Electron spin echo envelope modulation (ESEEM) spectroscopy as a tool to investigate the coordination environment of metal centers

Deligiannakis, Yiannis; Louloudi, Maria; Hadjiliadis, Nick

doi:10.1016/s0010-8545(99)00218-0

Cited by 167 publications

(210 citation statements)

References 292 publications

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“…Information on this superhyperfine coupling can be provided by ESEEM spectroscopy, a variant of EPR spectroscopy [62,[69][70][71]. The superhyperfine coupling constants reported for 14 N are in the range 1-8 MHz and vary with the nature, position, and orientation of the ligands [72][73][74].…”

Section: Validation Of the Dft Methodsmentioning

confidence: 99%

Application of DFT methods to the study of the coordination environment of the VO2+ ion in V proteins

et al. 2012

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Density functional theory (DFT) methods were used to simulate the environment of vanadium in several V proteins, such as vanadyl-substituted carboxypeptidase (sites A and B), vanadyl-substituted chloroplast F(1)-ATPase (CF(1); site 3), the reduced inactive form of vanadium bromoperoxidase (VBrPO; low- and high-pH sites), and vanadyl-substituted imidazole glycerol phosphate dehydratase (IGPD; sites α, β, and γ). Structural, electron paramagnetic resonance, and electron spin echo envelope modulation parameters were calculated and compared with the experimental values. All the simulations were performed in water within the framework of the polarizable continuum model. The angular dependence of [Formula: see text] and [Formula: see text] on the dihedral angle θ between the V=O and N-C bonds and on the angle φ between the V=O and V-N bonds, where N is the coordinated aromatic nitrogen atom, was also found. From the results it emerges that it is possible to model the active site of a vanadium protein through DFT methods and determine its structure through the comparison between the calculated and experimental spectroscopic parameters. The calculations confirm that the donor sets of sites B and A of vanadyl-substituted carboxypeptidase are [[Formula: see text], H(2)O, H(2)O, H(2)O] and [N(His)(||), N(His)(⊥), [Formula: see text], H(2)O], and that the donor set of site 3 of CF(1)-ATPase is [[Formula: see text], OH(Thr), H(2)O, H(2)O, [Formula: see text]]. For VBrPO, the coordination modes [N(His)(||), N(His)(∠), OH(Ser), H(2)O, H(2)O(ax)] for the low-pH site and [N(His)(||), N(His)(∠), OH(Ser), OH(-), H(2)O(ax)] or [N(His)(||), N(His)(∠), [Formula: see text], H(2)O] for the high-pH site, with an imidazole ring of histidine strongly displaced from the equatorial plane, can be proposed. Finally, for sites α, β, and γ of IGPD, the subsequent deprotonation of one, two, and three imidazole rings of histidine and the participation of a carboxylate group of a glutamate residue ([N(His)(||), [Formula: see text], H(2)O, H(2)O], [N(His)(||), N(His)(||), [Formula: see text], H(2)O], and [N(His)(||), N(His)(||), [Formula: see text], OH(-), [Formula: see text]], respectively) seems to be the most plausible hypothesis.

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Section: Validation Of the Dft Methodsmentioning

confidence: 99%

Application of DFT methods to the study of the coordination environment of the VO2+ ion in V proteins

et al. 2012

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“…ESEEM techniques, especially three-pulse ESEEM and HYSCORE, are used to investigate weakly coupled nitrogens in metalloproteins and their model systems (4). Often, no single crystals can be grown, so that the experiments have to be done on frozen solutions.…”

Section: Experiments Versus Simulationsmentioning

confidence: 99%

“…Electron spin echo envelope modulation (ESEEM) techniques are now used extensively to investigate paramagnetic systems (1)(2)(3)(4). The standard ESEEM methods are the onedimensional two-pulse and three-pulse ESEEM (1-3) and the two-dimensional HYSCORE (hyperfine sublevel correlation) experiments (5).…”

Section: Introductionmentioning

confidence: 99%

Numerical Simulation of One- and Two-Dimensional ESEEM Experiments

Mádi¹,

Doorslaer²,

Schweiger³

2002

Journal of Magnetic Resonance

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“…The results lead to unique insights into the electronic and geometric structure of paramagnetic centers in biological systems [2,3], as they allow for the determination of small hyperfine and quadrupole couplings of nuclear spins in the molecular environment of unpaired electrons.…”

Section: Introductionmentioning

confidence: 99%

5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems

Kasumaj

Stoll

2008

Journal of Magnetic Resonance

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Electron spin echo envelope modulation (ESEEM) spectroscopy as a tool to investigate the coordination environment of metal centers

Cited by 167 publications

References 292 publications

Application of DFT methods to the study of the coordination environment of the VO2+ ion in V proteins

Application of DFT methods to the study of the coordination environment of the VO2+ ion in V proteins

Numerical Simulation of One- and Two-Dimensional ESEEM Experiments

5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems

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