Variable Stoichiometry Research Articles

Mechanism of Thermodynamically Rationalized Selective Growth of a Two-Dimensional Ternary Ferromagnet on Insulating Substrates.

Two-dimensional (2D) semiconducting ferromagnet Fe3GeTe2 holds great promise for advanced spintronic applications because of its gate-tunable ferromagnetic ordering at room temperature, whereas the controllable growth of large-area single crystals remains very challenging due to its ternary nature and variable stoichiometry inducing many competitive phases. Here, we theoretically probe the mechanism of selective growth of monolayer Fe3GeTe2 on various epitaxial substrates. Thermodynamic analysis shows that the corresponding phase-pure chemical potential windows for the selective growth of Fe3GeTe2 can be reasonably attained in ternary phase space on insulating and chemically inert c-plane sapphire and Ga2O3(0001) substrates by properly modulating the interfacial interaction and employing suitable feedstocks to avoid competitive growth of possible impurity phases with different stoichiometry ratios. It is also revealed that both the weak edge-substrate interaction and interlayer coupling of Fe3GeTe2 together lead to a surface-dominated nucleation behavior and, thereby, energetically favor lateral growth of the monolayer rather than vertical growth of the multilayer. Importantly, straight protocols for the experimentally selective growth of phase-pure ternary Fe3GeTe2 are also provided by establishing the relationship between the feedstock chemical potential and growth parameters on a thermochemical basis. Our insightful study can also be reasonably extended to guide future experimental design for the selective growth of other multicomponent 2D materials.

Species‐specific stoichiometric effects of leaf litter on algal growth, production, and cell quotas

AbstractDissolved organic matter and nutrients released from leaf litter are important cross‐ecosystem resources supporting freshwater food webs. Dissolved organic matter supports heterotrophic organisms in freshwater communities. However, the role of nutrients released from leaf litter in the autochthonous production in aquatic ecosystems is not well understood. Therefore, we investigated how dissolved nutrients released from leaf litter affect algal growth, biomass production, and cellular elemental ratios. Specifically, we experimentally examined the response of green algae to nitrogen (N) and phosphorus (P) released from leaf litter of 11 temperate tree species and the degree of deficiency of nutrient elements other than N and P relative to algal demand in these litter leachates by supplementing these elements. We found that algal growth did not significantly increase with dissolved N or P in the leaf leachates. In contrast, algal biomass production increased with dissolved N concentration, regardless of amendment. Algal growth and production limitation by deficiency of elements other than N and P was found only in the leachate of Japanese hemlock, indicating that the concentrations or release efficiencies of these elements in this leaf litter were lower than those of N and P relative to algal requirements. More importantly, leaf litter leachates from different tree species altered algal cell quotas and C:N:P ratios, which would affect secondary production. These results suggest that variations in leaf litter leachate stoichiometry caused by vegetation change would affect the abundance and chemical composition of phytoplankton, and thus the trophic transfer efficiency between phytoplankton and herbivorous zooplankton.

Structural Study on the Novel Plasmonic Optical Materials with Copper Selenide Nanoparticles

