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A Stereochemical Aspect of Pyridoxal 5' -Phosphate Dependent Enzyme Reactions and Molecular Evolution

  • Jhee, Kwang-Hwan;Tohru, Yoshimura;Yoichi, Kurokawa;Nobuyoshi, Esaki;Kenji, Soda
    • Journal of Microbiology and Biotechnology
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    • v.9 no.6
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    • pp.695-703
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    • 1999
  • We have studied the stereospecificities of various pyridoxal 5'-phosphate (PLP) dependent enzymes for the hydrogen transfer between the C-4' of a bound coenzyme and the C-2 of a substrate in the transamination catalyzed by the enzymes. Stereospecificities reflect the structures of enzyme active-sites, in particular the geometrical relationship between the coenzyme-substrate Schiff base and the active site base participating in an $\alpha$-hydrogen abstraction. The PLP enzymes studied so far catalyze only a si-face specific (pro-S) hydrogen transfer. This stereochemical finding suggests that the PLP enzymes have the same topological active-site structures, and that the PLP enzymes have evolved divergently from a common ancestral protein. However, we found that o-amino acid aminotransferase, branched chain L-amino acid aminotransferase, and 4-amino-4-deoxychorismate lyase, which have significant sequence homology with one another, catalyze a re-face specific (pro-R) hydrogen transfer. We also showed that PLP-dependent amino acid racemases, which have no sequence homology with any aminotransferases, catalyze a non-stereospecific hydrogen transfer: the hydrogen transfer occurs on both faces of the planar intermediate. Crystallographical studies have shown that the catalytic base is situated on the re-face of the C-4' of the bound coenzyme in o-amino acid aminotransferase and branched chain L-amino acid aminotransferase, whereas the catalytic base is situated on the si-face in other aminotransferases (such as L-aspartate aminotransferase) catalyzing the si-face hydrogen transfer. Thus, we have clarified the stereospecificities of PLP enzymes in relation with the primary structures and three-dimensional structures of the enzymes. The characteristic stereospecificities of these enzymes for the hydrogen transfer suggest the convergent evolution of PLP enzymes.

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The Influence of Skin surface temperature on Transdermal Absorption of Active Substances and Changes in Skin Condition (피부표면온도가 유효물질 경피 흡수 및 피부 상태변화에 미치는 영향)

  • Kwon, Hye-Jin;Han, Sa-Ra;Jung, Na-Seul
    • Journal of the Korean Applied Science and Technology
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    • v.36 no.1
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    • pp.299-304
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    • 2019
  • This study was conducted to investigate the effects of skin surface temperature on transdermal absorption of active substances and changes in skin condition. A transdermal absorption test was conducted using an emulsion containing 10% heat-resistant niacinamide, and the same emulsion was used in a clinical trial to test the thermal effects. As a result, absorption was found to be 2 times greater at 10 minutes and 3 times greater at 15 minutes after application at $42^{\circ}C$ than that of compared to normal skin temperature. During the clinical evaluation on skin, no clinical subjects showed any specific adverse reactions, while moisture and oiliness showed statistically significant effects at higher temperatures. Based on these results, it was confirmed that thermal warmer improves the absorption of active substances and had a positive effect on skin condition. It is deemed that this study will provide a preliminary data to support the development of various beauty devices using heat.

In vitro and in vivo Evaluations of LB 10517, a Novel Parenteral Broad-Spectrum Cephalosporin

  • Song, Hye-Kyong;Nishino, Takeshi;Seo, Mi-Kyeong;Kim, Mu-Yong;Lee, Yong-Hee;Kim, In-Chull;Kwak, Jin-Hwan
    • Archives of Pharmacal Research
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    • v.19 no.1
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    • pp.46-51
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    • 1996
  • The in vitro activity of LB 10517, a new catechol-substituted cephalosporin, was compared with those of E-1077, cefpirome and ceftazidime 1034 clinical isolates collected in Japan. LB10517 showed a broad-spectrum antibacterial activity against a wide range of grampositive and gram-negative bacteria including non-glucose fermenting rods, Pseudomonas aeruginosa. Against the methicillin-susceptible strains of Staphylococcus aureus (MSSA) and Strptoccus pyogenes, the $MIC_{90}$ values of LB10517 which required to inhibit 90% of the strains wre $3.13\mug/ml\; and\; 0.1\mug/ml$, respectively. It was as active as E-1077 but more active than cefpirome and ceftazidime. Methicillin-resistant strains of S.aureus (MRSA) and Enterococcus spp. were highly resistant to all the test compunds. LB10517 was highly active against most members of the family Enterobacteriaceae, 90% of which were inhibited at a concentration of less than $0.78\mug/ml$, except for Enterobacter cloacae ($1.56\mug/ml$) and Serratia marcescens ($3.13\mug/ml$)Its activity was comparable to those of E-1077 and cefpirome but it was greater than that of ceftazidime. Against Pseudomonas aeruginosa, LB10517 showed the most potent antibacterial activity among the compounds tested. Ninety percent of P. aeruginosa isolates were susceptible at the concentration of $0.39\mug/ml$. Its activity was 32-to 128 fold higher than those of E-1077, cefpirome and ceftazidime. Against imipenem- or ofloxacin-resistant P. aeruginosa, LB10517 with $MIC_{90}\; of\; 6.25 \\mug/ml\; and\; 3.13\mug/ml$, respectively, showed 16-fold more potent activity than the other test compounds. LB10517 showed a relatively high plasma level and long plasma elimination half-life in rats $(t_{1/2}(\beta,\; 52 min)\; and\; dogs\; (t_{1/2}(\beta),\; 103 min)$.

