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Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2015

Nanometric distance measurements between Mn(II)DOTA centers

Résumé

Pulse electron-electron double resonance (PELDOR) is a versatile technique for probing the structures and functions of complex biological systems. Despite the recent interest in high-spin metal-ions for high field/frequency applications, PELDOR measurements of Mn(II) remain relatively underexplored. Here we present Mn(II)-Mn(II) PELDOR distance measurements at 94 GHz on polyproline II (PPII) helices doubly spin-labeled with Mn(II) DOTA, which are distinguished by their small zero-field interaction. The measured Mn-Mn distances and distribution profiles were in good agreement with the expected values from molecular models. Additional features in the frequency-domain spectra became apparent at certain combinations of detect and pump frequencies. Spin-Hamiltonian calculations showed that they likely arose from contributions from the pseudo-secular component of the dipolar interaction that were found to be non-negligible for Mn(II) DOTA. However, the influence of the pseudo-secular component on the distance distribution profiles apparently was limited. The results show the potential of Mn(II) DOTA spin labels for high-field PELDOR distance measurements in proteins and other biological systems.
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Dates et versions

hal-01362854 , version 1 (09-09-2016)

Identifiants

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H. Y. Vincent Ching, Paul Demay-Drouhard, Hélène C. Bertrand, Clotilde Policar, Leandro C. Tabares, et al.. Nanometric distance measurements between Mn(II)DOTA centers. Physical Chemistry Chemical Physics, 2015, 17 (36), pp.23368-23377. ⟨10.1039/c5cp03487f⟩. ⟨hal-01362854⟩
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