• Title/Summary/Keyword: Ligand oxidation

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Chlorine Effect on Thermal Aging Behaviors of BR and CR Composites

  • Choi, Sung-Seen;Kim, Jong-Chul
    • Bulletin of the Korean Chemical Society
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    • 제31권9호
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    • pp.2613-2617
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    • 2010
  • Chloroprene is a chlorine substituent of 1,3-butadiene. Butadiene rubber (BR) and chloroprene rubber (CR) composites were thermally aged at 60, 70, 80, and $90^{\circ}C$ for 2 - 185 days in a convection oven and changes of the crosslink densities by the accelerated thermal aging were investigated. The crosslink densities increased as the aging time elapsed and as the aging temperature became higher. Degrees of the crosslink density changes of the BR composite were on the whole larger than those of the CR one except the short-term thermal aging at 60 and $70^{\circ}C$. The crosslink densities abnormally increased after themal aging at high temperatures for a long time. Activation energies for the crosslink density changes of the rubber composites tended to increase with increase of the aging time and the variation showed a local minimum. The activation energies of the CR composite were lower than those of the BR one. The experimental results were explained with a role of ligand of chlorine atom of CR in a zinc complex, steric hindrance by chlorine atom of CR, and oxidation of rubber chain.

Src Protein Tyrosine Kinases in Stress Responses

  • Grishin, Anatoly;Corey, Seth J.
    • Animal cells and systems
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    • 제6권1호
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    • pp.1-12
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    • 2002
  • A role of Src family protein Tyrosine kinases (SFK) as mediators of receptor-ligand initiated responses is well established. Well documented, but less well understood is the role of SFK in cellular reaction to stresses. Evidence from the wide variety of experimental systems indicates that SFK mediate responses to all major classes of stress, including oxidation, DNA damage, mechanical impacts, and protein denaturing. SFK may be activated by stresses directly or via regulatory circuits whose identity is not yet fully understood. Depending on the cell type and the nature of activating stimulus, SFK may activate known downstream signaling cascades leading to cell survival, proliferation, cytoskeletal rearrangement, and apoptosis; the identity of these cascades is discussed. As in the case of receptor-initiated signaling, roles of individual SFK in various stress response may be redundant or non-redundant. Although signals generated by different stresses are generally transduced via distinct SFK pathways, these pathways may overlap or exhibit crosstalk. In some cell types stress-induced activation of SFK promotes survival and inhibits apoptosis, whereas the opposite may be true for other cell types. Stress responses constitute a new and rapidly developing area of SFK-mediated signaling.

Crystal Structure of Glycerol Dehydrogenase from Klebsiella pneumoniae

  • Gyeong Soo Ko;Thang Quyet Nguyen;Seri Koh;Wonchull Kang
    • 대한화학회지
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    • 제68권1호
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    • pp.32-39
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    • 2024
  • Glycerol dehydrogenase (GlyDH) plays a crucial role in the glycerol metabolism pathway by catalyzing the oxidation of glycerol to dihydroxyacetone (DHA). Previous studies of GlyDH have predominantly focused on unraveling the structural features of the active site and its binding interactions with ligand. However, the structural details of GlyDH in complex with both NAD+ and the substrate bound have remained elusive. In this study, we present the crystal structures of Klebsiella pneumoniae GlyDH (KpGlyDH) in the absence and presence of NAD+ at a resolution of 2.1 Å. Notably, both structures reveal the binding of the substrate, ethylene glycol, to the zinc ion. Interestingly, a significant change in the coordination number of the zinc ion is observed, with three in the absence of NAD+ and four in its presence. These findings shed light on the structural aspects of GlyDH and its interactions with NAD+ and the substrate.

네자리 리간드-황아미노산 금속착물의 산화반응에 의한 배위된 황원자의 sulfoxide 원자단으로의 전환 (Conversion of Coordinated Sulfur Atom into Sulfoxide Group via Oxidation Reaction of Metal Complexes of Tetradentates and Sulfur Amino Acids)

