Interspecies comparison of metabolism of two novel prototype PFAS

As a result of proposed global restrictions and regulations on current-use per-and polyfluoroalkyl substances (PFAS), research on possible alternatives is highly required. In this study, phase I in vitro metabolism of two novel prototype PFAS in human and rat was investigated. These prototype chemicals are intended to be safer-by-design and expected to mineralize completely, and thus be less persistent in the environment compared to the PFAS available on the market. Following incubation with rat liver S9 (RL-S9) fractions, two main metabolites per initial substance were produced, namely an alcohol and a short-chain carboxylic acid. While with human liver S9 (HL-S9) fractions, only the short-chain carboxylic acid was detected. Beyond these major metabolites, two and five additional metabolites were identified at very low levels by non-targeted screening for the ether- and thioether-linked prototype chemicals, respectively. Overall, complete mineralization during the in vitro hepatic metabolism of these novel PFAS by HL-S9 and RL-S9 fractions was not observed. The reaction kinetics of the surfactants was determined by using the metabolite formation, rather than the substrate depletion approach. With rat liver enzymes, the formation rates of primary metabolite alcohols were at least two orders of magnitude higher than those of secondary metabolite carboxylic acids. When incubating with human liver enzymes, the formation rates of single metabolite carboxylic acids, were similar or smaller than those experienced in rat. It also indicates that the overall metabolic rate and clearance of surfactants are significantly higher in rat liver than in human liver. The maximum formation rate of the thioether congener exceeded 10-fold that of the ether in humans but were similar in rats. Overall, the results suggest that metabolism of the prototype chemicals followed a similar trend to those reported in studies of fluorotelomer alcohols.</p

Ávinningur góðrar vörumerkjastjórnunar

Útivistarfatnaður hefur lengi vel verið staðalbúnaður allra Íslendinga. Ekki er langt síðan íslenska vörumerkið 66°Norður var eitt síns lið á markaði en í dag hafa fleiri útivistarmerki verið að koma inn á markað, íslensk jafn sem erlend. En fleira hefur breyst síðan 66°Norður kom fyrst á markað og má þar einna helst nefna hvað útivistarfatnaður hafa færst nær lífsstíls- og tískufatnaði og eru mörkin á milli vöruflokka stöðugt að minnka, því fólk vill geta nýtt fatnaðinn við ólík tilefni. 66°Norður er eitt elsta fyrirtækið hér á landi og hefur því lengi verið þekkt. Megin markmið þessa verkefnis er að skoða hvernig 66°Norður tekst á við að skapa sterka stöðu á markaði og þar með rýna í fræði vörumerkjastjórnunar samhliða því

Dermal bioavailability of perfluoroalkyl substances using in vitro 3D human skin equivalent models

Perfluoroalkyl substances (PFAS) have been identified in various products that come in contact with human skin, ranging from school uniforms to personal care products. Despite this, knowledge on human dermal uptake of PFAS is lacking. Thus, the human dermal absorption of 17 PFAS was assessed, for the first time, using in vitro 3D-human skin equivalent models exposed to 500 ng/cm2 PFAS dissolved in methanol over 24-36 h. The distribution of target PFAS is presented, based on three fractions: absorbed, un-absorbed, and retained within skin tissue (absorbable dose). Perfluoropentanoic acid (PFPeA) and perfluorobutane sulfonate (PFBS) had the highest absorbed fraction, 58.9 % and 48.7 % respectively, with the absorbed fraction decreasing with increasing carbon chain length of the studied perfluorocarboxylic acids (PFCAs) (r = 0.97, p = 0.001) and perfluorosulfonic acids (PFSAs) (r = 0.97, p = 0.004). Interestingly, while longer chain PFAS (Cn ≥ 9) were not directly absorbed, a large fraction of the exposure dose was detected within the skin tissue at the end of the exposure. This was most apparent for perfluoroundecanoic acid (PFUnDA) and perfluorononane sulfonate (PFNS) for which 66.5 % and 68.3 % of the exposure dose was found within the skin tissue, while neither compound was detected in the absorbed fraction. For compounds with a carbon chain length &gt; 11, the fraction found within the skin tissue, decreases with increasing chain length. Physicochemical properties played a role in dermal permeation of PFAS, with a clear inverse correlation between logKOW and absorbed fraction for both PFCAs (r = -0.97; p ≤ 0.001) and PFSAs (r = -0.99; p ≤ 0.001). Steady-state flux (JSS) and permeation coefficients (Papp) were determined for target compounds with significant permeation after 36 h exposure (C5-C8 PFCAs and C4-C7 PFSAs). In general, both the flux and permeation coefficient decreased with increasing chain length. </p

Dermal bioavailability of perfluoroalkyl substances using in vitro 3D human skin equivalent models

