Fluoroether Double-Chain Phosphate Surfactants: An Exploration of Alternatives to Fluorotelomer Surfactants.

While legacy fluorosurfactants have already been categorized as persistent organic pollutants, there appeared to be many strategies to develop alternatives. In this work, fluoroether double-chain phosphate surfactants (C72 diPAP-Na and C72 diPAP-NH4) were designed and synthesized with the initial intention of exploring the creation of new fluorosurfactants containing oxygen heteroatoms in the fluorocarbon chain segments to provide an alternative to the legacy long-chain fluorosurfactants. Furthermore, it was expected that they would even exceed the existing 6:2 fluorotelomer surfactants (6:2 diPAP-Na and 6:2 diPAP-NH4). Compared with characterizations of surface activity, foam performance, and wettability, the results showed that each of them has its own distinctive performance. Although the C72 series as new fluoroether surfactants cannot fully replace the 6:2 series of fluorosurfactants in terms of performance, there is a possibility of substitution in some aspects, which is of positive significance for further exploration to improve alternatives to legacy fluorosurfactants.

Synthesis, Surface Activity, and Foamability of Two Short-Chain Fluorinated Sulfonate Surfactants with Ether Bonds.

Fluorinated surfactants are widely used in many fields because of their excellent surface active properties, but their high stability has caused many environmental problems. With the ban and restriction of classical long-chain fluorinated surfactants such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) worldwide, the development and replacement of their alternatives is now a major challenge. How to reduce environmental persistence, bioaccumulation, and biotoxicity while maintaining high surface activity has become an important issue in the development of fluorinated surfactants. Using short-chain fluorinated surfactants is one of the important solutions to resolve the pollution of organic fluorinated compounds. In this article, we synthesized two short-chain fluorinated surfactants with ether bonds. One of them 6:2 FTESNa (2) used the perfluoroalkyl chain (n-C6F13-) and the other C72 FEESNa (4) used the fluoroether segment with six fluorinated carbons and two oxygens (CF3OCF(CF3)CF2OCF(CF3)). The surface activity, foam performance, and wettability of the two molecules were measured. The surface tensions at critical micelle concentration (γcmc) and the critical micelle concentration (cmc) of 2 and 4 were 17.6 mN/m (2.2 g/L) and 20.2 mN/m (4.6 g/L), respectively. Both of them were significantly superior to the surface activity of 6:2 FTSNa (7) which is one of the current alternatives for PFOS. Additionally, the foamability and foam stability of both 2 and 4 were better than that of 7. In the aspect of wettability on PTFE, that of 4 was greater than those of 2 and 7. In summary, this work provided a new choice for alternatives of PFOS and PFOA.

Novel Perfluoroalkyl Ether Carboxylic Acids (PFECAs) and Sulfonic Acids (PFESAs): Occurrence and Association with Serum Biochemical Parameters in Residents Living Near a Fluorochemical Plant in China.

Although perfluoroalkyl ether carboxylic (PFECAs) and sulfonic acids (PFESAs) have been widely detected in environmental matrices, their occurrence in humans and impact on human health remains insufficiently understood. Here, we report on 13 PFECAs and PFESAs in 977 sera samples collected from residents living near a fluorochemical plant in Shandong, China. The sum concentration of these emerging PFECAs accounted for 13% of the total PFASs in the serum of the participants, with the frequent detection of several PFECAs (>95%) (PFMOAA, PFO4DA, and PFO5DoDA at median concentrations of 12.91, 0.142, and 0.987 ng/mL, respectively) and PFESAs (98.7%) (Nafion byproduct 2 at a median concentration of 0.097 ng/mL). Serum PFMOAA, PFO5DoDA, and 6:2 Cl-PFESA levels were significantly higher in males than in females. Positive relationships were observed between age and PFMOAA, 6:2 Cl-PFESA, and H-PFMO2OSA levels, whereas HFPO-TA and PFO5DoDA serum concentrations in the 0-40-year age group were lower than that in the >40-year age group. Furthermore, multivariate linear regression models and sensitivity analyses showed positive associations among PFO5DoDA levels, elevated lipid parameters (cholesterol, low-density lipoprotein cholesterol, and triglycerides), liver function markers (albumin levels and alanine transaminase, aspartate aminotransferase, and glutamyl transpeptidase activities), and uric acid levels. Thus, our results suggest potential health risks from exposure to novel PFESAs and PFECAs (especially PFO5DoDA).

A Series of Deoxyfluorination Reagents Featuring OCF2 Functional Groups.

Research on perfluoroalkyl ether carboxylic acids (PFECAs) as alternatives for perfluoroalkyl substances continues with the goal of protecting the environment. However, very little is known about the utilization of decomposition products of PFECAs. We report herein a new series of deoxyfluorination reagents featuring OCF2 functional groups derived from certain PFECAs. Alkyl fluorides were generated from various alcohols in ≤97% yield by these novel reagents. The mechanistic experiment verified in situ generation of carbonic difluoride (COF2).

Perfluoropolyether carboxylic acids (novel alternatives to PFOA) impair zebrafish posterior swim bladder development via thyroid hormone disruption.

Perfluoropolyether carboxylic acids (PFECAs, CF3(OCF2)nCOO-, n = 2-5) are novel alternatives to perfluorooctanoic acid (PFOA) and are widely used in industrial production. However, although they have been detected in surface water and human blood, their toxicities on aquatic organisms remain unknown. We used zebrafish embryos to compare the developmental toxicities of various PFECAs (e.g., perfluoro (3,5,7-trioxaoctanoic) acid (PFO3OA), perfluoro (3,5,7,9-tetraoxadecanoic) acid (PFO4DA), and perfluoro (3,5,7,9,11-pentaoxadodecanoic) acid (PFO5DoDA)) with that of PFOA and to further reveal the key events related to toxicity caused by these chemicals. Results showed that, based on half maximal effective concentrations (EC50), toxicity increased in the order: PFO5DoDA > PFO4DA > PFOA > PFO3OA, with uninflated posterior swim bladders the most frequently observed malformation. Similar to PFOA, PFECA exposure significantly lowered thyroid hormone (TH) levels (e.g., T3 (3,5,3'-L-triiodothyronine) and T4 (L-thyroxine)) in the whole body of larvae at 5 d post-fertilization following disrupted TH metabolism. In addition, the transcription of UDP glucuronosyltransferase 1 family a, b (ugt1ab), a gene related to TH metabolism, increased dose-dependently. Exogeneous T3 or T4 supplementation partly rescued PFECA-induced posterior swim bladder malformation. Our results further suggested that PFECAs primarily damaged the swim bladder mesothelium during early development. This study is the first to report on novel emerging PFECAs as thyroid disruptors causing swim bladder malformation. Furthermore, given that PFECA toxicity increased with backbone OCF2 moieties, they may not be safer alternatives to PFOA.