• Title/Summary/Keyword: catalysis

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Mechanism of Biological Nitrogen Fixation in Azotobacter vinelandii (Azotobacter vinelandii에서의 생물학적 질소고정 작용 메카니즘)

  • Kim, Yong-Ung;Han, Jae-Hong
    • Applied Biological Chemistry
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    • v.48 no.3
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    • pp.189-200
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    • 2005
  • Biological nitrogen fixation is an important process for academic and industrial aspects. This review will briefly compare industrial and biological nitrogen fixation and cover the characteristics of biological nitrogen fixation studied in Azotobacter vinelandii. Various organisms can carry out biological nitrogen fixation and recently the researches on the reaction mechanism were concentrated on the free-living microorganism, A. vinelandii. Nitrogen fixation, which transforms atmospheric $N_2$ into ammonia, is chemically a reduction reaction requiring electron donation. Nitrogenase, the biological nitrgen fixer, accepts electrons from biological electron donors, and transfers them to the active site, FeMo-cofactor, through $Fe_4S_4$ cluster in Fe protein and P-cluster in MoFe protein. The electron transport and the proton transport are very important processes in the nitrogenase catalysis to understand its reaction mechanism, and the interactions between FeMo-cofactor and nitrogen molecule are at the center of biological nitrogen fixation mechanism. Spectroscopic studies including protein X-ray crystallography, EPR and $M{\ddot{o}}ssbauer$, biochemical approaches including substrate and inhibitor interactions as well as site-directed mutation study, and chemical approach to synthesize the FeMo-cofactor model compounds were used for biological nitrogen fixation study. Recent research results from these area were presented, and finally, a new nitrogenase reaction mechanism will be proposed based on the various research results.

Biochemical Characterization of Cysteine(-) Mutant Alanine Racemase from Bacillus pseudomycoides (Bacillus pseudomycoides로 부터 분리된 alanine racemase 유전자의 cysteine 치환 및 생화학적 특성)

  • Kang, Han-Chul;Yoon, Sang-Hong;Lee, Chang-Muk;Koo, Bon-Sung
    • Journal of Applied Biological Chemistry
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    • v.53 no.4
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    • pp.195-201
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    • 2010
  • A gene encoding an alanine racemase in B. pseudomycoides was cloned and one (Cys316) or both of two cysteines (Cys316 and Cys365) was (were) substituted with alanine. The cysteine (-) alanine racemases were expressed in E. coli BL21 (DE3) using a pET-21 vector. The expressed enzymes were purified through affinity chromatography using 6xHis ligand. The purified enzymes all showed major one bands by SDS-PAGE analysis, corresponding to 46 kDa. The cysteine (-) alanine racemases as well as the wild type enzyme showed alanine racemase activities, indicating that the enzyme is an alanine racemase and the cysteines in the enzyme may not be involved in the catalysis and/or substrate binding. Thermal stabilities of Cys (-) alanine racemases decreased considerably and half-lives were 26 (wild type), 21 (C316A) and 18 min (C316-365A), respectively at $60^{\circ}C$ pH 8.0, suggesting that cysteine is considerably contributive to the thermal stability of the alanine racemase.

A Study on the Safety Improvement in Incineration System from the Case Study of Acrylic acid manufacturing process Accident (아크릴산 제조공정 사고사례를 통한 소각 시스템의 안전성 향상 방안)

  • Ma, Byung-Chol;Lee, Keun-Won;Im, Ji-Pyo;Kim, Young-Chul
    • Journal of the Korean Institute of Gas
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    • v.16 no.4
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    • pp.52-58
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    • 2012
  • Recently, waste gas incineration is increasing due to strong environmental regulatory system in Korea. These incinerating facilities are usually connected with the top of the storage tank through pipeline and incinerate off gas with the flame. Therefore, the flame originated from these facilities is likely to move back into pipeline and might cause an explosion of the storage tank. Accordingly, the purpose of this study is to suggest the preventive measures and the way to improve the safety of these incineration systems through the cause analysis of a major industrial accident occurred in a acrylic acid manufacturing process in Korea. As a result of the study, the preventive measures are suggested as follows. (1) Air or inert gas inflow facilities should be well designed to dilute flammable gases into air or inert gas sufficiently before the blower is restarted in order to prevent the explosion (2) It is needed for the detonation-type flame arresters to be installed on the top of the storage tanks. (3) In case of using the deflagration-type flame arresters, it is necessary to install a rupture disk before the arresters, or blow off the flame outside tanks by connecting the tank top and the incinerator with hood-type pipe. (4) TDR should be installed to be restarted automatically after the momentary power failure.

