Continuous Flow Routes toward Designer Metal Nanocatalysts

Mono‐ and multimetallic nanoparticles (NPs) have diverse and tunable physicochemical properties that arise from their compositions as well as crystallite size and shape. The ability to control precisely the composition and structure of NPs through synthesis is central to achieving state‐of‐the‐art designer metal NPs for use as catalysts and electrocatalysts. However, a major limitation to the use of designer metal NPs as catalysts is the ability to scale their syntheses while maintaining structural precision. To address this challenge, continuous flow routes to metal NPs involving the use of droplet microreactors are being developed, providing the synthetic versatility necessary to achieve known and completely new nanostructures. This progress report outlines how the chemistry and process parameters of droplet microreactors can be used to achieve high performing nanocatalysts through control of NP composition, size, shape, and architecture and outlines directions toward previously unimaginable nanostructures.     

Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion

Carbon‐based heteroatom‐coordinated single‐atom catalysts (SACs) are promising candidates for energy‐related electrocatalysts because of their low‐cost, tunable catalytic activity/selectivity, and relatively homogeneous morphologies. Unique interactions between single metal sites and their surrounding coordination environments play a significant role in modulating the electronic structure of the metal centers, leading to unusual scaling relationships, new reaction mechanisms, and improved catalytic performance. This review summarizes recent advancements in engineering of the local coordination environment of SACs for improved electrocatalytic performance for several crucial energy‐convention electrochemical reactions: oxygen reduction reaction, hydrogen evolution reaction, oxygen evolution reaction, CO₂ reduction reaction, and nitrogen reduction reaction. Various engineering strategies including heteroatom‐doping, changing the location of SACs on their support, introducing external ligands, and constructing dual metal sites are comprehensively discussed. The controllable synthetic methods and the activity enhancement mechanism of state‐of‐the‐art SACs are also highlighted. Recent achievements in the electronic modification of SACs will provide an understanding of the structure–activity relationship for the rational design of advanced electrocatalysts.     

Uncovering Atomic‐Scale Stability and Reactivity in Engineered Zinc Oxide Electrocatalysts for Controllable Syngas Production

In this study, scalable, flame spray synthesis is utilized to develop defective ZnO nanomaterials for the concurrent generation of H₂ and CO during electrochemical CO₂ reduction reactions (CO₂RR). The designed ZnO achieves an H₂/CO ratio of ≈1 with a large current density (j) of 40 mA cm^?2 during long‐term continuous reaction at a cell voltage of 2.6 V. Through in situ atomic pair distribution function analysis, the remarkable stability of these ZnO structures is explored, addressing the knowledge gap in understanding the dynamics of oxide catalysts during CO₂RR. Through optimization of synthesis conditions, ZnO facets are modulated which are shown to affect reaction selectivity, in agreement with theoretical calculations. These findings and insights on synthetic manipulation of active sites in defective metal‐oxides can be used as guidelines to develop active catalysts for syngas production for renewable power‐to‐X to generate a range of fuels and chemicals.     

Plant carbon allocation drives turnover of old soil organic matter in permafrost tundra soils

Carbon cycle feedbacks from permafrost ecosystems are expected to accelerate global climate change. Shifts in vegetation productivity and composition in permafrost regions could influence soil organic carbon (SOC) turnover rates via rhizosphere (root zone) priming effects (RPEs), but these processes are not currently accounted for in model predictions. We use a radiocarbon (bomb‐¹⁴C) approach to test for RPEs in two Arctic tall shrubs, alder (Alnus viridis (Chaix) DC.) and birch (Betula glandulosa Michx.), and in ericaceous heath tundra vegetation. We compare surface CO₂ efflux rates and ¹⁴C content between intact vegetation and plots in which below‐ground allocation of recent photosynthate was prevented by trenching and removal of above‐ground biomass. We show, for the first time, that recent photosynthate drives mineralization of older (>50 years old) SOC under birch shrubs and ericaceous heath tundra. By contrast, we find no evidence of RPEs in soils under alder. This is the first direct evidence from permafrost systems that vegetation influences SOC turnover through below‐ground C allocation. The vulnerability of SOC to decomposition in permafrost systems may therefore be directly linked to vegetation change, such that expansion of birch shrubs across the Arctic could increase decomposition of older SOC. Our results suggest that carbon cycle models that do not include RPEs risk underestimating the carbon cycle feedbacks associated with changing conditions in tundra regions.     

