2023, Laag, Christian, Lagroix, France, Kreutzer, Sebastian, Chapkanski, Stoil, Zeeden, Christian, Guyodo, Yohan

Colorimetric measurements are valuable in studying paleoenvironmental changes in sediment archives such as loess-paleosol sequences. These measurements allow for the identification of climate-sensitive minerals such as hematite, goethite, and secondary carbonates, as well as the observation of stratigraphic changes influenced by paleoclimate variations. Herein, a detailed workflow protocol emphasizing mineral abundance extraction by determining true band amplitudes is presented. Moreover, we present a protocol for colorimetric measurements that eliminates container bias, allowing the analysis and re-analysis of stored sediment quickly and inexpensively. Finally, we introduce a new R-package ('LESLIE') for graphical data display and enhancement. The protocol and its validation are demonstrated on the Suhia Kladenetz loess-paleosol sequence of northern Bulgaria. • A detailed workflow protocol eliminating container bias in colorimetric measurements and extracting mineral abundances is presented. • The protocol is independently validated with aid of Attenuated Total Reflectance Fourier Transform mid-infrared (ATR-FTIR) spectroscopic experiments. • Stratigraphic color enhancement using the R-package 'LESLIE' is facilitated by a user-friendly R-shiny application.

2021, Elsaesser, Thomas, Schauss, Jakob, Kundu, Achintya, Fingerhut, Benjamin P.

Electric interactions have a strong impact on the structure and dynamics of biomolecules in their native water environment. Given the variety of water arrangements in hydration shells and the femto- to subnanosecond time range of structural fluctuations, there is a strong quest for sensitive noninvasive probes of local electric fields. The stretching vibrations of phosphate groups, in particular the asymmetric (PO2)− stretching vibration νAS(PO2)−, allow for a quantitative mapping of dynamic electric fields in aqueous environments via a field-induced redshift of their transition frequencies and concomitant changes of vibrational line shapes. We present a systematic study of νAS(PO2)− excitations in molecular systems of increasing complexity, including dimethyl phosphate (DMP), short DNA and RNA duplex structures, and transfer RNA (tRNA) in water. A combination of linear infrared absorption, two-dimensional infrared (2D-IR) spectroscopy, and molecular dynamics (MD) simulations gives quantitative insight in electric-field tuning rates of vibrational frequencies, electric field and fluctuation amplitudes, and molecular interaction geometries. Beyond neat water environments, the formation of contact ion pairs of phosphate groups with Mg2+ ions is demonstrated via frequency upshifts of the νAS(PO2)− vibration, resulting in a distinct vibrational band. The frequency positions of contact geometries are determined by an interplay of attractive electric and repulsive exchange interactions.