• Title/Summary/Keyword: Catalytic Metal

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A Mechanistic Study on Reactions of Aryl Benzoates with Ethoxide, Aryloxides and Acetophenone oximates in Absolute Ethanol

  • 엄익환;오수진;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.17 no.9
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    • pp.802-807
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    • 1996
  • Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (+0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

Identification and Characterization of a Novel Thermostable GDSL-Type Lipase from Geobacillus thermocatenulatus

  • Jo, Eunhye;Kim, Jihye;Lee, Areum;Moon, Keumok;Cha, Jaeho
    • Journal of Microbiology and Biotechnology
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    • v.31 no.3
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    • pp.483-491
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    • 2021
  • Two putative genes, lip29 and est29, encoding lipolytic enzymes from the thermophilic bacterium Geobacillus thermocatenulatus KCTC 3921 were cloned and overexpressed in Escherichia coli. The recombinant Lip29 and Est29 were purified 67.3-fold to homogeneity with specific activity of 2.27 U/mg and recovery of 5.8% and 14.4-fold with specific activity of 0.92 U/mg and recovery of 1.3%, respectively. The molecular mass of each purified enzyme was estimated to be 29 kDa by SDS-PAGE. The alignment analysis of amino acid sequences revealed that both enzymes belonged to GDSL lipase/esterase family including conserved blocks with SGNH catalytic residues which was mainly identified in plants before. While Est29 showed high specificity toward short-chain fatty acids (C4-C8), Lip29 showed strong lipolytic activity to long-chain fatty acids (C12-C16). The optimal activity of Lip29 toward p-nitrophenyl palmitate as a substrate was observed at 50℃ and pH 9.5, respectively, and its activity was maintained more than 24 h at optimal temperatures, indicating that Lip29 was thermostable. Lip29 exhibited high tolerance against detergents and metal ions. The homology modeling and substrate docking revealed that the long-chain substrates showed the greatest binding affinity toward enzyme. Based on the biochemical and insilico analyses, we present for the first time a GDSL-type lipase in the thermophilic bacteria group.

Development of a novel endolysin, PanLys.1, for the specific inhibition of Peptostreptococcus anaerobius

  • Joonbeom Moon;Hanbeen Kim;Dongseok Lee;Jakyeom Seo
    • Animal Bioscience
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    • v.36 no.8
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    • pp.1285-1292
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    • 2023
  • Objective: The objective of this study was to develop a novel endolysin (PanLys.1) for the specific killing of the ruminal hyper-ammonia-producing bacterium Peptostreptococcus anaerobius (P. anaerobius). Methods: Whole genome sequences of P. anaerobius strains and related bacteriophages were collected from the National Center for Biotechnology Information database, and the candidate gene for PanLys.1 was isolated based on amino acid sequences and conserved domain database (CDD) analysis. The gene was overexpressed using a pET system in Escherichia coli BL21 (DE3). The lytic activity of PanLys.1 was evaluated under various conditions (dosage, pH, temperature, NaCl, and metal ions) to determine the optimal lytic activity conditions. Finally, the killing activity of PanLys.1 against P. anaerobius was confirmed using an in vitro rumen fermentation system. Results: CDD analysis showed that PanLys.1 has a modular design with a catalytic domain, amidase-2, at the N-terminal, and a cell wall binding domain, from the CW-7 superfamily, at the C-terminal. The lytic activity of PanLys.1 against P. anaerobius was the highest at pH 8.0 (p<0.05) and was maintained at 37℃ to 45℃, and 0 to 250 mM NaCl. The activity of PanLys.1 significantly decreased (p<0.05) after Mn2+ or Zn2+ treatment. The relative abundance of P. anaerobius did not decrease after administration PanLys.1 under in vitro rumen conditions. Conclusion: The application of PanLys.1 to modulate P. anaerobius in the rumen might not be feasible because its lytic activity was not observed in in vitro rumen system.

