Heptadecafluorooctanesulfonic Acid Research Articles

Per- and Polyfluoroalkyl Substances: Impacts on Morphology, Behavior and Lipid Levels in Zebrafish Embryos.

The presence of per- and polyfluoroalkyl substances (PFASs) in aquatic environments is often persistent and widespread. Understanding the potential adverse effects from this group of chemicals on aquatic communities allows for better hazard characterization. This study examines impacts on zebrafish (Danio rerio) embryo physiology, behavior, and lipid levels from exposure to perfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHxS), and heptadecafluorooctanesulfonic acid (PFOS). Embryos were exposed to lethal and sublethal levels of each chemical and monitored for alterations in physiological malformations, mortality, lipid levels, and behavior (only PFOA and PFHxS). The predicted 50% lethal concentrations for 120 hpf embryos were 528.6 ppm PFOA, 14.28 ppm PFHxS, and 2.14 ppm PFOS. Spine curvature and the inability of the 120 hpf embryos to maintain a dorsal-up orientation was significantly increased at 10.2 ppm PFHxS and 1.9 ppm PFOS exposure. All measured 120 hpf embryo behaviors were significantly altered starting at the lowest levels tested, 188 ppm PFOA and 6.4 ppm PFHxS. Lipid levels decreased at the highest PFAS levels tested (375 PFOA ppm, 14.4 PFHxS ppm, 2.42 ppm PFOS). In general, the PFAS chemicals, at the levels examined in this study, increased morphological deformities, embryo activity, and startle response time, as well as decreased lipid levels in 120 hpf zebrafish embryos.

Adsorption of perfluorooctanoic carboxylic and heptadecafluorooctane sulfonic acids via magnetic chitosan: isotherms and modeling.

This paper evaluates the adsorption mechanism of perfluorooctanoic carboxylic acid (PFCA) and heptadecafluorooctane sulfonic acid (HFOSA) on magnetic chitosan for the first time via a statistical physics modeling. Magnetic chitosan (MC-CoFe2O4) was produced from shrimp wastes and used in standard batch adsorption systems to remove PFCA and HFOSA. The experimental isotherms indicated that the maximum adsorption capacities ranged from 14 to 27.12 mg/g and from 19.16 to 45.12 mg/g for PFCA and HFOSA, respectively, where an exothermic behavior was observed for both compounds. The adsorption data were studied via an advanced model hypothesizing that a multilayer process occurred for these adsorption systems. This theoretical approach indicated that the total number of formed layers of PFCA and HFOSA adsorbates is about 3 (Nt = 2.83) at high temperatures (328 K) where a molecular aggregation process was noted during the adsorption. The maximum saturation-multilayer adsorption of PFCA and HFOSA on magnetic chitosan was 30.77 and 50.26 mg/g, respectively, and the corresponding adsorption mechanisms were successfully investigated. Two energies were responsible for the formed adsorbate layer directly on the surface and the vertical layers were computed and interpreted, reflecting that physical interactions were involved to bind these molecules on the adsorbent surface at different temperatures where the calculated adsorption energies ranged from 14 to 31 kJ/mol. Overall, this work provides theoretical insights to understand the adsorption mechanism of PFCA and HFOSA using the statistical physics modeling and its results can be used to improve the adsorbent performance for engineering applications.

Defect Healing in FAPb(I1‐xBrx)3 Perovskites: Multifunctional Fluorinated Sulfonate Surfactant Anchoring Enables >21% Modules with Improved Operation Stability

