Stoichiometry control and automated growth of alkali antimonide photocathode films by molecular beam deposition
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photocathodes, stoichiometry, thin film growth↗
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Ecological stoichiometry as a foundation for omics-enabled biogeochemical models of soil organic matter decomposition
Coupled biogeochemical cycles drive ecosystem ecology by influencing individual-to-community scale behaviors; yet the development of process-based models that accurately capture these dynamics remains elusive. Soil organic matter (SOM) decomposition in particular is influenced by resource stoichiometry that dictates microbial nutrient acquisition (‘ecological stoichiometry’). Despite its basis in biogeochemical modeling, ecological stoichiometry is only implicitly considered in high-resolution microbial investigations and the metabolic models they inform. State-of-science SOM decomposition models in both fields have advanced largely separately, but they agree on a need to move beyond seminal pool-based models. This presents an opportunity and a challenge to maximize the strengths of various models across different scales and environmental contexts. To address this challenge, we contend that ecological stoichiometry provides a framework for merging biogeochemical and microbiological models, as both explicitly consider substrate chemistries that are the basis of ecological stoichiometry as applied to SOM decomposition. We highlight two gaps that limit our understanding of SOM decomposition: (1) understanding how individual microorganisms alter metabolic strategies in response to substrate stoichiometry and (2) translating this knowledge to the scale of biogeochemical models. We suggest iterative information exchange to refine the objectives of high-resolution investigations and to specify limited dynamics for representation in large-scale models, resulting in a new class of omics-enabled biogeochemical models. Assimilating theoretical and modelling frameworks from different scientific domains is the next frontier in SOM decomposition modelling; advancing technologies in the context of stoichiometric theory provides a consistent framework for interpreting molecular data, and further distilling this information into tractable SOM decomposition models.
Carbon cycling↗
Resonant x-ray scattering method for measuring cation stoichiometry in BaSnO 3 thin films
In this study, we develop a resonant scattering technique to measure cation stoichiometry of lanthanum-doped BaSnO 3 (BSO) thin films on a DyScO 3 substrate. Samples are grown by a hybrid molecular beam epitaxy method and display high room-temperature carrier mobilities. The measured thin films are grown with widely differing cation arrival rates, with Ba being evaporated from an elemental source and Sn from a SnO 2 source. Differences in mobilities in these films may arise from differences in Ba/Sn cation stoichiometry. Owing to the similar scattering strength of the Ba and Sn cations, odd-order Bragg peaks of BSO are particularly sensitive to the material's cation stoichiometry, i.e., the Ba/Sn ratio. Sensitivity to cation stoichiometry is further enhanced using the technique of resonant x-ray scattering, which changes the scattering strength of a single element across the Ba L absorption edges. We determine that the Ba/Sn cation stoichiometry varies from unity by less than 1% for films of mobility ranging from 84.8 to 144 cm 2 /(V s) and conclude that the mobility of these films scales with film thickness and growth rate rather than stoichiometry.
36 MATERIALS SCIENCE↗
Improved robustness of sequentially deposited potassium cesium antimonide photocathodes achieved by increasing the potassium content towards theoretical stoichiometry
Alkali antimonide semiconductor photocathodes are promising candidates for high-brightness electron sources for advanced accelerators, including free-electron lasers (FEL), due to their high quantum efficiency (QE), low emittance, and high temporal resolution. Two challenges with these photocathodes are (1) the lack of a universal deposition recipe to achieve crystal stoichiometries and (2) their high susceptibility to vacuum contamination, which restricts their operation pressure to ultrahigh vacuums and leads to a short lifetime and low extraction charge. To resolve these issues, it is essential to understand the elemental compositions of deposited photocathodes and correlate them to robustness. Here, we report depth profiles for potassium cesium antimonide photocathodes, which were investigated using synchrotron radiation x-ray photoelectron spectroscopy, and the robustness of those photocathodes. We prepared two types of photocathodes with different potassium contents via sequential thermal evaporation. Depth profiles revealed that the photocathodes with a potassium deficit had excess cesium at the surface, while the ratio of potassium and cesium to antimony decreased rapidly within the film. In contrast, the photocathodes with sufficient potassium had close to the theoretical stoichiometry of K 2 CsSb at the surface and maintained that stoichiometry for over half the entire film thickness. Both photocathode types had a similar maximum QE at 532 nm; however, exposure to oxygen revealed that the photocathode with a crystalline stoichiometry of K 2 CsSb maintained QE at one order of magnitude higher pressure compared to its potassium-deficit counterpart. These results highlight the importance of synthesizing potassium cesium antimonide photocathodes with sufficient potassium to achieve the theoretical crystalline stoichiometry for both high QE and improved robustness.
