• Title/Summary/Keyword: Electron paramagnetic resonance(EPR)

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Synthesis, Structure and Characterization of Nd2XCd2-3XSiO4 (0.01≤X≤0.21) Solid-Solutions (Nd2XCd2-3XSiO4 (0.01≤X≤0.21) 고용체의 합성과 구조 규명)

  • Ramesh, S.;Das, B.B.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.502-508
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    • 2011
  • Synthesis of $Nd_{2x}Cd_{2-3x}SiO_4$ ($0.01{\leq}x{\leq}0.21$) [S1-S3: x=0.01, 0.11 and 0.21] solid solutions were prepared by solgel method. Powder x-ray diffraction (XRD) results show monoclinic unit cell with space group P21/m. The average crystallite sizes are found to be 20 to 45 nm. The Scanning Electron Microcopy (SEM) images show morphology of the sample is in globular nature. The energy dispersive analysis of x-rays (EDX) and X-ray mapping results confirmed that all the constituent elements of the composites were present and that were distributed in uniformly. The optical absorption band at ~750 nm was due to $^4I_{9/2}{\rightarrow}^4F_{7/2}+^4S_{3/2}$ transition optically active $Nd^{3+}$ ions. Electron Paramagnetic Resonance (EPR) lineshapes of S1-S3 at 10, 40, 77 and 300 K show a broad unresolved isotropic lineshapes were observed due to rapid spin lattice relaxation of $Nd^{3+}$.

Inhibitory Effects of Exogenous Cu2+ and Zn2+ on the Cytochrome c Oxidase Activity

  • Min, Tong-Pil;Han, Sang-Hwa
    • BMB Reports
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    • v.28 no.4
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    • pp.311-315
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    • 1995
  • Exogenous $Cu^{2+}$ or $Zn^{2+}$ at micromolar concentration had a strong inhibitory effect on detergent-solubilized cytochrome c oxidase. A similar effect was observed when $Cu^{2+}$ was added to vesicular cytochrome c oxidase, although the extent of inhibition was significantly larger for the uncoupled state than for the coupled state. Interestingly, the inhibition by $Zn^{2+}$ was almost negligible for both the coupled and uncoupled states. These results suggest that the binding sites for $Cu^{2+}$ ions are exposed to the extravesicular side. whereas those for $Zn^{2+}$ are exposed to the matrix side. The EPR spectra of bound $Cu^{2+}$ ions at 77 K indicate that each of the first two $Cu^{2+}$ ions is ligated by three or four histidine residues, as evidenced by distinct $^{14}N$ superhyperfine splitting. These $Cu^{2+}$ ions can not be removed readily by EDTA and inhibit the enzyme activity by as much as 80%.

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Cadaverine Protects Vibrio vulnificus from Superoxide Stress

  • Kang, In-Hye;Kim, Ju-Sim;Kim, Eui-Jin;Lee, Jeong
    • Journal of Microbiology and Biotechnology
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    • v.17 no.1
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    • pp.176-179
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    • 2007
  • An electron paramagnetic resonance (EPR) signal characteristic of the 5,5'-dimethyl-l-pyrroline-N-oxide (DMPO)-OH spin adduct, which is formed from the reaction of DMPO with superoxide radicals generated by xanthine oxidasemediated reaction, was significantly reduced by the cadaverine or Escherichia coli Mn-containing superoxide dismutase (MnSOD). Likewise, cytochrome c reduction by superoxide was inhibited by cadaverine, and the inhibition level increased in proportion to the level of cadaverine. The cadA mutant of Vibrio vulnificus, which does not produce cadaverine because of the lack of lysine decarboxylase, exhibits less tolerance to superoxide stress in comparison with wild type. The results indicate that cadaverine scavenges superoxide radicals, and protects cells from oxidative stress.

