Aryl‐ether‐free anion‐exchange ionomers (AEIs) and membranes (AEMs) have become an important benchmark to address the insufficient durability and power‐density issues associated with AEM fuel cells (AEMFCs). Here, we present aliphatic chain‐containing poly(diphenyl‐terphenyl piperidinium) (PDTP) copolymers to reduce the phenyl content and adsorption of AEIs and to increase the mechanical properties of AEMs. Specifically, PDTP AEMs possess excellent mechanical properties (storage modulus>1800 MPa, tensile strength>70 MPa), H2 fuel‐barrier properties (<10 Barrer), good ion conductivity, and ex‐situ stability. Meanwhile, PDTP AEIs with low phenyl content and high‐water permeability display excellent peak power densities (PPDs). The present AEMFCs reach outstanding PPDs of 2.58 W cm−2 (>7.6 A cm−2 current density) and 1.38 W cm−2 at 80 °C in H2/O2 and H2/air, respectively, along with a specific power (PPD/catalyst loading) over 8 W mg−1, which is the highest record for Pt‐based AEMFCs so far.
Low-cost anion exchange membrane fuel cells have been investigated as a promising alternative to proton exchange membrane fuel cells for the last decade. The major barriers to the viability of anion exchange membrane fuel cells are their unsatisfactory key components—anion exchange ionomers and membranes. Here, we present a series of durable poly(fluorenyl aryl piperidinium) ionomers and membranes where the membranes possess high OH− conductivity of 208 mS cm−1 at 80 °C, low H2 permeability, excellent mechanical properties (84.5 MPa TS), and 2000 h ex-situ durability in 1 M NaOH at 80 °C, while the ionomers have high water vapor permeability and low phenyl adsorption. Based on our rational design of poly(fluorenyl aryl piperidinium) membranes and ionomers, we demonstrate alkaline fuel cell performances of 2.34 W cm−2 in H2-O2 and 1.25 W cm−2 in H2-air (CO2-free) at 80 °C. The present cells can be operated stably under a 0.2 A cm−2 current density for ~200 h.
Summary Numerous thiol-reactive compounds cause oxidative stress where cells counteract by activation of survival strategies regulated by thiol-based sensors. In Streptomyces coelicolor, a model actinomycete, a sigma/antisigma pair SigR/RsrA controls the response to thiol-oxidative stress. To unravel its full physiological functions, chromatin immuno-precipitation combined with sequence and transcript analyses were employed to identify 108 SigR target genes in S. coelicolor and to predict orthologous regulons across actinomycetes. In addition to reported genes for thiol homeostasis, protein degradation and ribosome modulation, 64 additional operons were identified suggesting new functions of this global regulator. We demonstrate that SigR maintains the level and activity of the housekeeping sigma factor HrdB during thiol-oxidative stress, a novel strategy for stress responses. We also found that SigR defends cells against UV and thiol-reactive damages, in which repair UvrA takes a part. Using a refined SigR-binding sequence model, SigR orthologues and their targets were predicted in 42 actinomycetes. This revealed a conserved core set of SigR targets to function for thiol homeostasis, protein quality control, possible modulation of transcription and translation, flavin-mediated redox reactions, and Fe-S delivery. The composition of the SigR regulon reveals a robust conserved physiological mechanism to deal with thiol-oxidative stress from bacteria to human.
With the increasing importance of electronic textiles as an ideal platform for wearable electronic devices, requirements for the development of functional electronic fibers with multilayered structures are increasing. In this paper, metal–polymer insulator–organic semiconductor (MIS) coaxial microfibers using the self‐organization of organic semiconductor:insulating polymer blends for weavable, fibriform organic field‐effect transistors (FETs) are demonstrated. A holistic process for MIS coaxial microfiber fabrication, including surface modification of gold microfiber thin‐film coating on the microfiber using a die‐coating system, and the self‐organization of organic semiconductor–insulator polymer blend is presented. Vertical phase‐separation of the organic semiconductor:insulating polymer blend film wrapping the metal microfibers provides a coaxial bilayer structure of gate dielectric (inside) and organic semiconductor (outside) with intimate interfacial contact. It is determined that the fibriform FETs based on MIS coaxial microfiber exhibit good charge carrier mobilities that approach the values of typical devices with planar substrate. It additionally exhibits electrical property uniformity over the entire fiber surface and improved bending durability. Fibriform organic FET embedded in a textile is demonstrated by weaving MIS coaxial microfibers with cotton and conducting threads, which verifies the feasibility of MIS coaxial microfiber for use in electronic textile applications.
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