Iridium-Cooperated, Symmetry-Broken Manganese Oxide Nanocatalyst for Water Oxidation.

The water oxidation reaction, the most important reaction for hydrogen production and other sustainable chemistry, is efficiently catalyzed by the Mn4CaO5 cluster in biological photosystem II. However, synthetic Mn-based heterogeneous electrocatalysts exhibit inferior catalytic activity at neutral pH under mild conditions. Symmetry-broken Mn atoms and their cooperative mechanism through efficient oxidative charge accumulation in biological clusters are important lessons but synthesis strategies for heterogeneous electrocatalysts have not been successfully developed. Here, we report a crystallographically distorted Mn-oxide nanocatalyst, in which Ir atoms break the space group symmetry from I41/amd to P1. Tetrahedral Mn(II) in spinel is partially replaced by Ir, surprisingly resulting in an unprecedented crystal structure. We analyzed the distorted crystal structure of manganese oxide using TEM and investigated how the charge accumulation of Mn atoms is facilitated by the presence of a small amount of Ir.

Combined effects of temperature and macronutrient balance on life-history traits in Drosophila melanogaster: implications for life-history trade-offs and fundamental niche.

Temperature and nutrition are amongst the most influential environmental determinants of Darwinian fitness in ectotherms. Since the ongoing climate warming is known to alter nutritional environments encountered by ectotherms, a precise understanding of the integrated effects of these two factors on ectotherm performance is essential for improving the accuracy of predictions regarding how ectotherms will respond to climate warming. Here we employed response surface methodology to examine how multiple life-history traits were expressed across a grid of environmental conditions representing full combinations of six ambient temperatures (13, 18, 23, 28, 31, 33 °C) and eight dietary protein:carbohydrate ratios (P:C = 1:16, 1:8, 1:4, 1:2, 1:1, 2:1, 4:1, 8:1) in Drosophila melanogaster. Different life-history traits were maximized in different regions in the two-dimensional temperature-nutrient space. The optimal temperature and P:C ratio identified for adult lifespan (13 °C and 1:16) were lower than those for early-life female fecundity (28 °C and 4:1). Similar divergence in thermal and nutritional optima was found between body mass at adult emergence (18 °C and P:C 1:1) and the rate of pre-adult development (28 °C and P:C 4:1). Pre-adult survival was maximized over a broad range of temperature (18-28 °C) and P:C ratio (1:8-8:1). These results indicate that the occurrence of life-history trade-offs is regulated by both temperature and dietary P:C ratio. The estimated measure of fitness was maximized at 23 °C and P:C 2:1. Based on the shape of the response surface constructed for this estimated fitness, we characterized the fundamental thermal and nutritional niche for D. melanogaster with unprecedented detail.

Giant Magnetic Anisotropy Induced by Ligand LS Coupling in Layered Cr Compounds.

We propose a novel origin of magnetic anisotropy to explain the unusual magnetic behaviors of layered ferromagnetic Cr compounds (3d^{3}) wherein the anisotropy field varies from ≲0.01 to ∼3 T on changing the ligand atom in a common hexagonal structure. The effect of the ligand p orbital spin-orbit (LS) coupling on the magnetic anisotropy is explored by using four-site full multiplet cluster model calculations for energies involving the superexchange interaction at different spin axes. Our calculation shows that the anisotropy energy, which is the energy difference for different spin axes, is strongly affected not only by the LS coupling strength but also by the degree of p-d covalency in the layered geometry. This anisotropy energy involving the superexchange appears to dominate the magnetic anisotropy and even explains the giant magnetic anisotropy as large as 3 T observed in CrI_{3}.

Comparing the impacts of macronutrients on life-history traits in larval and adult Drosophila melanogaster: the use of nutritional geometry and chemically defined diets.

