• 제목/요약/키워드: Catalytic mechanism

검색결과 313건 처리시간 0.029초

CO2 부가반응에 적용된 Silica 담지 이온성 액체 촉매 (Application of Silica-supported Ionic Liquid Catalysts to Cycloaddition of CO2)

  • 김동우;김현국;조득희
    • 공업화학
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    • 제27권3호
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    • pp.239-244
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    • 2016
  • 본 총설에서는 $CO_2$와 에폭시 화합물의 부가반응에서 무정형, SBA, MCM 또는 상업적으로 쉽게 이용 가능한 다양한 silica 지지체에 담지된 이온성 액체의 촉매적 적용가능성에 대하여 검토하였다. $CO_2$ 부가반응에 의한 5원환 카보네이트의 합성에 대하여 담지된 이온성 액체의 구조적인 영향과 silica 지지체의 종류에 따른 촉매 활성을 검토한 바, 관능기 또는 금속을 보유한 이온성 액체인 경우에 촉매 성능이 개선됨을 알 수 있었다. 또한 silica에 담지된 이온성 액체(SSIL) 촉매의 재사용성과 반응메커니즘을 조사하여 제시하였다.

다기능성 함불소고분자/Blocked-HMDI 블렌드계의 가교화 반응에서의 촉매 영향 (Catalyst Effects on Cross-linking of a Multi-Functional Fluoropolymer/Blocked-HMDI Blends)

  • 안원술
    • 한국산학기술학회논문지
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    • 제13권5호
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    • pp.2408-2413
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    • 2012
  • 불소를 함유하는 다기능성 함불소고분자의 가교화 반응을 위하여 페놀로 blocking된 HMDI를 사용하고 반응의 촉진을 위하여 주석계 촉매(stanous catalyst)를 사용하여 DSC 및 TGA를 사용하여 반응에 미치는 촉매의 영향을 살펴보았다. 용매 및 HMDI의 blocking제로 사용된 페놀이 약 $150^{\circ}C$에 이르기까지 해리되면서 휘발하게 되고 $230-250^{\circ}C$ 온도에서 가교 생성반응이 이루어지는 것이 관찰되었다. 촉매의 농도에 따른 반응기구의 변화는 없는 대신 촉매가 도입될 경우 100배 이상 빨라지는 급격한 반응속도의 변화가 관찰되었으며, 이에 따른 활성화 에너지는 비촉매계에 대한 81.8 kJ/mol로부터 1 phr 촉매계의 대하여 61.7 kJ/mol까지 감소하는 것이 관찰되었다.

Pyrocarbon Whisker Growth on the Catalytic Mullite Substrate by the Pyrolysis of Methane

  • Rhee, Bosung;Park, Young-Tae
    • Carbon letters
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    • 제6권2호
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    • pp.101-105
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    • 2005
  • Like bamboo-sprouts after rains, numerous sub${\mu}m$-sized pyrocarbon whiskers growth on the Mullite ($3Al_2O_3{\cdot}2H_2O$) substrate could be observed through a looking glass during methane pyrolysis at the temperature of $1050^{\circ}C$ in this study. If the surface of substrate would be scrubbed strongly with iron metals, then finely sticked iron particles were more effective catalytic for nm-sized whisker growth. Numerous fine flakes of pyrolytic carbon were hanging by invisible nm-whiskers as like as small spiders hanging by a spiderweb. This is the identification of nm-sized whisker growth. Therefore if the pyrolysis would be stopped at the initial stage of the whisker growth, the primary lengthening growth was nm-sized whisker. So could we vary arbitrarily sizes of whisker from nm- to ${\mu}m$-sizes. But ${\mu}m$- and nm-whiskers grown with the different growth mechanism; the former was straight and the latter has twigs, The lengthening growth of whisker was depended on the flow pattern pyrolysis species on the active sites of substrate and on the growth duration. We could obtained straight whisker length of 10~20 ${\mu}m$/min during the primary growth and laboratory spiral whisker of 30~40 ${\mu}m$-diameter/hr during the secondary growth.

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An Essential Histidine Residue in the Catalytic Mechanism of the Rat Kidney γ-Glutamyl Transpeptidase

  • Kim, Soo-Ja;Ko, Moon-Kyu;Chai, Kyu-Yun;Cho, Seong-Wan;Lee, Woo-Yiel
    • Bulletin of the Korean Chemical Society
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    • 제28권2호
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    • pp.271-275
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    • 2007
  • γ -Glutamyl transpeptidase (EC 2.3.2.2) plays a key role in glutathione metabolism by catalyzing the transfer of the γ -glutamyl residue and hydrolysis of glutathione. The functional residues at the active site of the rat kidney γ -glutamyl transpeptidase were investigated by kinetic studies at various pH, the treatment of diethylpyrocarbonate (DEPC), and photooxidation in presence of methylene blue. An ionizable group affecting the enzymatic activity with an apparent pKa value of 7.1, which is in the range of pKa values for a histidine residue in protein, was obtained by examining the pH-dependence of kinetic parameters. The pH effect on the photoinduced inactivation rate of the enzyme corresponds to that expected for the photooxidation of the free histidine. The involvement of a histidine in the catalytic site of the enzyme was further supported by DEPC modification accompanied by an increase in absorbance at 240 nm, indicating the formation of Ncarbethoxyhistidine. The histidine located at the position of 382 in the precursor of the enzyme is primarily suspected based on the amino acid sequence alignment of the transpeptidases from various organisms.