AbstractFormamidinium lead triiodide‐based perovskite solar cells have emerged as one of the most promising candidates that can be potentially used to develop photovoltaic technologies in the future. The commercial use of perovskite solar cell modules (PSCMs) is limited as it is challenging to fabricate high‐quality, efficient, and stable large‐area perovskite light‐absorbing films. Heptadecafluorooctanesulfonic acid tetraethylammonium salt (HFSTT), containing fluorinated long alkyl chains as hydrophobic tails and sulfonic acid groups (SO3−) as hydrophilic heads, which exhibit a great synergistic potential in large‐area film uniform fabrication, crystallization orientation modulation, defect passivation, and device operation stability enhancement, are introduced. The HFSTT‐modified films exhibit a prominent (100) orientation and lower trap‐state density as well as enhanced carrier mobilities and diffusion lengths, facilitating a champion unit device with an impressive power conversion efficiency (PCE) of 23.88% (0.14 cm2) and 22.52% (1 cm2) with a low voltage deficit around 0.341 V. The unencapsulated device retains ≈70% of its initial efficiency after 1000 h under heat damping test (60 °C and ≈60% RH). Moreover, the PSCMs exhibiting PCEs of 21.05% (with notable fill factor 0.79) and 18.27% are characterized by the active areas of 25.98 and 60.68 cm2, respectively.

Locomotion of a Nonaqueous Liquid Marble Induced by Near-Infrared-Light Irradiation.

Micrometer-sized hydrophobic polyaniline (PANI) grains were synthesized via an aqueous chemical oxidative polymerization protocol in the presence of dopant carrying perfluoroalkyl or alkyl groups. The critical surface tensions of the PANIs synthesized in the presence of heptadecafluorooctanesulfonic acid and sodium dodecyl sulfate dopants were lower than that of PANI synthesized in the absence of dopant, indicating the presence of hydrophobic dopant on the grain surfaces. The PANI grains could adsorb to air-liquid interfaces, and aqueous and nonaqueous liquid marbles (LMs) were successfully fabricated using liquids with surface tensions ranging between 72.8 and 42.9 mN/m. Thermography studies confirmed that the surface temperature of the LMs increased by near-infrared light irradiation thanks to the photothermal property of the PANI, and the maximum temperatures measured for nonaqueous LMs were higher than that measured for aqueous LM. We demonstrated that transport of the LMs on a planar water surface can be achieved via Marangoni flow generated by the near-infrared light-induced temperature gradient. Numerical analyses indicated that the LMs containing liquids with lower specific heat and thermal conductivity and higher density showed longer path length per one light irradiation shot and longer decay time. This is because generated heat could efficiently transfer from the LMs to the water surface and larger inertial force could work on the LMs. The LMs could also move over the solid substrate thanks to their near-spherical shapes. Furthermore, it was also demonstrated that the inner liquids of the LMs could be released on site by an external stimulus.

Particle Monolayer-Stabilized Light-Sensitive Liquid Marbles from Polypyrrole-Coated Microparticles

Liquid marbles are water droplets coated with solid particles that prevent coalescence and allow storage, transport, and handling of liquids in the form of a powder. Here, we report on the formation of liquid marbles that are stabilized entirely by a single monolayer of solid particles and thus minimize the amount of required solid material. As stabilizing particles, we synthesize relatively-monodisperse, 80 m-sized polystyrene (PS) particles coated with heptadecafluorooctanesulfonic acid-doped polypyrrole (PPy-C8F) shell (PS/PPy-C8F particles) by aqueous chemical oxidative seeded polymerization of pyrrole using FeCl3 as an oxidant and heptadecafluorooctanesulfonic acid as a hydrophobic dopant. We characterize the physicochemical properties of the particles as a function of the PPy-C8F loading. Laser diffraction particle size analyses of dilute aqueous suspensions indicate that the polymer particles disperse stably in water medium before and after coating with the PPy-C8F shell. X-ray photoelectron spectroscopy studies indicate the formation of a PPy-C8F shell around the PS seed particles, which was further supported by a deflated morphologies observed by scanning electron microscopy after extraction of the PS component from the PS/PPy-C8F particles. We investigate the capabilities of the dried PS/PPy-C8F particles to act as a liquid marble stabilizer. Stereo- and laser microscope observations, as well as gravimetric studies, confirm that the PS/PPy-C8F particles adsorb to the water droplet surface in the form of a particle monolayer with the characteristic hexagonal close-packed structure expected for spherical (colloidal) particles. Mechanical integrity of the liquid marble increases with an increase of PPy-C8F loading of the PS/PPy-C8F particles. The water contact angle of the PS/PPy-C8F particles at air-water interface increases from 82±12º to 102±17º with an increase of PPy-C8F loading. This increase in water contact angle directly correlates with the shape of the LM, with higher contact angles giving more spherical LMs. Furthermore, the broadband light absorption properties of the PPy coating was used to control evaporation rate of the enclosed water phase on demand by irradiation with a near infrared laser. The evaporation rate could be finely controlled by the thickness of the PPy-C8F shell of the particles stabilizing the liquid marbles.

