DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites

Sciortino, Giuseppe; Lubinu, Giuseppe; Maréchal, Jean-Didier; Garribba, Eugenio

doi:10.3390/magnetochemistry4040055

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DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites

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Departament de Química, Universitat Autònoma de Barcelona, 08193 Cerdanyola del Vallés, Barcelona, Spain

Dipartimento di Chimica e Farmacia, Università di Sassari, Via Vienna 2, I-07100 Sassari, Italy

Author to whom correspondence should be addressed.

Magnetochemistry 2018, 4(4), 55; https://doi.org/10.3390/magnetochemistry4040055

Received: 26 October 2018 / Revised: 20 November 2018 / Accepted: 21 November 2018 / Published: 3 December 2018

(This article belongs to the Special Issue A Themed Issue in Honor of Late Professor Samiran Mitra)

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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 A_z is: B3LYP > B3PW91 ~ B3P86 > PBE0 > CAM-B3LYP > TPSSh > BH and HLYP > B2PLYP > MPW1PW91 > ω-B97x-D >> M06; and for g_z 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_{z}^{\exp t l}

is 8.6% with a SD of 4.2%, while with PBE0 the MAPD with respect to

g_{z}^{\exp t l}

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 A_z. The computational procedure was applied to predict the values of g_z and A_z of the adducts formed by Cu(II) with albumin and two fragments of prion protein, 106–126 and 180–193. View Full-Text

Keywords: copper; EPR spectroscopy; DFT methods; human serum albumin; prion protein

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MDPI and ACS Style

Sciortino, G.; Lubinu, G.; Maréchal, J.-D.; Garribba, E. DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites. Magnetochemistry 2018, 4, 55. https://doi.org/10.3390/magnetochemistry4040055

AMA Style

Sciortino G, Lubinu G, Maréchal J-D, Garribba E. DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites. Magnetochemistry. 2018; 4(4):55. https://doi.org/10.3390/magnetochemistry4040055

Chicago/Turabian Style

Sciortino, Giuseppe, Giuseppe Lubinu, Jean-Didier Maréchal, and Eugenio Garribba. 2018. "DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites" Magnetochemistry 4, no. 4: 55. https://doi.org/10.3390/magnetochemistry4040055

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DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites

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