PFAS: A Review of the State of the Art, from Legislation to Analytical Approaches and Toxicological Aspects for Assessing Contamination in Food and Environment and Related Risks

Schiavone, Consolato; Portesi, C.

doi:10.3390/app13116696

Cited by 16 publications

(2 citation statements)

References 120 publications

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“…Per- and polyfluoroalkyl substances (PFAS), the ubiquitous and “forever” class of chemicals, which number over 7000 compounds, have been found in human blood, human breast milk, neonates, and children. − The association of PFAS compounds with adverse human health outcomes has emerged as a major societal and governmental health concern. − PFAS-associated toxicity includes reproductive effects (decreased fertility), elevated levels of blood pressure, late onset of development in children, risk for cancers, and complications due to compromised immunity. PFAS is also a known obesogen.…”

Section: Introductionmentioning

confidence: 99%

An Atomic and Molecular Insight into How PFOA Reduces α-Helicity, Compromises Substrate Binding, and Creates Binding Pockets in a Model Globular Protein

Yadav,

Vuković,

Narayan

2024

J. Am. Chem. Soc.

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Per-and polyfluoroalkyl substances (PFAS) pose significant health risks due to their widespread presence in various environmental and biological matrices. However, the molecular-level mechanisms underlying the interactions between PFAS and biological constituents, including proteins, carbohydrates, lipids, and DNA, remain poorly understood. Here, we investigate the interactions between a legacy PFAS, viz. perfluorooctanoic acid (PFOA), and the milk protein β-lactoglobulin (BLG) obtained using a combination of experimental and computational techniques. Circular dichroism studies reveal that PFOA perturbs the secondary structure of BLG, by driving a dose-dependent loss of α-helicity and alterations in its β-sheet content. Furthermore, exposure of the protein to PFOA attenuates the on-rate constant for the binding of the hydrophobic probe 8anilino-1-naphthalene sulfonic acid (ANS), suggesting potential functional impairment of BLG by PFOA. Steered molecular dynamics and umbrella sampling calculations reveal that PFOA binding leads to the formation of an energetically favorable novel binding pocket within the protein, when residues 129−142 are steered to unfold from their initial α-helical structure, wherein a host of intermolecular interactions between PFOA and BLG's residues serve to insert the PFOA into the region between the unfolded helix and beta-sheets. Together, the data provide a novel understanding of the atomic and molecular mechanism(s) by which PFAS modulates structure and function in a globular protein, leading to a beginning of our understanding of altered biological outcomes.

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Section: Introductionmentioning

confidence: 99%

An Atomic and Molecular Insight into How PFOA Reduces α-Helicity, Compromises Substrate Binding, and Creates Binding Pockets in a Model Globular Protein

Yadav,

Vuković,

Narayan

2024

J. Am. Chem. Soc.

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“…The introduction of fluorine atoms into organic molecules (usually replacing hydrogen) imparts a unique set of physicochemical properties that often enhance pharmacokinetic profiles, metabolic stability, and receptor interactions but keep many of the good properties of the parent compounds. On the other hand, per- and polyfluoroalkyl substances (PFAS) have garnered unprecedented attention in recent years, becoming a focal point of scientific inquiry, regulatory concern, and public discourse. − These synthetic compounds, characterized by their remarkable stability and hydrophobic nature, open new perspectives in industrial and commercial applications. , However, their persistent presence in the environment, coupled with potential adverse health effects, has propelled PFAS to the forefront of global environmental and health agendas. Thus, it seems clear that a detailed theoretical understanding of fluorinated organic drugs and PFAS, in particular their thermodynamic properties and kinetic stability, is of high general interest. − …”

Section: Introductionmentioning

confidence: 99%

Influence of Steric and Dispersion Interactions on the Thermochemistry of Crowded (Fluoro)alkyl Compounds

