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The rectangular cyclobutadiene (CBD, C4H4) is a unique moiety for building nonbenzenoid polycyclic conjugated hydrocarbons with interesting electron‐accepting properties. Herein, the investigation on chemical reduction of several CBD‐containing polycyclic hydrocarbons with increasing conjugation length is reported: biphenylene (C12H8), dimethyl[2]naphthalene (C22H16), and tetramethyl‐dibenzo‐[3]phenylene (C30H22). The two‐step sequential reduction is first demonstrated by in situ spectroscopic investigation and then confirmed by the isolation of single crystals of the reduced products. The X‐ray crystallographic analysis reveals the formation of several mono‐ and doubly reduced products in solvent‐separated and complexed forms. The crystal structures for both neutral parents and corresponding reduced products unravel the changes in bond alternation in each ring of the fused systems. Density functional theory (DFT) and nucleus‐independent chemical shift (NICS) scan calculations reveal that the two‐electron addition reduces the aromatic character in the benzenoid rings but has minor influence on the antiaromatic CBD rings.more » « less
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ABSTRACT Cyanobacteria are foundational drivers of global nutrient cycling, with high intracellular iron (Fe) requirements. Fe is found at extremely low concentrations in aquatic systems, however, and the ways in which cyanobacteria take up Fe are largely unknown, especially the initial step in Fe transport across the outer membrane. Here, we identified one TonB protein and four TonB-dependent transporters (TBDTs) of the energy-requiring Fe acquisition system and six porins of the passive diffusion Fe uptake system in the model cyanobacterium Synechocystis sp. strain PCC 6803. The results experimentally demonstrated that TBDTs not only participated in organic ferri-siderophore uptake but also in inorganic free Fe (Fe′) acquisition. 55 Fe uptake rate measurements showed that a TBDT quadruple mutant acquired Fe at a lower rate than the wild type and lost nearly all ability to take up ferri-siderophores, indicating that TBDTs are critical for siderophore uptake. However, the mutant retained the ability to take up Fe′ at 42% of the wild-type Fe′ uptake rate, suggesting additional pathways of Fe′ acquisition besides TBDTs, likely by porins. Mutations in four of the six porin-encoding genes produced a low-Fe-sensitive phenotype, while a mutation in all six genes was lethal to cell survival. These diverse outer membrane Fe uptake pathways reflect cyanobacterial evolution and adaptation under a range of Fe regimes across aquatic systems. IMPORTANCE Cyanobacteria are globally important primary producers and contribute about 25% of global CO 2 fixation. Low Fe bioavailability in surface waters is thought to limit the primary productivity in as much as 40% of the global ocean. The Fe acquisition strategies that cyanobacteria have evolved to overcome Fe deficiency remain poorly characterized. We experimentally characterized the key players and the cooperative work mode of two Fe uptake pathways, including an active uptake pathway and a passive diffusion pathway in the model cyanobacterium Synechocystis sp. PCC 6803. Our finding proved that cyanobacteria use ferri-siderophore transporters to take up Fe′, and they shed light on the adaptive mechanisms of cyanobacteria to cope with widespread Fe deficiency across aquatic environments.more » « less
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Abstract Electronic textiles (e‐textiles) that combine the wearing comfort of textiles and the functionality of soft electronics are highly demanded in wearable applications. However, fabricating robust high‐performance stretchable e‐textiles with good abrasion resistance and high‐resolution aesthetic patterns for high‐throughput manufacturing and practical applications remains challenging. Herein, the authors report a new multifunctional e‐textile fabricated via screen printing of the water‐based silver fractal dendrites conductive ink. The as‐fabricated e‐textiles spray‐coated with the invisible waterproofing agent exhibit superior flexibility, water resistance, wearing comfort, air permeability, and abrasion resistance, achieving a low sheet resistance of 0.088 Ω sq−1, high stretchability of up to 154%, and excellent dynamic stability for over 1000 cyclic testing (ε = 100%). The printed e‐textiles can be explored as strain sensors and ultralow voltage‐driven Joule heaters driven for personalized thermal management. They finally demonstrate an integrated aesthetic smart clothing made of their multifunctional e‐textiles for human motion detection and body‐temperature management. The printed e‐textiles provide new opportunities for developing novel wearable electronics and smart clothing for future commercial applications.more » « less
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