Explore the vast range of titles available.

Manipulation of inorganic materials with organic macromolecules enables organisms to create biominerals such as bones and seashells, where occlusion of biomacromolecules within individual crystals generates superior mechanical properties. Current understanding of this process largely comes from studying the entrapment of micron-size particles in cooling melts. Here, by investigating micelle incorporation in calcite with atomic force microscopy and micromechanical simulations, we show that different mechanisms govern nanoscale occlusion. By simultaneously visualizing the micelles and propagating step edges, we demonstrate that the micelles experience significant compression during occlusion, which is accompanied by cavity formation. This generates local lattice strain, leading to enhanced mechanical properties. These results give new insight into the formation of occlusions in natural and synthetic crystals, and will facilitate the synthesis of multifunctional nanocomposite crystals. The occlusion of biomacromolecules can endow biominerals with enhanced mechanical properties. Here, the authors use in situ atomic force microscopy and micromechanical simulations to trace micelle incorporation in calcite to shed light on the mechanism of occlusion and cavity formation.

Recent advances in 3D printing have enabled the manufacture of porous electrodes which cannot be machined using traditional methods. With micron-scale precision, the pore structure of an electrode can now be designed for optimal energy efficiency, and a 3D printed electrode is not limited to a single uniform porosity. As these electrodes scale in size, however, the total number of possible pore designs can be intractable; choosing an appropriate pore distribution manually can be a complex task. To address this challenge, we adopt an inverse design approach. Using physics-based models, the electrode structure is optimized to minimize power losses in a flow reactor. The computer-generated structure is then printed and benchmarked against homogeneous porosity electrodes. We show how an optimized electrode decreases the power requirements by 16% compared to the best-case homogeneous porosity. Future work could apply this approach to flow batteries, electrolyzers, and fuel cells to accelerate their design and implementation.

In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors ( g CD ) of up to 10 −2 . Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. This concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality. Hybrid metal halide semiconductors typically rely on chiral A-site ammonium cations for chiral induction in the lattice. Now it has been shown that chirality in low-dimensional achiral metal halide semiconductors can be induced by non-ammonium, non-A-site chiral molecules through remote stereocontrol of the inorganic framework.

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding—perhaps most importantly the temporal dynamic changes occurring therein—serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO 2 system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt 0  − O vacancy−Ce 3+ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction. Revealing the structure and dynamics of active sites is essential to understand catalytic mechanisms. Here the authors demonstrate the dynamic nature of perimeter Pt 0 −O vacancy−Ce 3+ sites in Pt/CeO 2 and the key effects of their dynamics on the mechanism of the water gas shift reaction.

Background Despite their widespread distribution and ecological importance, protists remain one of the least understood components of the soil and rhizosphere microbiome. Knowledge of the roles that protists play in stimulating organic matter decomposition and shaping microbiome dynamics continues to grow, but there remains a need to understand the extent to which biological and environmental factors mediate protist community assembly and dynamics. We hypothesize that protists communities are filtered by the influence of plants on their rhizosphere biological and physicochemical environment, resulting in patterns of protist diversity and composition that mirror previously observed diversity and successional dynamics in rhizosphere bacterial communities. Results We analyzed protist communities associated with the rhizosphere and bulk soil of switchgrass (SG) plants ( Panicum virgatum ) at different phenological stages, grown in two marginal soils as part of a large-scale field experiment. Our results reveal that the diversity of protists is lower in rhizosphere than bulk soils, and that temporal variations depend on soil properties but are less pronounced in rhizosphere soil. Patterns of significantly prevalent protists groups in the rhizosphere suggest that most protists play varied ecological roles across plant growth stages and that some plant pathogenic protists and protists with omnivorous diets reoccur over time in the rhizosphere. We found that protist co-occurrence network dynamics are more complex in the rhizosphere compared to bulk soil. A phylogenetic bin-based null model analysis showed that protists’ community assembly in our study sites is mainly controlled by homogenous selection and dispersal limitation, with stronger selection in rhizosphere than bulk soil as SG grew and senesced. Conclusions We demonstrate that environmental filtering is a dominant determinant of overall protist community properties and that at the rhizosphere level, plant control on the physical and biological environment is a critical driver of protist community composition and dynamics. Since protists are key contributors to plant nutrient availability and bacterial community composition and abundance, mapping and understanding their patterns in rhizosphere soil is foundational to understanding the ecology of the root-microbe-soil system. 5stCu76cmNPcXaeF7W4bD3 Video Abstract

Polymer-encapsulated dye nanoparticle sensors are a valuable approach to achieving in situ analyte measurements with luminescence; however, typical emulsion-based nanosensors are poorly suited for large-scale biological samples due to limitations of synthesis scalability and stability. Branched polyethylenimine (PEI) is a versatile polymer scaffold ideal for constructing nanoparticles with various covalently conjugated moieties due to their high density of reactive primary amines, high water solubility, and biological stability. In this work, we used branched polyethylenimine as a scaffold-based approach for making a stable and scalable ratiometric oxygen sensor. Pt (II) tetracarboxyporphine was used as an oxygen-sensing dye and coumarin 343 as a reference dye, all covalently linked to the PEI scaffold producing a product that could withstand sterilization procedures and easily be scaled. To minimize toxicity from the PEI scaffold, we conjugated it with 2000 MW PEG. The applicability of the sensors was demonstrated in a 200 mL Saccharomyces cerevisiae yeast culture, using orthogonal luminescent and electrochemical oxygen measurements to validate sensor response and measure the metabolic activity of the yeast in our culture. This approach was able to match the sensitivity of our electrochemical measurements while improving upon drawbacks of other luminescent methods of oxygen detection, demonstrating effective monitoring for at least 20 h. Our scaffold-based approach is a modular and easily translatable technology that could be useful in various biotechnological applications. Graphical abstract