Synthesis of hydrophobic polyanilines as a light-responsive liquid marble stabilizer

Hydrophobic and electrically conductive polyanilines were synthesized by single-step aqueous chemical oxidative polymerization in the presence of a perfluoroalkyl dopant, heptadecafluorooctane sulfonic acid. The resulting polyanilines were extensively characterized with respect to their morphology, surface/bulk chemical composition, wettability by water, (photo)thermal properties and conductivity. Scanning electron microscopy indicated that the polyanilines consisted of flocs of primary particles with sizes from submicrometer to a few hundreds of micrometers. Contact angle measurement and X-ray photoelectron spectroscopy confirmed the presence of perfluoroalkyl dopant on the surface of the dried polyanilines, which led to a water-repellent character. The conductivity of the pressed pellets increased from 3.2 × 10−3 S cm−1 to 1.4 S cm−1 as the dopant concentration used in the polymerization was increased, and the conductivities were higher than that of polyaniline synthesized in the absence of perfluoroalkyl dopant. The resulting polyaniline powder was able to function as a liquid marble stabilizer with photothermal properties. The liquid marble exhibited locomotion due to Marangoni propulsion on a planar water surface under irradiation with a near-infrared laser, and its transfer from water to solid surfaces was also achieved. The liquid marbles could be disrupted via an external stimulus to release their internal contents.

Immobilized metal affinity chromatography on collapsed Langmuir-Blodgett iron(III) stearate films and iron(III) oxide nanoparticles for bottom-up phosphoproteomics

Phosphorylation is the enzymatic reaction of site-specific phosphate transfer from energy-rich donors to the side chains of serine, threonine, tyrosine, and histidine residues in proteins. In living cells, reversible phosphorylation underlies a universal mechanism of intracellular signal transduction. In this context, analysis of the phosphoproteome is a prerequisite to better understand the cellular regulatory networks. Conventionally, due to the low contents of signaling proteins, selective enrichment of proteolytic phosphopeptides by immobilized metal affinity chromatography (IMAC) is performed prior to their LC–MS or -MS/MS analysis. Unfortunately, this technique still suffers from low selectivity and compromised analyte recoveries. To overcome these limitations, we propose IMAC systems comprising stationary phases based on collapsed Langmuir-Blodgett films of iron(III) stearate (FF) or iron(III) oxide nanoparticles (FO) and mobile phases relying on ammonia, piperidine and heptadecafluorooctanesulfonic acid (PFOS). Experiments with model phosphopeptides and phosphoprotein tryptic digests showed superior binding capacity, selectivity and recovery for both systems in comparison to the existing commercial analogs. As evidenced by LC–MS/MS analysis of the HeLa phosphoproteome, these features of the phases resulted in increased phosphoproteome coverage in comparison to the analogous commercially available phases, indicating that our IMAC protocol is a promising chromatographic tool for in-depth phosphoproteomic research.

