Chiral Sum Frequency Generation Spectroscopy Reveals How Mirror-image β-sheets Organize Water Superstructures With Opposite Chirality

Perets, Ethan Alexander

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https://hdl.handle.net/2142/111449 Copy

Description

Title

Chiral Sum Frequency Generation Spectroscopy Reveals How Mirror-image β-sheets Organize Water Superstructures With Opposite Chirality

Author(s)

Perets, Ethan Alexander

Contributor(s)

• Yan, Elsa
• Hammes-Schiffer, Sharon
• Velarde, Luis
• Santiago, Ty
• Konstantinovsky, Daniel

Issue Date

2021-06-25

Keyword(s)

Chirality and stereochemistry

Abstract

\begin{wrapfigure}{r}{0pt} \includegraphics[scale=0.2]{ISMS_Perets.eps} \end{wrapfigure} The structure and function of biomacromolecules depend on water structures in the hydration shell. However, elucidating the architectures of hydration shells around biomacromolecules has proven challenging. We used heterodyne chiral vibrational sum frequency generation (SFG) spectroscopy to study the structure of the solvation shell around an antiparallel $\beta$-sheet protein. Heterodyne chiral SFG spectroscopy reveals that water molecules form chiral superstructures around the protein, and that these water superstructures are induced by the chirality of the protein. Enantiomeric (L-) or (D-) proteins give rise to enantiomeric water superstructures. Molecular dynamics simulations expose the chiral architecture of the water superstructures around the protein. Modeling the chiral SFG response of the hydration shell suggests that hydrogen bonding between water and protein is a driving force behind the formation of the chiral water superstructures. Our work demonstrates the promise of chiral SFG spectroscopy to reveal structures and dynamics of hydration shells around biomacromolecules. We speculate on the involvement of chiral water superstructures in biomolecular recognition, and the role of chiral water superstructures in the origins of biological homochirality.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Permalink

http://hdl.handle.net/2142/111449

DOI

10.15278/isms.2021.FM13

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