Background: Semiconductor-doped materials have been treated actively throughout the last decades and continue to be of great interest because of the challenges of the features due to various nanosize effects. Among other semiconductors, copper chalcogenides demonstrate the interesting plasmonic properties in line with quantum confinement effects provided by the size factor. Objective: This study aims to study the structural and optical features of the sol-gel-derived silica glasses with copper selenide nanoparticles, demonstrating the appearance of the plasmonic light absorption in the near IR range. Method: The samples under study were fabricated through an original sol-gel technique, which realized the simultaneous synthesis of copper selenide and sintering of mesoporous silica. The copper selenide glasses were characterized with X-Ray Diffraction (XRD), Transmission Electron Microscopy (TEM), and optical absorption spectroscopy. Results: Formation of nanocrystalline Cu2-xSe particles of the size range from 10 nm through 100-150 nm is established with XRD and TEM techniques. The principal optical properties are presented by the featured absorption in the visible and near-IR ranges. Eg was evaluated for the direct transitions in the range of 2.10-2.36 eV. The plasmonic resonance in the nanoparticles due to increased carrier concentration originated by intrinsic deficiency of Cu2-xSe nanoparticles with variable stoichiometry. Its energy can be controlled by the Cu/Se ratio in the synthesis procedure. Conclusion: The silica sol-gel glasses with copper selenide nanoparticles were fabricated and characterized by XRD and TEM methods, and their optical absorbance spectra were investigated. The principal optical properties are presented by the featured absorption in the visible and near-IR ranges: the steplike proper absorption of the semiconductor particles characterized by Eg and the intense near-IR band is associated with the localized plasmonic resonance in the nanoparticles due to increased carrier concentration.

Combustion synthesis of the (Ti,Zr)B2-(Zr,Ti)C eutectic composites: Structure formation and properties

The macrokinetic characteristics of combustion of the quaternary Ti-Zr-B-C mixture as well as the mechanism and stages of phase formation for the synthesis products were investigated. The mechanical and thermophysical properties of the hot-pressed boride/carbide ceramics with eutectic composition (Ti,Zr)B2-43%at.(Zr,Ti)C were measured. Preliminary mechanical alloying (MA) of the (Zr + Ti) mixture was shown to yield Ti/Zr granules having a laminar structure and consisting of alternating layers of titanium, zirconium, and (Zr,Ti)ss solid solution. The method used to prepare reaction mixtures and the initial temperature T0 increased within the range of 20–370 °C have virtually no effect on combustion temperature, which is 2260–2400 °C, while higher T0 increases the combustion rate by a factor of 1.5–2. The use of MA Ti/Zr granules reduces the combustion rate as well as the specific heat release amount and the heat release rate. Time-resolved X-ray diffraction data showed that binary carbides (Zr1-xTix)C and diborides (Ti1-yZry)B2 of variable stoichiometry are formed in the combustion wave of the Ti-Zr-B-C reaction mixtures within less than 0.25 s. The carbide and diboride phases are formed simultaneously; the use of MA Ti/Zr granules in the reaction mixtures reduces the content of solid solutions of variable stoichiometry among the reaction products. The ceramics fabricated using a combination of combustion synthesis and hot pressing have a dense and homogeneous structure that consist of bonded grains of the diboride (Ti0.80Zr0.20)B2 and carbide (Zr0.83Ti0.17)C phases having the following properties: density, 5.3 g/cm3; hardness, 22.9 GPa; fracture toughness, 4.7 MPa m0.5; heat capacity, 0.52 J/(g·K); thermal diffusivity, 11.67 mm2/s; and thermal conductivity, 33.28 W/(m·K).

Structural insights into the mechanism and dynamics of proteorhodopsin biogenesis and retinal scavenging

Microbial ion-pumping rhodopsins (MRs) are extensively studied retinal-binding membrane proteins. However, their biogenesis, including oligomerisation and retinal incorporation, remains poorly understood. The bacterial green-light absorbing proton pump proteorhodopsin (GPR) has emerged as a model protein for MRs and is used here to address these open questions using cryo-electron microscopy (cryo-EM) and molecular dynamics (MD) simulations. Specifically, conflicting studies regarding GPR stoichiometry reported pentamer and hexamer mixtures without providing possible assembly mechanisms. We report the pentameric and hexameric cryo-EM structures of a GPR mutant, uncovering the role of the unprocessed N-terminal signal peptide in the assembly of hexameric GPR. Furthermore, certain proteorhodopsin-expressing bacteria lack retinal biosynthesis pathways, suggesting that they scavenge the cofactor from their environment. We shed light on this hypothesis by solving the cryo-EM structure of retinal-free proteoopsin, which together with mass spectrometry and MD simulations suggests that decanoate serves as a temporary placeholder for retinal in the chromophore binding pocket. Further MD simulations elucidate possible pathways for the exchange of decanoate and retinal, offering a mechanism for retinal scavenging. Collectively, our findings provide insights into the biogenesis of MRs, including their oligomeric assembly, variations in protomer stoichiometry and retinal incorporation through a potential cofactor scavenging mechanism.