47 OTHER INSTRUMENTATION↗
Bulk Stoichiometry-Controlled Surface Reconstruction of Nanosized Ni−In Intermetallic Catalysts Steers Methanol Selectivity in CO2 Hydrogenation
Intermetallic compounds (IMCs) are attractive platforms for elucidating structure−catalysis relationships due to their ordered atomic structure and well-defined bulk composition. Yet, how their surfaces reconstruct under reaction conditions and how such reconstruction is governed by bulk stoichiometry remain poorly understood. Here, we show that SiO2-supported Ni−In IMCs undergo reaction-driven surface reconstruction during CO2 hydrogenation and that bulk stoichiometry can be used to steer this evolution toward methanol formation. Among the compositions examined (Ni2In1, Ni1In1, Ni2In3, and Ni1In2), Ni2In3/SiO2 exhibits the highest methanol selectivity (∼70%) and a methanol space-time yield of 652 mg·gmetal−1·h−1 at 250 °C and 30 bar. Combined structural, surface characterization, and kinetic analyses suggest that the intermetallic bulk remains largely preserved, whereas the surface departs from the stoichiometric bulk and evolves toward InOx-enriched surface domains coupled to an electron-rich Ni−In intermetallic phase. The extent of this evolution depends strongly on the bulk Ni:In stoichiometry and is most pronounced for Ni2In3/SiO2. These findings identify bulk stoichiometry as a handle for tuning the working-state surface of intermetallic catalysts and provide a basis for designing methanol synthesis catalysts through controlled surface reconstruction.
Wang, Caiqi [ORNL] (ORCID:0000000198849990)↗
Photosystem stoichiometry adjustment is a photoreceptor-mediated process in Arabidopsis
Abstract Plant growth under spectrally-enriched low light conditions leads to adjustment in the relative abundance of the two photosystems in an acclimatory response known as photosystem stoichiometry adjustment. Adjustment of photosystem stoichiometry improves the quantum efficiency of photosynthesis but how this process perceives light quality changes and how photosystem amount is regulated remain largely unknown. By using a label-free quantitative mass spectrometry approach in Arabidopsis here we show that photosystem stoichiometry adjustment is primarily driven by the regulation of photosystem I content and that this forms the major thylakoid proteomic response under light quality. Using light and redox signaling mutants, we further show that the light quality-responsive accumulation of photosystem I gene transcripts and proteins requires phytochrome B photoreceptor but not plastoquinone redox signaling as previously suggested. In far-red light, the increased acceptor side limitation might deplete active photosystem I pool, further contributing to the adjustment of photosystem stoichiometry.