Protein and carbohydrate are the two major macronutrients that exert profound influences over fitness in many organisms, including Drosophila melanogaster. Our understanding of how these macronutrients shape the components of fitness in D. melanogaster has been greatly enhanced by the use of nutritional geometry, but most nutritional geometric analyses on this species have been conducted using semi-synthetic diets that are not chemically well defined. Here, we combined the use of nutritional geometry and chemically defined diets to compare the patterns of larval and adult life-history traits expressed across 34 diets systematically varying in protein:carbohydrate (P:C) ratio and in protein plus carbohydrate (P+C) concentration. The shape of the response surfaces constructed for all larval and adult traits differed significantly from one another, with the nutritional optima being identified at P:C 1:4 for lifespan (P+C 120 g l-1), 1:2 for egg-to-adult viability (120 g l-1), 1:1 for female body mass at adult eclosion (240 g l-1) and lifetime fecundity (360 g l-1), 2:1 for larval developmental rate (60 g l-1) and 8:1 for egg production rate (120 g l-1). Such divergence in nutritional optima among life-history traits indicates that D. melanogaster confined to a single diet cannot maximize the expression of these traits simultaneously and thus may face a life-history trade-off. Our data provide the most comprehensive and nutritionally explicit analysis of the impacts of macronutrients on life-history traits in D. melanogaster and support the emerging notion that the fundamental trade-offs among life-history traits are mediated by macronutrients.

Hybridization gap and Fano resonance in SmB6.

Hybridization between conduction electrons and the strongly interacting f-electrons in rare earth or actinide compounds may result in new states of matter. Depending on the exact location of the concomitant hybridization gap with respect to the Fermi energy, a heavy fermion or an insulating ground state ensues. To study this entanglement locally, we conducted scanning tunneling microscopy and spectroscopy (STS) measurements on the "Kondo insulator" SmB6. The vast majority of surface areas investigated were reconstructed, but infrequently, patches of varying sizes of nonreconstructed Sm- or B-terminated surfaces also were found. On the smallest patches, clear indications for the hybridization gap with logarithmic temperature dependence (as expected for a Kondo system) and for intermultiplet transitions were observed. On nonreconstructed surface areas large enough for coherent cotunneling, we were able to observe clear-cut Fano resonances. Our locally resolved STS indicated considerable finite conductance on all surfaces independent of their structure, not proving but leaving open the possibility of the existence of a topologically protected surface state.

Macronutrient Balance Modulates the Temperature-Size Rule in an Ectotherm.

Most ectotherms mature at a larger body size in colder conditions, a phenomenon known as the temperature-size rule. While a number of hypotheses have been proposed to explain this rule, little work has been done to understand it from a nutritional perspective. We have used the final-instar caterpillars of Spodoptera litura to investigate how dietary protein∶carbohydrate (P∶C) balance influences the relationship between temperature and body size. The strength and direction of the thermal reaction norm for body size were significantly altered by dietary P∶C balance. The slope of the reaction norm was nearly flat for caterpillars raised on a balanced food ([Formula: see text]) but was significantly negative for those on nutritionally imbalanced foods (1∶5 or 5∶1), especially when carbohydrates were in considerable excess. These nutrient-dependent effects of temperature on body size were caused mainly by corresponding changes in body lipid storage. When allowed to choose between imbalanced diets, caterpillars increased their preference for carbohydrates to meet high energy demands at higher temperatures. The slope of the thermal reaction norm for body size was substantially reduced by such a temperature-driven shift in nutrient preference, indicating that the impact of high temperature on body size was buffered by altered food selection. This study highlights the importance of macronutrient balance as a key factor modulating the relationship between temperature and body size in ectotherms and provides a novel approach for understanding the temperature-size rule.

Tunable ion energy barrier modulation through aliovalent halide doping for reliable and dynamic memristive neuromorphic systems.

