TY - JOUR
T1 - How Do Nuclei Couple to the Magnetic Moment of a Paramagnetic Center? A New Theory at the Gauntlet of the Experiments
AU - Cerofolini, Linda
AU - Silva, José Malanho
AU - Ravera, Enrico
AU - Romanelli, Maurizio
AU - Geraldes, Carlos F. G. C.
AU - Macedo, Anjos L.
AU - Fragai, Marco
AU - Parigi, Giacomo
AU - Luchinat, Claudio
N1 - The support from Fondazione Cassa di Risparmio di Firenze, MIUR PRIN 2012SK7ASN, and the "Progetto Dipartimenti di Eccellenza 2018-2019" allocated to the Department of Chemistry "Ugo Schiff", and Instruct-ERIC, an ESFRI Landmark, supported by national member subscriptions is also acknowledged. Specifically, we thank the Instruct -ERIC Core Centre CERM, Italy. J.M.S. acknowledges FCT for the doctoral fellowship PD/BD/135180/2017 integrated in the Ph.D. Program in NMR applied to chemistry, materials, and biosciences (PD/00065/2013).
PY - 2019/7/5
Y1 - 2019/7/5
N2 - The recent derivation, based on pure quantum chemistry (QC) first-principles, of the pseudocontact shifts (PCSs) caused by a paramagnetic metal center on far away nuclei has cast doubts on the validity of the semiempirical (SE) theory, predicting PCSs to arise from the metal magnetic susceptibility anisotropy. The SE theory has been used and applied countless times, especially in the last 2 decades, to obtain structural information on proteins containing paramagnetic metal ions. We show here that the QC and SE predictions can be directly tested against experiments, provided a suitable macromolecular system is used. The SE approach yields a good prediction of the experimental PCSs while the QC one does not. It appears that the classic theory is able to grasp satisfactorily the underlying physics.
AB - The recent derivation, based on pure quantum chemistry (QC) first-principles, of the pseudocontact shifts (PCSs) caused by a paramagnetic metal center on far away nuclei has cast doubts on the validity of the semiempirical (SE) theory, predicting PCSs to arise from the metal magnetic susceptibility anisotropy. The SE theory has been used and applied countless times, especially in the last 2 decades, to obtain structural information on proteins containing paramagnetic metal ions. We show here that the QC and SE predictions can be directly tested against experiments, provided a suitable macromolecular system is used. The SE approach yields a good prediction of the experimental PCSs while the QC one does not. It appears that the classic theory is able to grasp satisfactorily the underlying physics.
UR - http://www.scopus.com/inward/record.url?scp=85068179277&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.9b01128
DO - 10.1021/acs.jpclett.9b01128
M3 - Article
C2 - 31181162
AN - SCOPUS:85068179277
VL - 10
SP - 3610
EP - 3614
JO - JOURNAL OF PHYSICAL CHEMISTRY LETTERS
JF - JOURNAL OF PHYSICAL CHEMISTRY LETTERS
IS - 13
ER -