59 BASIC BIOLOGICAL SCIENCES↗
Structural bases for stoichiometry‐selective calcium potentiation of a neuronal nicotinic receptor
Background and Purpose α4β2 nicotinic acetylcholine (nACh) receptors assemble in two stoichiometric forms, one of which is potentiated by calcium. The sites of calcium binding that underpin potentiation are not known. Experimental Approach To identify calcium binding sites, we applied cryo‐electron microscopy (cryo‐EM) and molecular dynamics (MD) simulations to each stoichiometric form of the α4β2 nACh receptor in the presence of calcium ions. To test whether the identified calcium sites are linked to potentiation, we generated mutants of anionic residues at the sites, expressed wild type and mutant receptors in clonal mammalian fibroblasts, and recorded ACh‐elicited single‐channel currents with or without calcium. Key Results Both cryo‐EM and MD simulations show calcium bound to a site between the extracellular and transmembrane domains of each α4 subunit (ECD‐TMD site). Substituting alanine for anionic residues at the ECD‐TMD site abolishes stoichiometry‐selective calcium potentiation, as monitored by single‐channel patch clamp electrophysiology. Additionally, MD simulation reveals calcium association at subunit interfaces within the extracellular domain. Substituting alanine for anionic residues at the ECD sites reduces or abolishes stoichiometry‐selective calcium potentiation. Conclusions and Implications Stoichiometry‐selective calcium potentiation of the α4β2 nACh receptor is achieved by calcium association with topographically distinct sites framed by anionic residues within the α4 subunit and between the α4 and β2 subunits. Stoichiometry‐selective calcium potentiation could result from the greater number of calcium sites in the stoichiometric form with three rather than two α4 subunits. The results are relevant to modulation of signalling via α4β2 nACh receptors in physiological and pathophysiological conditions.
Pharmacology & Pharmacy↗
Double-Crucible Vertical Bridgman Technique for Stoichiometry-Controlled Chalcogenide Crystal Growth
Precise stoichiometry control in single-crystal growth is essential for both technological applications and fundamental research. However, conventional growth methods often face challenges such as non-stoichiometry, compositional gradients, and phase impurities, particularly in non-congruent melting systems. Even in congruent melting systems like Bi₂Se₃, deviations from the ideal stoichiometric composition can lead to significant property degradation, such as excessive bulk conductivity, which limits its topological applications. In this study, we introduce the double-crucible vertical Bridgman (DCVB) method, a novel approach that enhances stoichiometry control through the combined use of continuous source material feeding, traveling-solvent growth, and liquid encapsulation, which suppresses volatile element loss under high pressure. Using Bi₂Se₃ as a model system, we demonstrate that crystals grown via DCVB exhibit enhanced stoichiometric control, significantly reducing defect density and achieving much lower carrier concentrations compared to those produced by conventional Bridgman techniques. Moreover, the continuous feeding of source material enables the growth of large crystals. As a result, this approach presents a promising strategy for synthesizing high-quality, large-scale crystals, particularly for metal chalcogenides and pnictides that exhibit challenging non-congruent melting behaviors.
Crystal structure↗
Non-ideal stoichiometry and thermochemistry of aqueous iridium oxide nanoparticles in proton-coupled electron transfer and oxygen-atom transfer
Reported here are reactions of aqueous colloidal IrO x nanoparticles (NPs) with proton-coupled electron transfer (PCET) and oxygen-atom transfer (OAT) organic reagents, determining the reaction stoichiometries and thermochemistry. IrO x NPs have attracted much attention for their high electrocatalytic activity, but understanding of their fundamental reaction chemistry is limited. This IrO x NP model system is simple, with UV-vis titrations demonstrating reversible interconversion between predominantly Ir IV and predominantly Ir III NPs. This simplicity allows studies that reveal their complex non-idealities. The NP redox chemistry has a “super-Nernstian” stoichiometry of ∼1.3H + per 1e − transferred during both PCET and OAT reactions, as measured with electrochemistry and chemical methods. Spectroelectrochemistry revealed a broad distribution of surface IrO x –H bond dissociation free energies (BDFEs), becoming weaker as more H is added. Such variation in binding strengths—a non-ideal binding isotherm—is common for surface adsorbates. For IrO x , the variation of BDFE(IrO–H)s is fit well to a Frumkin isotherm with a width of 6.5 kcal mol −1 . For OAT from the reactive oxygen atoms of IrO x NPs, bracketing experiments gave 93 ± 24 kcal mol −1 for the average BDFE(O x Ir–O), with a predicted spread much larger than that for the BDFE(IrO–H). Taken together, the results show the importance of non-ideal stoichiometry and thermochemistry for IrO x NPs, and they open a path to more complete models to understand catalytic redox reactions at such surfaces.