Evolution of 2PB/3PB Transport Pathways in Oxygen Electrodes during Degradation Test: A Perspective from Electro-Chemo-Mechanical Coupling on Microstructures

The solid oxide electrolysis cell (SOEC) has garnered significant attention over the past decades for hydrogen generation integrated with intermittent renewable energy [1]. However, a major hurdle in the commercialization of SOEC is cell degradation when operated beyond 1000 hours [2]. SOEC degrades two times more quickly than the same cell operated in fuel cell mode [3]. Perovskite oxygen electrodes (OEs), such as La1-xSrxCo1-yFeyO3-δ (LSCF), exhibit flexible oxygen stoichiometry [4-6] depending on the operating conditions. The delamination failure in perovskite OEs arises from a mismatch between the slower O2 evolution rate at the surface and the rapid O2 current in the bulk from the electrolyte (EL), which causes variations in oxygen stoichiometry. This variation in oxygen stoichiometry enhances bonding, contracts lattice volume, and leads to chemical stress at the OE/EL interface [7].In this research, we aim to construct an electro-chemo-mechanically coupled model with synthetic microstructures (Fig.1a) to explore the intricate interactions between delamination at the OE/EL interface and oxygen ion transport pathway evolution. The Dream 3D software will be utilized for microstructure generation, Matlab for mesh preparation, and Comsol for Multiphysics simulation. We will examine two OE configurations known for achieving high electrocatalytic activity [8]: single layer and bilayer OEs . For the single layer configuration, La0.6Sr0.4Co0.4Fe0.6O3 (LSCF) [9, 10] serves as the sole electrode material. For bilayer OEs, we incorporate SrTa0.1Co0.9O3 (SCT) [11, 12] as the capping layer for electrocatalytic activity, with LSCF acting as the supporting backbone. The evolution of two transport pathways (Fig.1b&c), double phase boundary (2PB) and tripe phase boundary (3PB), in different configurations during long-term degradation tests will be evaluated by coupling the models with experimental polarization curves and electrochemical impedance spectra. The investigations will focus on the effects of delamination resulting from lattice volume variations on shifting of transport pathways (Fig.1d) in different OE configurations. References Nechache, A. and S. Hody, Alternative and innovative solid oxide electrolysis cell materials: A short review. Renewable and Sustainable Energy Reviews, 2021. 149.Rashkeev, S.N. and M.V. Glazoff, Atomic-scale mechanisms of oxygen electrode delamination in solid oxide electrolyzer cells. International Journal of Hydrogen Energy, 2012. 37(2): p. 1280-1291.Moçoteguy, P. and A. Brisse, A review and comprehensive analysis of degradation mechanisms of solid oxide electrolysis cells. International Journal of Hydrogen Energy, 2013. 38(36): p. 15887-15902.Adler, S.B., Chemical Expansivity of Electrochemical Ceramics. Journal of the American Ceramic Society, 2001. 84(9): p. 2117-2119.Atkinson, A. and T.M.G.M. Ramos, Chemically-induced stresses in ceramic oxygen ion-conducting membranes. Solid State Ionics, 2000. 129(1): p. 259-269.Bishop, S.R., K.L. Duncan, and E.D. Wachsman, Defect equilibria and chemical expansion in non-stoichiometric undoped and gadolinium-doped cerium oxide. Electrochimica Acta, 2009. 54(5): p. 1436-1443.Cook, K., J. Wrubel, Z. Ma, K. Huang, and X. Jin, Modeling Electrokinetics of Oxygen Electrodes in Solid Oxide Electrolyzer Cells. Journal of The Electrochemical Society, 2021. 168(11): p. 114510.Laguna-Bercero, M.A., H. Monzón, A. Larrea, and V.M. Orera, Improved stability of reversible solid oxide cells with a nickelate-based oxygen electrode. Journal of Materials Chemistry A, 2016. 4(4): p. 1446-1453.Mogensen, M.B., M. Chen, H.L. Frandsen, C. Graves, J.B. Hansen, K.V. Hansen, A. Hauch, T. Jacobsen, S.H. Jensen, T.L. Skafte, and X. Sun, Reversible solid-oxide cells for clean and sustainable energy. Clean Energy, 2019. 3(3): p. 175-201.Jiang, S.P., Challenges in the development of reversible solid oxide cell technologies: a mini review. Asia-Pacific Journal of Chemical Engineering, 2016. 11(3): p. 386-391.Huang, K. and Y. Wen, Electrochemical Performance of New Bilayer Oxygen Electrode for Reversible Solid Oxide Cells. ECS Meeting s, 2021. MA2021-03(1): p. 138-138.Huang, K., Method to Make Isostructural Bilayer Oxygen Electrode. 2020, University of South Carolina: US. Figure 1

