Synthesis of Sulfonated Poly(Arylene Ether Sulfone)s Containing Aliphatic Moieties for Effective Membrane Electrode Assembly Fabrication by Low-Temperature Decal Transfer Methods.

The purpose of this study was to investigate the effect of the aliphatic moiety in the sulfonated poly(arylene ether sulfone) (SPAES) backbone. A new monomer (4,4'-dihydroxy-1,6-diphenoxyhexane) was synthesized and polymerized with other monomers to obtain partially alkylated SPAESs. According to differential scanning calorimetry analysis, the glass transition temperature (Tg) of these polymers ranged from 85 to 90 °C, which is 100 °C lower than that of the fully aromatic SPAES. Due to the low Tg values obtained for the partially alkylated SPAESs, it was possible to prepare a hydrocarbon electrolyte membrane-based membrane electrode assembly (MEA) with Nafion® binder in the electrode through the use of a decal transfer method, which is the most commercially suitable system to obtain an MEA of proton exchange membrane fuel cells (PEMFCs). A single cell prepared using this partially alkylated SPAES as an electrolyte membrane exhibited a peak power density of 539 mW cm-2.

Helicity Modulation Improves the Selectivity of Antimicrobial Peptoids.

The modulation of conformational flexibility in antimicrobial peptides (AMPs) has been investigated as a strategy to improve their efficacy against bacterial pathogens while reducing their toxicity. Here, we synthesized a library of helicity-modulated antimicrobial peptoids by the position-specific incorporation of helix-inducing monomers. The peptoids displayed minimal variations in hydrophobicity, which permitted the specific assessment of the effect of conformational differences on antimicrobial activity and selectivity. Among the moderately helical peptoids, the most dramatic increase in selectivity was observed in peptoid 17, providing more than a 20-fold increase compared to fully helical peptoid 1. Peptoid 17 had potent broad-spectrum antimicrobial activity that included clinically isolated multi-drug-resistant pathogens. Compared to pexiganan AMP, 17 showed superior metabolic stability, which could potentially reduce the dosage needed, alleviating toxicity. Dye-uptake assays and high-resolution imaging revealed that the antimicrobial activity of 17 was, as with many AMPs, mainly due to membrane disruption. However, the high selectivity of 17 reflected its unique conformational characteristics, with differential interactions between bacterial and erythrocyte membranes. Our results suggest a way to distinguish different membrane compositions solely by helicity modulation, thereby improving the selectivity toward bacterial cells with the maintenance of potent and broad-spectrum activity.

BODIPY-Based Conjugated Polymers for Use as Dopant-Free Hole Transporting Materials for Durable Perovskite Solar Cells: Selective Tuning of HOMO/LUMO Levels.

Recently, perovskite solar cells (PSCs) have emerged as an excellent photovoltaic device owing to the outstanding power conversion efficiency (PCE). Nevertheless, device instability remains a critical issue in this field. To overcome device instability without deteriorating PCE, dopant-free hole transporting materials (HTMs) are needed to separate the air-sensitive perovskite layer from extrinsic factors, which induce its degradation. Herein, we developed novel conjugate polymers of benzo[1,2- b:4,5- b']dithiophene (BDT) and 4,4-difluoro-4-bora-3 a,4 a-diaza- s-indacene (BODIPY) for use as HTMs without dopants. The pBDT-BODIPY polymer allows individual "dialing" of the highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO) levels with small modifications to the molecular structure, enabling study of the impact of the frontier molecular orbital on PSC performance. Different alkyl chains on BDT can minutely adjust the HOMO level, and meso-substituents on BODIPYs can selectively set the LUMO level of the resulting polymers. Application of BODIPY-containing polymer into the perovskite solar cell as an HTM leads to a high PCE value (16.02%) and exceptional solar cell stability shown by the fact that over 80% of its original PCE value was maintained after 10 days under ambient air conditions.

D-A-D-type narrow-bandgap small-molecule photovoltaic donors: pre-synthesis virtual screening using density functional theory.

A new series of D-A-D-type small-molecule photovoltaic donors are designed and virtually screened before synthesis using time-dependent density functional theory calculations carefully validated against various polymeric and molecular donors. In this series of new design, benzodithiophene is kept as D to achieve the optimum highest-occupied molecular orbital energy level, while thienopyrroledione is initially chosen as A but later replaced by difluorinated benzodiathiazole or its selenide derivative to achieve the optimum band gap. The D-A-D core is end-capped by pyridone units which could not only enhance their self-assembly via hydrogen bonds but also play a role as an acceptor (A') to form an extended A'-D-A-D-A' small-molecule donor.