SNARE Assembly and Membrane Fusion: A Paramagnetic Electron Magnetic Resonance Study

  • Kweon, Dae-Hyuk
    • Proceedings of the Korean Biophysical Society Conference
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    • 2003.06a
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    • pp.32-32
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    • 2003
  • In the neuron, SNARE (soluble N-ethylmaleimide-sensitive factor attachment protein receptors) assembly plays a central role in driving membrane fusion, a required process for neurotransmitter release. In the cytoplasm, vesicular SNARE VAMP2 (vesicle-associated membrane protein 2) engages with two plasma membrane SNAREs syntaxin 1A and SNAP-25 (synaptosome-associated protein of 25 kDa) to form the core complex that bridges two membranes. While various factors regulate SNARE assembly, the membrane also plays the regulatory role by trapping VAMP2 in the membrane. The fluorescence and EPR analyses revealed that the insertion of seven C-terminal core-forming residues into the membrane controls complex formation of the entire core region, even though preceding 54 core-forming residues are fully exposed and freely moving. When two interfacial Trp residues in this region were replaced with hydrophilic serine residues, the mutation supported rapid complex formation.

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EPR Studies of the Active Sites of Carbon Monoxide Dehydrogenase from Clostridium thermoaceticum

  • Shin, Woonsup;Lindahl, Paul A.
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.869-876
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    • 1995
  • The active sites of the nickel and iron-containing enzyme, carbon monoxide dehydrogenase (CODH) from clostridium thermoaceticum were investigated using Electron Paramagnetic Resonance (EPR) technique. CODH exhibits several spectral features called NiFeC, $g_{ave}=1.82$, $g_{ave}=1.86$. FCII signals which are originated from different clusters in this enzyme. CODH is know to catalyze two different kinds of reactions - acetyl-CoA synthesis and CO oxidation. The acetyl-CoA synthesis activity can be followed by monitoring CO/acetyl-CoA exchange. The addition of 1,10-phenanthroline (phen) to CODH selectively destroyed the CO/acetyl-CoA exchange activity and eliminated the NiFeC signal completely. CO oxidation activity and other EPR signals were unaffected. Such behavior demonstrates that CODH has two distinct active sites and that the NiFe complex is only responsible for the CO/acctyl-CoA exchange activity. Phen caused the removal of only 30% of Ni in the NiFe complex ($0.3Ni/{\alpha}{\beta}$) as shown by the quantitative metal analysis. The phen-treated CODH could be reactivated fully by incubation In $Ni^{2+}$ solution. Radioactive $^{63}Ni^{2+}$ was used to quantitate the amount of the $Ni^{2+}$ incorporated into phen-treated enzyme and showed that the amount was the same as the removed by the phen treatment. i.e. $0.3Ni/{\alpha}{\beta}$. This indicates that only 30% of NiFe complexes are labile and responsible for the CO/acctyl-CoA exchange activity, the other 70% are non-labile and have no exchange activity. This is the first clear evidence that the NiFe complex is heterogencous and labile and non-labile Ni sites arc interacting differently with substrates and chelating agents like phen.

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Formation of Au Particles in Cu2-xICu2IIO3-δ (x ≈ 0.20; δ ≈ 0.10) Oxide Matrix by Sol-Gel Growth