Physiology, fast and slow: bacterial response to variable resource stoichiometry and dilution rate.

All organisms experience suboptimal growth conditions due to low nutrient and energy availability. Their ability to survive and reproduce under such conditions determines their evolutionary fitness. By imposing suboptimal resource ratios under different dilution rates on the model organism Pseudomonas putida KT2440, we show that this bacterium dynamically adjusts its elemental composition, morphology, pools of biomolecules, and levels of gene expression. By examining the ability of bacteria to respond to C:N:P imbalance, we can begin to understand how stoichiometric flexibility manifests at the cellular level and impacts the flow of energy and elements through ecosystems.

Temporal Variations in Aboveground Biomass, Nutrient Content, and Ecological Stoichiometry in Young and Middle-Aged Stands of Chinese Fir Forests.

Understanding the ecological dynamics of forest ecosystems, particularly the influence of forest age structure on soil carbon (C), nitrogen (N), and phosphorus (P) content, is crucial for effective forest management and conservation. This study aimed to investigate the nutrient storage and ecological stoichiometry across different-aged stands of Chinese fir forests. Soil samples were collected from various depths (0-15 cm, 15-30 cm, and 30-45 cm) across four age groups of Chinese fir forests (8-year-old, 12-year-old, 20-year-old, and 25-year-old) in the Forest Farm, Pingjiang County, China. Soil organic carbon (SOC), total nitrogen (TN), and total phosphorus (TP) were measured, and their stoichiometries were calculated. The results showed that both individual tree biomass and stand biomass, along with SOC, TN, and TP content, increased with stand age, highlighting the significant importance of stand age on biomass production and nutrient accumulation in forests. Specifically, soil C and P contents significantly increased as the forest aged, while variation in N content was relatively minor. Soil C/N and C/P ratios exhibited variation corresponding to forest age, suggesting alterations in the ecological stoichiometry characteristics of the forests over time. These findings are crucial for understanding the dynamics of ecosystem functioning and nutrient cycling within Chinese fir forests and provide a solid scientific basis for the effective management and conservation of these vital forest ecosystems.

