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  1. Accumulation of Soil Microbial Necromass Controlled by Microbe–Mineral Interactions

    Soil organic matter (SOM) is a key reservoir for global carbon (C), supporting soil fertility and influencing greenhouse gas emissions. Microbial residues, composed of dead cells and cellular fragments, are major contributors to SOM formation. Yet, mechanisms by which minerals enhance the accumulation of microbial residues remain poorly understood. Here, we used 13C-labeled glucose in a year-long incubation to trace microbial residue in sandy and silty soils. Across both soils, approximately 89% of retained microbial 13C was recovered in the fine (<53 μm) mineral-associated organic matter (MAOM) pool. Within this pool, the light MAOM fraction, enriched in poorly crystalline Femore » minerals, held 4.3 times more 13C than the heavy, phyllosilicate-dominated MAOM fraction, despite accounting for only 17.2% of the total MAOM mass and 12.3% of the total soil mass. Along with 13C enrichment, the light MAOM fraction showed greater abundance of N-containing groups, e.g., (amides and amino groups), indicative of microbial-derived compounds like proteins and amino sugars. Fe oxides in light MAOM from both soils were spatially dispersed. Microbial residue accumulation was greater in finer-textured silty soil. These findings demonstrate that mineral composition and texture jointly regulate microbial necromass accrual, highlighting light MAOM as a key pool for enhancing soil C storage.« less
  2. Influence of strain-rate on the response of elastomeric architected materials

    Architected materials have shown substantial promise in impact mitigation and protective applications, and there has accordingly been great interest in better characterizing their response at elevated strain rates due to impact. There remains ambiguity regarding the contribution of inertial and material responses to strain rate sensitivity, and, in particular, when these effects begin to gain dominance in the impact response of an architected material. The response of soft polymer architected materials as a function of strain rate, in particular, has been little investigated. We characterize the experimental impact response of four soft polymer architected lattice geometries across varying strain ratesmore » in the intermediate strain rate regime (∼103 s−1) using split-Hopkinson pressure bar loading and high speed video characterization of the resulting deformation fields. In conclusion, our results highlight the interplay of influence between constituent material, lattice geometry, length scale, and strain rate in determining the onset of significant inertia effects.« less
  3. Optimizing 2D passivation for enhancing performance of fully air-processed carbon electrode-based perovskite solar cells

    Air-processed carbon-based perovskite solar cells (C-PSCs) offer scalable and cost-effective photovoltaic manufacturing but face efficiency loss compared to metal-contact perovskite solar cells. Surface passivation of three-dimensional (3D) perovskites with two-dimensional (2D) perovskite layers has emerged as a promising strategy to enhance device performance. However, the mechanisms by which 2D perovskites more effectively improve C-PSC efficiency and stability remain underexplored. This study investigates the efficacy of 2D/3D heterostructures using n-hexylammonium bromide (C6Br), phenethylammonium iodide (PEAI), and n-octylammonium iodide (OAI) as surface passivators for C-PSCs. C-PSCs treated with C6Br achieved a champion power conversion efficiency (PCE) of 21.0%. This enhancement is attributedmore » to superior defect passivation, improved charge extraction, and suppressed non-radiative recombination. Transient ion-drift characterization demonstrates that C6Br and OAI reduce ionic conductivity by 2–3 orders of magnitude, correlating with enhanced operational stability under continuous illumination. Our findings highlight the role of short-chain bromide cations (C6Br) in optimizing halide-mediated defect healing and interfacial band alignment, positioning 2D-passivated C-PSCs as viable competitors to conventional metal-contact perovskite solar cells.« less
  4. Formation of Carbon–Carbon Interlinkage Bonds under High Pressure

    The formation of carbon–carbon interlinkage bonds (CCIBs) via the chemical binding of interlayer carbon atoms of many sp2-bonded carbon precursors is an essential step for synthesizing various diamond and diamond-like materials. Although the existence of CCIBs may be reasonably assumed under high-pressure conditions, direct experimental evidence has been scarce. Micro-Raman spectroscopy is here employed to track in situ the evolution of C–C bonds in a pressure range from ambient to 54 GPa. A pressure-induced two-stage (polynomial and linear) shift of the G peak and new generation of the CCIB peak at about 1550 cm–1 are observed in multiple types ofmore » layer-structured carbon precursors, including glassy carbon, natural graphite, and carbon nanotubes. In conclusion, the experimental discovery of CCIBs holds significance in comprehending phase transitions of sp2-bonded carbon materials and has implications for the advancement of novel carbon structures.« less
  5. Dielectric Barrier Discharge Electrothermal Heating and Additive Manufacturing of Thermoset Parts

    Additive manufacturing of thermosets requires a mechanism for solidifying deposited layers in order to prevent part collapse. To accomplish this, non‐equilibrium plasma is proposed for its ability to target, heat, and cure printed thermosetting resin. Non‐equilibrium plasmas have not been used for the curing of liquid thermoset composites, and so their impact on an uncured resin is unknown. Here this work investigates the mechanism through which dielectric barrier discharge (DBD) heats an epoxy/carbon nanotube (CNT) composite under atmospheric conditions. Plasma applied to resin surfaces is found to cause rapid heating, with heating rate controlled by adjusting the applied power. Heatingmore » is localized to within the top 0.5 mm of the sample surface and maximum temperature is found to depend on sample conductivity, indicating the heating reaction occurs through a combination of electron conduction and ion bombardment. Characterization of composites cured using plasma shows oxidation and roughening of the surface. Based on the heating and surface studies, several demonstrative prints are performed using in situ plasma curing. This work shows the potential of DBD plasma to rapidly heat liquid substrates and demonstrates how plasma curing expands the capability of existing direct ink write (DIW) printer technologies.« less
  6. Levelized cost and carbon intensity of solar hydrogen production via water splitting using a scalable and intrinsically safe photocatalytic Z-scheme raceway system

