• 제목/요약/키워드: NMR measurements

검색결과 157건 처리시간 0.019초

$^{15}N$ NMR Relaxation Studies of Backbone Motion of the catalytic Residues in Free and Steroid-bound ${\Delta}^5$-3-Ketosteroid Isomerase

  • Lee, Hee-Cheon;Sunggoo Yun
    • 한국자기공명학회논문지
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    • 제5권2호
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    • pp.130-137
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    • 2001
  • Backbone dynamics of the catalytic residues in free and steroid-bound $\Delta$$^{5}$ -3- ketosteroid isomerase from Pseudomonas testosteroni has been examined by $^{15}$ N relaxation measurements. The relaxation data were analyzed using the model-free formalism to extract the model-free parameters (S$^2$, $\tau$$_{e}$, and R$_{ex}$). Tyr-34 and Asp-99 exhibit enhanced high-frequency (pico- to nanosecond) internal motions in the free enzyme, which are restricted upon ligand binding, while Asp-38 experiences severe restriction of the internal motions in the fee enzyme, suggesting that Tyr-14 and Asp-99 are more actively involved in the ligand binding than Asp-38. The results also indicate that the H-bond network in the catalytic cavity might be slightly strengthened upon ligand binding, which may have some implications on the enzyme mechanism.he enzyme mechanism.m.

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Poly$({\gamma}-benzyl\;L-glutamate)$/Poly(ethylene oxide)-Lactoselactone 블록공중합체와 이들의 미립자 제조 및 특성 (Preparation and Characterization of Poly$({\gamma}-benzyl\;L-glutamate)$/Poly(ethylene oxide)-Lactoselactone Block Copolymers and Their Microspheres)

  • 김영훈;조종수;성용길;정병호;이강춘
    • Journal of Pharmaceutical Investigation
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    • 제22권3호
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    • pp.237-240
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    • 1992
  • A series of biodegradable block copolymers consisting of $poly({\gamma}-benzyl\;L-glutamate)$ (PBLG) and poly(ethylene oxide) (PEO)-lactoselactone were prepared by polymerization of PEO-lactoselactone and ${\gamma}-benzyl$ L-glutamate-N-carboxyanhydride and characterized by IR and NMR. From circular dichroism measurements, it was found that the polymers exist in the ${\alpha}-helical$ conformation. Block copolymer microspheres were prepared by solvent-extraction-precipitation method for their primary evaluation for medical and biological applications.

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Phase Transitions in $KTiOPO_4$Studied by$^{31}$P Nuclear Magnetic Relaxation

  • Kim, K. S.;Lee, C. H.;Lee, Cheol-Eui;N. S. Dalal;R. Fu;S. Y. Jeong;Kim, J. N.;Kim, S. C.
    • Journal of Magnetics
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    • 제5권3호
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    • pp.73-75
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    • 2000
  • Undoped and Cr-doped samples of electrooptic material KTiOPO$_4$ were studied by $^{31}$P nuclear magnetic resonance (NMR). Spin-lattice relaxation time ($T_1$) measurements manifested phase transition behaviors that are attributed to changes in the dominant charge carriers in different temperature ranges.

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NMR Study on the Internal Dynamics of Ketosteroid Isomerase

  • Lee, Hee-Cheon
    • 한국생물물리학회:학술대회논문집
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    • 한국생물물리학회 2003년도 정기총회 및 학술발표회
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    • pp.26-26
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    • 2003
  • The backbone dynamics of ketosteroid isomerase, a homodimeric enzyme with 125 amino acid residues per subunit, has been studied in the presence/absence of a steroid ligand and 5% trifluoroethanol (TFE) by $^{15}$ M relaxation measurements. The relaxation data were analyzed using the model-free formalism to extract the model-free parameters (S$^2$, $\tau$$_{e}$, and R$_{ex}$ ). The results show that a large number of the residues, particularly those involved in the dimer interaction, exhibit reduced order parameters (S$^2$) in the steroid-bound enzyme, indicating the increased high-frequency (pico- to nanosecond) motions in the interface region upon ligand binding. The results also show that that the presence of 5 % TFE in free enzyme causes little change or slight increase in the order parameters for a number of residues in the dimer interface region. However, the majority of the residues in free enzyme exhibit reduced order parameters in the presence of 5 % TFE, indicating that the increase in entropy is partially responsible for the increased stability of KSI by 5% TFE.E.E.

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Regio- and Diastereoselective 1,3-Dipolar Cycloaddition between Perfluoro-2-methyl-2-pentene and Nitrones: A Facile Approach to Partially-Fluorinated Isoxazolidines

  • Moon, Mi-Eun;Park, Joo-Yeon;Jeong, Eun-Ha;Vajpayee, Vaishali;Kim, Hyun-Uk;Chi, Ki-Whan
    • Bulletin of the Korean Chemical Society
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    • 제31권6호
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    • pp.1515-1518
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    • 2010
  • Regio- and diastereoselective 1,3-dipolar cycloaddition reactions of nitrones {(Z)-${\alpha}$-phenyl-N-methylnitrone (1a) and (Z)-${\alpha}$-propyl-N-butylnitrone (1b)} with electron-deficient perfluoro-2-methyl-2-pentene (2) lead to novel isoxazolidines {5-fluoro-5-pentafluoroethyl-4,4-bis-trifluoromethyl-2-methyl-3-phenyl-isoxazolidine (3a) and 2-butyl-5-fluoro-5-pentafluoroethyl-4,4-bis-trifluoromethyl-3-propyl-isoxazolidines (3b) respectively} as major constituents. These derivatives were characterized by IR, $^1H$ and $^{19}F$ NMR, GC-MS and NOE measurements, and the absolute structure of 3a was confirmed by X-ray crystallography.

