• Title/Summary/Keyword: catalysis

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Substrate Ground State Binding Energy Concentration Is Realized as Transition State Stabilization in Physiological Enzyme Catalysis

  • Britt, Billy Mark
    • BMB Reports
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    • v.37 no.5
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    • pp.533-537
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    • 2004
  • Previously published kinetic data on the interactions of seventeen different enzymes with their physiological substrates are re-examined in order to understand the connection between ground state binding energy and transition state stabilization of the enzyme-catalyzed reactions. When the substrate ground state binding energies are normalized by the substrate molar volumes, binding of the substrate to the enzyme active site may be thought of as an energy concentration interaction; that is, binding of the substrate ground state brings in a certain concentration of energy. When kinetic data of the enzyme/substrate interactions are analyzed from this point of view, the following relationships are discovered: 1) smaller substrates possess more binding energy concentrations than do larger substrates with the effect dropping off exponentially, 2) larger enzymes (relative to substrate size) bind both the ground and transition states more tightly than smaller enzymes, and 3) high substrate ground state binding energy concentration is associated with greater reaction transition state stabilization. It is proposed that these observations are inconsistent with the conventional (Haldane) view of enzyme catalysis and are better reconciled with the shifting specificity model for enzyme catalysis.

Chemoselective Alkylation of Aromatics with Benzyl Alcohol over Mesoporous ZSM-5

  • Jin, Hailian;Ansari, Mohd Bismillah;Jeong, Eun-Young;Park, Sang-Eon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.200-200
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    • 2011
  • Hierarchical mesoporous ZSM-5 with enhanced mesoporosity was synthesized by microwave through the rapid assembly via ionic interaction between sulfonic acid functionalized ZSM-5 nano particles and cationic surfactant. The catalytic performance of enhanced accessibility due to mesoporosity and acidity were investigated in the alkylation of mesitylene with benzyl alcohol as alkylating agent. The effect of mole ratio of aromatic with benzyl alcohol, reaction time and alkylation agent were also studied. The enhanced mesoporosity and acidity of sulfonic acid functionalized mesoporous ZSM-5 induced activity enhancement compared with non-functionalized mesoporous ZSM-5, sulfonic functionalized mesoporous ZSM-5 synthesized by hydrothermal method and conventional microporous ZSM-5. The sulfonic acid functionalized mesoporous ZSM-5 showed much higher chemoselectivity of benzylated mesitylene than others, whereas the others mainly show dibenzyl ether as product. This significant difference in catalytic selectivity was resulted from the existence of mesopores, which definitely allowed the benzylation in mesopores.

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Application of Chiral Ligands Heterogenized over Solid Supports on Enantioselective Catalysis (고체 담체에 고정화된 키랄리간드의 비대칭 촉매반응에의 응용)

  • Lee, Kwang-Yeon;Kawthekar, Rahul B.;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.17 no.6
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    • pp.565-574
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    • 2006
  • The trend towards the application of single enantiomers of chiral compounds is undoubtedly increasing. Among the various methods to obtain one single enantio-riched compound selectively, enantioselective catalysis is the most attractive method. Especially, it is important to increase the activity, selectivity and lifetime of usually expensive chiral catalysts with a minute quantity in the enantioselective synthesis. Immobilization of active homogeneous catalysts is a fashionable topic in asymmetric catalysis, providing the inherent advantage of easy separation and better handling properties. Many different ways have been investigated to improve the enantioselectivity of products and to recycle the catalysts. This review mainly focused on the present scope and limitations of different types of enantioselective heterogeneous catalysts.

Removal of Cu (II) and Cd (II) Ions Onto Water Hyacinth Based Carbonaceous Materials

  • Amina, A. Attia;Shouman, Mona.A.;Khedr, S.A.;El-Nabarawy, Th.
    • Carbon letters
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    • v.7 no.4
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    • pp.249-258
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    • 2006
  • Treatment of water hyacinth with sulphuric acid produces carbonaceous materials that have been used to remove Cu(II) and Cd (II) ions from aqueous solutions. Untreated water hyacinth was also used for the subject of comparison. The textural properties of the carbonaceous materials were determined from nitrogen adsorption at 77 K. The optimum pH for the sorption of Cu (II) and Cd (II) ions on the investigated sorbents was determined. Dynamic adsorption measurements have been taken at 298 K whereas equilibrium measurements were carried out at 298, 313 and 323 K. The adsorption of nitrogen at 77 K on the untreated sample was too low and the surface areas of the treated samples 2, 3 and 4 were found between $70-208\;m^2/g$. The total pore volumes of these samples which were determined for the carbonaceous materials investigated were found to be 0.076-0.140 ml/g. The kinetic adsorption data of Cu (II) and Cd(II) were applicable to both pseudo - first and pseudo-second order but fit more the latter order. The equilibrium adsorption data were found to fit Freundlich and Langmiur equations. The values of DG, DH and DS are all negative indicating the feasibility and the spontaneous nature of the sorption of Cu (II) and Cd (II) ions by the sorbents investigated.

