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To determine the effect of heat application on the setting and chemical properties of HiFlow BC Sealer and compare to other calcium silicate (CSBS) and epoxy resin-based root canal sealers. AH Plus, BioRoot RCS (BioRoot), Endosequence BC (Endosequence), and HiFlow BC (HiFlow) sealers were placed at 37 °C or subjected to heat at 200 °C for 10 or 30 s, followed by incubation at 37 °C in a humidified incubator during experiments. Setting time, viscosity, and flow were assessed, and changes in chemical structure were evaluated using the Fourier-transform infrared spectroscopy (FTIR). Thermogravimetric analysis was also used to evaluate the weight change (%) of the sealers upon heating from room temperature to 37 °C or 200 °C at a rate of 20 °C/min. Data were analyzed using a two-way ANOVA with a Bonferroni post-hoc test (p = 0.05). Application of heat extended the setting time for Endosequence and HiFlow but resulted in a faster setting of AH Plus and BioRoot. The highest flow and lower viscosity were observed in HiFlow at high temperature (p < 0.05), whereas the lowest flow with the highest viscosity and greatest weight loss were observed in BioRoot after heat application (p < 0.05). FTIR spectra demonstrated no changes to functional groups after heat application, except for the strong H-O-H absorption peak corresponding to water in BioRoot. Endosequence and HiFlow showed similar chemical properties with a higher flow and lower viscosity in HiFlow after heat application. Heat application resulted in reduced flow, increased viscosity, and weight loss for BioRoot. The setting of AH Plus was fastened with heat, while its weight loss, viscosity, and flow characteristics were stable. HiFlow, Endosequence, and AH Plus can be all used with WVC obturation techniques. Heat application resulted in minor changes in their physical properties including setting time, flow, weight loss, and chemical properties, while BioRoot showed a significant amount of weight loss, increase in viscosity, and reduced flowability after heat application.

Per- and polyfluoroalkyl substances (PFASs) are exceptionally stable chemicals due to their strong C F bonds. Nanoscale zero-valent iron (nZVI) particles have the potential to remove and degrade PFASs through redox activity. In this study, we deposited nZVI onto two-dimensional reduced graphene oxide (rGO) nanosheets and tested these synthesized rGO-nZVI nanohybrid (NH) for the treatment of a mixture of short- and long-chain PFASs in water with and without H2O2. All PFASs were removed at a higher efficiency by the rGO-nZVI NH than by the parent materials rGO and nZVI. Notably, the long-chain PFASs were removed at a faster rate than the short-chain PFASs. After a 10 min exposure to the rGO-nZVI NH without H2O2, the long-chain PFASs (perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA)) were removed by 85 % and 39 %, respectively, while short-chain PFASs (perfluoropentane sulfonic acid and perfluoropentanoic acid) were removed by 19 % and 18 %, respectively. The addition of H2O2 enhanced the PFAS treatment performance by 10–18 %, which can be attributed to the generation of reactive oxygen species by the rGO-nZVI NH. Liquid chromatography high-resolution mass spectrometry analysis confirmed the formation of unique shorter chain and partially defluorinated PFAS-Fe complexes from both PFOS and PFOA.

An anionic iron(II) tetrahedral molecular cage (FeMOP) was studied for its ability to interact with various per- and polyfluoroalkyl substances (PFASs) in aqueous media. Liquid chromatography tandem mass spectrometry revealed that longer-chain-length (more than six carbons) perfluorocarboxylic, -sulfonic, and fluorotelomers were removed from solution. In contrast, the steric bulk of N-ethyl substituted fluorosulfonamido acetic acid PFASs hindered association with the cage. Solution binding studies in D2O using 19F nuclear magnetic resonance (NMR) titrations and a Job plot show a 1:1 binding stoichiometry for perfluorohexanoic acid (PFHxA) and perfluoroheptanoic acid (PFHpA) with an association constant (Ka) of

