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Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence

Enantioselective electrocatalysis shows unique potential for the sustainable assembly of enantiomerically enriched molecules. This approach allows electro-oxidative C–H activation to be performed paired to the hydrogen evolution reaction. Recent progress has featured scarce transition metals with limited availability. Here we reveal that the earth-abundant 3d transition metals nickel and cobalt exhibit distinctive performance for enantioselective electrocatalysis with chemodivergent reactivity patterns. Enantioselective desymmetrizations of strained bicyclic alkenes were achieved through C–H annulations. A data-driven optimization of chiral N,O-bidentate salicyloxazoline-type ligands was crucial for enhancing enantioselectivity in nickel electrocatalysis. Notably, in the transition state of the enantio-determining step, secondary weak attractive ππ and CH–π interactions were identified, reflecting the informed adaptations in the ligand design. Detailed mechanistic investigations by experimental and computational studies revealed for the nickel electrocatalysis a C–N bond-forming reductive elimination from nickel(III) and for the cobalt electrocatalysis a C–C bond-forming nucleophilic addition from cobalt(III) as the product-determining steps.

Enantioselective synthesis of chiroplasmonic helicoidal nanoparticles by nanoconfinement in chiral dielectric shells

Helicoid metal nanoparticles with intrinsic chirality have unveiled tailorable properties and unlocked many chirality-related applications across various fields. Nevertheless, the existing strategies for enantioselective synthesis of helicoid metal nanoparticles have been predominantly limited to gold. Here, we demonstrate a robust and versatile strategy for the enantioselective synthesis of helicoid nanoparticles beyond gold, leveraging chiral nanoconfinement provided by chiral SiO2 or nanoshells. The chiral nanoconfinement strategy enables the decoupling of ligand-directed crystal growth from chiral induction, allowing for the independent tuning of these two critical aspects. As a result, this approach can not only facilitate the replication of chiral shapes from the chiral nanoshells but also allow the generation of alternative chiral shapes. By employing this approach, we demonstrate the enantioselective synthesis of helicoid Pt, Au@Pt, Au@Pd, Au@Ag, and Au@Cu nanoparticles. The chiroplasmonic properties of Pt- and Pd-based chiral nanoparticles have been discovered, and the inversion of chiroplasmonic properties of Ag-based chiral nanoparticles via facet control has been documented and theoretically explained. The chiral nanoconfinement strategy enriches the toolbox for creating chiral nanoparticles and supports their exploration in diverse applications.

Photo-assisted technologies for environmental remediation

Industrial processes can lead to air and water pollution, particularly from organic contaminants such as toluene and antibiotics, posing threats to human health. Photo-assisted chemical oxidation technologies leverage light energy to mineralize these contaminants. In this Review, we discuss the mechanisms and efficiencies of photo-assisted advanced oxidation processes for wastewater treatment and photothermal technologies for air purification. The integration of solar energy enhances degradation efficiency and reduces energy consumption, enabling more efficient remediation methods. We evaluate the technological aspects of photo-assisted technologies, such as photo-Fenton, photo-persulfate activation, photo-ozonation and photoelectrochemical oxidation, emphasizing their potential for practical applications. Finally, we discuss the challenges in scaling up photo-assisted technologies for specific environmental remediation needs. Photo-assisted technologies have demonstrated effectiveness in environmental remediation, although large-scale applications remain constrained by high costs. Future potential applications of photo-assisted technologies will require that technology selection be tailored to specific pollution scenarios and engineering processes optimized to minimize costs.

Astrocyte-to-neuron H2O2 signalling supports long-term memory formation in Drosophila and is impaired in an Alzheimer’s disease model

Astrocytes help protect neurons from potential damage caused by reactive oxygen species (ROS). While ROS can also exert beneficial effects, it remains unknown how neuronal ROS signalling is activated during memory formation, and whether astrocytes play a role in this process. Here we discover an astrocyte-to-neuron H2O2 signalling cascade in Drosophila that is essential for long-term memory formation. Stimulation of astrocytes by acetylcholine induces an increase in intracellular calcium ions, which triggers the generation of extracellular superoxide (O2) by astrocytic NADPH oxidase. Astrocyte-secreted superoxide dismutase 3 (Sod3) converts O2 to hydrogen peroxide (H2O2), which is imported into neurons of the olfactory memory centre, the mushroom body, as revealed by in vivo H2O2 imaging. Notably, Sod3 activity requires copper ions, which are supplied by neuronal amyloid precursor protein. We also find that human amyloid-β peptide, implicated in Alzheimer’s disease, inhibits the nAChRα7 astrocytic cholinergic receptor and impairs memory formation by preventing H2O2 synthesis. These findings may have important implications for understanding the aetiology of Alzheimer’s disease.

Higher temperature sensitivity of forest soil methane oxidation in colder climates

Forest soils, serving as an important sink for atmospheric methane (CH4), modulate the global CH4 budget. However, the direction and magnitude of the forest soil CH4 sink under warming remain uncertain, partly because the temperature response of microbial CH4 oxidation varies substantially across geographical scales. Here, we reveal the spatial variation in the response of forest soil microbial CH4 oxidation to warming, along with the driving factors, across 84 sites spanning a broad latitudinal gradient in eastern China. Our results show that the temperature sensitivity of soil microbial CH4 oxidation significantly declines with increasing site mean annual temperature, with a range of 0.03 to 0.77 μg CH4 g–1 soil d–1 °C–1. Moreover, soil resources and type II methanotrophs play crucial roles in shaping the temperature sensitivity of soil microbial CH4 oxidation. Our findings highlight the importance of incorporating climate, soil resources, and methanotroph groups into biogeochemical models to more realistically predict forest soil CH4 sink under warming.

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