title: Ab initio modeling of CW-ESR spectra of the double spin labeled peptide Fmoc-(Aib-Aib-TOAC)2-Aib-OMe in acetonitrile.
abstract: In this work we address the interpretation, via an ab initio integrated computational approach, of the CW-ESR spectra of the double spin labeled, 310-helical, peptide Fmoc-(Aib-Aib-TOAC)2-Aib-OMe dissolved in acetonitrile. Our approach is based on the determination of geometric and local magnetic parameters of the heptapeptide by quantum mechanical density functional calculations taking into account solvent and, when needed, vibrational averaging contributions. The system is then described by a stochastic Liouville equation for the two electron spins interacting with each other and with two 14N nuclear spins, in the presence of diffusive rotational dynamics. Parametrization of the diffusion rotational tensor is provided by a hydrodynamic model. CW-ESR spectra are simulated with minimal resorting to fitting procedures, proving that the combination of sensitive ESR spectroscopy and sophisticated modeling can be highly helpful in providing 3D structural and dynamic information on molecular systems.
authors.affiliation: Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, I-35131 Padova, Italy.
authors.forename: Mirco
authors.initials: M
authors.lastname: Zerbetto
authors.forename: Silvia
authors.initials: S
authors.lastname: Carlotto
authors.forename: Antonino
authors.initials: A
authors.lastname: Polimeno
authors.forename: Carlo
authors.initials: C
authors.lastname: Corvaja
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Franco
authors.forename: Claudio
authors.initials: C
authors.lastname: Toniolo
authors.forename: Fernando
authors.initials: F
authors.lastname: Formaggio
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Barone
authors.forename: Paola
authors.initials: P
authors.lastname: Cimino
mesh_terms: D000097:Acetonitriles; D003198:Computer Simulation; D004578:Electron Spin Resonance Spectroscopy; D008958:Models, Molecular; D009842:Oligopeptides / Q000737:chemistry*; D012997:Solvents; D013113:Spin Labels; D013269:Stochastic Processes
chemical_list: D000097:Acetonitriles; C520070:Fmoc-(Aib-Aib-TOAC)2-Aib-OMe; D009842:Oligopeptides; D012997:Solvents; D013113:Spin Labels; C032159:acetonitrile