Various states of water species in an anion exchange membrane characterized by Raman spectroscopy under controlled temperature and humidity.

Anion exchange membrane fuel cells (AEMFCs) hold the key to future mass commercialisation of fuel cell technology, even though currently, AEMFCs perform less optimally than proton exchange membrane fuel cells (PEMFCs). Unlike PEMFCs, AEMFCs have demonstrated the capability to operate independently of Pt group metal-based catalysts. Water characterization inside the membrane is one factor that significantly influences the performance of AEMFCs. In this paper, different water species inside an anion exchange membrane (AEM), QPAF-4, developed at the University of Yamanashi, were studied for the first time using micro-Raman spectroscopy. Spectra of pure water, alkaline solutions, and calculations based on density functional theory were used to identify the water species in the AEM. The OH stretching band was deconvoluted into nine unique Gaussian bands. All the hydrogen-bonded OH species increased steadily with increasing humidity, while the CH and non-H-bonded OH remained relatively constant. These results confirm the viability of micro-Raman spectroscopy in studying the various water-related species in AEMs. The availability of this technique is an essential prerequisite in improving the ionic conductivity and effectively solving the persisting durability challenge facing AEMFCs, thus hastening the possibility of mass commercialisation of fuel cells.

Toward the Creation of Induced Pluripotent Small (iPS) Molecules: Establishment of a Modular Synthetic Strategy for the Heronamide C-type Polyene Macrolactams and Their Conformational and Reactivity Analysis.

A highly modular synthetic strategy for the heronamide C-type polyene macrolactams was established by synthesizing 8-deoxyheronamide C (2). The developed strategy enabled not only the total synthesis of 8-deoxyheronamide C (2) but also the unified synthesis of four heronamide-like molecules named "heronamidoids" (5-8). Conformational and reactivity analysis of the heronamidoids clarified that (1) the C19 stereochemistry mainly affected the conformation of the amide linkage, resulting in the change of alignment of two polyene units and reactivity toward photochemical [6π + 6π] cycloaddition, and (2) the C8,C9-diol moiety is important for the conversion to the heronamide A-type skeleton from the heronamide C skeleton.

Design, Synthesis, and Antifungal Activity of 16,17-Dihydroheronamide C and ent-Heronamide C.

16,17-Dihydroheronamide C (8) and ent-heronamide C (ent-1) were designed as probes for the mode-of-action analysis of heronamide C (1). These molecules were synthesized by utilizing a highly modular strategy developed in the preceding paper. The evaluation of the antifungal activity of these compounds revealed the exceptional importance of the C16-C17 double bond for the antifungal activity of heronamide C and the existence of chiral recognition between heronamide C (1) and cell membrane components.

Coherent anti-Stokes Raman scattering spectroscopy system for observation of water molecules in anion exchange membrane.

Anion exchange membrane fuel cells (AEMFCs) provide one of the most feasible remedies to fuel cells' dependency on the dwindling Pt group catalysts. Nevertheless, AEMFCs still suffer reduced durability, which requires an in-depth understanding of their membranes. The low thermal endurance of the anion exchange membranes (AEMs) usually limits the direct application of powerful techniques, such as Raman spectroscopy. We sought to establish a system for coherent anti-Stokes Raman scattering (CARS) spectroscopy capable of taking measurements inside an AEM rapidly and accurately without photodamage. A 785 nm CARS system was newly developed to study the water species in an AEM (QPAF-4) located vertically in a fuel cell. From the results of water measurement in a QPAF-4 membrane, the OH-related region was deconvoluted into nine Gaussian peaks: Five H-bonded OH peaks, non-H-bonded OH, OH-, and two CH peaks. The H-bonded species increased with increasing relative humidity, but the other species remained constant. These results open unlimited possibilities for studying and comparing different AEMFCs, enabling more rapid technology optimization.

Operando Monitoring of Oxygen Drop in Catalyst Layers Accompanied by a Water Increase in Running Proton Exchange Membrane Fuel Cells.

Accurate understanding of internal phenomena and their feedback is intrinsically important for improving the performance and durability of proton exchange membrane fuel cells. The oxygen partial pressure (p(O2)) at 10 µm from the cathode catalyst layer (CL) in the gas diffusion layer was measured by using an optical fiber with an oxygen-sensitive dye applied to the apex, when the current density was abruptly increased. p(O2) decreased with increasing current density at constant air utilization. This decrease in oxygen partial pressure is attributed to the increased amount of water at the CL at the cathode due to the oxygen reduction reaction and electro-osmotic drag, as previously proposed. A shortage of oxygen in the CL for 1 s was also detected by using this p(O2) monitoring. These results are consistent with the previous results obtained by operando time-resolved measurements of the water distribution in the electrolyte membranes of a running fuel cell.