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This paper presents a study of designing phase-specific and -mixed Ir−Ru−Mn trimetallic electrocatalysts with enhanced performance. By changing the content of Ru, the alloy electrocatalyst evolved from a face-centered tetragonal (fct) phase to a mixture of fct and hexagonal close-packed (hcp) phases and finally to the hcp phase. Among these trimetallic systems, the hcp-phase Ir0.23Ru0.20Mn0.57 electrocatalyst (Ru/Ir = 0.47:0.53) delivered the best performance toward the oxygen evolution reaction (OER), achieving an overpotential of 226 mV at 10 mA cm−2 and a Tafel slope of ∼46.8 mV dec−1. Interestingly, this low-Ir hcp-phase catalyst maintained stable operation for >57 h at a current density of 100 mA cm−2 in 0.1 M HClO4, whereas the Ir-rich fct-phase counterpart (Ir0.35Ru0.07Mn0.58) degraded within 22 h under identical conditions. Potentiodynamic polarization curve study indicated that oxidative dissolution is the dominant degradation pathway, and the structural characterizations indicated that the hcp-phase alloy remained intact, while rutile-type IrRuMnOx oxide was formed for the fct-phase alloy electrocatalyst. These results underscore the effect of the crystal phase on OER durability of the electrocatalyst and point to a design strategy for improving the durability of OER electrocatalysts without increasing the Ir content.more » « less
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Abstract Heterologous expression of polyketide synthase (PKS) genes inEscherichia colihas enabled the production of various valuable natural and synthetic products. However, the limited availability of malonyl-CoA (M-CoA) inE. coliremains a substantial impediment to high-titer polyketide production. Here we address this limitation by disrupting the native M-CoA biosynthetic pathway and introducing an orthogonal pathway comprising a malonate transporter and M-CoA ligase, enabling efficient M-CoA biosynthesis under malonate supplementation. This approach substantially increases M-CoA levels, enhancing fatty acid and polyketide titers while reducing the promiscuous activity of PKSs toward undesired acyl-CoA substrates. Subsequent adaptive laboratory evolution of these strains provides insights into M-CoA regulation and identifies mutations that further boost M-CoA and polyketide production. This strategy improvesE. colias a host for polyketide biosynthesis and advances understanding of M-CoA metabolism in microbial systems.more » « less
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Abstract Temperature and water stress are important factors limiting the gross primary productivity (GPP) in terrestrial ecosystems, yet the extent of their influence across ecosystems remains uncertain. This study examines how surface air temperature, soil water availability (SWA) and vapor pressure deficit (VPD) influence ecosystem light use efficiency (LUE), a critical metric for assessing GPP, across different ecosystems and climatic zones at 80 flux tower sites based on in situ measurements and data assimilation products. Results indicate that LUE increases with temperature in spring, with higher correlation coefficients in colder regions (0.79–0.82) than in warmer regions (0.68–0.78). LUE reaches a plateau earlier in the season in warmer regions. LUE variations in summer are mainly driven by SWA, exhibiting a positive correlation indicative of a water‐limited regime. The relationship between the daily LUE and daytime temperature shows a clear seasonal hysteresis at many sites, with a higher LUE in spring than in fall under the same temperature, likely resulting from younger leaves being more efficient in photosynthesis. Drought stress influences LUE through SWA in all ranges of water availability; VPD variation under moderate conditions does not have a clear influence on LUE, but extremely high VPD (exceeding the threshold of 1.6 kPa, often observed during extreme drought‐heat events) causes a dramatic reduction of LUE. Our findings provide insight into how ecosystem productivities respond to climate variability and how they may change under the influence of more frequent and severe heat and drought events projected for the future.more » « less
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