DFT Protocol for EPR prediction of paramagnetic Cu(II) complexes and application to protein binding sites
Sciortino, Giuseppe (Universitat Autònoma de Barcelona. Departament de Química)
Lubinu, Giuseppe (Dipartimento di Chimica e Farmacia, Università di Sassar)
Maréchal, Jean-Didier (Universitat Autònoma de Barcelona. Departament de Química)
Garribba, Eugenio (Dipartimento di Chimica e Farmacia, Università di Sassar)

Date:	2018
Abstract:	With the aim to provide a general protocol to interpret electron paramagnetic resonance (EPR) spectra of paramagnetic copper(II) coordination compounds, density functional theory (DFT) calculations of spin Hamiltonian parameters g and A for fourteen Cu(II) complexes with different charges, donor sets, and geometry were carried out using ORCA software. The performance of eleven functionals was tested, and on the basis of the mean absolute percent deviation (MAPD) and standard deviation (SD), the ranking of the functionals for Az is: B3LYP > B3PW91 ~ B3P86 > PBE0 > CAM-B3LYP > TPSSh > BH and HLYP > B2PLYP > MPW1PW91 > ω-B97x-D » M06; and for gz is: PBE0 > BH and HLYP > B2PLYP > ω-B97x-D > B3PW91~B3LYP~B3P86 > CAM-B3LYP > TPSSh~MPW1PW91 » M06. With B3LYP the MAPD with respect to A exp tl z is 8. 6% with a SD of 4. 2%, while with PBE0 the MAPD with respect to g exp tl z is 2. 9% with a SD of 1. 1%. The results of the validation confirm the fundamental role of the second order spin-orbit contribution to Az. The computational procedure was applied to predict the values of gz and Az of the adducts formed by Cu(II) with albumin and two fragments of prion protein, 106-126 and 180-193.
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Subject:	Copper ; EPR spectroscopy ; DFT methods ; Human serum albumin ; Prion protein
Published in:	Magnetochemistry, Vol. 4 (2018) , p. 1-19, ISSN 2312-7481

DOI: 10.3390/magnetochemistry4040055

19 p, 2.4 MB

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