Species identity and diversity of filter‐feeding bivalves impact green and brown food webs

Abstract In freshwater ecosystems, consumers can play large roles in nutrient cycling by modifying nutrient availability for autotrophic and heterotrophic microbes. Nutrients released by consumers directly support green food webs based on primary production and brown food webs based on decomposition. While much research has focused on impacts of consumer driven nutrient dynamics on green food webs, less attention has been given to studying the effects of these dynamics on brown food webs. Freshwater mussels (Bivalvia: Unionidae) can dominate benthic biomass in aquatic systems as they often occur in dense aggregations that create biogeochemical hotspots that can control ecosystem structure and function through nutrient release. However, despite functional similarities as filter‐feeders, mussels exhibit variation in nutrient excretion and tissue stoichiometry due in part to their phylogenetic origin. Here, we conducted a mesocosm experiment to evaluate how communities of three phylogenetically distinct species of mussels individually and collectively influence components of green and brown food webs. We predicted that the presence of mussels would elicit a positive response in both brown and green food webs by providing nutrients and energy via excretion and biodeposition to autotrophic and heterotrophic microbes. We also predicted that bottom‐up provisioning of nutrients would vary among treatments as a result of stoichiometric differences of species combinations, and that increasing species richness would lead to greater ecosystem functioning through complementarity resulting from greater trait diversity. Our results show that mussels affect the functioning of green and brown food webs through altering nutrient availability for both autotrophic and heterotrophic microbes. These effects are likely to be driven by phylogenetic constraints on tissue nutrient stoichiometry and consequential excretion stoichiometry, which can have functional effects on ecosystem processes. Our study highlights the importance of measuring multiple functional responses across a gradient of diversity in ecologically similar consumers to gain a more holistic view of aquatic food webs.

Nanotubes and other nanostructures of VS2, WS2, and MoS2: Structural effects on the hydrogen evolution reaction

Vanadium sulfide (VS2) is a layered transition metal dichalcogenide (TMD), comparable in crystal structure to the well-known MoS2 and WS2. Theoretical predictions attribute much potential to VS2, since it is metallic-like and has an active basal plane, essential for catalytic performance. However, it is much less studied than other members of the TMD family due to the difficulties in synthesizing specific structures with controlled properties. Here we present unique structures of VS2 nanotubes and conduct a comparative study with other well-known inorganic nanotubes and nanostructures of MoS2 and WS2. We evaluate the effect of the curvature and strain, the abundance of surface defects, and the availability of surface sites in various structures by electrochemical methods. We show that MoS2 has the best intrinsic activity, which is enhanced by an extensive electrochemical surface area. The woven-like structure of the MoS2 nanotube walls provides a combined effect of strain, crystallinity, and defects. For WS2 structures, the strained surface of the nanotubes results in sites with higher intrinsic activity than the edge sites, but structures such as the nano-triangles, which provide a higher number of edge sites, exhibit competing activity. As for the VS2 structures, although theoretical calculations predict optimal active sites for the hydrogen evolution reaction (HER), they are extremely sensitive to stoichiometry variations that hamper their catalytic activity. Our findings contribute insights to the improvement and design of VS2–based nanocatalysts for the HER and shed light on the general factors that govern the activity in the unique TMD nanotubes family.

CALPHAD, preparation, and mechanical properties of quaternary solid solution nitrides with various nitrogen stoichiometry

High-entropy ceramics have gained increasing interest due to unique properties unattainable by traditional materials. Though a large number of high-entropy ceramics have emerged, there was still in lack of theoretical predictions of phase composition on multicomponent solid solutions, which was probably caused by the composition complexity. In this work, employing Thermo-Calc and TCHEA4 database, a series of equilibrium phase data was generated from quaternary solid solution nitrides formed by the five elements of Ti, V, Cr, Zr, and N, while five quaternary solid solution nitrides with various nitrogen stoichiometry were prepared by SPS utilizing commercially available transition metal and their nitrides at 1600 °C. The detection of phase composition during the experiment and thermodynamic calculation confirmed that an increase in nitrogen content was beneficial for the formation of a single-phase solid solution. Due to the variation of nitrogen stoichiometry, the concentrations of nitrogen-metal bonds changed accordingly, resulting in different relative densities and mechanical properties. On the basis of the experimental data, CALPHAD, with a maximum absolute error of only 8.31 %, was established, providing a powerful tool for predicting phase in the complex composition-temperature space of compositionally complex ceramics.

