• Title/Summary/Keyword: catalytic acid - sites

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Interaction of ${\alpha}$-Ketoglutarate Dehydrogenase Complex with Allosteric Regulators Detected by a Fluorescence Probe, 1,1'-bi(4-aniline)naphthalene-5,5'-disulfonic acid, an Inhibitor of Catalytic Activity

  • Hong, Sung-Youl;Bak, Choong-Il;Ryu, Jae-Ha;Song, Byoung-J.;Huh, Jae-Wook
    • BMB Reports
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    • v.29 no.3
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    • pp.230-235
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    • 1996
  • The interaction of ${\alpha}-ketoglutarate$ dehydrogenase complex (${\alpha}-KGDC$) with a hydrophobic fluorescent probe [1,1'-bi(4-aniline)naphthalene-5,5'-disulfonic acid] (bis-ANS) was studied. The punfied ${\alpha}-KGDC$ was potently inhibited by bis-ANS with an apparent half maximal inhibitory concentration ($IC_{50}$) of 9.8 ${\mu}m$ at pH 8.0. The catalytic activities of both the E1o and E2o subunits were predominantly inhibited while that of the E3 component was hardly affected. The binding of bis-ANS to the enzyme caused a marked enhancement and blue shift from 523 nm to 482 nm in the fluorescence emission spectrum. The dissociation constant ($K_d$) and the number of binding sites (n) were calculated to be 0.87 mM and 158, respectively. Allosteric regulators such as purine nucleotides and divalent cations further increased the fluorescence intensity of the $bis-ANS-{\alpha}-KGDC$ binary complex. These data suggest that the binding of these allosteric regulators to ${\alpha}-KGDC$ may cause the conformational changes in the enzyme and that bis-ANS could be used as a valuable probe to study the interaction of the multi-enzyme complex and its allosteric regulators.

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Aldol Condensation over Acid-Base Bifunctional Metal-Organic Framework Catalysts (산, 염기 이원기능 금속-유기 구조체 촉매를 이용한 알돌 축합반응)

  • Chung, Young-Min
    • Clean Technology
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    • v.20 no.2
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    • pp.116-122
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    • 2014
  • Various types of MOFs (metal-organic frameworks) were prepared via hydrothermal and post-grafting methods and applied as catalysts for the synthesis of jasminaldehyde, one of the representative perfume intermediates, by Aldol condensation of benzaldehyde with heptanal. Although both acid and base sites could catalyze the reaction, the catalytic performance was strongly dependent on the physical properties as well as the nature of functionalization on MOFs. While the use of sulfonated MOF catalysts led to decrease of jasminaldehyde selectivity regardless of MOFs used, the selectivity change was found to rely on the MOF types in the case of the amine-functionalization. Among the catalysts tested, MIL-101 shows the best catalytic performance, which may suggest that MIL-101 has suitable acid properties to promote the Aldol condensation and the large pore of MIL-101 is also advantageous to alleviate the diffusion problem of bulky products.

Alkylation of Isobutane with 1-Butene over Heteropoly Acid Catalysts (헤테로폴리산 촉매상에서 1-부텐에 의한 i-부탄의 알킬화반응)

  • Hong, Sung Hee;Lee, Wha Young;Song, In Kyu
    • Applied Chemistry for Engineering
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    • v.8 no.2
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    • pp.211-219
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    • 1997
  • Liquid or gas phase alkylation of isobutane with 1-butene for i-octane production was carried out over Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$. Pretreatment temperature of the catalyst played an important role on the catalytic activity of heteropoly acids in the liquid phase alkylation. Cation-exchanged $H_3PW_{12}O_{40}$ showed a better total yield and i-octane selectivity than the mother acid in the liquid phase alkylation, and $(NH_4)_{2.5}H_{0.5}PW_{12}O_{40}$ was more efficient than $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ in terms of i-octane selectivity. It was found that the acidic property (deactivation of acid sites) of the catalyst was closely related to the catalytic activity of Cs- or $NH_4$-exchanged $H_3PW_{12}O_{40}$ in the gas phase alkylation. $C_5-C_7$ were mainly formed in the early stage of gas phase alkylation due to the strong acidic property of the catalyst, whereas $C_8$ and $+C_9$ were mainly produced as the reaction proceeded due to the deactivation of acid sites. $Cs_{2.5}H_{0.5}PW_{12}O_{40}$ showed the highest total yield in the gas phase alkylation among the catalysts examined.