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Computational Study on the Soot Blowing Method for Enhancing the Performance of the SCR System (SCR 시스템의 효율적인 운영을 위한 Soot Blowing 방법에 대한 해석적 연구)

  • Seo, MoonHyeok;Chang, HyukSang
    • Particle and aerosol research
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    • v.8 no.3
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    • pp.99-110
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    • 2012
  • In the SCR (selective catalytic reduction) system which is used for controlling the NOx emission from the Diesel engines, the soot deposited on the catalysis causes degradation of the system performance. Numerical study was done to evaluate the performance of soot blower which is proposed as a method for removing the soot on the catalysis. The spray conditions and the effect of the compressed air from the AIG (air inlet gun) were analyzed numerically to evaluate the overall effective method of the soot blowing. The characteristics of the final velocity distribution and velocity waves across the inlet section of the catalysis were evaluated with respect to the geometries of the AIG outlets and pressure conditions. An experimental model was used to validate the results of the numerical calculation that is used for finding the effective removal blowing momentum transfer quantities of soot the inlet section of the catalysis, and it is proposed that the required minimum blowing momentum transfer quantities are over than 0.499 $kg/m{\bullet}t_{eff}$ in the current study.

Application of Hybrid Polymeric Complexes to Solid State and Materials Chemistry

  • Josik Portier;Guy Campet;Nadine Treuil;Armel Poquet;Kim, Young Il;Kwon, Soon Jae;Kwak, Seo Young;Choy, Jin Ho
    • Journal of the Korean Chemical Society
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    • v.42 no.4
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    • pp.487-500
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    • 1998
  • A bird's-eye view on preparation, structure and properties of polymeric complexes in the field of Inorganic-Organic-Hybrids is presented in the view point of solid state and materials chemistry. These materials are useful precursors for preparing nanoparticles and fine grain oxides. Some of them are electroactive and are used as protonic or lithium electrolytes, electrochromic materials or membranes for sensors and actuators. New results on bio-hybrids, a class of material not far from polymeric complexes, are also described.

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Industrial Utilization and Outlook on Nanoporous Materials (나노세공체 촉매소재의 산업적 활용과 전망)

  • Chang, Jong-San;Hwang, Young Kyu;Park, Yong-Ki;Choi, Won Choon
    • Prospectives of Industrial Chemistry
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    • v.17 no.2
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    • pp.8-20
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    • 2014
  • 나노세공체는 고표면적, 균일한 다공성, 분자크기의 세공구조, 높은 흡착용량, 이온교환 특성, 높은 촉매활성, 분자크기의 형상선택성 등의 특징을 갖기 때문에 촉매 및 흡착제로 나노소재 분야에서 가장 오랫동안 활용되어 왔던 중요한 물질 가운데 하나로 정유 및 석유화학 산업을 비롯한 화학산업과 환경 산업에 광범위하게 사용되고 있다. 본 고찰에서는 결정성 나노세공체 가운데 가장 중요한 제올라이트와 최근 연구가 활발한 하이브리드 나노세공체의 산업적 응용 및 기술개발 동향과 향후 발전 전망에 대해 간략히 기술하였다.