Memristive neuromorphic computing has emerged as a promising computing paradigm for the upcoming artificial intelligence era, offering low power consumption and high speed. However, its commercialization remains challenging due to reliability issues from stochastic ion movements. Here, we propose an innovative method to enhance the memristive uniformity and performance through aliovalent halide doping. By introducing fluorine concentration into dynamic TiO2-x memristors, we experimentally demonstrate reduced device variations, improved switching speeds, and enhanced switching windows. Atomistic simulations of amorphous TiO2-x reveal that fluoride ions attract oxygen vacancies, improving the reversible redistribution and uniformity. A number of migration barrier calculations statistically show that fluoride ions also reduce the migration energies of nearby oxygen vacancies, facilitating ionic diffusion and high-speed switching. The detailed Voronoi volume analysis further suggests design principles in terms of the migrating species' electrostatic repulsion and migration barriers. This work presents an innovative methodology for the fabrication of reliable memristor devices, contributing to the realization of hardware-based neuromorphic systems.

Emergence of the isotropic Kitaev honeycomb latticeα-RuCl3and its magnetic properties.

We present a comprehensive investigation of the crystal and magnetic structures of the van der Waals antiferromagnetα-RuCl3using single crystal x-ray and neutron diffraction. The crystal structure at room temperature is a monoclinic (C2/m). However, with decreasing temperature, a remarkable first-order structural phase transition is observed, leading to the emergence of a rhombohedral (R3-) structure characterized by three-fold rotational symmetry forming an isotropic honeycomb lattice. On further cooling, a zigzag-type antiferromagnetic order develops belowTN=6∼6.6K. The critical exponent of the magnetic order parameter was determined to beß=0.11(1), which is close to the two-dimensional Ising model. Additionally, the angular dependence of the magnetic critical field of the zigzag antiferromagnetic order for the polarized ferromagnetic phase reveals a six-fold rotational symmetry within theab-plane. These findingsreflect the symmetry associated with the Ising-like bond-dependent Kitaev spin interactions and underscore the universality of the Kitaev interaction-dominated antiferromagnetic system.

Thermal and nutritional environments during development exert different effects on adult reproductive success in Drosophila melanogaster.

Environments experienced during development have long-lasting consequences for adult performance and fitness. The "environmental matching" hypothesis predicts that individuals perform best when adult and developmental environments match whereas the "silver spoon" hypothesis expects that fitness is higher in individuals developed under favorable environments regardless of adult environments. Temperature and nutrition are the two most influential determinants of environmental quality, but it remains to be elucidated which of these hypotheses better explains the long-term effects of thermal and nutritional histories on adult fitness traits. Here we compared how the temperature and nutrition of larval environment would affect adult survivorship and reproductive success in the fruit fly, Drosophila melanogaster. The aspect of nutrition focused on in this study was the dietary protein-to-carbohydrate (P:C) ratio. The impact of low developmental and adult temperature was to improve adult survivorship. High P:C diet had a negative effect on adult survivorship when ingested during the adult stage, but had a positive effect when ingested during development. No matter whether adult and developmental environments matched or not, females raised in warm and protein-enriched environments produced more eggs than those raised in cool and protein-limiting environments, suggesting the presence of a significant silver spoon effect of larval temperature and nutrition. The effect of larval temperature on adult egg production was weak but persisted across the early adult stage whereas that of larval nutrition was initially strong but diminished rapidly after day 5 posteclosion. Egg production after day 5 was strongly influenced by the P:C ratio of the adult diet, indicating that the diet contributing mainly to reproduction had shifted from larval to adult diet. Our results highlight the importance of thermal and nutritional histories in shaping organismal performance and fitness and also demonstrate how the silver spoon effects of these aspects of environmental histories differ fundamentally in their nature, strength, and persistence.

Microbially Guided Discovery and Biosynthesis of Biologically Active Natural Products.

The design of small molecules that inhibit disease-relevant proteins represents a longstanding challenge of medicinal chemistry. Here, we describe an approach for encoding this challenge-the inhibition of a human drug target-into a microbial host and using it to guide the discovery and biosynthesis of targeted, biologically active natural products. This approach identified two previously unknown terpenoid inhibitors of protein tyrosine phosphatase 1B (PTP1B), an elusive therapeutic target for the treatment of diabetes and cancer. Both inhibitors appear to target an allosteric site, which confers selectivity, and can inhibit PTP1B in living cells. A screen of 24 uncharacterized terpene synthases from a pool of 4464 genes uncovered additional hits, demonstrating a scalable discovery approach, and the incorporation of different PTPs into the microbial host yielded alternative PTP-specific detection systems. Findings illustrate the potential for using microbes to discover and build natural products that exhibit precisely defined biochemical activities yet possess unanticipated structures and/or binding sites.

