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Thorp, Holden (Ed.)Ancestral metabolic processes involve the reversible oxidation of molecular hydrogen by hydrogenase. Extant hydrogenase enzymes are complex, comprising hundreds of amino acids and multiple cofactors. We designed a 13–amino acid nickel-binding peptide capable of robustly producing molecular hydrogen from protons under a wide variety of conditions. The peptide forms a di-nickel cluster structurally analogous to a Ni-Fe cluster in [NiFe] hydrogenase and the Ni-Ni cluster in acetyl-CoA synthase, two ancient, extant proteins central to metabolism. These experimental results demonstrate that modern enzymes, despite their enormous complexity, likely evolved from simple peptide precursors on early Earth.more » « less
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In the Equatorial Atlantic nitrogen availability is assumed to control phytoplankton dynamics. However, in situ measurements of phytoplankton physiology and productivity are surprisingly sparse in comparison with the North Atlantic. In addition to the formation of the Equatorial cold tongue in the boreal summer, tropical instability waves (TIWs) and related short-term processes may locally cause episodic events of enhanced nutrient supply to the euphotic layer. Here, we assess changes in phytoplankton photophysiology in response to such episodic events as well as short-term nutrient addition experiments using a pair of custom-built fluorometers that measure chlorophyll a (Chl a ) variable fluorescence and fluorescence lifetimes. The fluorometers were deployed during a transatlantic cruise along the Equator in the fall of 2019. We hypothesized that the Equatorial Atlantic is nitrogen-limited, with an increasing degree of limitation to the west where the cold tongue is not prominent, and that infrequent nitrate injection by TIW related processes are the primary source alleviating this limitation. We further hypothesized phytoplankton are well acclimated to the low levels of nitrogen, and once nitrogen is supplied, they can rapidly utilize it to stimulate growth and productivity. Across three TIW events encountered, we observed increased productivity and chlorophyll a concentration concurrent with a decreased photochemical conversion efficiency and overall photophysiological competency. Moreover, the observed decrease in photosynthetic turnover rates toward the western section suggested a 70% decrease in growth rates compared to their maximum values under nutrient-replete conditions. This decrease aligned with the increased growth rates observed following 24 h incubation with added nitrate in the western section. These results support our hypotheses that nitrogen is the limiting factor in the region and that phytoplankton are in a state of balanced growth, waiting to “body surf” waves of nutrients which fuel growth and productivity.more » « less
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Abstract The core metabolic reactions of life drive electrons through a class of redox protein enzymes, the oxidoreductases. The energetics of electron flow is determined by the redox potentials of organic and inorganic cofactors as tuned by the protein environment. Understanding how protein structure affects oxidation–reduction energetics is crucial for studying metabolism, creating bioelectronic systems, and tracing the history of biological energy utilization on Earth. We constructed ProtReDox (https://protein-redox-potential.web.app), a manually curated database of experimentally determined redox potentials. With over 500 measurements, we can begin to identify how proteins modulate oxidation–reduction energetics across the tree of life. By mapping redox potentials onto networks of oxidoreductase fold evolution, we can infer the evolution of electron transfer energetics over deep time. ProtReDox is designed to include user‐contributed submissions with the intention of making it a valuable resource for researchers in this field.more » « less
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