Cardiac glycosides, steroid derivatives extracted from the foxglove plants, have been used for the treatment of heart failure since the 18th century. A method based on liquid chromatography coupled with high-resolution tandem mass spectrometry (LC/MS2) has been developed to characterize and quantify cardiac glycosides in fresh-leaf extracts of the foxglove (Digitalis sp.) plants [1]. In this report, the fragmentation spectra of additional authentic standards of cardiac glycoside (digitoxigenin, digoxigenin, β-acetyldigoxin) and cardenolides identified in the leaves of Digitalis lanata (D. lanata) and Digitalis purpurea (D. purpurea) were provided with high resolution. The exact mass of signature peaks for the aglycones and the sugar units of cardenolides were measured. This dataset is valuable to researchers interested in characterizing cardenolides in plants, or quantifying cardenolides in drug tablets, or studying cardenolide toxicities in animals. The fragmentation patterns of authentic cardenolide standards provided in these data can be used to validate relevant cardenolides in various biological samples and to infer chemical structures of unknown cardiac glycosides.

The present study focuses on the determination of the occurrence and levels of per- and polyfluoroalkyl substances (PFASs) in the drinking and source water from the Philippines and Thailand. A total of 46 samples (18 commercial bottled waters, 5 drinking water from vending machine (re-fill stations) and 23 source water) were analyzed using liquid chromatography with tandem high-resolution mass spectrometry. Using the targeted method, 12 different PFASs were detected in the drinking water samples with total quantifiable PFASs (∑PFASs) levels ranging from 7.16 to 59.49 ng/L; 15 PFASs were detected in source water with ∑PFASs ranging from 15.55 to 65.65 ng/L. A 100% detection frequency was observed for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorosulfonic acid (PFOS) in all water samples. Six other PFASs, not included in the targeted analysis, were detected using the suspect screening approach. For the first time, the presence of 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA) in drinking water is reported, and 3 novel PFASs (C5H5OF8, C6H4O2F6, and C9H2O2F16) were detected using suspect screening in source water. Combined results from target and suspect screening analysis showed that PFASs detected were predominantly (52%) short-chain (with fluorinated alkyl chain of ≤6) which could be explained by their high mobility in the environment. The detected PFASs levels in drinking water will not likely pose immediate health risk to consumers according to US EPA health advisory for PFOS and PFOA of 70 ng/L, but inclusion of bottled and drinking water from re-fill stations in monitoring programs is warranted.

Application of animal manure on agricultural lands is one of the main sources of estrogen contamination in the environment. Poultry and cow manure contain free and conjugated forms of the natural estrogens (e.g., estrone [E1] and estradiol [E2]) that can enter surface waters during runoff events. Estrone has been identified as the major form of estrogen in the environment; therefore, this study is focused on the evaluation of the degree of mineralization and fate of E1 in a simulated poultry litter and cow manure runoff water. A time-course study was conducted using simulated runoff water that consisted of 0.5 mg cow manure or poultry litter dissolved in 1 L of water spiked with radiolabeled E1 (C-E1). Samples were analyzed for estrogen concentrations at Day 0, 0.5, 1, 2, 3, 5, and 7 using liquid chromatography with tandem mass spectrometry. In the poultry litter simulated runoff water, E1 was biotransformed to 17β-estrone-3-sulfate (E1-3S) but was eventually mineralized to CO; a total E1 mineralization of 92.2% occurred after 7 d of aerobic incubation. In contrast, the concentrations of E1 and other forms of endogenous estrogens detected in the cow manure simulated runoff water, such as E1-3S, 17α-estradiol (α-E2), and 17β-estradiol (β-E2), remained relatively constant and persisted over the 7 d of aerobic incubation. Results of this study demonstrate the differences in the fate of estrone in the simulated poultry litter and cow manure runoff water, highlighting the ability of the endogenous microbial community from poultry litter to mineralize estrogens to CO.

