Influence of Electrolyte Concentration on Single-Molecule Sensing of Perfluorocarboxylic Acids

Perfluorocarboxylic acids (PFCAs) are an emerging class of persistent organic pollutants. During the fabrication process, it is unavoidable to form PFCA homologs or isomers which exhibit distinct occurrence, bioaccumulation, and toxicity. The precision measurement of PFCAs is therefore of significant importance. However, the existing characterization techniques, such as LC-MS/MS, cannot fully meet the requirement of isomer-specific analysis, largely due to the lack of authentic standards. Single-molecule sensors (SMSs) based on nanopore electrochemistry may be a feasible solution for PFCAs determination, thanks to their ultra-high spatiotemporal resolutions. Hence, as a first step, this work was to elucidate the influence of electrolyte concentration on the four most critical indicators of nanopore measurements, and furthermore, performance of nanopore SMSs. More specifically, three of the most representative short-chain PFCAs, perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA), were adopted as the target analytes, aerolysin nanopore was employed as the sensing interface, and 2, 3 and 4 M KCl solutions were used as electrolytes. It was found that, when the concentration of KCl solution increased from 2 to 4 M, the conductance of aerolysin nanopore increased almost linearly at a rate of 0.5 nS per molar KCl within the whole voltage range, the current blockade of PFPeA at −50 mV increased from 61.74 to 66.57% owing to the enhanced steric exclusion effect, the maximum dwell time was more than doubled from 14.5 to 31.5 ms, and the barrier limited capture rate increased by 8.3 times from 0.46 to 3.85 Hz. As a result, when using 4 M KCl as the electrolyte, over 90% of the PFPeA, PFHxA and PFHpA were accurately identified from a mixed sample, and the calculated limit of detection of PFPeA reached 320 nM, more than 24 times lower than in 2 M KCl. It was thus clear that tuning the electrolyte concentration was a simple but very effective approach to improve the performance of nanopore SMSs for PFCAs determination.

A Simple and Rapid Method for Quantitative HPLC MS/MS Determination of Selected Perfluorocarboxylic Acids and Perfluorosulfonates in Human Serum

Per- and polyfluorinated alkyl substances (PFASs) are ubiquitous environmental contaminants, present in the environment and in the human body. They have raised global concern because of their diffusion in the environment, particularly in water, causing cases of human overexposure due to consumption of contaminated drinking water. Human biomonitoring is the most effective way to characterize human exposure to PFASs, and it is important that as many labs as possible could easily perform this kind of analysis. Analytical methods for quantitation of PFAS mixtures in human serum have been developed, but most of them required materials that are not always easily available in all the laboratories. This paper describes a very simple and accessible HPLC MS/MS method of analysis and quantification of 13 perfluorocarboxylic acids and perfluorosulfonate compounds (belonging to the class of per- and polyfluorinated alkyl substances (PFASs)) in human serum. Method development data provide detailed descriptions of the optimization process in terms of sample preparation, laboratory analysis of human serum samples, determination of analytes by HPLC MS/MS, and describing the pump gradient time, working conditions, and acquisition.

Hydrated-electron-based short chain perfluorosulfonic acid decomposition in VUV/sulfite system

Perfluorosulfonic acids (PFSAs) have attracted increasing attention due to their global distribution, high chemical stability and persistence. As a powerful reductant, hydrated electron () shows extraordinary reactivity towards halogenated organic substances like PFSAs. In this study, -based photo-decomposition of perfluorohexane sulfonate (PFHxS) in a VUV/sulfite system was investigated. The kobs of PFHxS decomposition in the studied system was 0.0049 ± 0.0005 min−1, which was 24.5-fold faster than that in a sole VUV system. It was demonstrated that was the main reactive species responsible for PFHxS decomposition. PFHxS decomposition kinetics were accelerated at higher initial solution pH and sulfite dosage, but were restrained when higher initial PFHxS concentration was introduced. Co-existence of chloride showed slight enhancement of PFHxS decomposition, whereas nitrate and bicarbonate suppressed PFHxS decomposition. Accompanying PFHxS decomposition, short chain perfluorocarboxylic acids (PFCAs) were detected as main intermediate products. PFHxS decomposition started with C-S bond fracture, followed by perfluoroalkyl radical hydrolysis reactions and perfluorohexanoic acid (PFHxA) formation. Afterwards, PFHxA was defluorinated by stepwise loss of CF2 units to generate other short chain PFCAs.