  • 이숭실;;최승락;전무진
    • 대한화학회지
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    • 제33권5호
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    • pp.516-521
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    • 1989
  • 주게원자가 질소원자와 산소원자인 N2O2형 네자리 리간드 ethylenediamine-N,N'-S-${\alpha}$-isobutylacetic acid(SS-eniba)의 디클로로 로듐(III)$[Rh(SS-eniba)Cl_2]$-의 합성에서 ${\Delta}-s-cis$${\wedge}-uns-cis$ 이성체를 분리하였다. ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]$- 착물과 S-methyl-L-cystcine(Smc)의 반응으로부터 ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ 착물을 합성한 다음 $H_2O_2$를 이용한 산화반응으로부터 배위된 황원자가 sulfoxide 원자단으로 산화된 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+(Smc-o=S-methyl-L-cysteine sulfoxide)$ 착물이 형성됨을 관찰하였다. 한편 S-methyl-L-cysteine을 $H_2O_2$와 반응시켜 sulfoxide 원자단으로 산화시킨 S-methyle-L-cysteine sulfoxide의 합성을 별도로 진행한 후 ${\Delta}-s-cis-[Rh(SS-eniba)Cl_2]^+$ 착물에 배위시켜 표준착물인 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$를 합성한 다음 ${\Delta}-s-cis-[Rh(SS-eniba(Smc)]^+$ 착물을 산화시켜 얻은 ${\Delta}-s-cis-[Rh(SS-eniba)(Smc-o)]^+$착물과 비교하여 배위된 항원자가 sulfoxide 원자단으로 전환되었음을 또한 관찰하였다.

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Rutin alleviated lipopolysaccharide-induced damage in goat rumen epithelial cells

  • Jinshun Zhan;Zhiyong Gu;Haibo Wang;Yuhang Liu;Yanping Wu;Junhong Huo
    • Animal Bioscience
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    • 제37권2호
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    • pp.303-314
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    • 2024
  • Objective: Rutin, also called vitamin P, is a flavonoids from plants. Previous studies have indicated that rutin can alleviate the injury of tissues and cells by inhibiting oxidative stress and ameliorating inflammation. There is no report on the protective effects of rutin on goat rumen epithelial cells (GRECs) at present. Hence, we investigated whether rutin can alleviate lipopolysaccharide (LPS)-induced damage in GRECs. Methods: GRECs were cultured in basal medium or basal medium containing 1 ㎍/mL LPS, or 1 ㎍/mL LPS and 20 ㎍/mL rutin. Six replicates were performed for each group. After 3-h culture, the GRECs were harvested to detect the relevant parameters. Results: Rutin significantly enhanced the cell activity (p<0.05) and transepithelial electrical resistance (TEER) (p<0.01) and significantly reduced the apoptosis rate (p<0.05) of LPS-induced GRECs. Rutin significantly increased superoxide dismutase, glutathione peroxidase, and catalase activity (p<0.01) and significantly decreased lactate dehydrogenase activity and reactive oxygen species and malondialdehyde (MDA) levels in LPS-induced GRECs (p<0.01). The mRNA and protein levels of interleukin 6 (IL-6), IL-1β, and C-X-C motif chemokine ligand 8 (CXCL8) and the mRNA level of tumor necrosis factor-α (TNF-α) and chemokine C-C motif ligand 5 (CCL5) were significantly increased in LPS-induced GRECs (p<0.05 or p<0.01), while rutin supplementation significantly decreased the mRNA and protein levels of IL-6, TNF-α, and CXCL8 in LPS-induced GRECs (p<0.05 or p<0.01). The mRNA level of toll-like receptor 2 (TLR2), and the mRNA and protein levels of TLR4 and nuclear factor κB (NF-κB) was significantly improved in LPS-induced GRECs (p<0.05 or p<0.01), whereas rutin supplementation could significantly reduce the mRNA and protein levels of TLR4 (p<0.05 or p<0.01). In addition, rutin had a tendency of decreasing the protein levels of CXCL6, NF-κB, and inhibitor of nuclear factor kappa-B alpha (0.05

2-아닐리노 피리딘을 배위자로 하는 이핵 로듐착물의 두 산소첨가 생성물에 대한 합성 및 전기화학적 성질 (Synthesis, ESR and Electrochemical Characterization of Dioxygen Binding to Dirhodium Complexes with 2-anilinopyridinato Bridging Ligand)