Variations in soil enzyme stoichiometry and microbial nutrient limitations in Camellia oleifera plantations with different ages

The alteration of stand age instigates modifications in soil properties and microbial communities. Understanding the impacts of stand age on soil enzyme stoichiometry and microbial nutrient limitations in Camellia oleifera plantation is crucial for nutrient management. Taking C. oleifera plantation across four age groups (<10 a, 15-25 a, 30-50 a, >60 a) in a subtropical red soil region as test objects, we examined the response of soil enzyme stoichiometry and microbial nutrient limitations to change in stand age and analyzed the pathways for such responses. The results showed that, compared to that of stand age <10 a, enzyme C:N in the 15-25 a was increased and enzyme N:P was significantly reduced. Microbial biomass carbon (MBC), microbial biomass nitrogen (MBN), and microbial biomass phosphorus (MBP) exhibited a trend of initially decreasing and then increasing with stand age. MBN and MBN:MBP were significantly higher in the <10 a compared to that in the 30-50 a. MBC:MBN was significantly higher in the 30-50 a and >60 a compared to the <10 a and 15-25 a. Results of redundancy analysis revealed that soil nutrients, microbial biomass and their stoichiometry explained 92.4% of the variations in enzyme stoichiometry. Partial least squares path modeling (PLS-PM) results demonstrated that soil organic carbon (SOC) had a positive effect on microbial C limitation; MBN, MBN:MBP, MBC:MBP, SOC, and total nitrogen had a nega-tive overall effect on microbial P limitation, whereas soil C:N had a positive overall effect on microbial P limitation. There was a significant positive correlation between microbial C and P limitations. With increasing stand age, microbial nutrient limitation shifted from N and P limitation (<10 a) to C and P limitation (15-25 a, 30-50 a, >60 a).

Structural transitions, octahedral rotations, and electronic properties of A3Ni2O7 rare-earth nickelates under high pressure

Motivated by the recent observation of superconductivity with Tc ~ 80 K in pressurized La3Ni2O71, we explore the structural and electronic properties of A3Ni2O7 bilayer nickelates (A = La-Lu, Y, Sc) as a function of pressure (0–150 GPa) from first principles including a Coulomb repulsion term. At ~ 20 GPa, we observe an orthorhombic-to-tetragonal transition in La3Ni2O7 at variance with x-ray diffraction data, which points to so-far unresolved complexities at the onset of superconductivity, e.g., charge doping by variations in the oxygen stoichiometry. We compile a structural phase diagram that establishes chemical and external pressure as distinct and counteracting control parameters. We find unexpected correlations between Tc and the in-plane Ni-O-Ni bond angles for La3Ni2O7. Moreover, two structural phases with significant c+ octahedral rotations and in-plane bond disproportionations are uncovered for A = Nd-Lu, Y, Sc that exhibit a pressure-driven electronic reconstruction in the Ni eg manifold. By disentangling the involvement of basal versus apical oxygen states at the Fermi surface, we identify Tb3Ni2O7 as an interesting candidate for superconductivity at ambient pressure. These results suggest a profound tunability of the structural and electronic phases in this novel materials class and are key for a fundamental understanding of the superconductivity mechanism.

Characteristics of leaf stoichiometry and the driving factors of Ammopiptanthus mongolicus, China

