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The proton activity term is typically ignored in the Nernst equation because of the definition of the unit activity of protons within catalyst layers in proton-exchange membrane fuel cells although the relative humidities of an anode (RHA) and a cathode (RHC) can be different. Herein, we investigate the effect of proton activity on the open-circuit voltage (OCV) of a H2/H2 cell by individually controlling RHA and RHC at ≤30%. The OCV was thermodynamically estimated by applying the correlations of the RH and water uptake of a Nafion® membrane. The OCV experimentally increased with an increase in the humidity difference: the highest OCV of 77 mV was observed at RHA 30% and RHC 0%. The electro-osmotic coefficient (ξ) was calculated and found to be 0.73 at 5%-30% RHC and 30% RHA. The kinetic current (i k ) of the oxygen-reduction reaction was measured by the rotating disk electrode method to verify the influence of proton activity (a H+ ). i k was described as i k ∝ a H+ -β , with β values of 0.29 and 0.45 for H2SO4 and CF3SO3H, respectively, at 0.9 V. The results demonstrate that for the dry operation of fuel cells, especially for heavy-duty applications, proton activity effects within ionomers must be considered.

Polymer -electrolyte-fuel-cell open-circuit voltages (OCVs) are exactly defined by equation (1), where cathode and anode proton activities [(aH+)cathode and (aH+)anode, respectively] usually are identical, so the third term in the right-hand side of equation (2) is ignored. OCV=E0+RT/2F*ln(a1/2 O2*(a2 H+)cathode/aH2O)-RT/2F*ln((a2 H+)anode/aH2) (1) =E0+RT/2F*ln(a1/2 O2*aH2/aH2O)+RT/2F*ln((a2 H+)cathode/(a2 H+)anode) (2) Water vapor pressure is a colligative property that fundamentally correlates to electrolyte concentrations in aqueous solutions. Proton activity is a function of acid concentration, such as pH, when electrolytes are acids. In polymer-electrolyte membranes, water vapor pressure and acid concentration are understood as relative humidity (RH) and water uptake (λ), respectively, where λ represents number of water molecules per sulfonic acid molecule. Several investigations have reported the relationship between RH and λ, meaning that proton activities and associated water uptakes are intimately related to RH. In actual fuel cell operation, cathode RH is determined by ambient-atmosphere and/or humidifier RH(s), and anode RH depends on hydrogen-circulator RH. Therefore, RH is not always identical at both electrodes, and the difference between electrode RHs is considerable during dry operation of polymer electrolyte fuel cells. Therefore, the third term in the right-hand side of equation (2) may be significant for dry operation. We measured OCVs when hydrogen was supplied to both electrodes at 80°C. One electrode (A) was fixed at 30% RH, while RH at the other electrode (B) was varied (0, 5, 10, 20, and 30%). Measured OCVs varied from 0 to 75 mV. For fuel cell tests, electrode A was supplied with hydrogen at 30% RH; electrode B, oxygen at 0, 5, 10, 20, and 30% RH. OCVs deviated from that measured when RH at electrode B was 30%, increasing from 0 to 60 mV with decreasing RH at electrode B. Results are also shown in Figure 1. Proton activities of both electrodes were thermodynamically calculated. The Gibbs–Duhem relation was applied to obtain molar Gibbs free energies of water and sulfonic acid, and proton activity coefficient was calculated using the Gibbs free energy of sulfonic acid and the relationship between RH and λ1–4, assuming that protons and sulfonic anions show identical ionic-activity coefficients. OCVs were estimated using the third term in the right-hand side of equation (2). Results are shown in Figure 1. Fuel-cell current–voltage performance was poor when RHs at the anode and cathode were 30 and 20%, respectively. To determine kinetic current, we measured the oxygen-reduction reaction (ORR) using a rotating-disk electrode (RDE) in concentrated-acid aqueous solutions, which modeled catalyst-layer ionomers. Kinetic currents decreased with acid concentrations. References T. A. Zawodzinski, Jr., C. Derouin, S. Radzinski, R. J. Sherman, V. T. Smith, T. E. Springer and S. Gottesfeld , J. Electrochem. Soc., 140,1041 (1993) P. K. Das and A. Z. Weber, Proceedings of the ASME 2013 11th Fuel Cell Science, Engineering and Technology Conference, Fuel Cell 18010 (2013) V. A. Sethuraman, J. W. Weidner, A. T. Haug, S. Motupally,b and L. V. Protsailo, J. Electrochem. Soc., 155, B50 (2008) A. Kusoglu and A. Z. Weber, Chem. Rev., 117, 987 (2017) Figure 1

