Stendardo, Emiliano (2010) Structural and Dynamic Effects in Physico-chemical Properties of Biomolecules: An Integrated Computational Approach. [Tesi di dottorato] (Inedito)

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Tipologia del documento:	Tesi di dottorato
Lingua:	English
Titolo:	Structural and Dynamic Effects in Physico-chemical Properties of Biomolecules: An Integrated Computational Approach.
Autori:	Autore Email Stendardo, Emiliano stendardoemiliano@yahoo.it
Data:	30 Novembre 2010
Numero di pagine:	113
Istituzione:	Università degli Studi di Napoli Federico II
Dipartimento:	Chimica "Paolo Corradini"
Scuola di dottorato:	Scienze chimiche
Dottorato:	Scienze chimiche
Ciclo di dottorato:	23
Coordinatore del Corso di dottorato:	nome email Previtera, Lucio previter@unina.it
Tutor:	nome email Barone, Vincenzo [non definito]
Data:	30 Novembre 2010
Numero di pagine:	113
Parole chiave:	Nitroxides EPR/ESR AMBER QM/MM
Settori scientifico-disciplinari del MIUR:	Area 03 - Scienze chimiche > CHIM/02 - Chimica fisica
Depositato il:	02 Dic 2010 08:33
Ultima modifica:	30 Apr 2014 19:46
URI:	http://www.fedoa.unina.it/id/eprint/8363

Abstract

In this thesis we present an integrated computational approach for the accurate prediction of magnetic properties of medium to large molecular systems in vacuo and in condensed phases. The strategy adopted relies on the integration of sophisticated quantum mechanical models with tailored force field methods; the results obtained show that, in the specific context of magnetic parameters, the approach provides answers that are as accurate as even the highest-level full quantum mechanics calculations, at a fraction of the computational cost. In particular, the extension of the popular AMBER force field to medium-large organic free radical nitroxides in vacuo and in condensed phase is presented. New atom types have been introduced whose parameters were fitted on the geometry, vibrational frequencies and potential energy surfaces (PES) derived by density functional theory (DFT) calculations on selected classes of nitroxides. Force field parameterization has been extended to include specific structural features that are often present alongside the paramagnetic center, e.g. in α-amino acidic nitroxides. This required the development of a force-field description for the peptide bonds of strongly helicogenic residues with serious steric restrictions. The resulting molecular mechanical method has been employed in an integrated computational characterization of the role of structural, environmental and short-time dynamic effects in tuning the hyperfine and gyromagnetic tensors of nitroxide spin probes, with results that are quite comparable with the available experimental counterparts.

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