A long-term record of early to mid-Paleozoic marine redox change

The extent to which Paleozoic oceans differed from Neoproterozoic oceans and the causal relationship between biological evolution and changing environmental conditions are heavily debated. Here, we report a nearly continuous record of seafloor redox change from the deep-water upper Cambrian to Middle Devonian Road River Group of Yukon, Canada. Bottom waters were largely anoxic in the Richardson trough during the entirety of Road River Group deposition, while independent evidence from iron speciation and Mo/U ratios show that the biogeochemical nature of anoxia changed through time. Both in Yukon and globally, Ordovician through Early Devonian anoxic waters were broadly ferruginous (nonsulfidic), with a transition toward more euxinic (sulfidic) conditions in the mid–Early Devonian (Pragian), coincident with the early diversification of vascular plants and disappearance of graptolites. This ~80-million-year interval of the Paleozoic characterized by widespread ferruginous bottom waters represents a persistence of Neoproterozoic-like marine redox conditions well into the Phanerozoic.

Selection of tobacco etch virus protease variants with enhanced oxidative stability for tag-removal in refolding of two disulfide-rich proteins

Tobacco etch virus protease (TEVp) is a powerful enzymatic reagent for removing fusion tag. In this work, we constructed nine TEVp variants with introducing one to three mutations of C19S, C110S and C130S into the soluble TEVp variant, TEVp5M. Using the C-terminal green fluorescent protein (GFP) variant reporter, all constructs showed different solubility levels among four E. coli strains. The TEVp5M containing the C110S and/or C130S mutations in the hyperoxic strain showed the enhanced the cleavage activity. Addition of dithiothreitol to the cultural medium increased the activity of certain constructs produced in the BL21(DE3), contrary to the added hydrogen peroxide, due to cytoplasmic redox change measured by the redox sensitive GFP construct. The more cysteine residues in the purified TEVp5M were modified specifically than those in the other variants. All purified constructs showed similar specific activities in the presence of 5 mM dithiothreitol. In the buffer containing the compounds to aid disulfide bond formation of the refolded protein, the double mutant TEVp5MC110S/C130S exhibited the highest cleavage efficiency. This variant was efficient for removing the fusion tag after refolding of cellulose-binding module tagged disulfide-rich proteins including bovine enteropeptidase and maize peroxidase absorbed on the regenerated amorphous cellulose.

Magnetostratigraphic evidence for post-depositional distortion of osmium isotopic records in pelagic clay and its implications for mineral flux estimates

Chemical stratigraphy is useful for dating deep-sea sediments, which sometimes lack radiometric or biostratigraphic constraints. Oxic pelagic clay contains Fe–Mn oxyhydroxides that can retain seawater 187Os/188Os values, and its age can be estimated by fitting the isotopic ratios to the seawater 187Os/188Os curve. On the other hand, the stability of Fe–Mn oxyhydroxides is sensitive to redox change, and it is not clear whether the original 187Os/188Os values are always preserved in sediments. However, due to the lack of independent age constraints, the reliability of 187Os/188Os ages of pelagic clay has never been tested. Here we report inconsistency between magnetostratigraphic and 187Os/188Os ages in pelagic clay around Minamitorishima Island. In a ~ 5-m-thick interval, previous studies correlated 187Os/188Os data to a brief (< 1 million years) isotopic excursion in the late Eocene. Paleomagnetic measurements revealed at least 12 polarity zones in the interval, indicating a > 2.9–6.9 million years duration. Quartz and feldspars content showed that while the paleomagnetic chronology gives reasonable eolian flux estimates, the 187Os/188Os chronology leads to unrealistically high values. These results suggest that the low 187Os/188Os signal has diffused from an original thin layer to the current ~ 5-m interval, causing an underestimate of the deposition duration. The preservation of the polarity patterns indicates that a mechanical mixing such as bioturbation cannot be the main process for the diffusion, so diagenetic redistribution of Fe–Mn oxyhydroxides and associated Os may be responsible. The paleomagnetic chronology presented here also demands reconsiderations of the timing, accumulation rate, and origins of the high content of rare-earth elements and yttrium in pelagic clay around Minamitorishima Island.

Ligand-Based H2 Transfer with Dihydrazonopyrrole Complexes of Nickel

Biology uses precise control over proton, electron, H-atom, or H₂ transfer to mediate challenging reactivity. While synthetic complexes have made incredible strides in replicating secondary coordination electron or proton donors, there are comparatively fewer examples of ligands that can mediate both proton and electron storage. Rarer still are ligands that can store full H₂ equivalents. Here we report a dihydrazonopyrrole Ni complex where an H₂ equivalent can be stored on the ligand periphery without any redox change at the metal center. This ligand-based storage of H₂ can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests a rate determining H₂ binding step followed by comparatively facile H–H scission to hydrogenate the ligand. This system is an unusual example where a synthetic system can mimic biology’s ability to mediate H₂ transfer via secondary coordination sphere-based processes.

Ligand-Based H2 Transfer with Dihydrazonopyrrole Complexes of Nickel

Biology uses precise control over proton, electron, H-atom, or H₂ transfer to mediate challenging reactivity. While synthetic complexes have made incredible strides in replicating secondary coordination electron or proton donors, there are comparatively fewer examples of ligands that can mediate both proton and electron storage. Rarer still are ligands that can store full H₂ equivalents. Here we report a dihydrazonopyrrole Ni complex where an H₂ equivalent can be stored on the ligand periphery without any redox change at the metal center. This ligand-based storage of H₂ can be leveraged for catalytic hydrogenations. Kinetic and computational analysis suggests a rate determining H₂ binding step followed by comparatively facile H–H scission to hydrogenate the ligand. This system is an unusual example where a synthetic system can mimic biology’s ability to mediate H₂ transfer via secondary coordination sphere-based processes.

The ferrocenium/ferrocene couple: a versatile redox switch

Woodward and co-workers in 1952 characterised the unique structural features of ferrocene (the first sandwich compound), demonstrated its aromatic nature and observed that on treatment with mild oxidising agents (aqueous Ag2SO4, p-benzoquinone in organic solvents) the orange solution of ferrocene (Fc) turned blue due to the formation of ferrocenium (Fc+). A few months later, the one-electron Fc/Fc+ redox change was characterised polarographically by Page and Wilkinson with E1/2 = 0.31 V vs SCE (0.56 V vs NHE) in ethanol/water 9:1. Since then ferrocene has become an icon of organometallic electrochemistry. Owing to the stability of its molecular framework, to the ease of functionalisation at the cyclopentadienyl rings and to the fast, reversible and kinetically uncomplicated Fc/Fc+ redox change, ferrocene has been used as a building block for the design of switchable functional systems. In this review, we will consider (1) electrochemical sensors for metal ions, anions and metal–anion pairs operating through the Fc/Fc+ redox change, (2) ferrocene-based redox switches of fluorescence and (3) cross-transport of electrons and anions through a liquid membrane mediated by lipophilic ferrocene derivatives. Graphic abstract