SUMMARY: Morphology, phylogeny and azaspiracid (AZA) production of a strain of Amphidoma languida isolated from the subtropical Mexican Pacific were examined. Scanning electron microscopy showed the thecal plate arrangement of Am. languida from Mexico as Po, cp, X, 6′, 6′′, 6C, 5S, 6′′′, 2′′′′, with the prominent apical pore complex, the ventral pore on the anterior of the 1′ plate near the suture to the 6′ plate, and the antapical pore on the 2′′′′ plate, which are congruent with those of Am. languida reported from the Atlantic. The ventral depression was occasionally observed on the anterior end of Sa plate. Cells had a dinokaryotic nucleus positioned in the posterior part of the cell and parietal yellowish chloroplasts with a spherical pyrenoid in the episome. Transmission electron microscopy showed crystalline vesicles and tubular cytoplasmic invaginations in the pyrenoid, which resembled those reported from the most related non‐toxigenic species Amphidoma fulgens. The intracellular components, different from Am. fulgens, were oil droplets and lipid‐associated membranous structures. AZA‐2 was detected from the strain by liquid chromatography‐tandem mass spectrometry with a cell quota of 30.9 fg cell−1. Three other AZA‐related compounds were also detected. This is the first report of AZA‐producing Am. languida in the Pacific Ocean. [ABSTRACT FROM AUTHOR]

Introduction: Several fluorescent proteins (FPs) and chromoproteins (CPs) are present in anthozoans and play possible roles in photoprotection. Coral tissues in massive corals often display discoloration accompanied by inflammation. Incidences of the pink pigmentation response (PPR) in massive Porites, described as inflammatory pink lesions of different shapes and sizes, has recently increased worldwide. FPs are reported to be present in PPR lesions, wherein a red fluorescent protein (RFP) appears to play a role in reducing reactive oxygen species. However, to date, the biochemical characterization and possible roles of the pigments involved are poorly understood. The present study aimed to identify and characterize the proteins responsible for pink discoloration in massive Porites colonies displaying PPRs, as well as to assess the differential distribution of pigments and the antioxidant properties of pigmented areas. Method: CPs were extracted from PPR lesions using gel-filtration chromatography and identified via genetic analysis using liquid chromatography-tandem mass spectrometry. The coexistence of CPs and RFP in coral tissues was assessed using microscopic observation. Photosynthetic antivity and hydrogen peroxide-scavenging activitiy were measured to assess coral stress conditions. Results: The present study revealed that the same CP (plut2.m8.16902.m1) isolated from massive Porites was present in both the pink spot and patch morphologies of the PPR. CPs were also found to coexist with RFP in coral tissues that manifested a PPR, with a differential distribution (coenosarc or tip of polyps’ tentacles). High hydrogen peroxide-scavenging rates were found in tissues affected by PPR. Discussion and Conclusion: The coexistence of CPs and RFP suggests their possible differential role in coral immunity. CPs, which are specifically expressed in PPR lesions, may serve as an antioxidant in the affected coral tissue. Overall, this study provides new knowledge to our understanding of the role of CPs in coral immunity. [ABSTRACT FROM AUTHOR]