Abnormalities in eelpout Zoarces viviparus upon chemical exposure

Elevated frequencies of abnormal embryos in female eelpout Zoarces viviparus have been demonstrated in Danish, Swedish and German monitoring programmes at certain geographic locations with high levels of anthropogenic input. Pollutants present in areas with high malformation frequencies were selected and tested in a controlled laboratory experiment for their potential to induce abnormalities among eelpout embryos upon injection into pregnant eelpout. Tributyltin, 2,3,7,8-tetrachlorodibenzo-p-dioxin, pyrene, nonylphenol, 2,2′,4,4′-tetrabromophenylether and heptadecafluorooctanesulfonic acid were tested, either individually or combined. Generally, the chemicals were transferred to eggs and/or embryos. Some of the exposures increased the proportion of broods with more than 10% abnormal or 5% malformed embryos, although the average percentages of abnormal development were not affected. Spinal, cranial and eye deformities were evident, similarly to what is seen in nature. Some of the exposures resulted in increased percentages of females with as well a low reproductive capacity as embryos with a low condition index.

Inhibition of cellular efflux pumps involved in multi xenobiotic resistance (MXR) in echinoid larvae as a possible mode of action for increased ecotoxicological risk of mixtures

In marine organisms the multi xenobiotic resistance (MXR) mechanism via e.g. P-glycoprotein (P-gp) and multidrug resistance-associated protein (MRP) is an important first line of defense against contaminants by pumping contaminants out of the cells. If compounds would impair the MXR mechanism, this could result in increased intracellular levels of other compounds, thereby potentiating their toxicity. A calcein-AM based larval cellular efflux pump inhibition assay (CEPIA) was developed for echinoid (Psammechinus miliaris) larvae and applied for several contaminants. The larval CEPIA revealed that triclosan (TCS) and the nanoparticles P-85(®) (P-85) were 124 and 155× more potent inhibitors (IC(50) 0.5 ± 0.05 and 0.4 ± 0.1 μM, respectively) of efflux pumps than the model inhibitor Verapamil (VER). PFOS (heptadecafluorooctane sulfonic acid) and pentachlorophenol also were more potent than VER, 24 and 5×, respectively. Bisphenol A and o,p'-dichlorodiphenyltrichloroethane (o,p'-DDT) inhibited efflux pumps with a potency 3× greater than VER. In a 48 h early life stage bioassay with P. miliaris, exposure to a non-lethal concentration of the inhibitors TCS, VER, the model MRP inhibitor MK-571, the nanoparticles P-85 and the model P-gp inhibitor PSC-833, increased the toxicity of the toxic model substrate for efflux pumps vinblastine by a factor of 2, 4, 4, 8 and 16, respectively. Our findings show that several contaminants accumulating in the marine environment inhibit cellular efflux pumps, which could potentiate toxic effects of efflux pumps substrates.

Early life developmental effects of marine persistent organic pollutants on the sea urchin Psammechinus miliaris

A new 16-day echinoid early life stage (ELS) bioassay was developed to allow for prolonged observation of possible adverse effects during embryogenesis and larval development of the sea urchin Psammechinus miliaris. Subsequently, the newly developed bioassay was applied to study the effects of key marine persistent organic pollutants (POPs). Mortality, morphological abnormalities and larval development stages were quantified at specific time points during the 16-day experimental period. In contrast to amphibians and fish, P. miliaris early life development was not sensitive to dioxin-like toxicity in the prolonged early life stage test. Triclosan (TCS) levels higher than 500 nM were acutely toxic during embryo development. Morphological abnormalities were induced at concentrations higher than 50 nM hexabromocyclododecane (HBCD) and 1000 nM tetrabromobisphenol A (TBBPA). Larval development was delayed above 25 nM HBCD and 500 nM TBBPA. Heptadecafluorooctane sulfonic acid (PFOS) exposure slightly accelerated larval development at 9 days post-fertilization (dpf). However, the accelerated development was no longer observed at the end of the test period (16 dpf). The newly developed 16-day echinoid ELS bioassay proved to be sensitive to toxic effects of POPs that can be monitored for individual echinoid larvae. The most sensitive and dose related endpoint was the number of developmental penalty points. By manipulation of the housing conditions, the reproductive season could be extended from 3 to 9 months per year and the ELS experiments could be performed in artificial sea water as well.