  • Das, Bidhu Bhusan;Palanisamy, Kuppan;venugopal, Potu;Sandeep, Eesam;Kumar, Karrothu Varun
    • Journal of the Korean Chemical Society
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    • v.61 no.1
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    • pp.29-33
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    • 2017
  • Formation of Au particles in nonstoichiometric $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxide from aniline + hydrochloric acid mixtures and chloroauric acid in the ratios 30 : 1; 60 : 1; 90 : 1 (S1-S3) by volume and 0.01 mol of copper acetate, $Cu(OCOCH_3)_2.H_2O$, in each case is performed by sol-gel growth. Powder x-ray diffraction (XRD) results show Au particles are dispersed in tetragonal nonstoichiometric dicopper (I) dicopper (II) oxides, $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$). Average crystallite sizes of Au particles determined using Scherrer equation are found to be in the approximate ranges ${\sim}85-140{\AA}$, ${\sim}85-150{\AA}$ and ${\sim}80-150{\AA}$ in S1-S3, respectively which indicate the formation of Au nano-micro size particles in $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Hysteresis behaviour at 300 K having low loop areas and magnetic susceptibility values ${\sim}5.835{\times}10^{-6}-9.889{\times}10^{-6}emu/gG$ in S1-S3 show weakly ferromagnetic nature of the samples. Broad and isotropic electron paramagnetic resonance (EPR) lineshapes of S1-S4 at 300, 77 and 8 K having $g_{iso}$-values ${\sim}2.053{\pm}0.008-2.304{\pm}0.008$ show rapid spin-lattice relaxation process in magnetic $Cu^{2+}$ ($3d^9$) sites as well as delocalized electrons in Au ($6s^1$) nano-micro size particles in the $Cu_{2-x}{^I}Cu{_2}^{II}O_{3-{\delta}}$ ($x{\approx}0.20$; ${\delta}{\approx}0.10$) oxides. Broad and weak UV-Vis diffuse reflectance optical absorption band ~725 nm is assigned to $^2B_{1g}{\rightarrow}^2A_{1g}$ transitions, and the weak band ~470 nm is due to $^2B_{1g}{\rightarrow}^2E_g$ transitions from the ground state $^2B_{1g}$(${\mid}d_{x^2-y^2}$>) of $Cu^{2+}$ ($3d^9$) ions in octahedral coordination having tetragonal distortion.

Membrane Topology of Helix 0 of the Epsin N-terminal Homology Domain

  • Kweon, Dae-Hyuk;Shin, Yeon-Kyun;Shin, Jae Yoon;Lee, Jong-Hwa;Lee, Jung-Bok;Seo, Jin-Ho;Kim, Yong Sung
    • Molecules and Cells
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    • v.21 no.3
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    • pp.428-435
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    • 2006
  • Specific interaction of the epsin N-terminal homology(ENTH) domain with the plasma membrane appears to bridge other related proteins to the specific regions of the membrane that are invaginated to form endocytic vesicles. An additional $\alpha$-helix, referred to as helix 0 (H0), is formed in the presence of the soluble ligand inositol-1,4,5-trisphosphate [$Ins(1,4,5)P_3$] at the N terminus of the ENTH domain (amino acid residues 3-15). The ENTH domain alone and full-length epsin cause tubulation of liposomes made of brain lipids. Thus, it is believed that H0 is membrane-inserted when it is coordinated with the phospholipid phosphatidylinositol-4,5-bisphosphate [$PtdIns(4,5)P_2$], resulting in membrane deformation as well as recruitment of accessory factors to the membrane. However, formation of H0 in a real biological membrane has not been demonstrated. In the present study, the membrane structure of H0 was determined by measurement of electron paramagnetic resonance (EPR) nitroxide accessibility. H0 was located at the phosphate head-group region of the membrane. Moreover, EPR line-shape analysis indicated that no pre-formed H0-like structure were present on normal acidic membranes. $PtdIns(4,5)P_2$ was necessary and sufficient for interaction of the H0 region with the membrane. H0 was stable only in the membrane. In conclusion, the H0 region of the ENTH domain has an intrinsic ability to form H0 in a $PtdIns(4,5)P_2$-containing membrane, perhaps functioning as a sensor of membrane patches enriched with $PtdIns(4,5)P_2$ that will initiate curvature to form endocytic vesicles.