Decay and renormalization of a longitudinal mode in a quasi-two-dimensional antiferromagnet.

An ongoing challenge in the study of quantum materials, is to reveal and explain collective quantum effects in spin systems where interactions between different modes types are important. Here we approach this problem through a combined experimental and theoretical study of interacting transverse and longitudinal modes in an easy-plane quantum magnet near a continuous quantum phase transition. Our inelastic neutron scattering measurements of Ba2FeSi2O7 reveal the emergence, decay, and renormalization of a longitudinal mode throughout the Brillouin zone. The decay of the longitudinal mode is particularly pronounced at the zone center. To account for the many-body effects of the interacting low-energy modes in anisotropic magnets, we generalize the standard spin-wave theory. The measured mode decay and renormalization is reproduced by including all one-loop corrections. The theoretical framework developed here is broadly applicable to quantum magnets with more than one type of low energy mode.

Context-dependent effects of temperature on starvation resistance in Drosophila melanogaster: Mechanisms and ecological implications.

Temperature can modulate the responses of ectotherms to environmental stressors, such as food shortage. Temperature-mediated plasticity in starvation resistance can arise by changes in the amount of energy stored, the speed of energy expenditure, or the threshold energy reserves required for survival. However, few studies have investigated how temperature affects these physiological mechanisms underlying starvation resistance. In this study, we first examined the mechanistic basis of the temperature dependence of starvation resistance in Drosophila melanogaster. We then tested whether the effects of temperature on starvation resistance would depend on diet and developmental stage in this species. We found that exposure to high temperature during starvation significantly reduced the capacity of D. melanogaster to resist starvation. This warming-induced decrease in starvation resistance was mainly caused by faster depletion of body lipids and not by lower threshold lipid content for survival. D. melanogaster exposed to higher temperatures during feeding accumulated more body lipids and thus became more starvation resistant. Such positive effect of high feeding temperature on starvation resistance was pronounced when D. melanogaster consumed carbohydrate-rich diets. D. melanogaster raised as larvae at low temperature (18 °C) had a weaker starvation resistance at adult emergence compared to those raised at higher temperatures (23 and 28 °C). These results demonstrate that the effects of temperature on starvation responses are highly context-dependent in D. melanogaster.

The genetic basis for mating-induced sex differences in starvation resistance in Drosophila melanogaster.

Multiple genetic and environmental factors interact to influence starvation resistance, which is an important determinant of fitness in many organisms, including Drosophila melanogaster. Recent studies have revealed that mating can alter starvation resistance in female D. melanogaster, but little is known about the behavioral and physiological mechanisms underlying such mating-mediated changes in starvation resistance. In the present study, we first investigated whether the effect of mating on starvation resistance is sex-specific in D. melanogaster. As indicated by a significant sex×mating status interaction, mating increased starvation resistance in females but not in males. In female D. melanogaster, post-mating increase in starvation resistance was mainly attributed to increases in food intake and in the level of lipid storage relative to lean body weight. We then performed quantitative genetic analysis to estimate the proportion of the total phenotypic variance attributable to genetic differences (i.e., heritability) for starvation resistance in mated male and female D. melanogaster. The narrow-sense heritability (h(2)) of starvation resistance was 0.235 and 0.155 for males and females, respectively. Mated females were more resistant to starvation than males in all genotypes, but the degree of such sexual dimorphism varied substantially among genotypes, as indicated by a significant sex×genotype interaction for starvation resistance. Cross-sex genetic correlation was greater than 0 but less than l for starvation resistance, implying that the genetic architecture of this trait was partially shared between the two sexes. For both sexes, starvation resistance was positively correlated with longevity and lipid storage at genetic level. The present study suggests that sex differences in starvation resistance depend on mating status and have a genetic basis in D. melanogaster.