  • 박광하;전무진
    • 대한화학회지
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    • 제33권6호
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    • pp.633-643
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    • 1989
  • 두 개의 아닐린계 질소와 두 개의 피리딘계 질소가 각각의 로듐이온에 트란스형으로 결합된 $Rh_2(ap)_4$(2,2-trans) 이성질체는 -0.40 V vs SCE에서 디 옥시젼의 한 전자를 환원시킬 수 있음을 보여주고 있다. 123K에서의 ESR 스펙트럼에 의하면 한 로듐이온에 산소 1분자가 측쇄 결합하여 $[Rh_2(ap)_4(O_2)]^-$이온을 형성하고, 착물은 $Rh_2^{III}$ 산화수를 가짐을 알 수 있다. 이 착물은 시안화메틸/염화메틸렌 혼합용액에서 Rh-$O_2^-$결합의 분열없이 [$Rh_2(ap)_4(O_2)(CH_3CN)]^-$을 형성한다. -0.25, 0.55V에서 산화되었을 때 [$Rh_2(ap)_4(O_2)]^-$$Rh_2(ap)_4(O_2)$와 [$Rh_2(ap)_4(O_2)]^+$을 형성하기 위하여 두 단계의 한 전자 산화과정이 일어난다. 두 화학종은 모두 초산소가 측쇄 결합되어 있지만, 전자는 $Rh^{II}Rh^{III}$, 후자는 $Rh_2^{III}$의 산화수를 갖는다. 반면에, ESR 스펙트럼과 $CH_3CN$ 부가 연구에서 보면 후자 착물이 로듐이온에 위치한 부대전자와 함께 [$Rh^{II}Rh^{III}(ap)_4(O_2)]^+$로 기술되고 그 착물은 측쇄 배위결합된 산소분자를 가지고 있음을 보여주고 있다. 또한 전기화학적, ESR 연구는 디 옥시젼의 활동도가 전기화학적 산화환원전위와 관계 있음을 보여주고 있다.

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V(IV) Species, Location and Adsorbate Interactions in VH-SAPO-42 Studied by ESR and Electron Spin-Echo Modulation Spectroscopies

  • Back, Gern-Ho;Yu, Jong-Sung;Lee, Hye-Young;Kim, Min-Sik;Lee, Yong-Ill
    • 한국자기공명학회논문지
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    • 제11권2호
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    • pp.95-109
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    • 2007
  • Vanadium-incorporated aluminophosphate microporous molecular sieve VH-SAPO-42 has been studied by electron spin resonance(ESR) and electron spin-echo modulation (ESEM) spectroscopies to determine the vanadium location and interaction with various adsorbate molecules. The results are interpreted in terms of V(IV) ion location and coordination geometry. Assynthesized VH-SAPO-42 contains only vanadyl species with distorted octahedral or trigonal bipyramidal coordination. Vanadium incorporated into H-SAPO-42 occupied extra-framework site. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. Species A is identified as a $VO(H_2O)_2^{2+}$ complex coordinated to three framework oxygen atoms bonded to aluminum. When hydrated VH-SAPO-42 is dehydrated at elevated temperature by calcination, species A loses its water ligand and transforms to $VO^{2+}$ ions coordinated to three framework oxygens (species B). Species B reduces its intensities significantly after treatment with $O_2$ at high temperature, thus suggesting oxidation of $V^{4+}$ to $V^{5+}$. When dehydrated VH-SAPO-42 makes contact with $D_2O$ at room temperature, the ESR signal of species A is regained. The species is assumed as a $VO(O_f)_3(D_2O)_2$ by considering three framework oxygens. Adsorption of deuterated methanol on dehydrated VH-SAPO-42 results in another new vanadium species D, which is identified as a $VO(CD_3OH)_2$ complex. When deuterated ethylene is adsorbed on dehydrated VH-SAPO-42, another new vanadium species E identified as a $VO(C_2D_4)^{2+}$, is observed. Possible coordination geometries of these various complexes are discussed.

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Molecular Characterization and Expression Analysis of the Peroxisome Proliferator Activated Receptor Delta (PPARδ) Gene before and after Exercise in Horse