A Study on the Safety Improvement in a Venting System from the HCl Release Accident of a Petrochemical Company (석유화학공장의 염화수소 누출사고를 통한 대기벤트 시스템의 안전성 향상 방안)

  • Ma, Byung-Chol;Lee, Keun-Won;Im, Ji-Pyo;Kim, Young-Chul
    • Journal of the Korean Institute of Gas
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    • v.16 no.4
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    • pp.38-43
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    • 2012
  • The purpose of this study is to carry out the consequence analysis of an accident related to the release of Hydrogen chloride occurred in a petrochemical company in Korea and suggest the measures to prevent similar accidents from happening again. The total amount released through the safety valve of HCl Column was calculated based on the rated capacity of the safety valve, the ideal gas equation and mechanical energy balance, respectively. As a result of the calculation, we found that the amount of HCl released through the safety valve was at least 76.8 kg. Also, we predicted the dispersion concentration at the position of the injured workers(more than 350 m away from the accident location) using simulation programs such as PHAST. The results of ALOHA and K-CARM are 304 ppm and 1,700 ppm respectively. However, PHAST calculation indicated that the concentration is less than l ppm. From these results, we can understand that workers were injured by HCl gas released from the safe valve and the concentration of gas might be less than 1 ppm. Also, it is important for toxic gases such as HCl to be vented safely to the atmosphere after scrubbing.

Improvement of Transglycosylation Efficiency using a Glycosynthase Mutant derived from Thermoplasma acidophilum ${\alpha}$-Glucosidase (Thermoplasma acidophilum 유래 ${\alpha}$-glucosidase로 부터 생산된 glycosynthase 돌연변이 단백질의 개선된 당전이 효율)

  • Hwang, Sung-Min;Seo, Seong-Hwa;Park, In-Myoung;Choi, Kyoung-Hwa;Kim, Do-Man;Cha, Jae-Ho
    • Microbiology and Biotechnology Letters
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    • v.40 no.2
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    • pp.104-110
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    • 2012
  • Glycosynthase is an active site nucleophile mutant enzyme, prepared from glycosidase, which is capable of synthesizing oligosaccharide derivatives without the hydrolysis of the product. Thermoacidophilic ${\alpha}$-glucosidase of Thermoplasma acidophilum (AglA) exhibits a transglycosylating activity yielding various glycosides. AglA was converted to glycosynthase by the substitution of the catalytic nucleophile Asp-408 residue into non-nucleophile glycine in order to increase its ability to synthesize various glycosides by transglycosylation. The glycosynthase mutant was purified by Ni-NTA chromatography and its glycoside-synthesizing activity was measured by using an external nucleophile, sodium formate buffer, providing maltose as a donor and p-nitrophenyl-${\alpha}$-D-glucopyranoside ($pNP{\alpha}G$) as an acceptor, respectively. In addition, $pNP{\alpha}G$ was examined for its feasibility to act as both a donor and an acceptor, and products were compared with those of the wildtype enzyme. The mutant enzyme was found to catalyze the formation of a specific product from $pNP{\alpha}G$ with a yield of 42.5% without further hydrolysis, while the wild-type enzyme produced two $pNP{\alpha}G$ products at low yields. The results demonstrate the possibility of satisfactory yields for the reactions in the presence of small amounts of acceptor, and demonstrate that the high activity of the mutant, at pHs below neutrality, was applicable in the transfer of glucose from the natural donor.