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Development of Solid Base Catalyst K2CO3/γ-Al2O3 for the Production of Biodiesel (바이오디젤 생산을 위한 K2CO3/γ-Al2O3 고체염기촉매의 개발)

  • Sim, Yeon Ju;Kim, Jong Hoon;Kim, Eui Yong
    • Korean Chemical Engineering Research
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    • v.54 no.1
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    • pp.64-69
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    • 2016
  • The applications of heterogeneous catalyst have been relatively active area of research in the biodiesel process. These catalysts have the benefit of easy recovery and reusability of the catalyst. The objective of this study is to find out significant effect of calcination temperature on $K_2CO_3/{\gamma}-Al_2O_3$ catalytic activity in the biodiesel formation reaction. As a results, the temperature at which a catalyst was calcined had very important influence on the catalytic activity. The catalytic activity increased up to $600^{\circ}C$, but it severely decreased above the temperature. The reduction of catalyst activity at high temperature would be due to the deduction of the active sites of Al-O-K and $Al-O_2-K$.

Methanol-to-Olefin Conversion over UZM-9 Zeolite: Effect of Transition Metal Ion Exchange on its Deactivation (UZM-9 제올라이트에서 메탄올의 올레핀으로 전환반응: 전이금속 이온 교환이 촉매의 활성저하에 미치는 영향)

  • Kim, Sun Jung;Jang, Hoi-Gu;Seo, Gon
    • Korean Chemical Engineering Research
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    • v.51 no.2
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    • pp.181-188
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    • 2013
  • The effect of transition metal ion exchange into UZM-9 zeolite with LTA framework on its deactivation in methanol-to-olefin (MTO) conversion was discussed. The ion exchange of copper, cobalt, nickel, and iron did not induce any notable change in the crystallinity, crystal morphology, and acidity of UZM-9. The small cage entrance of UZM-9 caused the high selectivity to lower olefins in the MTO conversion, while its large cages allowed the rapid further cyclecondensation of active intermediates, polymethylbenzenes including hexamethylbenzene, resulting in a rapid deactivation. The UZM-9 containing copper and cobalt ions showed considerably slow deactivations. The interaction between transition metal ions and polymethylbenzene cation radicals, the active intermediates, generated in the MTO conversion stabilized the radicals and slowed down the deactivation of UZM-9.

Measurement of Hydrogen Crossover by Gas Chromatograph in PEMFC (고분자전해질 연료전지에서 기체 크로마토그래프에 의한 수소투과도 측정)

  • Jeong, Jaejin;Jeong, Jaehyeun;Kim, Saehoon;Ahn, Byungki;Ko, Jaijoon;Park, Kwonpil
    • Korean Chemical Engineering Research
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    • v.52 no.4
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    • pp.425-429
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    • 2014
  • Until a recent day, degradation of PEMFC MEA(membrane and electrode assembly) has been studied, separated with membrane degradation and electrode degradation, respectively. But membrane and electrode were degraded coincidentally at real PEMFC operation condition. During simultaneous degradation, there was interaction between membrane degradation and electrode degradation. Hydrogen permeability was used often to measure degradation of electrolyte membrane in PEMFC. In case of hydrogen permeability measured by LSV(Linear Sweep Voltammetry) method, the degradation of electrode decrease the value of hydrogen crossover current due to LSV methode's dependence on electrode active area. In this study hydrogen permeability was measured by gas chromatograph(GC) when membrane and electrode degraded at the same time. It was showed that degradation of electrode did not affect the hydrogen permeability measured by GC because of GC methode's independence on electrode active area.

Recent Progress in Inorganic Nanoparticles with Enzyme-Mimetic Activities and Their Applications to Diagnosis and Therapy (효소 모사 활성 무기 나노입자의 진단 및 치료 응용연구 동향)

  • Lee, Junsoo;Kim, Taeyeon;Kim, Bong-Geun;Na, Hyon Bin
    • Applied Chemistry for Engineering
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    • v.31 no.4
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    • pp.352-359
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    • 2020
  • Inorganic nanoparticles have been actively applied to the bio-medical field by utilizing their physical properties derived from the nanometer size regime, such as optical and magnetic properties. In recent years, diagnostic detection methods have been developed by employing chemical activity, particularly enzyme-mimetic activities, as well as physical properties of inorganic nanoparticles. After the initial study of verifying the enzyme-mimetic activities, the scope of research has been expanded to the direct use of therapeutic effects with active control of activity through understanding of the catalytic mechanism. This review summarizes recent research works on the active control of the enzyme-mimetic activities and newly demonstrated applications on the diagnosis and treatment of diseases, focusing on inorganic nanoparticles, so-called "nanozyme". It is expected that the enzyme-mimetic activity of inorganic nanoparticles will be combined with their inherent physical properties, leading to the development of new diagnostic and therapeutic methods.