  • Cho, Hyun-Woo;Shin, Sangsu;Park, Jeong-Woong;Choi, Jae-Young;Kim, Nam-Young;Lee, Woon-Kyu;Lee, Hak-Kyo;Song, Ki-Duk;Cho, Byung-Wook
    • Asian-Australasian Journal of Animal Sciences
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    • 제28권5호
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    • pp.697-702
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    • 2015
  • While athletic abilities such as speed, endurance and recovery are important in the horse, genes related to these abilities have not been extensively investigated. Here, we characterized the horse peroxisome proliferator-activated receptor delta ($PPAR{\delta}$) gene and analyzed the expression of $PPAR{\delta}$ during exercise. $PPAR{\delta}$ is a known regulator of ${\beta}$-oxidation, muscle fiber transformation, and running endurance. Through evolutionary analysis using the synonymous and non-synonymous mutation ratio, it was revealed that positive selection occurred in the horse $PPAR{\delta}$ gene. Two important domains related to nuclear hormone receptors, C4 zinc finger and ligand binding domain, were also found to be conserved well in horse $PPAR{\delta}$. Horse $PPAR{\delta}$ was expressed ubiquitously in many tissues, but the expression level was various depending on the tissues. In the skeletal muscle, $PPAR{\delta}$ increased about 2.5 folds after 30 min of exercise. Unlike in muscle, the increase of $PPAR{\delta}$ expression was observed at 60 min but not 30 min of exercise in leukocytes. This finding might be useful for testing the endurance of horse using blood samples. Conclusively, the horse $PPAR{\delta}$ gene is evolutionarily conserved well and can be used as a biomarker of endurance in horse.

Ethylenediamine-N,N'-di-${\alpha}$-Isobutyric Acid의 코발트(III) 착물 (Cobalt(III) Complex of Ethylenediamine-N,N'-di-${\alpha}$-Isobutyric Acid)

  • 전무진;한창윤;박장우;최승락;박광하
    • 대한화학회지
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    • 제30권1호
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    • pp.84-89
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    • 1986
  • 주게원자가 ONNO인 새로운 네자리 리간드인 ethylenediamine-N,N'-di-${\alpha}$-isobutyric acid(eddib)를 합성하고 이 리간드의 디클로로 코발트(III)착물을 공기산화법에 의하여 합성하였다. Eddib리간드가 코발트(III)이온에 배위될 때 S-cis이성체만이 선택적으로 만들어짐이 관찰되었는데 이것은 ring strain과 steric hinderance 때문이다. 그리고 eddib의 디클로로 코발트 (III)착물을 용액중에서 $[Co(eddib)L]^{n+}$ $(L = Cl{\cdot}(H_2O),\;CO_3^{2-},\;(H_2O)_2)$로 치환반응을 시켰을 때 이들의 흡수 스펙트럼의 흡수띠 위치가 분광학적계열과 일치함을 알 수 있었다. 합성된 착물의 구조는 원소분석, 적외선 흡광분석법, 핵자기 공명 및 전자흡수 스펙트럼으로 확인하였다.

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Dioxygen Binding to Dirhodium(Ⅱ, Ⅱ), (Ⅱ, Ⅲ), and (Ⅲ, Ⅲ) Complexes. Spectroscopic Characterization of $[Rh_{2}(ap)_{4}(O_{2})]^{+},\;Rh_{2}(ap)_{4}(O_{2}),\;and\;[Rh_{2}(ap)_{4}(O_{2})]^-$, where ap=2-anilinopyridinate Ion

  • Lee, Jae-Duck;Yao, Chao-Liang;Capdevielle, Francoise J.;Han, Bao-Cheng;Bear, John L.;Kadish, Karl M.
    • Bulletin of the Korean Chemical Society
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    • 제14권2호
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    • pp.195-200
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    • 1993
  • The neutral, reduced, and oxidized 2,2-trans isomers of $Rh_2(ap)_4$ (ap=2-anilinopyridinate) were investigated with respect to dioxygen binding in $CH_2Cl_2$ containing 0.1 M tetrabutyl-ammonium perchlorate. $Rh_2(ap)_4$ binds dioxygen in nonaqueous media and forms a $Rh^{II}Rh^{III}$ superoxide complex, $Rh_2(ap)_4(O_2)$. This neutral species was isolated and is characterized by UV-visible and IR spectroscopy, mass spectrometry and cyclic voltammetry. It can be reduced by one electron at $E_{1/2}$ = -0.45 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^-$ as demonstrated by the ESR spectrum of a frozen solution taken after controlled potential reduction. The superoxide ion in ${[Rh_2(ap)_4(O_2)]}^-$ is axially bound to one of the two rhodium ions, both of which are in a +2 oxidation state. $Rh_2(ap)_4(O_2)$ can also be stepwise oxidized in two one-electron transfer steps at $E_{1/2}$ = 0.21 V and 0.85 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^+$ followed by ${[Rh_2(ap)_4(O_2)]}^{2+}$. ESR spectra demonstrate that the singly oxidized complex is best described as ${[Rh^{II}Rh^{III}(ap)_4(O_2)]}^+$ where the odd electron is delocalized on both of the two rhodium ions and the axial ligand is molecular oxygen.