Pillared Bentonite Materials as Potential Solid Acid Catalyst for Diethyl Ether Synthesis: A Brief Review

  • Puji Wahyuningsih;Karna Wijaya;Aulia Sukma Hutama;Aldino Javier Saviola;Indra Purnama;Won-Chun Oh;Muhammad Aziz
    • Korean Journal of Materials Research
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    • v.34 no.5
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    • pp.223-234
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    • 2024
  • This review explores the potential of pillared bentonite materials as solid acid catalysts for synthesizing diethyl ether, a promising renewable energy source. Diethyl ether offers numerous environmental benefits over fossil fuels, such as lower emissions of nitrogen oxides (NOx) and carbon oxides (COx) gases and enhanced fuel properties, like high volatility and low flash point. Generally, the synthesis of diethyl ether employs homogeneous acid catalysts, which pose environmental impacts and operational challenges. This review discusses bentonite, a naturally occurring alumina silicate, as a heterogeneous acid catalyst due to its significant cation exchange capacity, porosity, and ability to undergo modifications such as pillarization. Pillarization involves intercalating polyhydroxy cations into the bentonite structure, enhancing surface area, acidity, and thermal stability. Despite the potential advantages, challenges remain in optimizing the yield and selectivity of diethyl ether production using pillared bentonite. The review highlights the need for further research using various metal oxides in the pillarization process to enhance surface properties and acidity characteristics, thereby improving the catalytic performance of bentonite for the synthesis of diethyl ether. This development could lead to more efficient, environmentally friendly synthesis processes, aligning with sustainable energy goals.

Morphology Control of Nanostructured Graphene on Dielectric Nanowires

  • Kim, Byeong-Seong;Lee, Jong-Un;Son, Gi-Seok;Choe, Min-Su;Lee, Dong-Jin;Heo, Geun;Nam, In-Cheol;Hwang, Seong-U;Hwang, Dong-Mok
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.375-375
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    • 2012
  • Graphene is a sp2-hybridized carbon sheet with an atomic-level thickness and a wide range of graphene applications has been intensely investigated due to its unique electrical, optical, and mechanical properties. In particular, hybrid graphene structures combined with various nanomaterials have been studied in energy- and sensor-based applications due to the high conductivity, large surface area and enhanced reactivity of the nanostructures. Conventional metal-catalytic growth method, however, makes useful applications difficult since a transfer process, used to separate graphene from the metal substrate, should be required. Recently several papers have been published on direct graphene growth on the two dimensional planar substrates, but it is necessary to explore a direct growth of hierarchical nanostructures for the future graphene applications. In this study, uniform graphene layers were successfully synthesized on highly dense dielectric nanowires (NWs) without any external catalysts. We also demonstrated that the graphene morphology on NWs can be controlled by the growth parameters, such as temperature or partial pressure in chemical vapor deposition (CVD) system. This direct growth method can be readily applied to the fabrication of nanoscale graphene electrode with designed structures because a wide range of nanostructured template is available. In addition, we believe that the direct growth growth approach and morphological control of graphene are promising for the advanced graphene applications such as super capacitors or bio-sensors.

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The Characteristics of HI Decomposition using Pt/Al2O3 Catalyst Heat Treated in Air and Hydrogen Atmosphere (공기 및 수소 분위기에서 열처리 된 Pt/Al2O3 촉매의 HI분해반응 특성)

  • Park, Eun Jung;Ko, Yun Ki;Park, Chu Sik;Kim, Chang Hee;Kang, Kyoung Soo;Cho, Won Chul;Jeong, Seong Uk;Bae, Ki Kwang;Kim, Young Ho
    • Transactions of the Korean hydrogen and new energy society
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    • v.25 no.3
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    • pp.219-226
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    • 2014
  • In HI decomposition, $Pt/Al_2O_3$ has been studied by several researchers. However, after HI decomposition, it could be seen that metal dispersion of $Pt/Al_2O_3$ was greatly decreased. This reason was expected of platinum loss and sintering, which platinum was aggregated. Also, this decrease of metal dispersion caused catalytic deactivation. This study was conducted to find the condition to minimize platinum sintering and loss. In particular, heat treatment atmosphere and temperature were examined to improve the activity of HI decomposition reaction. First of all, although $Pt/Al_2O_3$ treated in hydrogen atmosphere had low platinum dispersion between 13 and 18%, it was shown to suitable platinum form that played an important role in improving HI decomposition reaction. Oxygen in the air atmosphere made $Pt/Al_2O_3$ have high platinum dispersion even 61.52% at $500^{\circ}C$. Therefore, in order to get high platinum dispersion and suitable platinum form in HI decomposition reaction, air heat treatment at $500^{\circ}C$ was needed to add before hydrogen heat treatment. In case of 5A3H, it had 51.13% platinum dispersion and improved HI decomposition reaction activity. Also, after HI decomposition reaction it had considerable platinum dispersion of 23.89%.