In Vitro and in Vivo Antibacterial Activities of a New Parenteral Cephalosporin, LB10522 (주사제용 세파로스포린계 항생제 LB10522의 in vitro 및 in vivo 항균력)

  • Paek, Kyung-Sook;Oh, Jeong-In;Kim, Mu-Yong;Kim, In-Chull;Kwak, Jin-Hwan
    • YAKHAK HOEJI
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    • v.40 no.1
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    • pp.95-101
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    • 1996
  • The in vitro antibacterial activities of LB10522, a new catechol-substituted cephalosporin, were compared with those of cefpirome, ceftazidime, ceftriaxone, and cefoperaz one against clinical isolates and laboratory standard anaerobes. LB10522 had broad spectrum antibacterial activities against both gram-positive and gram-negative microorganisms. It was most active against gram-positve bacteria among the reference cephalosporins tested. Against gram-negative strains such as the family Enterobacteriaceae, LB10522 showed an activity comparable to that of cefpirome. But LB10522 was more potent than ceftazidime, ceftriaxone and cefoperazone. In particular, Pseudomonas aeruginosa was highly susceptible to LB10522, which was 32-fold and 64-fold more active than ceftazidime and cefpirome, respectively. Against anaerobic strains, the activity of LB10522 was similar to those of reference compounds. LB10522 exhibited potent therapeutic activities against experimental local infections in mice. The therapeutic effect of LB10522 against urinary tract infection (UTI) caused by P. aeruginosa 1912E in mice was superior to that of cefpirome. Against experimental respiratory tract infection (RTI) caused by K. pneumoniae DT-S in mice, LB10522 was as effective as cefpirome. The in vivo efficacy of LB10522 was correlated well with its in vitro activity.

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The Influence of the Internal Donors in the Heterogenous Olefin Polymerization Catalyst on the Molecular Structure of Linear Low Density Polyethylene (불균일계 올레핀 중합촉매내 내부전자공여체가 선형 저밀도폴리에틸렌 분자구조에 미치는 영향)

  • Ko, Young Soo
    • Korean Chemical Engineering Research
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    • v.45 no.4
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    • pp.410-413
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    • 2007
  • The effect of internal donor(ID) in the heterogeneous Ziegler-Natta catalyst on the ethylene-1-butene copolymerization and the molecular structure of the resulting copolymer was investigated. $SiO_2$-supported $TiCl_4$ catalysts having ID/Ti molar ratio of 0.5 were prepared with ethyaluminium dichloride, magnesium alkyl, 2-ethyl-1-hexanol and $TiCl_4$. Three different IDs were employed such as ethylbenzoate(EB), diisobuylphthalate(DIBP) and dioctylphthalate(DOP). ID-added catalyst showed a larger fraction of Ti(+3) compared to that of no ID-added catalyst. The EB-added catalyst showed the highest activity in copolymerization. Xylene soluble value decreased by more than 50 % with ID-added catalysts compared to that of no ID-added catalyst. Crystaf analysis showed the chemical compositional distribution of PE copolymer was improved in the case of DIBP-added catalyst significantly. It could be explained that the presence of ID could make more even active sites and block the non-stereospecific active sites.

Characteristics of South Korea's Geothermal Water in Relation to Its Geological and Geochemical Feature

  • Lee, Chung-Mo;Hamm, Se-Yeong;Lee, Cholwoo;Choi, Sung-Ja;Chung, Sang Yong
    • Journal of Soil and Groundwater Environment
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    • v.19 no.2
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    • pp.25-37
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    • 2014
  • The volcanic type of geothermal water is linked intimately to active or potentially active volcanoes and takes place near the plate boundaries. In contrast to the volcanic type, the geothermal water in Korea has a non-volcanic origin. Korea's geothermal water is classified into the residual magma (RM) type and deep groundwater (DG) type according to the criterion of $35^{\circ}C$. This study reviewed the relationship between the physical and chemical features of the 281 geothermal water sources in South Korea in terms of the specific capacity, water temperature, and chemical compositions of two different basements (igneous rock and metamorphic rock) as well as the geological structures. According to the spatial relationship between the geothermal holes and geological faults, the length of the major fault is considered a key parameter determining the movement to a deeper place and the temperature of geothermal water. A negligible relationship between the specific capacity (Q/s) and temperature was found for both the RM type and DG type with the greater specific capacities of the RM- and DG-igneous types than the RM- and DG-metamorphic types. No relationship was observed between Q/s and the chemical constituents ($K^+$, $Na^+$, $Ca^{2+}$, $Mg^{2+}$, $Zn^{2+}$, $Cl^-$, $SO_4{^{2-}}$, $HCO_3{^-}$, and $SiO_2$) in the DG-igneous and DG-metamorphic types. Furthermore, weak relationship between temperature and chemical constituents was found for both the RM type and DG type.