Perfluoroalkyl substances (PFAS) have been identified in various products that come in contact with human skin, ranging from school uniforms to personal care products. Despite this, knowledge on human dermal uptake of PFAS is lacking. Thus, the human dermal absorption of 17 PFAS was assessed, for the first time, using in vitro 3D-human skin equivalent models exposed to 500 ng/cm2 PFAS dissolved in methanol over 24-36 h. The distribution of target PFAS is presented, based on three fractions: absorbed, un-absorbed, and retained within skin tissue (absorbable dose). Perfluoropentanoic acid (PFPeA) and perfluorobutane sulfonate (PFBS) had the highest absorbed fraction, 58.9 % and 48.7 % respectively, with the absorbed fraction decreasing with increasing carbon chain length of the studied perfluorocarboxylic acids (PFCAs) (r = 0.97, p = 0.001) and perfluorosulfonic acids (PFSAs) (r = 0.97, p = 0.004). Interestingly, while longer chain PFAS (Cn ≥ 9) were not directly absorbed, a large fraction of the exposure dose was detected within the skin tissue at the end of the exposure. This was most apparent for perfluoroundecanoic acid (PFUnDA) and perfluorononane sulfonate (PFNS) for which 66.5 % and 68.3 % of the exposure dose was found within the skin tissue, while neither compound was detected in the absorbed fraction. For compounds with a carbon chain length &gt; 11, the fraction found within the skin tissue, decreases with increasing chain length. Physicochemical properties played a role in dermal permeation of PFAS, with a clear inverse correlation between logKOW and absorbed fraction for both PFCAs (r = -0.97; p ≤ 0.001) and PFSAs (r = -0.99; p ≤ 0.001). Steady-state flux (JSS) and permeation coefficients (Papp) were determined for target compounds with significant permeation after 36 h exposure (C5-C8 PFCAs and C4-C7 PFSAs). In general, both the flux and permeation coefficient decreased with increasing chain length. </p

Solid-State Structural Transformation and Photoluminescence Properties of Supramolecular Coordination Compounds

The combination of strong coordination bonds and hydrogen bonding interactions were used to generate a series of supramolecular coordination materials (SCMs), which was achieved by reacting a bis-pyridyl amide ligand, namely N-(4-pyridyl)nicotinamide (4PNA) with copper(II), zinc(II), and cadmium(II) benzoates. The SCMs were structurally characterized using X-ray diffraction and the key intermolecular interactions were identified via Hirshfeld surface analysis. The role of solvent molecules on the supramolecular architecture was analyzed by synthesizing the SCMs in different solvents/solvent mixtures. A solvent-mediated solid-state structural transformation was observed in copper(II) SCMs and we were able to isolate the intermediate form of the crystal-to-crystal transformation process. The luminescence experiments revealed that complexation enhanced the fluorescence properties of 4PNA in the zinc(II) and cadmium(II) SCMs, but a reverse phenomenon was observed in the copper(II) SCMs. This work demonstrated the tuning of supramolecular assembly in coordination compounds as a function of solvents for generating SCMs with diverse properties

Synthesis of mixed salts of the [Mo2O2(μ-S)2(SCN)6-n(L)n](4+n)− anion (n = 0–2); structures of [Mo2O2(μ-S)2(SCN)5(CH3CN)]3−, [Mo2O2(μ-S)2(CN)5]3−, and [Mo2O2(μ-S)2(CN)2(O)]2−, and probing the ligand exchange of thiocyanate and cyanide

Aqueous coordination of cyanide and verification of the composition of the resulting coordination compound is important to ensure confidence in its coordination. Isothiocyanato compounds 1–7 were synthesized employing different synthetic routes and the complex, [Mo2O2(μ-S)2(SCN)5(CH3CN)]3−, 4, was structurally characterized. Ligand exchange reaction of 4 with cyanide forms 8, a cyano complex. Complex 8 was isolated as an organosoluble salt and fully characterized and confirmed as the major product formed in the aqueous ligand exchange reaction of 4–7 with cyanide. The crystal structure of 8 revealed the unusual [Mo2O2(μ-S)2(CN)5]3− anion where the two molybdenum(V) centers are unsymmetrically coordinated. A second unsymmetric cyano complex [Mo2O3(μ-S)2(CN)2]2− 9, presumed hydrolysis product from an aqueous reaction, was isolated and structurally characterized revealing one square pyramidal Mo center and one tetrahedral Mo center in the binuclear core. Attempts to quantify the first order dissociative ligand substitution rate of thiocyanate in 4 to form 8 using the stopped-flow method gave an estimated minimum rate constant of 70 s−1. This confirms that the exchange reaction is sufficiently fast to be useful in aqueous coordination of cyanide