Iridium Oxide Nanoparticles (NPs)↗
High‐Nickel Heterostructured Cathodes with Local Stoichiometry Control for High‐Voltage Operation
The growing demand for lithium‐ion batteries to power electric vehicles and other energy‐dense devices continues to fuel the need for cathodes of increasingly higher nickel in cathodes. The relentless pursuit of high Ni content, however, raises concerns on compromising cell lifetime and safety, especially under high‐voltage operation. Alternative to the traditional design of uniform or core–shell composition, we report a rational control of local stoichiometry in high‐Ni cathodes, enabling their high thermal and cycling stabilities—up to 258 °C at the fully charged state and 91.4% capacity retention for 100 cycles between 2.7 and 4.4 V. Multimodal synchrotron X‐ray characterization unveils the heterostructure of secondary particles, featuring a high‐Ni core (LiNi 0.90 Mn 0.05 Co 0.05 O 2 ) covered by a thin Ni‐gradient layer that remains stable over prolonged cycling due to suppressed oxygen release and structural deterioration. This work underlines, the intricate interplay between local stoichiometry and redox reactions in stabilizing high‐Ni cathodes for high‐voltage operation while ensuring safety.
36 MATERIALS SCIENCE↗
Anion Binding by Macrocyclic Receptors: Computational Landscape of 1:1 and 2:1 Stoichiometries
Macrocyclic receptors play a crucial role in supramolecular chemistry, enabling the selective binding of guest molecules through non-covalent interactions. This study investigates the anion binding properties of three shape-persistent macrocycles, triazolophane, cyanostar, and tricarb, each featuring preorganized cavities with polarized CH hydrogen bond donors. In the 1:1 binding stoichiometries, the macrocycles preferentially bind anions that fit inside their two-dimensional cavities, with this preference being more pronounced in solution. Specifically, the triazolophane favors smaller anions like chloride and bromide, while the larger cavities offered by cyanostar and tricarb macrocycles preferentially bind the larger iodide. For large, polyatomic anions (SCN − , BF$^{−}_{4}$, ClO$^{−}_{4}$, and PF$^{−}_{6}$), the macrocycles self-assemble to form stable 2:1 sandwich complexes, exhibiting stronger binding. This shift in selectivity highlights the versatility of the macrocycles, making them promising candidates for anion sensing and regulation with various complexation stoichiometries.
Che, Minwei [Indiana University, Bloomington, IN (↗
Trap States in Reduced Colloidal Titanium Dioxide Nanoparticles Have Different Proton Stoichiometries
Added electrons and holes in semiconducting (nano)materials typically occupy “trap states,” which often determine their photophysical properties and chemical reactivity. However, trap states are usually ill-defined, with few insights into their stoichiometry or structure. Our laboratory previously reported that aqueous colloidal TiO 2 nanoparticles prepared from TiCl 4 + H 2 O have two classes of electron trap states, termed Blue and Red. Herein, we show that the formation of Red from oxidized TiO 2 requires 1e – + 1H + , while Blue requires 1e – + 2H + . The two states are in a protic equilibrium, Blue ⇌ Red + H + , with K eq = 2.65 mM. The Blue states in the TiO 2 NPs behave just like a soluble molecular acid with this K eq as their K a , as supported by solvent isotope studies. Because the trap states have different compositions, their population and depopulation occur with the making and breaking of chemical bonds and not (as commonly assumed) just by the movement of electrons. In addition, the direct observation of a 2H + /1e – trap state contradicts the emerging H atom transfer (1H + /1e – ) paradigm for oxide/solution interfaces. Finally, this work emphasizes the importance of chemical stoichiometries, not just electronic energies, in understanding and directing the reactivity at solid/solution interfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of non-stoichiometry and pressure on superconductivity in topological semimetal PdTe
Research into topological superconductivity has been at the forefront of condensed matter physics due to both fundamental interest and potential applications in quantum computing. PdTe, is such a superconductor with a transition temperature T c ∼ 4.5 K and exhibits a nontrivial topological electronic structure, thus receiving significant attention. We report an experimental and theoretical investigation of the pressure effect on superconductivity by applying chemical non-stoichiometry and hydrostatic pressure. While T c decreases with increasing pressure through electrical resistivity, magnetization, and specific heat measurements, chemical pressure has a distinct impact from hydrostatic pressure, which could increase T c by creating negative pressure via non-stoichiometric Pd x Te with x > 1. Accompanied with this is a sign change of the Hall coefficient from negative at x < 1 to positive at x > 1. This indicates extreme sensitivity of the electronic structure to chemical non-stoichiometry, which occurs as a Pd vacancy for x < 1 and Pd interstitial for x > 1.