Study of Proton Conductivity of Triazole-Based Electrolytes for High Temperature Fuel Cell Applications

4,5-Dicyano-1H-[1,2,3]-Triazole (DCTz) is a possible water replacement for proton transport in high temperature polymer electrolyte membranes since it exhibits a favorable proton affinity. In this study, some properties of DCTz doped with Trifluoromethanesulfonic Acid (TFMSA) and Heptadecafluorooctanesulfonic acid (C8HO3F17S-HDSA) are investigated. Thermal analysis as well as FTIR data indicated the formation of the salts. After proving to be stable up to 140°C, DCTz, DCTz_TFMSA and DCTz_HDSA salts were formed into membranes in a Polyacrylonitrile (PAN) polymeric binder. Thermogravimetric analysis (TGA) showed that adding the acid increases the stability of the membranes. Electrochemical measurements showed that the acid loading increases the conductivity of these polymeric membranes. Thus, a DCTZ_TFMSA doped PAN membrane has higher conductivity than a DCTZ doped PAN membrane over a temperature range of 20°C to 160°C at low relative humidity (RH). Similarly, increasing the weight % of DCTz_TFMSA in PAN membranes leads to an improved conductivity by an order of magnitude.

Characterization and Control of the Wettability of Conducting Polymer Thin Films

AbstractThe wettability of electrochemically deposited conducting polymer films is highly dependent on several parameters including the deposition conditions, the dopant, and the roughness of the working electrode. To produce superhydrophobic surfaces, one must be able to control the micro and nanostructure of the film. In this study, a template-free method of producing superhydrophobic (water contact angle of 154°) polypyrrole films was demonstrated. The polypyrrole was doped with the low surface-energy heptadecafluorooctanesulfonic acid and had microstructures with nanometer-scale roughness. The microstructures served to increase the roughness of the film and amplify the hydrophobicity of the surface. It is also of interest to be able to dynamically adjust the wettability of a polypyrrole surface after deposition. Applications of this functionality include microfluidics, self-cleaning surfaces, liquid lenses, and smart textiles. By oxidizing or reducing a polypyrrole film, one can change the surface morphology as well as the chemical composition, and control the wettability of the surface. This study characterizes the electrochemically-induced changes in surface energy of polypyrrole. The relationship between applied voltage, charge transferred, surface roughness, and water contact angle was investigated. Upon reduction, the polypyrrole film was switched to a superhydrophilic state and the maximum change in contact angle was observed to be 154°. Surface wettability was found to be not fully reversible, with some hysteresis occurring after the first electrochemical cycle.

Heptadecafluorooctanesulfonic Acid (C8F17SO3H) Catalyzed Intramolecular Hydroamination of Olefinic Sulfonamides in Fluorous Biphase System (FBS).

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Light-induced degradation of perfluorocarboxylic acids in the presence of titanium dioxide

The UV-photon-induced degradation of heptafluorobutanoic acid was investigated in acidic aqueous solutions in the presence of titanium dioxide. Heptafluorobutanoic acid could be degraded with this photocatalyst in a light-induced reaction generating carbon dioxide and fluoride anions. Carbon dioxide evolution in a significant amount occurred only in the presence of molecular oxygen and the photocatalyst. The light-induced degradation of trifluoroacetic acid, pentafluoropropanoic acid, nonafluorobutanoic acid, pentadecafluorooctanoic acid, nonafluorobutanesulfonic acid, and heptadecafluorooctanesulfonic acid in the presence of titanium dioxide was also studied. The perfluorocarboxylic acids under investigation are degraded to generate CO(2) and fluoride anions while both perfluorinated sulfonic acids are persistent under the experimental conditions employed in this study. For all compounds photonic efficiencies of the mineralization reaction were estimated to be smaller than 1x10(-5). To increase the photocatalytic activity mixed systems containing homogeneous phosphotungstic acid and heterogeneous titanium dioxide catalysts were also investigated. In the mixtures of these two photocatalysts, the formation rate of CO(2) increased with illumination time.

