Enhanced aggregation and interfacial adsorption of an aqueous film forming foam (AFFF) in high salinity matrices.

Per- and polyfluoroalkyl substances (PFAS) exist in contaminated groundwater, surface water, soil, and sediments from use of aqueous film forming foams (AFFFs). Under these conditions PFAS exhibit unusual behavior due to their surfactant properties, namely, aggregation and surface activity. Environmental factors such as salinity can affect these properties, and complicate efforts to monitor PFAS. The effect of high salinity matrices on the critical micelle concentration (CMC) of a AFFF formulation manufactured by 3M and the surface accumulation of PFAS was assessed with surface tension isotherm measurements and bench-scale experiments quantifying PFAS at the air-water interface. Conditions typical of brackish and saline waters substantially depressed the CMC of the AFFF by over 50% and increased the interfacial mass accumulation of PFAS in the AFFF mixture by up to a factor of 3, relative to values measured in ultrapure water. These results indicate that high salinity matrices increase the aggregation and surface activity of PFAS in mixtures, which are key properties affecting their transport.

An Artifact of Perfluoroalkyl Acid (PFAA) Removal Attributed to Sorption Processes in a Laccase Mediator System.

Fungi and laccase mediator systems (LMSs) have a proven track record of oxidizing recalcitrant organic compounds. There has been considerable interest in applying LMSs to the treatment of perfluoroalkyl acids (PFAAs), a class of ubiquitous and persistent environmental contaminants. Some laboratory experiments have indicated modest losses of PFAAs over extended periods, but there have been no clear demonstrations of a transformation mechanism or the kinetics that would be needed for remediation applications. We set out to determine if this was a question of identifying and optimizing a rate-limiting step but discovered that observed losses of PFAAs were experimental artifacts. While unable to replicate the oxidation of PFAAs, we show that interactions of the PFAA compounds with laccase and laccase mediator mixtures could cause an artifact that mimics transformation (≲60%) of PFAAs. Furthermore, we employed a surrogate compound, carbamazepine (CBZ), and electron paramagnetic resonance spectroscopy to probe the formation of the radical species that had been proposed to be responsible for contaminant oxidation. We confirmed that under conditions where sufficient radical concentrations were produced to oxidize CBZ, no PFAA removal took place.

10-Step Asymmetric Total Synthesis and Stereochemical Elucidation of (+)-Dragmacidin†D.

The asymmetric synthesis of dragmacidin D (1) was completed in 10 steps. Its sole stereocenter was set by using direct asymmetric alkylation enabled by a C2-symmetric tetramine and lithium N-(trimethylsilyl)-tert-butylamide as the enolization reagent. A central Larock indole synthesis was employed in a convergent assembly of the heterocyclic subunits. The stereochemical evidence from this work strongly supports the predicted S configuration at the 6''' position, which is consistent with other members of the dragmacidin family of natural products.