    Generating hydrogen from local energy resources such as solar or wind would unlock a low-carbon energy carrier that could be used to reduce greenhouse gas emissions in sectors such as industry and transportation. Yet, the allocation of new or existing power generation solely to hydrogen production remains contentious due to disputes regarding emissions accounting. Photocatalytic (PC) hydrogen production technologies offer a unique solution, as hydrogen is produced directly from solar energy and water, without the need for electricity generation. However, cost projections for all photocatalytic designs to date have suggested that they are not cost competitive compared to conventional electrolysismore » systems manufactured at scale. Herein, we offer the first illustrative benchmark of cost and carbon intensity of hydrogen produced in a type 2 “Z-scheme” photocatalytic reactor design, which employs suspended semiconducting nanoconductor particles organized into two stacked volumes in a raceway design. The “Z-scheme” system utilizes two separate photoabsorber particles, tuned to drive either the hydrogen evolution reaction or the oxygen evolution reaction individually, connected via a reversible, charge transfer redox couple in solution. Furthermore, the results suggest a highly competitive and scalable technology, that justifies further experimental validation and prototyping in the field.« less
  7. Performance of the spin-component-scaled methods for energy bands

    The performance of various spin-component-scaled parameterisations is examined for the second-order many-body Green's-function [MBGF(2)] calculations of valence energy bands, taking three of the experimentally well-characterised polymers as examples: polyethylene, polytetrafluoroethylene, and polyacetylene. The parameterisations considered are Grimme's original SCS parameter set, Jung et al.'s original SOS set (retaining the opposite-spin component only), Śmiga et al.'s SCS(IP) set (calibrated specifically for ionization energies), and Śmiga et al.'s SOS(IP) set (calibrated for ionization energies with the opposite-spin component only; implicit in the os-D2 model of Opoku et al.). The SCS(IP) and SOS(IP) parameterisations are found to shift both outer and inner valencemore » bands by up to a few electronvolts away from the experimental data. The original SCS and SOS parameter sets do not improve upon, but largely maintain the accuracy of the unscaled MBGF(2) methods. Given that the SOS-MBGF(2) method can be implemented in a quartic-scaling algorithm (for all roots), it is most promising for solid-state applications. Furthermore this observation is consistent with the success of the quartic-scaling GW methods without the vertex correction based on a density-functional theory reference.« less
  8. A Combined Crossed Molecular Beam and Theoretical Investigation of the Elementary Reaction of Tricarbon (C3(X1Σg+)) with Diacetylene (C4H2(X1Σg+)): Gas Phase Formation of the Heptatriynylidyne Radical (l-C7H(X2Π))

    An elucidation of the underlying formation pathways to acyclic hydrocarbons such as polyynes (CnH2), cumulenes (CnH2), and linear resonantly stabilized linear radicals (l-CnH) is indispensable to understand the hydrocarbon chemistry in extreme low and high temperature environments. In this study, we exploited the crossed molecular beam technique to investigate the reaction of tricarbon C3(X1Σg+) with diacetylene (butadiyne; HCCCCH; X1Σg+) at a collision energy of 47 ± 1 kJ mol⁻1. The experimental data were merged with ab initio calculations of the singlet C7H2 potential energy surface (PES) revealing that the reaction is initiated via the formation of an initial van dermore » Waals reactant complex in the entrance channel. Subsequent rearrangements lead to various carbene-type and cyclic intermediates via ring-opening, ring-closure, and hydrogen migration processes eventually forming acyclic C7H2 isomers prior to their barrierless unimolecular decomposition to the most stable linear isomer, heptatriynylidyne (C7H, X2Π) in an overall endoergic reaction (+57 kJ mol⁻1). The reaction exhibits strong similarities to the tricarbon – acetylene (C3 – C2H2). Furthermore, the significant energy threshold suggests that the tricarbon reaction with (poly)acetylenes forming resonantly stabilized linear radicals are open in high-temperature environments such as combustion flames and circumstellar envelopes of carbon stars and planetary nebulae as their descendants; however, these reactions are closed in low-temperature environments as in cold molecular clouds and hydrocarbon-rich atmospheres of planets and their moons such as in Titan.« less
  9. Hempseed cell wall polysaccharides are dominated by linear xylans and cellulose: Comprehensive structural profiling of ten cultivars of industrial hemp, Cannabis sativa L.

    Hempseed is a rich source of dietary fiber; however, there has been limited research on the variability of carbohydrate composition in hempseed cell walls. The primary aim of this study was to conduct a comprehensive chemical and structural analysis of the cell wall polysaccharides in ten hempseed cultivars. Water-soluble polysaccharides (WSP) and water-insoluble residues (WIR) were isolated and subsequently analyzed for their monosaccharide composition using HPAEC-PAD, glycosyl linkage analysis using GC–MS, and structural characterization via NMR spectroscopy. All hempseed cultivars contained a high proportion of insoluble fibers and smaller amounts of soluble polysaccharides. Glucose and xylose were the most abundantmore » components of the WIR fractions, while the WSP fractions contained abundant amounts of galactose, galacturonic acid, arabinose, rhamnose, and mannose. The results of linkage and spectroscopic analysis were consistent with the compositional analysis, identifying cellulose and acetylated linear xylans as primary components of WIR, and arabinogalactans, rhamnogalacturonans, heteromannans, xyloglucans, and arabinan as predominant in WSP. Altogether, the study revealed a comparable cell wall structure among the analyzed hemp seed varieties. The high fiber content of whole hempseed-based ingredients presents significant potential for food manufacturers seeking to develop products with enhanced dietary fiber content, offering both functional and nutritional benefits for consumers.« less
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