Bursch,

Grimme,

Hansen

2023

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Alkanes play a pivotal role in industrial, environmental, and biological processes. They are characterized by their carbon−carbon single-bond structure, remarkable stability, and conformational diversity. Fluorination of such compounds imparts unique physicochemical properties that often enhance pharmacokinetic profiles, metabolic stability, and receptor interactions while keeping beneficial properties. However, such per-and polyfluoroalkyl substances (PFAS) show a persistent presence in the environment and potential adverse health effects, which propelled them to the forefront of global environmental and health discussions. Alkyl compounds are also prototypical for stereoelectronic (SE) effects that are widely applied in chemistry. Substituents are typically described as electron-density-donating/withdrawing and/or responsible for sterically interacting with reagents or strategic groups in the molecule. That alkane branching can result in higher stability compared to less-branched isomers has been investigated in detail also by testing quantum chemical methods, in particular density functional theory (DFT). Alkane branching results in spatially compact structures with close intramolecular contacts so that at a specific size the detailed balance of attractive London dispersion and covalent versus repulsive Pauli exchange interactions shifts to new, chemically unfragile situations. This may lead to dissociation at room temperature and opens the central question: what is the smallest crowed alkane that cannot be made synthetically? In this Account, we try to shed light on the interplay among the various (free) energy components for crowded (fluoro)alkane dissociation. In this context, homolytic cleavage of the central C−C bond in a series of model alkanes of increasing size with tert-butyl (tBu), adamantyl (Ad), and [1.1.1]propellanyl (Prop) substituents is investigated. Reference energies are calculated at the PNO-LCCSD(T)-F12b level and used to benchmark the performance of contemporary DFT functionals. In line with previous conclusions, the application of dispersion corrections to density functionals is mandatory. For crowed structures, the accurate description of the midrange correlation effects, specifically repulsive van der Waals interactions, is crucial, and we observed that the density-dependent VV10 correction is superior to D4 in this context, although the asymptotic region is better described by the latter. The best available dispersion-inclusive functionals show systematic and reasonably small residual errors and can be safely applied to large systems (>100 atoms), for which coupled cluster methods with large basis sets are not computationally feasible anymore. For qualitatively correct predictions of synthetic accessibility under equilibrium conditions (free energy), the inclusion of thermostatistical (entropy) contributions is also essential. According to our results, tetra-tert-butylmethane (C17 tBu ) is the largest and mos...

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The Development and Evaluation of PFSA‐Free Polyacrylonitrile‐co‐Methyl Acrylate (PAN‐MA) Nanofiber Membranes for its Potential Application as a Proton Exchange Membrane in Fuel Cells

Seda,

Öner,

Remis

et al. 2024

Macro Materials & Eng

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The significance of hydrogen energy has grown considerably due to climate change and the depletion of fossil fuels. PEM fuel cells are the key hydrogen technologies. Commercial membranes based on perfluorosulfonic acid (PFSA) with a polymer structure containing fluorine are currently available. However, it has been determined that certain perfluorosulfonic acids (PFSAs) are hazardous, persistent, and bioaccumulative. Advancements in hydrogen technology rely on effective, inexpensive, and perfluorocarbon‐free membranes, specifically proton exchange membranes (PEMs). In this research, a PFSA‐free polyacrylonitrile‐co‐methyl acrylate (PAN‐MA) membrane doped with phosphoric acid is prepared using the electrospinning method and then characterized by SEM, FE‐SEM, XRD, FTIR, TGA, DMA, and EIS. The DMA analysis reveals that the storage modulus of the doped membrane increases from 0.98 to 5.66 MPa at 80 °C. The nanofiber composite membrane, with a thickness of 181 µm, exhibits the highest proton conductivity of 0.306 S m−1 at 20 °C, 1.76 times higher than that of the Nafion 212 membrane. The Nafion 212 membrane has an ionic conductivity of 0.173 S m−1 under the same conditions. These results indicate that the prepared nanofiber membranes are promising materials for evaluating fuel cell applications.

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PFAS: A Review of the State of the Art, from Legislation to Analytical Approaches and Toxicological Aspects for Assessing Contamination in Food and Environment and Related Risks

Cited by 16 publications

References 120 publications

An Atomic and Molecular Insight into How PFOA Reduces α-Helicity, Compromises Substrate Binding, and Creates Binding Pockets in a Model Globular Protein

An Atomic and Molecular Insight into How PFOA Reduces α-Helicity, Compromises Substrate Binding, and Creates Binding Pockets in a Model Globular Protein

Influence of Steric and Dispersion Interactions on the Thermochemistry of Crowded (Fluoro)alkyl Compounds

The Development and Evaluation of PFSA‐Free Polyacrylonitrile‐co‐Methyl Acrylate (PAN‐MA) Nanofiber Membranes for its Potential Application as a Proton Exchange Membrane in Fuel Cells

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