Superhydrophilicity of Titania Hybrid Coating Film Imposed by UV Irradiation without Heat-treatment (저온 경화형 초친수성 티타니아 하이브리드 졸의 제조와 친수성 특성 평가에 관한 연구)

  • Kim, Won-Soo;Park, Won-Kyu
    • Journal of Technologic Dentistry
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    • v.29 no.1
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    • pp.121-131
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    • 2007
  • A preparation process's conditions of aqueous sol which contains anatase-type nano titania particles with photocatalyic properties was established by using Yoldas process, so called, DCS(Destabilization of Colloidal Solution) process in this study. And crystal size change and phase transformation of titania particles in aqueous titania sol depending on reaction conditions was investigated by a light scattering method and XRD analysis of frozen dried powders, respectively. This sol with photo catalytic nano titania particles was used to the following hydrophilic hybrid coating film's fabrication and its properties was evaluated. Subsequently, for coating film using the above mentioned aqueous titania sol, non-aqueous titania sol was prepared without any chemical additives and its time stability according to aging time was investigate. By using the above mentioned aqueous titania sol and non-aqueous sol, a complex oxide coating sol for metal and ceramic substrate and a organic-inorganic hybrid coating sol for polymer substrate was prepared and it's hydrophilicity depending on UV irradiation conditions was evaluated. As a conclusions, the following results were obtained. (1)Aqueous titania sol The average particle size of titania in formed aqueous titania sol was distributed between 20$\sim$90nm range depending on reaction conditions. And the crystal phase of titania powders obtained by frozen drying method was changed from amorphous state to anatase and subsequently transformed to rutile crystal phase and it is attributed to concentration gradient in aqueous sol. (2)Non-aqueous titania sol Non-aqueous titania sol was prepared using methanol as a solvent and a little distilled water for hydrolysis and nitric acid as a catalyst were used. The obtained non-aqueous titania sol was stable at room temperature for 20 days. Additionally, non-aqueous titania sol with addition of chealating reagent such as acethylaceton and ethylene glycol prolonged the stability of sol by six months. (3)Complex sol and hybrid sol with super hydrophilicity The above mentioned aqueous titania sol as a main photocataylic component and non-aqueous titania sol as a binder for coating process was used to prepare a complex sol used for metal, ceramic and wood material substrate and also to prepare the organic-inorganic hybrid sol for polymer substrate such as polycarbonate and polyethylene, in which process APMS(3-Aminopropyltrimethoxysilane), GPTS(3-Glycidoxypropyl-trimethoxysilane) as a hydrophilic silane compound and HEMA(2-Hydroxyethyl methacrylate) as a forming network in hybrid coating film were used. The hybrid coating film such as prepared through this process showed a superhydrophilicity below 1$10^{\circ}$ depending on processing conditions and a pencil's hardness over 6 H.

