Ultrafast Chemical Exchange Dynamics of Hydrogen Bonds Observed via Isonitrile Infrared Sensors: Implications for Biomolecular Studies

Kübel, Joachim,1988Gothenburg University,Göteborgs universitet,Institutionen för kemi och molekylärbiologi,Department of Chemistry and Molecular Biology,Department of Chemistry and Molecular Biology, University of Gothenburg, 40530 Gothenburg, Sweden (author)

Local probes are indispensable to study protein structure and dynamics with site-specificity. The isonitrile functional group is a highly sensitive and H-bonding interaction-specific probe. Isonitriles exhibit large spectral shifts and transition dipole moment changes upon H-bonding while being weakly affected by solvent polarity. These unique properties allow a clear separation of distinct subpopulations of interacting species and an elucidation of their ultrafast dynamics with two-dimensional infrared (2D-IR) spectroscopy. Here, we apply 2D-IR to quantify the picosecond chemical exchange dynamics of solute solvent complexes forming between isonitrile-derivatized alanine and fluorinated ethanol, where the degree of fluorination controls their H-bond-donating ability. We show that the molecules undergo faster exchange in the presence of more acidic H-bond donors, indicating that the exchange process is primarily dependent on the nature of solvent-solvent interactions. We foresee isonitrile as a highly promising probe for studying of H-bonds dynamics in the active site of enzymes.

Lee, G.Department of Chemistry, Korea University, Seoul 02841, South Korea (author)
Ooi, Saik AnnGothenburg University,Göteborgs universitet,Institutionen för kemi och molekylärbiologi,Department of Chemistry and Molecular Biology,Department of Chemistry and Molecular Biology, University of Gothenburg, 40530 Gothenburg, Sweden(Swepub:gu)xooisa (author)
Westenhoff, Sebastian,1978Gothenburg University,Göteborgs universitet,Institutionen för kemi och molekylärbiologi,Department of Chemistry and Molecular Biology,Department of Chemistry and Molecular Biology, University of Gothenburg, 40530 Gothenburg, Sweden(Swepub:gu)xwests (author)
Han, H.Department of Chemistry, Korea University, Seoul 02841, South Korea (author)
Cho, M.Department of Chemistry, Korea University, Seoul 02841, South Korea;Center for Molecular Spectroscopy and Dynamics, Institute for Basic Science, Seoul 02841, South Korea (author)
Maj, MichalGothenburg University,Göteborgs universitet,Institutionen för kemi och molekylärbiologi,Department of Chemistry and Molecular Biology,Department of Chemistry and Molecular Biology, University of Gothenburg, 40530 Gothenburg, Sweden(Swepub:gu)xmajmi (author)
Göteborgs universitetInstitutionen för kemi och molekylärbiologi (creator_code:org_t)

In:Journal of Physical Chemistry Letters: American Chemical Society (ACS)10:24, s. 7878-78831948-7185

By the author/editor: Kübel, Joachim, ...; Lee, G.; Ooi, Saik Ann; Westenhoff, Seba ...; Han, H.; Cho, M.; show more...; Maj, Michal; show less...

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NATURAL SCIENCES: NATURAL SCIENCES; and Biological Scien ...; and Biochemistry and ...

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Physical Chemist ...

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