Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State super(17)O NMR Chemical Shifts in Various Biologically Relevant Oxygen-Containing Compounds

• Published in: The journal of physical chemistry. B Vol. 119; no. 35; pp. 11618 - 11625
• Main Authors: Rorick, Amber, Michael, Matthew A, Yang, Liu, Zhang, Yong
• Format: Journal Article
• Language: English
• Published: 03.09.2015
• Subjects: Biological effects; Bonding; Computation; Deviation; Mathematical analysis; Nonmetals; Nuclear magnetic resonance; Optimization
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.5b06536

Oxygen is an important element in most biologically significant molecules, and experimental solid-state super(17)O NMR studies have provided numerous useful structural probes to study these systems. However, computational predictions of solid-state super(17)O NMR chemical shift tensor properties are still challenging in many cases, and in particular, each of the prior computational works is basically limited to one type of oxygen-containing system. This work provides the first systematic study of the effects of geometry refinement, method, and basis sets for metal and nonmetal elements in both geometry optimization and NMR property calculations of some biologically relevant oxygen-containing compounds with a good variety of XO bonding groups (X = H, C, N, P, and metal). The experimental range studied is of 1455 ppm, a major part of the reported super(17)O NMR chemical shifts in organic and organometallic compounds. A number of computational factors toward relatively general and accurate predictions of super(17)O NMR chemical shifts were studied to provide helpful and detailed suggestions for future work. For the studied kinds of oxygen-containing compounds, the best computational approach results in a theory-versus-experiment correlation coefficient (R super(2)) value of 0.9880 and a mean absolute deviation of 13 ppm (1.9% of the experimental range) for isotropic NMR shifts and an R super(2) value of 0.9926 for all shift-tensor properties. These results shall facilitate future computational studies of super(17)O NMR chemical shifts in many biologically relevant systems, and the high accuracy may also help the refinement and determination of active-site structures of some oxygen-containing substrate-bound proteins.