerobic batch reactors. The apparent inhibitory effects of copper on the anaerobic degradation of propionate could be observed from behaviors of intermediates, ultimate methane yield(UMY) and specific methanogenic activity(SMA) There was little inhibition at the concentration of $2.5mg\;Cu^{2+}/L$. Beyond this concentration, the inhibitory effects increased with increasing dose of coppers. The 50% inhibition of UMY and SMA occurred at copper dosage of 33.8 and $24.1mg\;Cu^{2+}/gVSS$, respectively. The inhibitory effect based on the UMY was gradually reduced with the operation time dueprobably to the acclimation of microorganisms and/or binding of the added copper by ligands(and possibly ion exchange sites)contained on the cell membrane and extracellular polymer matrix whereas it based on the SMA might exclude the this phenomena. Therefore, the methodology for interpretation of inhibition data based on the SMA was more accurated than the UMY. There was no inhibitory effect in batch reactors supplemented with sulfate due to an antagonistic action of the sulfate reducing bacteria. Propionate degradation was initially retarded for copper inhibited samples but it gradually degraded afterward. Based on the mass removal considering take into account the propionate to acetate conversion, propionate degradation may appeal more affected than acetate. This result revealed that the hydrogenotrophic methanogens were the most affected by copper.

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UV Photodegradation of Chlorinated VOCs: Removal Efficiency and Products (염소계 VOCs의 UV 광분해 연구: 제거율 및 부산물)

  • Kang, InSun;Xi, Jinying;Wang, Can;Hu, Hong-Ying
    • Journal of Korean Society for Atmospheric Environment
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    • v.33 no.2
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    • pp.87-96
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    • 2017
  • In this study, 4 gases containing typical chlorinated volatile organic compounds (VOCs) were treated by ultraviolet (UV) irradiation. The typical chlorinated VOCs are dichloromethane (DCM), trichloromethane (TCM), carbon tetrachloride (CTC) and trichloroethylene (TCE). The removal efficiency (RE) and the products of chlorinated VOCs by UV irradiation are investigated. At this time, 2 types of background gas (air and nitrogen) were used to figure out the RE by photooxidation and photolysis. The specification of UV-lamp used in this study was low-pressure mercury lamp emitting wavelength of 185~254 nm. The experimental conditions were set as initial VOC concentration of $180{\pm}10ppm$, empty bed retention time (EBRT) of 53 s, temperature of $23{\pm}2^{\circ}C$ and relative humidity of $65{\pm}5%$. In the photolysis condition with nitrogen ($N_2$) as background gas, the averaged RE of the 4 types of chlorinated VOCs was about 24% higher than that with photooxidation; and the REs of VOCs except CTC were confirmed as >99%. The composition of off-gases after UV photooxidation in air was investigated and several intermediates from DCM, TCM and TCE were detected by GC/MS. Among them, phosgene which is a toxics was detected as an intermediate of TCM. In addition, the concentration of carbon dioxide ($CO_2$) in the off-gases was measured to calculate the mineralization rate (MR). With the photooxidation, TCE showed the highest RE (>99%) while MR was the lowest (17%); and the MR of DCM was the highest (86%). In addition, particulate matters (PM) in the off-gases was also detected and high concentrated $PM_{10}$ ($21,580{\mu}g{\cdot}m^{-3}$) and $PM_{2.5}$ ($6,346{\mu}g{\cdot}m^{-3}$) were detected in TCE off-gas. More than 99% of the chlorinated VOCs could be removed using UV254-185 nm lamp, while it is necessary to conduct further studies on the production and treatment of secondary pollutants.