Carbon-deuterium bonds as reporters of electric fields in solvent and protein environments.
2023; 122 (3S1): 481a
View details for DOI 10.1016/j.bpj.2022.11.2574
View details for PubMedID 36784478
Protein protic and aprotic interactions systematically mapped via IR spectroscopy and polarizable molecular dynamics.
2023; 122 (3S1): 309a
View details for DOI 10.1016/j.bpj.2022.11.1737
View details for PubMedID 36783549
Nitrile Infrared Intensities Characterize Electric Fields and Hydrogen Bonding in Protic, Aprotic, and Protein Environments.
Journal of the American Chemical Society
Nitriles are widely used vibrational probes; however, the interpretation of their IR frequencies is complicated by hydrogen bonding (H-bonding) in protic environments. We report a new vibrational Stark effect (VSE) that correlates the electric field projected on the -C=N bond to the transition dipole moment and, by extension, the nitrile peak area or integrated intensity. This linear VSE applies to both H-bonding and non-H-bonding interactions. It can therefore be generally applied to determine electric fields in all environments. Additionally, it allows for semiempirical extraction of the H-bonding contribution to the blueshift of the nitrile frequency. Nitriles were incorporated at H-bonding and non-H-bonding protein sites using amber suppression, and each nitrile variant was structurally characterized at high resolution. We exploited the combined information available from variations in frequency and integrated intensity and demonstrate that nitriles are a generally useful probe for electric fields.
View details for DOI 10.1021/jacs.2c00675
View details for PubMedID 35467853
Nitrile IR intensities directly measure electric fields in protic and non-protic environments
CELL PRESS. 2022: 414A
View details for Web of Science ID 000759523002558