nonstoichiometry↗
Superconducting phase diagram in Bi x Ni 1 – x thin films: The effects of Bi stoichiometry on superconductivity
The Bi-Ni binary system has been of interest due to possible unconventional superconductivity aroused therein, such as time-reversal symmetry breaking in Bi/Ni bilayers or the coexistence of superconductivity and ferromagnetism in Bi 3 Ni crystals. While Ni acts as a ferromagnetic element in such systems, the role of the strong spin-orbit coupling element Bi in superconductivity has remained unexplored. In this work, we systematically studied the effects of Bi stoichiometry on the superconductivity of Bi x Ni 1–x thin films (x ≈ 0.5–0.9) fabricated via a composition-spread approach. Here, the superconducting phase map of Bi x Ni 1–x thin films exhibited a superconducting composition region attributable to the intermetallic Bi 3 Ni phase with different amounts of excess Bi, revealed by synchrotron x-ray diffraction analysis. Interestingly, the mixed-phase region with Bi 3 Ni and Bi showed unusual increases in the superconducting transition temperature and residual resistance ratio as more Bi impurities were included, with the maximum T c (=4.2K) observed at x ≈ 0.79. A correlation analysis of structural, electrical, and magneto-transport characteristics across the composition variation revealed that the unusual superconducting “dome” is due to two competing roles of Bi: impurity scattering and carrier doping. We found that the carrier doping effect is dominant in the mild doping regime (0.74 ≤ x ≤ 0.79), while impurity scattering becomes more pronounced at larger Bi stoichiometry.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Imprint of tree species mycorrhizal association on microbial‐mediated enzyme activity and stoichiometry
Abstract Understanding the effects of tree species and their mycorrhizal association on soil processes is critical for predicting the ecosystem consequences of species shifts owing to global change and forest management decisions. While it is well established that forests dominated by different mycorrhizal types can vary in how they cycle carbon (C), nitrogen (N) and phosphorus (P), the degree to which these patterns are driven by microbial‐mediated enzyme activity (EA) and ecoenzymatic stoichiometry (ES) remains elusive. Here, we synthesized the effects of mycorrhizal association on seven soil enzymes involved in microbial C, N and P acquisition and ES using data from 56 peer‐reviewed papers. We found that relative to soil in ectomycorrhizal (EcM) trees, soil in arbuscular mycorrhizal (AM) trees exhibited greater activity of some C acquisition enzymes (e.g. beta‐glucosidase; BG) and higher ecoenzymatic ratios of BG/NAG (N‐acetyl‐glucosaminidase) and BG/AP (acid phosphatase). These results supported that AM trees had rapid C and nutrient turnover rates, inorganic nutrient economics and high soil microbial C limitation. We also found evidence for an organic nutrient economy and greater soil microbial demand for nutrients in EcM trees compared to AM trees. In addition, the effect of mycorrhizal association on the activity of certain soil enzymes and enzymatic stoichiometry (i.e. BG and BG/NAG ratio) appeared to be associated with the differences in soil pH, phylogenetic group (i.e. conifers and broadleaves) and leaf habit (i.e. evergreen and deciduous) between AM and EcM trees. The results from the global meta‐analysis suggested that soil EA and ES appear to play critical roles in shaping the differences in the nutrient economy between AM and EcM tree species, but leaf morphology and soil conditions should be considered in evaluations of soil processes in forests of different mycorrhizal associations. Given that most of the studies in the database were from the temperate and subtropical regions, further research in other biomes is needed to elucidate the underlying mechanisms driving the mycorrhizal effect at the global scale. Read the free Plain Language Summary for this article on the Journal blog.