Study of reaction mechanism in pre-reforming for MCFC (MCFC의 예비 개질 반응 메커니즘 연구)

  • Lee, Woo-Hyung;Park, Yong-Ki
    • Industry Promotion Research
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    • v.3 no.2
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    • pp.1-8
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    • 2018
  • In this study, the reaction mechanism of ethane and the reaction rate equation suitable for hydrocarbon reforming were studied. Through the reaction mechanism analysis, it was confirmed that three reactions (CO2 + H2, C2H6 + H2, C2H6 + H2O) proceed during the reforming reaction of ethane, each reaction rate (CO2+H2($r=3.42{\times}10-5molgcat.-1\;s-1$), C2H6+H2($r=3.18{\times}10-5mol\;gcat.-1s-1$), C2H6+H2O($r=1.84{\times}10-5mol\;gcat.-1s-1$)) was determined. It was confirmed that the C2H6 + H2O reaction was a rate determining step (RDS). And the reaction equation of this reaction can be expressed as r = kS * (KAKBPC2H6PH2O) / (1 + KAPC2H6 + KBPH2O) (KA = 2.052, KB = 6.384, $kS=0.189{\times}10-2$) through the Langmuir-Hinshelwood model. The obtained equation was compared with the derived power rate law without regard to the reaction mechanism and the power rate law was relatively similar fitting in the narrow concentration change region (about 2.5-4% of ethane, about 60-75% of water) It was confirmed that the LH model reaction equation based on the reaction mechanism shows a similar value to the experimental value in the wide concentration change region.

On-stream Activity and Surface Chemical Structure of CoO2/TiO2 Catalysts for Continuous Wet TCE Oxidation (습식 TCE 분해반응에서 CoO2/TiO2 촉매의 반응활성 및 표면화학적 구조)

  • Kim Moon Hyeon;Choo Kwang-Ho
    • Journal of Environmental Science International
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    • v.14 no.2
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    • pp.221-230
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    • 2005
  • Catalytic wet oxidation of trichloroethylene (TCE) in water has been conducted using $TiO_2-supported$ cobalt oxides at $36^{\circ}C$ with a weight hourly space velocity of $7,500\;h^{-1}.\;5\%\;CoO_x/TiO_2$, prepared by using an incipient wetness technique, might be the most promising catalyst for the wet oxidation although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. XPS spectra of both fresh and used Co surfaces gave different surface spectral features for each $CoO_x,\;Co\;2P_{3/2}$ binding energy for Co species in the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $CO_2TiO_4\;and\;CoTiO_3$. The used catalyst exhibited a 780.3-eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD patterns for $5\%\;CoO_x/TiO_2$ catalyst indicated that the phase structure of Co species in the catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present predominantly on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

Developing improvement technology in pre-etching process for the Shadow Mask quality of flat color TV

  • Park, Jong-Moo;Park, Kwang-Ho;Jung, Hyo-Jin
    • 한국정보디스플레이학회:학술대회논문집
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    • 2003.07a
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    • pp.1164-1167
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    • 2003
  • Recently CRT is getting flatted, As change of CRT trend from normal type to Flat type, the material of Shadow Mask was also changed from AK(Aluminum Killed) to Invar(Fe-Ni alloy) materials Until now we have used just AK(Aluminum Killed) for normal type TV(not flat type), but main raw material of shadow mask component was changed. . However recently Invar(Fe-Ni alloy) materials, which has advantage of Low Thermal Expansion and High Strength, has been developed as well as applying in mass production as CRT's trend has become more flat and fine pitch. As main raw material of shadow mask component was changed, conditions of process were changed. One of them, the importance of pre-etching process (assistant process for developing & etching) is improved because there are so many particles in the pre-etching bath because of Ni compounds. Since the solubility of Ni in pre-etching solvent is very low related to Fe's, so the compounds of Ni happen to make particles.(the solubility of Fe is twenty times Ni's) that particles happen to make process troubles and NG productions so to clear the particles we had to established high cost filtering system, but it is useless. As time goes by the quantity of particles (Ni compounds) was increased because of the capability of filtering system was not enough, the particles was produced continuous in bath, and it make quality problems. Hence we tried to develop the new pre-etching solution to remove the particles (Ni compounds) and to cost down the filtering system's running cost. But in improving the solution we discovered the new pre-etching solution made the PR developing better. In former solution there were three kinds of chemistry (COOH)2 , H2O2 , H2S04 .first the function of (COOH)2 is drilling the surface of Invar, during this mechanism Ni compounds occurred. Second the function of H202 is removing the PR fringe (half UV exposure zone on PR(PVA)), Third the function of H2S04 is the catalysis of (COOH)2 In those, (COOH)2 was the main reason to make the Ni compounds. So to improve the solutions we had to change (COOH)2 to the other material. the chemistry we improved was a complex chemistry based on H2S04 . after using this chemistry the particles problem was disappeared and there was another advantage cut down the PR fringe. The New solution made the function of H202 better so the PR developing improved. To be direct the catalyst of the new solution helped the H202. anyway First thing after change the solution the quality of shadow Mask for flat color TV was improved & the yield also improved. But the more important thing is how to control the new solution. So we accepted the new concept which was the degree of freshness. The degree of freshness is based on non-reacted solution which was 100% ( the degree of freshness) and calculated the melted Ni quantity as time goes by. So we made the gauging liner plot. In conclusion, many companies tried to make fine pitched Shadow Mask ,generally to make quality jump up it needed a lot of cost & persons .in this case the shift of core material made it possible.

