Spectroscopy of Retinoic Acid at the Air-Water Interface

The spectroscopy of all-trans-retinoic acid (ATRA), an important molecule of biological origin that can be found in nature, is investigated at the air-water interface using UV-Vis and IR reflection spectroscopy. We employ a UV-Vis reflection absorption spectroscopy (RAS) experiment along with infrared reflection absorption spectroscopy (IR-RAS) to probe ATRA at the air-water interface. We elucidate the factors influencing the spectroscopy of ATRA at the air-water interface and compare its spectra at the water surface with results of bulk samples obtained with conventional spectroscopic methods and computational chemistry. Monolayers of pure ATRA as well as mixed ATRA with stearic-d₃₅ acid were prepared, and the spectroscopy reveals that ATRA forms J-aggregates with itself, causing a significant redshift of its S₀ to S₁ electronic transition. Pure ATRA monolayers are found to be unstable at the air-water interface and are lost from the surface over time due to the formation of aggregates. The mixture of ATRA and stearic-d₃₅ acid has been shown to stabilize the monolayers and inhibit the loss of surface ATRA. On the basis of our observations, we propose that ATRA could be a significant photosensitizer in natural aqueous environments.