High-temperature decomposition chemistry of trimethylsiloxane surfactants, a potential Fluorine-Free replacement for fire suppression.

Per- and polyfluoroalkyl substances (PFAS) have become global environmental contaminants due to being notoriously difficult to degrade, and it has become increasingly important to employ suitable PFAS alternatives, especially in aqueous film-forming foams (AFFF). Trimethylsiloxane (TriSil) surfactants are potential fluorine-free replacements for PFAS in fire suppression technologies. Yet because these compounds may be more susceptible to high-temperature decomposition, it is necessary to assess the potential environmental impact of their thermal degradation products. Our study analyzes the high-temperature degradation of a truncated trimethylsiloxane (TriSil-1n) surfactant based on quantum mechanical methods. The degradation chemistry of TriSil-1n was studied through radical formation and propagation initiated from two prominent pathways (unimolecular and bimolecular reactions) at both 298 K and 1200 K, a relevant temperature in flames and thermal incinerators. Regardless of the pathway taken and temperature, all radical intermediates stemmed from the polyethylene glycol chain and primarily formed stable polydimethylsiloxanes (PDMS) and small organics such as ethylene, formaldehyde, and acetaldehyde, among other products. The major degradation products of TriSil-1n resulting from high-temperature thermal degradation as predicted by this study would be relatively less harmful to the environment compared to PFAS incineration/combustion products from previous research, supporting the replacement of PFAS with TriSil surfactants.

Conformational distributions of helical perfluoroalkyl substances and impacts on stability.

Per- and polyfluoroalkyl substances (PFAS) have been widely used the past 70 years in numerous applications due to their chemical and thermal stability. Due to their robust stability, they are environmentally recalcitrant which made them one of the most persistent environmental contaminants. In addition to strong CF bond strength, oleophobicity, hydrophobicity, and high reduction-oxidation (redox) potential of PFAS has led to their inefficient degradation by traditional means. A characteristic of their structure is also their preference to adopt helical conformations along the carbon backbone, contrary to their hydrocarbon analogues. This work investigates the helical nature of perfluoroalkanes through their conformational distributions, especially as a benchmark for determining the impact of polar head groups, heteroatoms, and radical center on helical conformations. Since structure governs reactivity and molecular properties, it is important to assess if minor chemical perturbations in the structure will lead to changes in the conformations. Based on density functional theory calculations and comprehensive conformational distributions, it was concluded that the helicity is a local structural property which changes significantly with the presence of heteroatoms in the perfluoroalkyl chain as well as with the presence of radical centers.

Computational protocol for predicting 19 F NMR chemical shifts for PFAS and connection to PFAS structure.

Per- and polyfluoroalkyl substances (PFAS) are robust "forever" chemicals that have become global environmental contaminants due to their inability to degrade using traditional techniques. In addition to the persistent nature of PFAS, the structural and functional diversity in PFAS creates a unique challenge in identification and remediation. Their identification is further complicated by the absence of standards for many PFAS. This work is aimed at developing a protocol for computing and establishing accurate 19 F NMR chemical shifts for PFAS using density functional theory (DFT), which can aid in the identification of PFAS. The impact of solvation and basis sets was evaluated by comparing the computed data with the experimental measurements. Results showed the addition of dispersion corrections in the methodology improve the accuracy of calculated NMR parameters within 4 ppm of the experimental values. Adding a second diffuse function and additional polarization did not improve the accuracy, likely because of the electronegativity of fluorine which does not allow the electron density of fluorine atoms to be polarized. The inclusion of various implicit solvation (DMSO, chloroform, and water) yielded negligible differences in accuracy, and were overall less accurate than the gas phase calculations. The most accurate methodology was then applied to more environmentally relevant PFAS, and the impact of helical nature on the NMR signatures was evaluated. The implication of this work is to be able to improve the identification of structurally diverse PFAS using the 19 F NMR.