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Creating Electrochemical Sensors Utilizing Ion Transfer Reactions Across Micro-liquid/liquid Interfaces (마이크로-액체/액체 계면에서의 이온 이동 반응을 이용한 전기화학 센서 개발)

  • Kim, Hye Rim;Baek, Seung Hee;Jin, Hye
    • Applied Chemistry for Engineering
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    • v.24 no.5
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    • pp.443-455
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    • 2013
  • Electrochemical studies on charge transfer reactions across the interface between two immiscible electrolyte solutions (ITIES) have greatly attracted researcher's attentions due to their wide applicability in research fields such as ion sensing and biosensing, modeling of biomembranes, pharmacokinetics, phase-transfer catalysis, fuel generation and solar energy conversion. In particular, there have been extensive efforts made on developing sensing platforms for ionic species and biomolecules via gelifying one of the liquid phases to improve mechanical stability in addition to creating microscale interfaces to reduce ohmic loss. In this review, we will mainly discuss on the basic principles, applications and future aspects of various sensing platforms utilizing ion transfer reactions across the ITIES. The ITIES is classified into four types : (i) a conventional liquid/liquid interface, (ii) a micropipette supported liquid/liquid interface, (iii) a single microhole or an array of microholes supported liquid/ liquid interface on a thin polymer film, and (iv) a microhole array liquid/liquid interface on a silicon membrane. Research efforts on developing ion selective sensors for water pollutants as well as biomolecule sensors will be highlighted based on the use of direct and assisted ion transfer reactions across these different ITIES configurations.

Structural and Functional Analysis of Nitrogenase Fe Protein with MgADP bound and Amino Acid Substitutions (MgADP 결합 및 아미노산 치환 Nitrogenase Fe 단백질의 구조 및 기능 분석)

  • Jeong, Mi-Suk;Jang, Se-Bok
    • Journal of Life Science
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    • v.14 no.5
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    • pp.752-760
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    • 2004
  • The function of the [4Fe-4S] cluster containing iron (Fe-) protein in nitrogenase catalysis is to serve as the nucleotide-dependent electron donor to the MoFe protein which contains the sites for substrate binding and reduction. The ability of the Fe protein to function in this manner is dependent on its ability to adopt the appropriate conformation for productive interaction with the MoFe protein and on its ability to change redox potentials to provide the driving force required for electron transfer. The MgADP-bound (or off) conformational state of the nitrogenase Fe protein structure described reveals mechanisms for long-range communication from the nucleotide-binding sites to control affinity of association with the MoFe protein component. Two pathways, termed switches I and II, appear to be integral to this nucleotide signal transduction mechanism. In addition, the structure of the MgADP bound Fe protein provides the basis for the changes in the biophysical properties of the [4Fe-4S] observed when Fe protein binds nucleotides. The structures of the nitrogenase Fe protein with defined amino acid substitutions in the nucleotide dependent signal transduction pathways of the Switch I and Switch II have been determined by X-ray diffraction methods. These two pathways have been also implicated by site directed mutagenesis studies, structural analysis and analogies to other proteins that utilize similar nucleotide dependent signal transduction pathways. We have examined the validity of the assignment of these pathways in linking the signals generated by MgATP binding and hydrolysis to macromolecular complex formation and intermolecular electron transfer. The results provide a structural basis for the observed biophysical and biochemical properties of the Fe protein variants and interactions within the nitrogenase Fe protein-MoFe protein complex.