Exposure to noise pollution across North American passerines supports the noise filter hypothesis

The noise filter hypothesis predicts that species using higher sound frequencies should be more tolerant of noise pollution, because anthropogenic noise is more intense at low frequencies. Recent work analysed continental‐scale data on anthropogenic noise across the USA and found that passerine species inhabiting more noise‐polluted areas do not have higher peak song frequency but have more complex songs. However, this metric of song complexity is of ambiguous interpretation, because it can indicate either diverse syllables or a larger frequency bandwidth. In the latter case, the finding would support the noise filter hypothesis, because larger frequency bandwidths mean that more sound energy spreads to frequencies that are less masked by anthropogenic noise. We reanalysed how passerine song predicts exposure to noise using a more thorough dataset of acoustic song measurements, and showed that it is large frequency bandwidths, rather than diverse syllables, that predict the exposure of species to noise pollution. Given that larger bandwidths often encompass higher maximum frequencies, which are less masked by anthropogenic noise, our result suggests that tolerance to noise pollution might depend mostly on having the high‐frequency parts of song little masked by noise, thus preventing acoustic communication from going entirely unnoticed at long distances.     

Unexpected side effects in biocrust after treating non‐native plants using carbon addition

Carbon addition has been proposed as an alternative to herbicide and manual removal methods to treat non‐native plants and reduce non‐target effects of treatments (e.g. impacts on native plants; surface disturbance). On Mojave Desert pavement and biocrust substrates after experimental soil disturbance and carbon addition (1,263 g C/m² as sucrose), we observed declines in lichens and moss cover in sucrose‐treated plots. To further explore this unforeseen potential side effect of using carbon addition as a non‐native plant treatment, we conducted biocrust surveys 5 and 7 years after treatments, sampled surface soils to observe if treatments additionally affected soil filamentous cyanobacteria, and conducted laboratory trials testing the effects of different levels of sucrose on cyanobacteria and desert mosses. Sucrose addition to biocrust plots reduced lichen and moss cover by 33–78% and species richness by 40–80%. Sucrose reduced biocrust cover in biocrust plots to levels similarly detected in pavement plots (<1%). While cyanobacteria in the field did not appear to be affected by sucrose, laboratory tests showed negative effects of sucrose on both cyanobacteria and mosses. Cyanobacteria declined by 41% 1 month after exposure to 5.4 g C/m² equivalent solutions. We detected injury to photosynthesis in mosses after 96 hour exposure to 79–316 g C/m² equivalent solutions. Caution is warranted when using carbon addition, at least in the form and concentration of sucrose, as a treatment for reducing non‐native plants on sites where conserving biocrust is a goal.     