The Chemically Induced Hot Electron Flows on Metal-Semiconductor Schottky nanodiodes During Hydrogen Oxidation

  • Lee, Hyosun;Lee, Youngkeun;Lee, Changhwan;Kim, Sunmi;Park, Jeong Young
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.152-152
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    • 2013
  • Mechanism of energy conversion from chemical to electrical during exothermic catalytic reactions at the metal surfaces has been a fascinating and crucial subject in heterogeneous catalysis. A metal-semiconductor Schottky nanodiode is novel device for direct detection of chemically induced hot electrons which have sufficient energy to surmount the Schottky barrier. We measured a continuous chemicurrent during the hydrogen oxidation under of 760 Torr of O2 and 6 Torr of H2 by using Pt/Si and Pt/TiO2 nanodiodes at reaction temperatures and compared the chemicurrent with the reaction turnover rate. The thermoelectric current was measured by carrying out an experiment under O2 condition for elimination of the background current. Gas chromatograph and source meter were used for measurement of the chemical turnover rate and the chemicurrent, respectively. The correlation between the chemicurrent and the chemical turnover rate under hydrogen oxidation implies how hot electrons generated on the metal surface affect hydrogen oxidation.

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Structural Study of Monomethyl Fumarate-Bound Human GAPDH

  • Park, Jun Bae;Park, Hayeong;Son, Jimin;Ha, Sang-Jun;Cho, Hyun-Soo
    • Molecules and Cells
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    • 제42권8호
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    • pp.597-603
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    • 2019
  • Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) is a core enzyme of the aerobic glycolytic pathway with versatile functions and is associated with cancer development. Recently, Kornberg et al. published the detailed correlation between GAPDH and di- or monomethyl fumarate (DMF or MMF), which are well-known GAPDH antagonists in the immune system. As an extension, herein, we report the crystal structure of MMF-bound human GAPDH at $2.29{\AA}$. The MMF molecule is covalently linked to the catalytic Cys152 of human GAPDH, and inhibits the catalytic activity of the residue and dramatically reduces the enzymatic activity of GAPDH. Structural comparisons between $NAD^+$-bound GAPDH and MMF-bound GAPDH revealed that the covalently linked MMF can block the binding of the $NAD^+$ cosubstrate due to steric hindrance of the nicotinamide portion of the $NAD^+$ molecule, illuminating the specific mechanism by which MMF inhibits GAPDH. Our data provide insights into GAPDH antagonist development for GAPDH-mediated disease treatment.

DNA-Dependent Protein Kinase Catalytic Subunit (DNA-PKcs): Beyond the DNA Double-Strand Break Repair

  • Ye-Rim Lee;Gi-Sue Kang;Taerim Oh;Hye-Ju Jo;Hye-Joon Park;G-One Ahn
    • Molecules and Cells
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    • 제46권4호
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    • pp.200-205
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    • 2023
  • DNA-dependent protein kinase catalytic subunit (DNA-PKcs), a member of the phosphatidylinositol 3-kinase-related kinase family is a well-known player in repairing DNA double-strand break through non-homologous end joining pathway. This mechanism has allowed us to understand its critical role in T and B cell development through V(D)J recombination and class switch recombination, respectively. We have also learned that the defects in these mechanisms lead to the severely combined immunodeficiency (SCID). Here we highlight some of the latest evidence where DNA-PKcs has been shown to localize not only in the nucleus but also in the cytoplasm, phosphorylating various proteins involved in cellular metabolism and cytokine production. While it is an exciting time to unveil novel functions of DNA-PKcs, one should carefully choose experimental models to study DNA-PKcs as the experimental evidence has been shown to differ between cells of defective DNA-PKcs and those of DNA-PKcs knockout. Moreover, while there are several DNA-PK inhibitors currently being evaluated in the clinical trials in an attempt to increase the efficacy of radiotherapy or chemotherapy, multiple functions and subcellular localization of DNA-PKcs in various types of cells may further complicate the effects at the cellular and organismal level.