The stoichiometric characteristics of leaves can reflect environmental adaptation of plants, and thus the study of the relationship between them is helpful for exploring plant adaptation strategies. In this study, taking the national second-level key protection species, Ammopiptanthus mongolicus, as the research object, we set up 26 plots to collect samples, and measured the content of carbon (C), nitrogen (N), phosphorus (P) and water use efficiency (WUE) of leaves. We analyzed the relationship between leaf stoichiometric characteristics and WUE, and quantified the contributions of soil, climate, and water use efficiency to the variations of leaf stoichiometry. The results showed that C, N, and P contents in the leaves were (583.99±27.93), (24.31±2.09), and (1.83±0.06) mg·g-1, respectively. The coefficients of variation were 4.8%, 8.6%, and 3.2%, respectively, all belonging to weak variability, indicating that foliar contents of C, N and P tended to a certain stable value. The average value of N:P was 13.3, indicating that the growth of A. mongolicus was mainly limited by N. WUE was not correlated with leaf C content, but was significantly positively correlated with leaf N and P contents and N:P, and significantly negatively correlated with C:N and C:P, indicating that there was a linear synergistic trend between WUE and leaf nutrient content. The main factors influencing leaf C content and C:P were climatic factors, the leaf N content and N:P were mainly affected by soil factors, and the water use efficiency mainly affected leaf P content and C:N, indicating that the driving factors of different stoichiometric characteristics were different. The results could help eva-luate the habitat adaptation of desert plants, which would provide a theoretical basis for the conservation and management of A. mongolicus.

Impact of typhoons on anthropogenic nitrogen sources in Lake Sihwa, South Korea

This study investigated the nitrate dual isotopic compositions (δ15NNO3 and δ18ONO3) of water samples to trace nitrate sources in Lake Sihwa, which encompasses various land-use types (e.g., urban, industry, wetland, and agriculture). The biogeochemical interactions of anthropogenic nitrogen sources (e.g., soil, road dust, and septic water) were also evaluated through multiple pathways from terrestrial boundaries to the water column. Based on increased concentrations of dissolved total nitrogen (DTN; 3.1 ± 1.6 mg/L) after typhoon, the variation of element stoichiometry (N:P:Si) in this system shifted to the relatively N-rich conditions (DIN/DIP; 14.1 ± 8.1, DIN/DSi; 1.4 ± 1.8), potentially triggering the occurrence of harmful algal blooms. Furthermore, discriminative isotopic compositions (δ15NNO3; 4.0 ± 2.1 ‰, δ18ONO3; 6.1 ± 4.3 ‰) after the typhoon suggested the increased DTN input of anthropogenic origins within Lake Sihwa would be mainly transported from urban sources (76 ± 9 %). Consequently, the isotopic-based approach may be useful for effective water quality management under increased anthropogenic activities near aquatic systems.

Enhancement of Perpendicular Magnetic Anisotropy in Tm3Fe5O12(111) Epitaxial Films via Synergistic Stoichiometry and Strain Engineering

AbstractEstablishing a reliable control of perpendicular magnetic anisotropy (PMA) is challenging but essential for the full utilization of rare‐earth iron garnets in spintronic devices. In this study, a feasible approach to enhance the PMA of ferrimagnetic thulium iron garnet (TmIG) films is presented. This approach involves precise adjustments in cation stoichiometry and epitaxial strain state. By fine‐tuning the pre‐ablation process and oxygen partial pressure during pulsed laser deposition, a series of high‐quality TmIG films can grow with variable cation stoichiometry, i.e., the Tm/Fe molar ratio. The finding reveals that cation stoichiometry plays a crucial role in determining the magnetic properties of the TmIG films. Particularly, the stoichiometric TmIG film has the strongest PMA due to the maximized magnetostriction coefficient. Combining this stoichiometry optimization and strain engineering, an unprecedented PMA strength of ≈30 kJ m−3 for TmIG is achieved. This achievement demonstrates a simple and effective method for harnessing the magnetic properties of rare‐earth iron garnet films, paving the way for their advanced applications in next‐generation spintronic devices.