ESR Study of Paramagnetic Defects of the ${\gamma}$-irradiated Potassium Sulfate Single Crystal (${\gamma}$-선에 조사된 황산칼륨 단결정의 상자성 결함에 관한 전자스핀공명 연구)

  • Yo Chul Hyun;Chung Won Yang;Jong In Hong;Eun Ok Kim;Jung Sung Yang
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.367-375
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    • 1981
  • Single crystals of Potassium Sulfate ($K_2SO_4$) have been grown from the saturated solution by the evaporation method at the optimum conditions. Radiation damages in the crystal by ${\gamma}$-irradiation of about $12{\times}10^6$ Roentgen have given rise to paramagnetic centers or paramagnetic defects. Electron spin resonance (ESR) spectra of the centers are obtained with the X-band EPR spectrometer at room temperature. The ESR peaks of the paramagnetic species are found to be anisotropic but the peak of $SO_3-$ radical is an isotropic of Gaussian shape at g = 2.0036. A number of ESR spectra of the crystal for angular variation of the anisotropic peaks are recorded at various orientations of rotation about a, b and c crystallographic axes respectively. The g-values are calculated from the line position between anisotropic peaks and the isotropic one and then principal g-values and its direction cosines of the species are obtained by diagonalization of 9 matrix elements of the corresponding g-values. All the paramagnetic defects are identified by the characteristic principal g-values and its direction cosines.

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EPR and Electrical Studies in Layered Na1.9Li0.1Ti3O7 and its Copper Doped Derivatives (층상구조의 Na1.9Li0.1Ti3O7과 그 구리 혼입 유도체의 EPR 및 전기적 연구)

  • Pal, D.;Chand, Prem;Tandon, R.P.;Shripal
    • Journal of the Korean Chemical Society
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    • v.49 no.6
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    • pp.560-566
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    • 2005
  • Sintered ceramic samples of pure and some copper doped layered sodium lithium tri-titanate ($Na_{1.9}Li_{0.1}Ti_{3-X}Cu_XO_{7-X}$) materials with different dopant molar percentages (0.0$Cu^{2+}$ at $Ti^{4+}$ sites in the lattice is proposed in this paper. Furthermore, three distinct regions have been identified in log(${\sigma}_{d.c.}T$) versus 1000/T plots. The lowest temperature region is attributed to electronic hopping conduction(polaron) for all copper doped derivatives and ionic conduction for lithium substituted $Na_2Ti_3O_7$.The mechanism of conduction in the intermediate region is associated interlayer ionic conduction and in the highest temperature region is associated modified interlayer ionic conduction.

Study on Mo(V) Species, Location and Adsorbates Interactions in MoH-SAPO-34 by Employing ESR and Electron Spin-Echo Modulation Spectroscopies (ESR, ESEM을 이용한 이온 교환된 MoH-SAPO-34에 대한 Mo의 화학종, 위치 및 흡착상호작용에 관한 연구)

  • Back, Gern-Ho;Jang, Chang-Ki;Ru, Chang-Kuk;Cho, Young-Hwan;So, Hyun-Soo;Kevan, Larry
    • Journal of the Korean Chemical Society
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    • v.46 no.1
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    • pp.26-36
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    • 2002
  • A solid-state reaction of $MoO_3$ with as-synthesized H-SAPO-34 generated paramagnetic Mo(V) species. The dehydration resulted in weak Mo(V) species, and subsequent activation resulted in the formation of Mo(V) species such as $Mo(V)_{5c}$ and $Mo(V)_{6c}$ that are characterized by ESR. The data of ESR and ESEM show the oxomolybdenum species, to be $(MoO_2)^+$ or $(MoO)^{3+}$. The $(MoO_2)^+$ species seems to be more probable. Since H-SAPO-34 has a low framework negative charge, $(MoO)^{3+}$ with a high positive charge can not be easily stabilized. A solution reaction between the solution of silico-molybdic acid and calcined H-SAPO-34 resulted in only $(MoO_2)^+$ species. A rhombic ESR signal is observed on adsorption of $D_2O$, $CD_3OH$, $CH_3Ch_2OD$ and $ND_3$. The Location and coordination structure of Mo(V) species has been determined by three-pulse electron spin-echo modulation data and their simulations. After the adsorption of methanol, ethylene, ammonia, and water for MoH-SAPO-34, three molecules, one molecule, one and one molecule, respectively, are directly coordinated to $(MoO_2)^+)$.