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Synthesis of FeAPSO-34 Materials and Their Catalytic Performance on Methanol Conversion (FeAPSO-34재료의 합성과 메탄올 전환에 놓인 촉매적 성능)

  • Eom, Myeong-Heon;Gang, Mi-Suk
    • Korean Journal of Materials Research
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    • v.9 no.8
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    • pp.798-803
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    • 1999
  • This study has been focused on the influence of Fe(III) incorporation into framework of SAPO-34(FeAPSO-34s;/su/Fe = 40,20 and 5) on the catalytic performance of methanol conversion. By rapid crystallization method, the XRD,SEM,ICP,TG-DTA, and BET sufrace areas. With an increase in the Fe content incorporated to the framework, the crystallinity identified from the intensity of XRD peaks slightly decreased and the particle size observed from SEM photographs decreased also. On the other hand, the acid sites in crystal decreased kin the Fe-incorporated samples, and the selectivity to ethylene for FeAPSO-34 catalyst on methanol conversion was enhanced compared with the nonmetal incorporated(SAPO-34)

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Gas-phase Dehydration of Glycerol over Supported Silicotungstic Acids Catalysts

  • Kim, Yong-Tae;Jung, Kwang-Deog;Park, Eun-Duck
    • Bulletin of the Korean Chemical Society
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    • v.31 no.11
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    • pp.3283-3290
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    • 2010
  • The gas-phase dehydration of glycerol to acrolein was carried out over 10 wt % HSiW catalysts supported on different supports, viz. $\gamma-Al_2O_3$, $SiO_2-Al_2O_3$, $TiO_2$, $ZrO_2$, $SiO_2$, AC, $CeO_2$ and MgO. The same reaction was also conducted over each support without HSiW for comparison. Several characterization techniques, $N_2$-physisorption, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), the temperature-programmed desorption of ammonia ($NH_3$-TPD), temperature-programmed oxidation (TPO) with mass spectroscopy and CHNS analysis were employed to characterize the catalysts. The glycerol conversion generally increased with increasing amount of acid sites. Ceria showed the highest 1-hydroxyacetone selectivity at $315^{\circ}C$ among the various metal oxides. The supported HSiW catalyst showed superior catalytic activity to that of the corresponding support. Among the supported HSiW catalysts, HSiW/$ZrO_2$ and HSiW/$SiO_2-Al_2O_3$ showed the highest acrolein selectivity. In the case of HSiW/$ZrO_2$, the initial catalytic activity was recovered after the removal of the accumulated carbon species at $550^{\circ}C$ in the presence of oxygen.

Random Sequence Analysis of the Genomic DNA of Methanopyrus kandleri and Molecular Cloning of the Gene Encoding a Homologue of the Catalytic Subunit of Carbon Monoxide Dehydrogenase

  • Shin, Hyun-Seock;Ryu, Jae-Ryeon;Han, Ye-Sun;Choi, Yong-Jin;Yu, Yeon-Gyu
    • Journal of Microbiology and Biotechnology
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    • v.9 no.4
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    • pp.404-413
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    • 1999
  • Methanopyrus kandleri is a hyperthermophilic methanogen that represents one of the most heat-resistant organisms: the maximum growth temperature of M. kandleri is $110^{\circ}C$. A random sequence analysis of the genomic DNA of M. kandleri has been performed to obtain genomic information. More than 200 unique sequence tags were obtained and compared with the sequences in the GenBank and PIR databases. About 30% of the analyzed tags showed strong sequence similarity to previously identified genes involved in various cellular processes such as biosynthesis, transport, methanogenesis, or metabolism. When statistics relating to the frequency of codons were examined, the sequenced open reading frames showed highly biased codon usage and a high content of charged amino acids. Among the identified genes, a homologue of the catalytic subunit of carbon monoxide dehydrogenase (CODH) that reduces $CO_2$ to CO was cloned and sequenced in order to examine its detailed gene structure. The cloned gene includes consensus promoters. The amino acid sequence of the cloned gene shows a strong homology with the CODH genes from methanogenic Archaea, especially in the presumed binding sites for Fe-S centers.

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Comparative Study of Nickel and Copper Catalysts Using Al2O3 and Hydrotalcite in Methanol Steam Reforming (메탄올 수증기 개질반응에서 알루미나 및 하이드로탈사이트를 이용한 니켈 및 구리 촉매 비교 연구)

  • Lee, Jae-hyeok;Jang, Seung Soo;Ahn, Ho-Geun
    • Journal of the Korean Institute of Gas
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    • v.26 no.2
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    • pp.14-20
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    • 2022
  • In this study, the catalytic reaction characteristics for producing hydrogen using methanol steam reforming were investigated. Nickel and copper are frequently used in steam reforming reaction and methanol synthesis, were used as main active metals. As a support, hydrotalcite has a high specific surface area, excellent porosity and thermal stability, and has weak Lewis acid sites and basic properties. Hydrotalcite was used to identify catalysts of methanol steam reforming with catalytic activity and their properties. In this research, high reactivity was shown in the catalyst of copper metal with high reducibility. And increasing of active metal loading showed the higher the methanol conversion and hydrogen selectivity.