Integrating Trait‐Based Stoichiometry in a Biogeochemical Inverse Model Reveals Links Between Phytoplankton Physiology and Global Carbon Export

AbstractThe elemental ratios of carbon, nitrogen, and phosphorus (C:N:P) within organic matter play a key role in coupling biogeochemical cycles in the global ocean. At the cellular level, these ratios are controlled by physiological responses to the environment. But linking these cellular‐level processes to global biogeochemical cycles remains challenging. We present a novel model framework that combines knowledge of phytoplankton cellular functioning with global scale hydrographic data, to assess the role of variable carbon‐to‐phosphorus ratios (RC:P) on the distribution of export production. We implement a trait‐based mechanistic model of phytoplankton growth into a global biogeochemical inverse model to predict global patterns of phytoplankton physiology and stoichiometry that are consistent with both biological growth mechanisms and hydrographic carbon and nutrient observations. We compare this model to empirical parameterizations relating RC:P to temperature or phosphate concentration. We find that the way the model represents variable stoichiometry affects the magnitude and spatial pattern of carbon export, with globally integrated fluxes varying by up to 10% (1.3 Pg C yr−1) across models. Despite these differences, all models exhibit strong consistency with observed dissolved inorganic carbon and phosphate concentrations (R2 &gt; 0.9), underscoring the challenge of selecting the most accurate model structure. We also find that the choice of parameterization impacts the capacity of changing RC:P to buffer predicted export declines. Our novel framework offers a pathway by which additional biological information might be used to reduce the structural uncertainty in model representations of phytoplankton stoichiometry, potentially improving our capacity to project future changes.

Effects of tree size and organ age on variations in carbon, nitrogen, and phosphorus stoichiometry in Pinus koraiensis

Carbon (C), nitrogen (N), and phosphorus (P) are of fundamental importance for growth and nutrient dynamics within plant organs and deserve more attention at regional to global scales. However, our knowledge of how these nutrients vary with tree size, organ age, or root order at the individual level remains limited. We determined C, N, and P contents and their stoichiometric ratios (i.e., nutrient traits) in needles, branches, and fine roots at different organ ages (0–3-year-old needles and branches) and root orders (1st–4th order roots) from 64 Pinus koraiensis of varying size (Diameter at breast height ranged from 0.3 to 100 cm) in northeast China. Soil factors were also measured. The results show that nutrient traits were regulated by tree size, organ age, or root order rather than soil factors. At a whole-plant level, nutrient traits decreased in needles and fine roots but increased in branches with tree size. At the organ level, age or root order had a negative effect on C, N, and P and a positive effect on stoichiometric ratios. Our results demonstrate that nutrient variations are closely related to organ-specific functions and ecophysiological processes at an individual level. It is suggested that the nutrient acquisition strategy by younger trees and organ fractions with higher nutrient content is for survival. Conversely, nutrient storage strategy in older trees and organ fractions are mainly for steady growth. Our results clarified the nutrient utilization strategies during tree and organ ontogeny and suggest that tree size and organ age or root order should be simultaneously considered to understand the complexities of nutrient variations.

Nanoscopic oxygen control of functional oxide nanoparticles by electro-chemical route at ambient temperature

La0.67Ca0.33MnOδ nanoparticles of approximate size ∼ 4 nm have been prepared by the chemical solution deposition method to investigate effect of oxygen stoichiometry in the nanoparticles without changing their sizes. Electrochemical oxidation method has been used to change the oxygen stoichiometry δ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\delta$$\\end{document} at room temperature, which unlike conventional methods to change oxygen stoichiometry by heating in controlled ambience, does not lead to any significant change in size. This has allowed us to investigate the effects of stoichiometry variations in the nanoparticles with no change in size. The unit cell volume, lattice constants and orthorhombic strains of the as prepared sample (with δ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\delta$$\\end{document} = 2.74) are changed by incorporation of oxygen by electrochemical oxidation which in turns affects the magnetic properties. In addition, oxidation leads to change in oxygen stoichiometry of the magnetically “dead” surface layer on the nanoparticles which also affects their magnetization and coercive field.

Structural Variability in Cocrystals: Occurrence of Variable Stoichiometry and High Z′ Forms in a Cocrystal System

Structural Variability in Cocrystals: Occurrence of Variable Stoichiometry and High <i>Z</i>′ Forms in a Cocrystal System