A Label-Free Fluorescent Amplification Strategy for High-Sensitive Detection of Pseudomonas aeruginosa based on Protective-EXPAR (p-EXPAR) and Catalytic Hairpin Assembly

  • Lu Huang;Ye Zhang;Jie Liu;Dalin Zhang;Li Li
    • Journal of Microbiology and Biotechnology
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    • 제34권7호
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    • pp.1544-1549
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    • 2024
  • This study presents a fluorescent mechanism for two-step amplification by combining two widely used techniques, exponential amplification reaction (EXPAR) and catalytic hairpin assembly (CHA). Pseudomonas aeruginosa (P. aeruginosa) engaged in competition with the complementary DNA in order to attach to the aptamer that had been fixed on the magnetic beads. The unbound complementary strand in the liquid above was utilized as a trigger sequence to initiate the protective-EXPAR (p-EXPAR) process, resulting in the generation of a substantial quantity of short single-stranded DNA (ssDNA). The amplified ssDNA can initiate the second CHA amplification process, resulting in the generation of many double-stranded DNA (dsDNA) products. The CHA reaction was initiated by the target/trigger DNA, resulting in the release of G-quadruplex sequences. These sequences have the ability to bond with the fluorescent amyloid dye thioflavin T (ThT), generating fluorescence signals. The method employed in this study demonstrated a detection limit of 16 CFU/ml and exhibited a strong linear correlation within the concentration range of 50 CFU/ml to 105 CFU/ml. This method of signal amplification has been effectively utilized to create a fluorescent sensing platform without the need for labels, enabling the detection of P. aeruginosa with high sensitivity.

Kinetic Investigation of CO2 Reforming of CH4 over Ni Catalyst Deposited on Silicon Wafer Using Photoacoustic Spectroscopy

  • Yang, Jin-Hyuck;Kim, Ji-Woong;Cho, Young-Gil;Ju, Hong-Lyoul;Lee, Sung-Han;Choi, Joong-Gill
    • Bulletin of the Korean Chemical Society
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    • 제31권5호
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    • pp.1295-1300
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    • 2010
  • The $CO_2-CH_4$ reaction catalyzed by Ni/silicon wafers was kinetically studied by using a photoacoustic technique. The catalytic reaction was performed at various partial pressures of $CO_2$ and $CH_4$ (50 Torr total pressure of $CO_2/CH_4/N_2$) in the temperature range of 500 - $650^{\circ}C$ in a static reactor system. The photoacoustic signal that varied with the $CO_2$ concentration during the catalytic reaction was recorded as a function of time. Under the reaction conditions, the $CO_2$ photoacoustic measurements showed the as-prepared Ni thin film sample to be inactive for the reaction, while the $CO_2/CH_4$ reactions carried out in the presence of the sample pre-treated in $H_2$ at $600^{\circ}C$ were associated with significant time-dependent changes in the $CO_2$ photoacoustic signal. The rate of $CO_2$ disappearance was measured from the $CO_2$ photoacoustic signal data in the early reaction period of 50 - 150 sec to obtain precise kinetic data. The apparent activation energy for $CO_2$ consumption was determined to be 6.9 kcal/mol from the $CO_2$ disappearance rates. The partial reaction orders, determined from the $CO_2$ disappearance rates measured at various $PCO{_2}'S$ and $PCH{_4}'S$ at $600^{\circ}C$, were determined to be 0.33 for $CH_4$ and 0.63 for $CO_2$, respectively. Kinetic data obtained in these measurements were compared with previous works and were discussed to construct a catalytic reaction mechanism for the $CO_2-CH_4$ reaction over Ni/silicon wafer at low pressures.

고체산 촉매에서의 1-펜텐의 골격이성화반응 (The Skeletal Isomerization of 1-Pentene over Solid Acid Catalysts)

  • 홍성수;우희철;이근대
    • 공업화학
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    • 제7권5호
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    • pp.902-912
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    • 1996
  • 여러 가지의 고체산 촉매에 의한 1-펜텐의 골격이성화 반응에서 반응활성, 선택도, 반응메카니즘 및 촉매의 산의 세기와 촉매활성과의 관계를 연구하였다. 여러 가지의 고체산 촉매중에서 천연제올라이트가 가장 높은 활성을 보여주었고, 불소나 황산으로 처리된 ${\eta}$-알루미나는 변형되지 않은 경우에 비해 활성이 크게 증가하였다. 한편 반응온도가 증가할수록 이소펜텐의 수율이 증가하였고, 접촉시간의 증가에 따라 이소펜텐의 수율이 증가하였다. 그러나 높은 반응온도와 아주 긴 접촉시간에서는 크래킹 반응의 생성물이 증가하였다. 금속이온으로 치환된 천연제올라이트에서의 활성은 감소하였고, 이것은 금속이온의 polarizing power와 관계가 있는 것으로 나타났다. 암모니아 승온탈착실험 결과에 의하면 촉매의 활성은 촉매의 산의 세기와 밀접한 관계가 있는 것으로 나타났다.

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