54 ENVIRONMENTAL SCIENCES↗
Energy coupling and stoichiometry of Zn 2+ /H + antiport by the prokaryotic cation diffusion facilitator YiiP
YiiP from Shewanella oneidensis is a prokaryotic Zn 2+ /H + antiporter that serves as a model for the Cation Diffusion Facilitator (CDF) superfamily, members of which are generally responsible for homeostasis of transition metal ions. Previous studies of YiiP as well as related CDF transporters have established a homodimeric architecture and the presence of three distinct Zn 2+ binding sites named A, B, and C. In this study, we use cryo-EM, microscale thermophoresis and molecular dynamics simulations to address the structural and functional roles of individual sites as well as the interplay between Zn 2+ binding and protonation. Structural studies indicate that site C in the cytoplasmic domain is primarily responsible for stabilizing the dimer and that site B at the cytoplasmic membrane surface controls the structural transition from an inward facing conformation to an occluded conformation. Binding data show that intramembrane site A, which is directly responsible for transport, has a dramatic pH dependence consistent with coupling to the proton motive force. A comprehensive thermodynamic model encompassing Zn 2+ binding and protonation states of individual residues indicates a transport stoichiometry of 1 Zn 2+ to 2–3 H + depending on the external pH. This stoichiometry would be favorable in a physiological context, allowing the cell to use the proton gradient as well as the membrane potential to drive the export of Zn 2+ .
59 BASIC BIOLOGICAL SCIENCES↗
Impacts of climate and disturbance on nutrient fluxes and stoichiometry in mixed-conifer forests
Elucidating climatic impacts on stream nutrient export and stoichiometry will improve the understanding of forest carbon (C) storage in a warmer world. We constructed C, nitrogen (N), and phosphorus (P) budgets in four watersheds within a rain-snow transition site and another four within a higher-elevation, snow-dominated site, in California’s mixed-conifer zone. We used these two sites in a space-for-time substitution to assess the potential effects of warming on nutrient cycles in currently snow-dominated areas that will become more rain-dominated. During a non-drought period (water year (WY) 2004 – 2011), mean annual stream exports of C and N in particulate forms at the transition site were double that at the snow-dominated site, suggesting that sediment-associated nutrient losses may increase with warming. The transition site had 12% lower N but double the P content in mineral horizons, lower N:P mass ratios in organic horizons, and lower stream export of dissolved inorganic N than the snow-dominated site. Furthermore, these differences suggest that montane forests may receive lower supply of N relative to P with warming. In addition, given strong interests in forest thinning to increase drought resiliency, we examined changes in stream nutrient export after thinning and during a major drought period (WY 2013 – 2015). Stream exports of C, N, and P were similar between unthinned and thinned watersheds during drought, suggesting negligible thinning impacts on stream nutrient export during excessively dry periods. Taken together, our results suggest that as the climate warms, California’s montane forests may lose more nutrients through erosion and receive less N input than P.
54 ENVIRONMENTAL SCIENCES↗
Model of photoemission and framework for relating quantum efficiency to stoichiometry
Simulating the quantum efficiency (QE) from photocathodes used in accelerators and photoinjectors requires accounting for the properties of the photoemissive material, the optical properties, scattering coefficients, and doping concentrations of which are dependent upon the stoichiometry. We present a rapid and flexible optical model that can be used to investigate the consequences of changes in the dielectric properties and their impact on the QE through such factors as reflectivity and laser penetration depth. Differences in materials can then be characterized by changes to parameters used to evaluate the dielectric function in a Lorentz–Drude–Resonant model. A method to characterize data is motivated by the example of copper and vetted by application to an exact analytical model. The effects of changes in parameters describing the resonant terms, which aggregate in the visible and UV regions of the spectrum, are shown.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