Heptadecafluorooctanesulfonic acid (C 8F 17SO 3H) catalyzed intramolecular hydroamination of olefinic sulfonamides in fluorous biphase system (FBS)

A practical, efficient, and environmentally benign intramolecular hydroamination of olefinic sulfonamides was carried out in fluorous biphase system (FBS) using commercially available heptadecafluorooctanesulfonic acid (C 8F 17SO 3H) as a catalyst and perfluorodecaline (C 10F 18, cis- and trans- mixture) as a fluorous solvent to produce the corresponding cyclic products in good yields. The Brønsted acid of C 8F 17SO 3H is easily recovered and recycled at least five times.

Heptadecafluorooctanesulfonic acid catalyzed ring opening reactions of methylenecyclopropanes with aromatic amines, sulfonamides and alcohols in supercritical carbon dioxide

The ring opening reactions of methylenecyclopropanes (MCPs) with ArNH2, RSO2NH2 and alcohols can be carried out in scCO2 in the presence of heptadecafluorooctanesulfonic acid which offer a way to synthesize homoallylic amines, sulfonamides and ethers in environmentally benign conditions.

Effect of Mobile Phase Components on the Separation of Polypeptides Using Carbon Dioxide-Based Mobile Phases

The effect of mobile phase modifier and additive on the chromatographic properties of various small polypeptides was explored under subcritical conditions. A polymeric column was used to separate various enkephalin analogs, bradykinin, and oxytocin using a carbon dioxide-based mobile phase with either an ethanol or a 2-methoxyethanol modifier. The role of the modifier was found to be secondary to that of the mobile phase additive. As progressively stronger acidic mobile phase additives were used, the peak profiles of the various polypeptides improved and retention decreased. Heptadecafluorooctanesulfonic acid was found to be the most useful additive for these types of solutes under near-critical conditions, while the potassium salt of heptadecafluorooctanesulfonic acid failed to elute any of the polypeptides. At low temperatures, pressure gradients with a carbon dioxide/ethanol/heptadecafluorooctanesulfonic acid ternary mobile phase produced reasonably good peak profiles with the polymeric column.

Effect of Mobile Phase Components on the Separation of Polypeptides Using Carbon Dioxide-Based Mobile Phases

The effect of mobile phase modifier and additive on the chromatographic properties of various small polypeptides was explored under subcritical conditions. A polymeric column was used to separate various enkephalin analogs, bradykinin, and oxytocin using a carbon dioxide-based mobile phase with either an ethanol or a 2-methoxyethanol modifier. The role of the modifier was found to be secondary to that of the mobile phase additive. As progressively stronger acidic mobile phase additives were used, the peak profiles of the various polypeptides improved and retention decreased. Heptadecafluorooctanesulfonic acid was found to be the most useful additive for these types of solutes under near-critical conditions, while the potassium salt of heptadecafluorooctanesulfonic acid failed to elute any of the polypeptides. At low temperatures, pressure gradients with a carbon dioxide/ethanol/heptadecafluorooctanesulfonic acid ternary mobile phase produced reasonably good peak profiles with the polymeric column.

8 - Contraception for the Male: Problems with Progress

Elevated frequencies of abnormal embryos in female eelpout Zoarces viviparus have been demonstrated in Danish, Swedish and German monitoring programmes at certain geographic locations with high levels of anthropogenic input. Pollutants present in areas with high malformation frequencies were selected and tested in a controlled laboratory experiment for their potential to induce abnormalities among eelpout embryos upon injection into pregnant eelpout. Tributyltin, 2,3,7,8-tetrachlorodibenzo-p-dioxin, pyrene, nonylphenol, 2,2′,4,4′-tetrabromophenylether and heptadecafluorooctanesulfonic acid were tested, either individually or combined. Generally, the chemicals were transferred to eggs and/or embryos. Some of the exposures increased the proportion of broods with more than 10% abnormal or 5% malformed embryos, although the average percentages of abnormal development were not affected. Spinal, cranial and eye deformities were evident, similarly to what is seen in nature. Some of the exposures resulted in increased percentages of females with as well a low reproductive capacity as embryos with a low condition index.