β‐amyloid model core peptides: Effects of hydrophobes and disulfides

The mechanism by which a disordered peptide nucleates and forms amyloid is incompletely understood. A central domain of β‐amyloid (Aβ21–30) has been proposed to have intrinsic structural propensities that guide the limited formation of structure in the process of fibrillization. In order to test this hypothesis, we examine several internal fragments of Aβ, and variants of these either cyclized or with an N‐terminal Cys. While Aβ21–30 and variants were always monomeric and unstructured (circular dichroism (CD) and nuclear magnetic resonance spectroscopy (NMRS)), we found that the addition of flanking hydrophobic residues in Aβ16–34 led to formation of typical amyloid fibrils. NMR showed no long‐range nuclear overhauser effect (nOes) in Aβ21–30, Aβ16–34, or their variants, however. Serial ¹H‐¹⁵N‐heteronuclear single quantum coherence spectroscopy, ¹H‐¹H nuclear overhauser effect spectroscopy, and ¹H‐¹H total correlational spectroscopy spectra were used to follow aggregation of Aβ16–34 and Cys‐Aβ16–34 at a site‐specific level. The addition of an N‐terminal Cys residue (in Cys‐Aβ16–34) increased the rate of fibrillization which was attributable to disulfide bond formation. We propose a scheme comparing the aggregation pathways for Aβ16–34 and Cys‐Aβ16–34, according to which Cys‐Aβ16–34 dimerizes, which accelerates fibril formation. In this context, cysteine residues form a focal point that guides fibrillization, a role which, in native peptides, can be assumed by heterogeneous nucleators of aggregation.     

Colonization history of Galapagos giant tortoises: Insights from mitogenomes support the progression rule

Galapagos giant tortoises (Chelonoidis spp.) are a group of large, long-lived reptiles that includes 14 species, 11 of which are extant and threatened by human activities and introductions of non-native species. Here, we evaluated the phylogenetic relationships of all extant and two extinct species (Chelonoidis abingdonii from the island of Pinta and Chelonoidis niger from the island of Floreana) using Bayesian and maximum likelihood analysis of complete or nearly complete mitochondrial genomes. We also provide an updated phylogeographic scenario of their colonization of the Galapagos Islands using chrono-phylogenetic and biogeographic approaches. The resulting phylogenetic trees show three major groups of species: one from the southern, central, and western Galapagos Islands; the second from the northwestern islands; and the third group from the northern, central, and eastern Galapagos Islands. The time-calibrated phylogenetic and ancestral area reconstructions generally align with the geologic ages of the islands. The divergence of the Galapagos giant tortoises from their South American ancestor likely occurred in the upper Miocene. Their diversification on the Galapagos adheres to the island progression rule, starting in the Pleistocene with the dispersal of the ancestral form from the two oldest islands (San Cristóbal and Española) to Santa Cruz, Santiago, and Pinta, followed by multiple colonizations from different sources within the archipelago. Our work provides an example of how to reconstruct the history of endangered taxa in spite of extinctions and human-mediated dispersal events and provides a framework for evaluating the contribution of colonization and in situ speciation to the diversity of other Galapagos lineages.     

UDP‐Api/UDP‐Xyl synthases affect plant development by controlling the content of UDP‐Api to regulate the RG‐II‐borate complex

Rhamnogalacturonan‐II (RG‐II) is structurally the most complex glycan in higher plants, containing 13 different sugars and 21 distinct glycosidic linkages. Two monomeric RG‐II molecules can form an RG‐II‐borate diester dimer through the two apiosyl (Api) residues of side chain A to regulate cross‐linking of pectin in the cell wall. But the relationship of Api biosynthesis and RG‐II dimer is still unclear. In this study we investigated the two homologous UDP‐D‐apiose/UDP‐D‐xylose synthases (AXSs) in Arabidopsis thaliana that synthesize UDP‐D‐apiose (UDP‐Api). Both AXSs are ubiquitously expressed, while AXS2 has higher overall expression than AXS1 in the tissues analyzed. The homozygous axs double mutant is lethal, while heterozygous axs1/+ axs2 and axs1 axs2/+ mutants display intermediate phenotypes. The axs1/+ axs2 mutant plants are unable to set seed and die. By contrast, the axs1 axs2/+ mutant plants exhibit loss of shoot and root apical dominance. UDP‐Api content in axs1 axs2/+ mutants is decreased by 83%. The cell wall of axs1 axs2/+ mutant plants is thicker and contains less RG‐II‐borate complex than wild‐type Col‐0 plants. Taken together, these results provide direct evidence of the importance of AXSs for UDP‐Api and RG‐II‐borate complex formation in plant growth and development.