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Hydrogen Production by Auto-thermal Reforming of Ethanol over $M/Al_2O_3$ (M = Mn, Fe, Co, Ni, Cu) Catalysts ($M/Al_2O_3$ (M = Mn, Fe, Co, Ni, Cu) 촉매 상에서 에탄올 자열개질반응에 의한 수소 제조)

  • Youn, Min-Hye;Seo, Jeong-Gil;Cho, Kyung-Min;Park, Sun-Young;Kim, Pil;Song, In-Kyu
    • Clean Technology
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    • v.13 no.4
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    • pp.287-292
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    • 2007
  • [ $M/Al_2O_3$ ] (M = Mn, Fe, Co, Ni, Cu) catalysts supported on commercial alumina ($Al_2O_3$) were prepared by an impregnation method, and were applied to the hydrogen production by auto-thermal reforming of ethanol. It was revealed that each catalyst retained its own metallic phase and product distribution strongly depended on the identity of active metal. Among the catalysts prepared, $Ni/Al_2O_3$ and $Co/Al_2O_3$ showed the best catalytic performance in the auto-thermal reforming of ethanol. However, the reaction mechanisms over these two catalysts were different. Ni/Al_2O_3 catalyst showed 100% ethanol conversion at $500^{\circ}C$, but it exhibited a rapid decrease in hydrogen selectivity. Although $Co/Al_2O_3$ catalyst showed an excellent performance in hydrogen selectivity, on the other hand, no significant improvement in hydrogen yield was observed due to the low ethanol conversion over the catalyst.

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The Effect of Inhibitors and Catalysts in the Synthesis of 2-Hydroxyethyl Methacrylate(2-HEMA) (2-Hydroxyethyl Methacrylate(2-HEMA)의 합성에 있어서 중합억제제와 촉매의 영향)

  • Park, Byeong-Deog;Chae, Heon-Seung;Jang, Heung;Oh, Seung-Mo;Lee, Yoon-Sik
    • Applied Chemistry for Engineering
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    • v.5 no.3
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    • pp.425-430
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    • 1994
  • The effect of inhibitors and catalysts in the synthesis of 2-hydroxyethyl methacrylate(2-HEMA) was studied. As catalysts, triethylamine(TEA), $FeCl_3{\cdot}6H_2O$, $Cu(NO_3)_2{\cdot}2H_2O$, $AlCl_3$, $Na_2Cr_2O_7$were selected. p-Methoxyphenol (PMP) of aq. $NaNO_3$ solution was used as an inhibitor in polymerization. in aq. $NaNO_3$ inhibitor system, triethylamine (TEA), $FeCl_3{\cdot}6H_2O$, and $Na_2Cr_2O_7$, showed good catalytic effects. When p-methoxyphenol(PMP) was used as a polymerization inhibitor, the reaction was very sluggish and noneffective because the metal ion such as $Fe^{3+}$ or $Cr^{6+}$ was reduced by PMP. On the contrary, when aq. $NaNO_3$ was used as an inhibitor in polymerization, the reaction was very fast without deactivation of the metal catalysts.

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SO2 Adsorption Characteristics of PAN-based Activated Carbon Fiber Impregnated with Palladium and Gold Nanoparticles (팔라듐과 금 나노입자를 첨착한 PAN계 활성탄소섬유의 SO2 흡착특성)

  • Lee, Jin-Jae;Jun, Moon-Gue;Kim, Young-Chai
    • Applied Chemistry for Engineering
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    • v.18 no.5
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    • pp.467-474
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    • 2007
  • The palladium and gold nanoparticles containing PAN-based active carbon fiber (ACF) with a high specific surface area were prepared. Using the BET, TEM, FE-SEM, and XPS, their specific surface area and pore volume, pore structure, and the change in surface oxygen groups with time were analyzed and $SO_2$ adsorption performances were investigated. Because of the impregnating process, the micropore volume was mostly decreased from 95.5% to 30.5~43.7% compared with the total pore volume. And the change in surface oxygen groups with time was higher for the metal salt than the nanoparticles. Also, $SO_2$ breakthrough time of PAN-ACFs impregnated with Au nanoparticles and metal salts did not change compared with that of the non-impregnated PAN-ACF. But the PAN-ACF impregnated with Pd nanoparticles (100 ppm) showed good $SO_2$ adsorption performance as the breakthrough time of 880 sec. These results indicated that the $SO_2$ adsorption performance depended on the change in surface oxygen groups with time and the moderate impregnation of Pd nanoparticles on the PAN-ACF caused the increase in the $SO_2$ adsorption performance by a catalytic action.