Effect of Polyphenols on the Ice-Nucleation Activity of Ultrafine Bubbles

Ultrafine bubbles (UFBs) in water provide a large amount of gas and a large gas-liquid interfacial area, and can release energy through their collapse. Such features may promote ice nucleation. Here, we examined the nucleation of ice in solutions containing polyphenols and UFBs. To reduce the likelihood of nucleation occurring on the container walls over that in previous studies, we used a much larger sample volume of 1 mL. In our experiments, UFBs (when present) had a number concentration of 10⁸ mL^-1. We quantified changes to the nucleation activity by examining the shift in the cumulative freezing (nucleation) probability distribution. Compared to pure water, this freezing curve shifts approximately 0.6 °C higher with the UFBs. Then, to the water, we added three polyphenols (tannic acid TA, tea catechin TC, and oligonol OLG), chosen because they had been reported to reduce the ice-nucleation activity of heterogeneous ice nuclei (e.g., AgI). We found experimentally that, without UFBs, all polyphenols instead shift the pure-water freezing curve to a higher temperature. Then, when UFBs are added, the additional temperature shift in the freezing curve is slightly higher for OLG, essentially unchanged for TA, and slightly lower for TC. To help to explain these differences, we examined the UFB size distributions using dynamic light scattering and freeze-fractured replicas with transmission electron microscopy, finding that OLG and TC alter the UFBs, but that TA does not.