Perfluorooctane sulfonate (PFOS) is a member of the anthropogenic class of perfluorinated alkyl acids (PFAAs) and one of the most frequently detected PFAAs in water, humans, mammals, and fish around the world. The zebrafish (Danio rerio) is a small freshwater fish considered an appropriate vertebrate model for investigating the toxicity of compounds. Previous investigations showed tissue-specific bioaccumulation and alterations in the expression of fatty acid-binding proteins (fabps) in male and female zebrafish, potentially due to interactions between PFAA and fatty acid transporters. In addition, a number of neurological impacts have been reported as a result of human and animal exposure to PFAAs. Therefore, the present comprehensive study was designed to investigate whether PFOS exposure affects the expression of genes associated with fatty acid metabolism (fabp1a, fabp2, and fabp10a) in zebrafish liver, intestine, heart, and ovary and genes involved in the nervous system (acetylcholinesterase, brain-derived neurotrophic factor, choline acetyltransferase, histone deacetylase 6, and nerve growth factor) in brain and muscle. The results indicate alterations in expression of genes associated with fatty acid metabolism and neural function that vary with both exposure concentration and sex. In addition, our findings highlight that expression of these genes differs according to exposure duration. The present results extend the knowledge base on PFOS effects to other tissues less often studied than the liver. The findings of the present investigation provide a basis for future studies on the potential risks of PFOS as one of the most abundant PFAAs in the environment. Environ Toxicol Chem 2020;39:437-449. © 2019 SETAC.

Chromatographic retention factors (k) and mass spectral fragmentation patterns of per- and polyfluoroalkyl substances (PFASs) were determined using the optimized parameters in liquid chromatography with tandem high-resolution mass spectrometry (LC-HRMS) analysis. Characteristic fragment ions obtained at various collision energies (MS2 fragmentation) were used to determine the structures of newly discovered (emerging) PFASs detected from industrial effluent and surface water samples. Moreover, COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) derived octanol-water partition coefficients (Kow), along with mean isotropic polarizabilities calculated from Density Functional Theory (DFT), of known PFASs were plotted against their experimental k values (kexp) to obtain a multivariable regression model that can be used to predict k values of unknown PFASs. The k values of different structural isomers of unknown PFASs were calculated and compared to kexp. The predicted k value for the isomer that matches the MS2 fragmentation observed was found to be within 4.2 % of kexp. This study demonstrates the applicability of an approach that combines the observed MS2 fragmentation patterns and k values, together with computationally-derived log Kow and polarizabilities, in assigning the structures of unknown PFASs at environmentally relevant conditions when no reference standards are available.

Plants of theDigitalisgenus contain a cocktail of cardenolides commonly prescribed to treat heart failure. Cardenolides inDigitalisextracts have been conventionally quantified by high-performance liquid chromatography yet the lack of structural information compounded with possible co-eluents renders this method insufficient for analyzing cardenolides in plants. The goal of this work is to structurally characterize cardiac glycosides in fresh-leaf extracts using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS) that provides exact masses. Fragmentation of cardenolides is featured by sequential loss of sugar units while the steroid aglycon moieties undergo stepwise elimination of hydroxyl groups, which distinguishes different aglycones. The sequence of elution follows diginatigenin→digoxigenin→gitoxigenin→gitaloxigenin→digitoxigenin for cardenolides with the same sugar units but different aglycones using a reverse-phase column. A linear range of 0.8-500 ng g−1has been achieved for digoxigenin,β-acetyldigoxin, and digitoxigenin with limits of detection ranging from 0.09 to 0.45 ng g−1. A total of 17 cardenolides have been detected with lanatoside A, C, and E as major cardenolides inDigitalis lanatawhile 7 have been found inDigitalis purpureaincluding purpurea glycoside A, B, and E. Surprisingly, glucodigifucoside inD. lanataand verodoxin and digitoxigenin fucoside inD. purpureahave also been found as major cardenolides. As the first MS/MS-based method developed for analyzing cardenolides in plant extracts, this method serves as a foundation for complete identification and accurate quantification of cardiac glycosides, a necessary step towards understanding the biosynthesis of cardenolide in plants.