Using Excimeric Fluorescence to Study How the Cooling Rate Determines the Behavior of Naphthalenes in Freeze-Concentrated Solutions: Vitrification and Crystallization.

Abstract

We utilized fluorescence spectroscopy to learn about the molecular arrangement of naphthalene (Np) and 1-methylnaphthalene (MeNp) in frozen aqueous solutions. The freezing induces pronounced compound aggregation in the freeze-concentrated solution (FCS) in between the ice grains. The fluorescence spectroscopy revealed prevalent formation of a vitrified solution and minor crystallization of aromatic compounds. The FCS is shown as a specific environment, differing significantly from not only the pure compounds but also the ice surfaces. The results indicate marked disparity between the behavior of the Np and the MeNp; the cooling rate has a major impact on the former but not on the latter. The spectrum of the Np solution frozen at a faster cooling rate (ca 20 K/min) exhibited a temperature-dependent spectral behavior, whereas the spectrum of the solution frozen at a slower rate (ca 2 K/min) did not alter before melting. We interpret the observation through considering the varied composition of the FCS: Fast freezing leads to a higher water content expressed by the plasticizing effect, allowing molecular rearrangement, while slow cooling produces a more concentrated and drier environment. The experiments were conceived as generalizable for environmentally relevant pollutants and human-made freezing.