Synthesis and Characterization of Cobalt(II)/(III), Nickel(II) and Copper(II) Complexes of New 14, 15 and 16-Membered Macrocyclic Ligands

  • El-Tabl, Abdou Saad
    • Bulletin of the Korean Chemical Society
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    • 제25권12호
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    • pp.1757-1763
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    • 2004
  • A new series of nickel(II), cobalt(II)/(III) and copper(II) complexes of 14, 15 and 16-membered of macrocyclic ligands have been prepared and characterized by elemental analyses, IR, UV-VIS and $^1H-NMR$ spectra, magnetic susceptibilities, conductivities, DTA and ESR measurements. Molar conductances in DMF solution indicate that, the complexes are nonelectrolytes except (9-12) complexes. The electronic spectra show that, all complexes are square planar or distorted octahedral geometry. The ESR spectra of solid complexes (4), (8) and (11) show square planar of axial type symmetry $(d_{x2-y2})$ with considerable covalent bond character. However, complex (12) shows a spectrum of octahedral geometry with $d_{z2}$ ground state. Complex (12) shows exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

Synthesis and Crystal Structures of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) Metal Complexes with NNO Functionalized Ligands

  • Jang, Yoon-Jung;Lee, Uk;Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • 제26권6호
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    • pp.925-929
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    • 2005
  • Some new metal(II) complexes, $M^{II}L_2$ [M = Mn (1), Co (2), Ni (3), Cu (4), and Zn (5)] of 2-acetylpyridine benzoylhydrazone ligand (HL) containing trifunctional NNO-donor system have been synthesized and crystallographically characterized for the complex 1 and 5. The complexes consist of two ligands to give sixcoordinate, which are bonded to the metal atom on a meridional plane through acetylpyridine ring nitrogen, azomethine nitrogen, and benzoyl oxygen atoms, respectively. The coordination geometry for other complexes was identified on the basis of the physicochemical data by elemental analyses, FAB -MS, IR, $^1H$ NMR, and electronic spectral measurements. The resulting data indicated that the complexes are accordance with the above formulation.

Polymeric Micelle Formation of Multiblock Copolymer Composed of Poly( $\gamma$-benzyl L-glutamate) and Poly(ethylene oxide)

  • 나재운;정영일;조종수
    • Bulletin of the Korean Chemical Society
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    • 제21권4호
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    • pp.383-388
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    • 2000
  • Multiblock copolymers consisting of poly( g-benzyl L-glutamate) (PBLG) as the hydrophobic part and poly(ethylene oxide) (PEO) as the hydrophilic part (GEG) were synthesized and characterized. GEG polymeric micelles were prepared by the dialysis technique. Particle size distributions based on intensity,volume, and number-average were 22.6 $\pm$ 11.9 nm, 23.5 $\pm$ 4.6 nm, and 23.7 $\pm$ 37 nm, respectively. It was observed that par-ticle size and size distribution of GEG polymeric micelles changed significantly with the choice of initial sol-vent. Transmission electron micrographs (TEM) showed the polymeric micelles to be spherically shaped, with sizes ranging from 20 nm to 40 nm in diameter. Fluorescence spectroscopy measurements suggested that GEG block copolymers wereassociated in water to form polymeric micelles, and the critical micelle concentrations (CMC) value of the block copolymers was 0.0094 g/L. Further evidenceof micelle formation of GEG block copolymers and limited mobility of the PBLG chain in the core ohe micelle was obtained with 1 H NMR in D2O.

Studies on Reaction of Formaldehyde with Naturally Occurring Thiol Compounds and Ascorbic Acid

  • Lajos-Trezl;Cho, Young-Bong;Maria, Peter-Di;Kim, Sang-Duk;Prabhakar-D.Lotlikar;Paik, Woon-Ki
    • Archives of Pharmacal Research
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    • 제11권2호
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    • pp.114-121
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    • 1988
  • To gain insight into possible cellular protective mechanisms against the insult of formaldehyde, we have investigated this molecule's reactivity with both naturally occurring thiol compounds including glutathione and L-ascorbic acid. By UV measurements, for maldehyde was found to rapidly react with glutathione forming an S-hydroxymethyl covalent adduct. The adduct which was confirmed by NMR is transiently stable. Formaldehydissimilar to its reaction with dimedone. The reaction of formaldehyde with glutathione was reduced by 40% in the presence of an excess amount of L-ascorbic acid, due to the trapping of formaldehyde by L-ascorbic acid. The data suggest that L-ascorbic acid may have a possible in vivo role in the metabolism of formaldehyde, thereby protecting cellular glutathione from possible depletion.

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NMR Studies of Lipid-Protein Interaction in Apolipoprotein B / Phosphatidylcholine Recombinants

  • Byong-Seok Choi;Cheal O Joe;Ke Won Kang
    • Bulletin of the Korean Chemical Society
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    • 제11권3호
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    • pp.238-240
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    • 1990
  • $^{31}P${$^1H$} nuclear Overhauser effects (NOEs) have been obtained for complexes formed between apolipoprotein B (apo B) and dipalmytoylphosphatidylcholine (DPPC) vesicles. NOE measurements have been conducted with broad-band irradiation of the entire $^1H$ spectrum in order to identify the proton source of the NOE. In a unilamellar vesicle formed spontaneously upon mixing aqueous suspensions of long-chain phospholipid with small amount of short-chain lecithin, the maximum NOE occurs at the N-methyl proton resonance position of the choline moiety. With addition of cholesterol to vesicles, the position of the NOE maximum shifts further away from the choline methyl frequency. For the ternary apo B-vesicle-cholesterol complex, the position of the maximum NOE lies halfway between those in vesicles with and without cholesterol.