DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites
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 set...
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ftmdpi:oai:mdpi.com:/2312-7481/4/4/55/ 2023-08-20T04:09:05+02:00 DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites Giuseppe Sciortino Giuseppe Lubinu Jean-Didier Maréchal Eugenio Garribba 2018-12-03 application/pdf https://doi.org/10.3390/magnetochemistry4040055 EN eng Multidisciplinary Digital Publishing Institute https://dx.doi.org/10.3390/magnetochemistry4040055 https://creativecommons.org/licenses/by/4.0/ Magnetochemistry; Volume 4; Issue 4; Pages: 55 copper EPR spectroscopy DFT methods human serum albumin prion protein Text 2018 ftmdpi https://doi.org/10.3390/magnetochemistry4040055 2023-07-31T21:52:54Z 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 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 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. Text Orca MDPI Open Access Publishing Magnetochemistry 4 4 55 |
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copper EPR spectroscopy DFT methods human serum albumin prion protein |
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copper EPR spectroscopy DFT methods human serum albumin prion protein Giuseppe Sciortino Giuseppe Lubinu Jean-Didier Maréchal Eugenio Garribba DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites |
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copper EPR spectroscopy DFT methods human serum albumin prion protein |
description |
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 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 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. |
format |
Text |
author |
Giuseppe Sciortino Giuseppe Lubinu Jean-Didier Maréchal Eugenio Garribba |
author_facet |
Giuseppe Sciortino Giuseppe Lubinu Jean-Didier Maréchal Eugenio Garribba |
author_sort |
Giuseppe Sciortino |
title |
DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites |
title_short |
DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites |
title_full |
DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites |
title_fullStr |
DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites |
title_full_unstemmed |
DFT Protocol for EPR Prediction of Paramagnetic Cu(II) Complexes and Application to Protein Binding Sites |
title_sort |
dft protocol for epr prediction of paramagnetic cu(ii) complexes and application to protein binding sites |
publisher |
Multidisciplinary Digital Publishing Institute |
publishDate |
2018 |
url |
https://doi.org/10.3390/magnetochemistry4040055 |
genre |
Orca |
genre_facet |
Orca |
op_source |
Magnetochemistry; Volume 4; Issue 4; Pages: 55 |
op_relation |
https://dx.doi.org/10.3390/magnetochemistry4040055 |
op_rights |
https://creativecommons.org/licenses/by/4.0/ |
op_doi |
https://doi.org/10.3390/magnetochemistry4040055 |
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Magnetochemistry |
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4 |
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4 |
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55 |
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1774721804521177088 |