Infrared Diffusion-Ordered Spectroscopy Reveals Molecular Size and Structure



Inspired by ideas from NMR, we have developed Infrared Diffusion-Ordered Spectroscopy (IR-DOSY), which simultaneously characterizes molecular structure and size. We rely on the fact that the diffusion coefficient of a molecule is determined by its size through the Stokes-Einstein relation, and achieve sensitivity to the diffusion coefficient by creating a concentration gradient and tracking its equilibration in an IR-frequency resolved manner. Analogous to NMR-DOSY, a two-dimensional IR-DOSY spectrum has IR frequency along one axis and diffusion coefficient (or equivalently, size) along the other, so the chemical structure and the size of a compound are characterized simultaneously. In an IR-DOSY spectrum of a mixture, molecules with different sizes are nicely separated into distinct sets of IR peaks. Extending this idea to higher dimensions, we also perform 3D-IR-DOSY, in which we combine the conformation sensitivity of femtosecond multi-dimensional IR spectroscopy with size sensitivity.


Supplementary material

Infrared Diffusion-Ordered Spectroscopy Reveals Molecular Size and Structure: Supplementary Information
Supplementary information includes: Reynolds number; Static spectra of acetone, BSA, and dialanine; IR-DOSY of the double mixture in heavy water; Analysis of IR-microscopy measurements of triple mixture; Fit of the 2DIR signals; Details of the fitting procedures.