Effect of Dispersed MoO3 Amount on Catalytic Activity of NiO-ZrO2 Modified with MoO3 for Acid Catalysis

  • Sohn, Jong-Rack;Lee, Sung-Gyu;Shin, Dong-Cheol
    • Bulletin of the Korean Chemical Society
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    • v.27 no.10
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    • pp.1623-1632
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    • 2006
  • NiO supported on zirconia modified with $MoO_3$ for acid catalysis was prepared by drying powdered $Ni(OH)_2-Zr(OH)_4$ with ammonium heptamolybdate aqueous solution, followed by calcining in air at high temperature. The characterization of prepared catalysts was performed using FTIR, Raman, XRD, and DSC. $MoO_3$ equal to or less than 15 wt% was dispersed on the surface of catalyst as two-dimensional polymolybdate or monomolybdate, while for $MoO_3$ above 15 wt%, crystalline orthorhombic phase of $MoO_3$ was formed, showing that the critical dispersion capacity of $MoO_3$ on the surface of catalyst is 0.18 g/g NiO-$ZrO_2$ on the basis of XRD analysis. Acidity and catalytic activities for acid catalysis increased with the amount of dispersed $MoO_3$. The high acid strength and acidity was responsible for the Mo=O bond nature of the complex formed by the interaction between $MoO_3$ and $ZrO_2$. The catalytic activity for acid catalysis was correlated with the acidity of the catalysts measured by the ammonia chemisorption method.

Evaluation of MALDI Biotyping for Rapid Subspecies Identification of Carbapenemase-Producing Bacteria via Protein Profiling

  • Somboro, Anou M.;Tiwari, Dileep;Shobo, Adeola;Bester, Linda A.;Kruger, Hendrik G.;Govender, Thavendran;Essack, Sabiha Y.
    • Mass Spectrometry Letters
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    • v.5 no.4
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    • pp.110-114
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    • 2014
  • The method of direct mass spectrometry profiling is reliable and reproducible for the rapid identification of clinical isolates of bacteria and fungi. This is the first study evaluating the approach of MALDI-TOF mass spectrometry profiling for rapid identification of carbapenemase-resistant enterobacteriaceae (CRE). Proof of concept was achieved by the discrimination of CRE using MALDI Biotyper MS based on the protein. This profiling appears promising by the visual observation of consistent unique peaks, albeit low intensity, that could be picked up from the mean spectra (MSP) method. The Biotyper MSP creation and identification methods needed to be optimized to provide significantly improved differences in scores to allow for subspecies identification with and without carbapenemases. These spectra were subjected to visual peak picking and in all cases; there were pertinent differences in the presence or absence of potential biomarker peaks to differentiate isolates. We also evaluated this method for potential discrimination between different carbapenemases bacteria, utilizing the same strategy. Based on our data and pending further investigation in other CREs, MALDI-TOF MS has potential as a diagnostic tool for the rapid identification of even closely related carbapenemases but would require a paradigm shift in which Biotyper suppliers enable more flexible software control of mass spectral profiling methods.

STM Tip Catalyzed Adsorption of Thiol Molecules and Functional Group-Selective Adsorption of a Bi-Functional Molecule Using This Catalysis

  • Min, Yeong-Hwan;Jeong, Sun-Jeong;Yun, Yeong-Sang;Park, Eun-Hui;Kim, Do-Hwan;Kim, Se-Hun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.197-197
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    • 2011
  • In this study, in contrast with cases in which Scanning Tunneling Microscopy (STM) tip-induced reactions were instigated by the tunneling electrons, the local electric field, or the mechanical force between a tip and a surface, we found that the tungsten oxide (WO3) covered tungsten (W) tip of a STM acted as a chemical catalyst for the S-H dissociative adsorption of phenylthiol and 1-octanethiol onto a Ge(100) surface. By varying the distance between the tip and the surface, the degree of the tip-catalyzed adsorption could be controlled. We have found that the thiol head-group is the critical functional group for this catalysis and the catalytic material is the WO3 layer of the tip. After removing the WO3 layer by field emission treatment, the catalytic activity of the tip has been lost. 3-mercapto isobutyric acid is a chiral bi-functional molecule which has two functional groups, carboxylic acid group and thiol group, at each end. 3-Mercapto Isobutyric Acid adsorbs at Ge(100) surface only through carboxylic acid group at room temperature and this adsorption was enhanced by the tunneling electrons between a STM tip and the surface. Using this enhancement, it is possible to make thiol group-terminated surface where we desire. On the other hand, surprisingly, the WO3 covered W tip of STM was found to act as a chemical catalyst to catalyze the adsorption of 3-mercapto isobutyric acid through thiol group at Ge(100) surface. Using this catalysis, it is possible to make carboxylic acid group-terminated surface where we want. This functional group-selective adsorption of bi-functional molecule using the catalysis may be used in positive lithographic methods to produce semiconductor substrate which is terminated by desired functional groups.

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