Transition-metal single-atom catalysts present extraordinary activity per metal atomic site, but suffer from low metal-atom densities (typically less than 5 wt% or 1 at.%), which limits their overall catalytic performance. Here we report a general method for the synthesis of single-atom catalysts with high transition-metal-atom loadings of up to 40 wt% or 3.8 at.%, representing several-fold improvements compared to benchmarks in the literature. Graphene quantum dots, later interweaved into a carbon matrix, were used as a support, providing numerous anchoring sites and thus facilitating the generation of high densities of transition-metal atoms with sufficient spacing between the metal atoms to avoid aggregation. A significant increase in activity in electrochemical CO2 reduction (used as a representative reaction) was demonstrated on a Ni single-atom catalyst with increased Ni loading.Transition-metal single-atom catalysts display excellent activity per metal atom site, but suffer from low metal atom densities (typically less than 5 wt% or 1 at.%), which limits their overall catalytic performance. Now, the use of a graphene-quantum-dot primary support, later interweaved into a carbon matrix, has enabled the synthesis of single-atom catalysts with high transition-metal atom loadings of up to 40 wt% or 3.84 at.%.

Recent progress has seen multiple Ta2O5 polymorphs generated by different synthesis techniques. However, discrepancies arise when these polymorphs are produced in widely varying thermodynamic conditions and characterized using different techniques. This work aimed to characterize and compare Ta2O5 particles formed at high and low temperatures using nanosecond pulsed laser ablation (PLA) and continuous wave (CW) laser heating of a local area of tantalum in either air or an 18O2 atmosphere. Scanning electron microscopy (SEM) and Raman spectroscopy of the micrometer-sized particles generated by PLA were consistent with either a localized amorphous Ta2O5 phase or a similar, but not identical, crystalline β-Ta2O5 phase. The Raman spectrum of the material formed at the point of CW laser impingement was in good agreement with the previously established ceramic “H-Ta2O5” phase. TEM and electron diffraction analysis of these particles indicated the phase structure matched an oxygen-vacated superstructure of monoclinic H-Ta2O5. Further from the point of laser impingement, CW heating produced particles with a Raman spectrum that matched β-Ta2O5. We confirmed that the high-temperature ceramic phase characterized in previous work by Raman spectroscopy was the same monoclinic phase characterized in different work by TEM and could be produced by direct laser heating of metal in air.

Currently, there are few examples of circularly recyclable polymers with all-carbon backbones, probably owing to the challenge of using selective C–C bond cleavage to efficiently produce monomers in recycling processes. Here we demonstrate a series of biologically sourced polymuconate polymers synthesized via simple free-radical polymerization that exhibit intrinsically weakened C–C bonds and controlled chemical recycling to monomers. Modifying the side chains and copolymerization ratios allows a wide range of mechanical property tuning, achieving performances comparable to those of commercial plastics such as polystyrene, polymethyl methacrylate and polybutadiene. Techno-economic analysis and life cycle assessment for production at a scale of 100 kilotons per year show that the materials are currently slightly more expensive and environmentally intensive compared with conventional rubbers. However, use of recycled materials via depolymerization can greatly decrease the cost and environmental impacts of polymuconate production (for example, down to US$1.59 per kilogram) to outperform its commercial counterparts. This study reports on biologically sourced polymuconate polymers with weakened C–C backbone bonds, designed for closed-loop chemical recycling to monomers. Synthesized via free-radical polymerization, these materials achieve tunable mechanical properties comparable to those of commercial plastics. A techno-economic analysis shows that recycling significantly reduces costs and environmental impacts, enhancing the competitiveness of these polymers in the sustainable plastics market.

Coulombic interactions can be used to assemble charged nanoparticles into higher-order structures, but the process requires oppositely charged partners that are similarly sized. The ability to mediate the assembly of such charged nanoparticles using structurally simple small molecules would greatly facilitate the fabrication of nanostructured materials and harnessing their applications in catalysis, sensing and photonics. Here we show that small molecules with as few as three electric charges can effectively induce attractive interactions between oppositely charged nanoparticles in water. These interactions can guide the assembly of charged nanoparticles into colloidal crystals of a quality previously only thought to result from their co-crystallization with oppositely charged nanoparticles of a similar size. Transient nanoparticle assemblies can be generated using positively charged nanoparticles and multiply charged anions that are enzymatically hydrolysed into mono- and/or dianions. Our findings demonstrate an approach for the facile fabrication, manipulation and further investigation of static and dynamic nanostructured materials in aqueous environments.Coulombic interactions can be used to assemble charged nanoparticles into higher-order structures, but this process typically requires similarly sized oppositely charged partners. Now, small anions or cations with as few as three charges have been shown to induce attractive interactions between oppositely charged nanoparticles in water, guiding the assembly of colloidal crystals.