Synergistic Effect of Copper and Cobalt in Cu-Co-O Composite Nanocatalyst for Catalytic Ozonation

  • Dong, Yuming;Wu, Lina;Wang, Guangli;Zhao, Hui;Jiang, Pingping;Feng, Cuiyun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3227-3232
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    • 2013
  • A novel Cu-Co-O composite nanocatalyst was designed and prepared for the ozonation of phenol. A synergistic effect of copper and cobalt was observed over the Cu-Co-O composite nanocatalyst, which showed higher activity than either copper or cobalt oxide alone. In addition, the Cu-Co-O composite revealed good activity in a wide initial pH range (4.11-8.05) of water. The fine dispersion of cobalt on the surface of copper oxide boosted the interaction between catalyst and ozone, and the surface Lewis acid sites on the Cu-Co-O composite were determined as the active sites. The Raman spectroscopy also proved that the Cu-Co-O composite was quite sensitive to the ozone. The trivalent cobalt in the Cu-Co-O composite was proposed as the valid state.

Kinetic Study of the Electrooxidation of Mefenamic Acid and Indomethacin Catalysed on Cobalt Hydroxide Modified Glassy Carbon Electrode

  • Saghatforoush, Lotfali.;Hasanzadeh, Mohammad.;Karim-Nezhad, Ghasem.;Ershad, Sohrab.;Shadjou, Nasrin.;Khalilzadeh, Balal.;Hajjizadeh, Maryam.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.6
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    • pp.1341-1348
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    • 2009
  • Electrocatalytic oxidation of two anti-inflammatory drugs (Mefenamic acid and Indomethacin) was investigated on a cobalt hydroxide modified glassy carbon (CHM-GC) electrode in alkaline solution. The process of oxidation and its kinetics were established by using cyclic voltammetry and chronoamperometry techniques as well as steady state polarization measurements. Voltammetric studies indicated that in the presence of under study drugs, the anodic peak current of low-valence cobalt species increased, followed by a decrease in the corresponding cathodic current. This result indicates that the drugs were oxidized via cobalt hydroxide species immobilized on the electrode surface via an E$\acute{C}$ mechanism. A mechanism based on the electrochemical generation of Co (IV) active sites and their subsequent consumption by the drugs in question was also investigated. The constants rate of the catalytic oxidation of the drugs and the electron-transfer coefficients reported.

Comparison of Removal Efficiency of Mn-loaded Natural Zeolites and Red Mud for the Catalytic Ozonation of 2-Butanone

  • Park, Youna;Lee, Jung Eun;Park, Young-Kwon
    • Applied Chemistry for Engineering
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    • v.33 no.3
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    • pp.328-334
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    • 2022
  • For the study of environmental application of natural zeolites (NZ) and red mud (RM), which are discharged from various industrial fields, the catalytic ozonation of 2-butaone (methyl ethyl ketone, MEK) was performed using the Mn-loaded NZ prepared according to the Mn content of 1, 3, 5, 7, and 10 wt%. By the addition of Mn to NZ, the BET (Brunaure-Emmett-Teller) specific surface area of Mn/NZ catalysts decreased while the ratio of Mn3+/[Mn3++Mn4+] intensively increased. Besides, the addition of Mn component to NZ increased the ratio of adsorbed oxygen (Oadsorbed) toward lattice oxygen (Olattice), Oadsorbed/Olattice from 0.076 of NZ to 0.465 of 10 wt% Mn/NZ according to the amount of Mn. It is known that the proportion of two species, Mn3+ and Oadsorbed, would greatly affect the catalytic activity. However, the balancing between the paired species, Mn3+ vs. Mn4+ and Oadsorbed vs. Olattice might be more essential for the catalytic ozonation of MEK at room temperature. Among the Mn-loaded NZ catalysts, the 3 wt% Mn/NZ showed the best activity for the removal of MEK and ozone. The 5, 7, and 10 wt% Mn/NZ catalysts are slightly inferior to the 3 wt% Mn/NZ. Compared to the pristine NZ, the Mn/NZ catalysts showed better activity for the catalytic ozonation of MEK. In addition, the 3 wt% Mn/NZ was confirmed to have the most available acid sites among them by the analysis of NH3-TPD (temperature programmed desorption). This might be the major reason for the best catalytic activity of 3 wt% Mn/NZ together with the adjusted distribution ratios of Mn3+/Mn4+ and Oadsorbed/Olattice. Considering the result of 3 wt% Mn/NZ, the 3 wt% Mn/RM was prepared to perform the catalytic activity for the removal of MEK and ozone, but the efficiency of 3 wt% Mn/RM was significantly lower than that of the 3 wt% Mn/NZ.