In this work, MoS2 was prepared as a supporting matrix for Pt via a hydrothermal method using different solvents, and the electrocatalytic activity of Pt/MoS2 for the ethanol oxidation reaction was investigated. To understand the influence of MoS2 on Pt, the catalyst was evaluated through both physical and electrochemical characterization. In addition, in situ electrochemistry-nuclear magnetic resonance, leveraging its advantages in structural analysis and real-time monitoring, was employed to track molecular changes in reaction products and to clarify the reaction mechanism of ethanol oxidation. The results demonstrate that the solvent has a large effect on the property of Pt/MoS2. The Pt/MoS2 hybrid fabricated in the solvent of DMF:H2O = 2:1 shows a significantly enhanced electrocatalytic activity compared with the other three kinds of catalyst due to the special structure and the enhancing electron transport. This work provides an effective strategy for studying the role of the solvent in the synthetic process.
This study developed and validated a non-invasive multi-metabolite magnetic resonance spectroscopy framework for preoperative molecular subtyping of adult diffuse gliomas. Using a cross-center, cross-vendor cohort of 268 patients, 48 features derived from 18 metabolites were systematically evaluated to identify discriminative metabolic signatures for predicting IDH mutation and 1p/19q codeletion status. The integrated metabolic model showed robust intra-center and cross-center performance for IDH prediction, with AUCs of 0.906 and 0.857, respectively, and for 1p/19q prediction, with AUCs of 0.858 and 0.787, respectively. These results suggest that synergistic metabolic profiling support molecular assessment in patients who may not be suitable for invasive biopsy.
[This corrects the article DOI: 10.1021/acsearthspacechem.6c00026.].
The seepage of agrochemicals into surface water and groundwater from treated fields poses a serious threat to freshwater ecosystems. The frequently used fungicide Mancozeb degrades in water into a metabolite, Ethylene thiourea (ETU), which is more persistent and often more toxic, with the potential to impact non-target zooplankton. This study evaluates the acute and chronic responses of abundant cladoceran zooplankton Ceriodaphnia cornuta Sars, 1885, through acute and chronic bioassays spanning six generations of continuous exposure. The susceptibility of C. cornuta neonates from the sixth generation was compared to that of neonates with no prior exposure, using an acute bioassay. Our results showed that Mancozeb contamination negatively affected the survival and reproduction of C. cornuta, and the effect was concentration-specific. Notably, exposure to 1.54 μg/L Mancozeb across six generations resulted in a significantly longer life expectancy at birth and higher reproductive rates. In contrast, the sixth-generation neonates (continuously exposed) had a lower 48 h LC50 for Mancozeb compared to naive organisms (no prior exposure). These findings suggest that continuous exposure of C. cornuta to environmental concentrations of Mancozeb across generations leads to increased sensitivity to Mancozeb in the offspring. This highlights the need for further research on the impacts and evolutionary consequences of commercial formulations on non-target crustaceans.
Glass pH electrodes are widely used to estimate proton activity (a H+ ) in aqueous solutions. However, at high proton activity, conventional linear calibration using standard NIST/DIN buffers breaks down due to nonlinear electrode response and strong nonideality, leading to severe pH overestimation. To alleviate this limitation, this study develops and validates a nonlinear, temperature-corrected calibration protocol that extends the measurable and reliable range of pH using glass electrodes down to (pH = -log a H+ ) = -5 (proton activity of 105) over a temperature range between 5 and 60 °C. The calibration is done using NIST buffers (pH 1.68 to 10.01) and sulfuric acid standards (concentrations ranging between 0.16 mmol·L-1 and 9.69 mol·L-1 H2SO4). Proton activities are calculated using the Pitzer model with the MacInnes assumption implemented in PHREEQC. At a given temperature, the response curve between pH and the electrode electromotive force in the low to negative pH range is modeled best with a logistic equation. Incorporation of temperature-dependent parameters enables construction of continuous nonlinear calibration curves across the studied temperature range. Application of this calibration protocol reduces systematic pH overestimation by up to >3 pH units and yields accurate proton activity under strongly acidic conditions. Sensitivity analysis demonstrates that meaningful measurements are achievable down to approximately pH ≈ -5, below which signal-to-noise constraints dominate. This work establishes a transferable and practical methodology that extends the operational range of conventional glass electrodes by several orders of magnitude in proton activity, enabling more reliable pH measurements in extreme natural and industrial environments.
Reconciling lower environmental impacts from agriculture with food security is a core national objective in China. We develop spatially explicit projections for nine major crops to 2030 and 2060 under Business-as-Usual (BAU), BAU with carbon-efficiency constraints (BAU-CE), and Sustainable Development Goal (SDG)-aligned pathway (SDG-60). Despite improved input-use efficiency, national output declines modestly by 2030 relative to 2020 (-11.4% BAU and -11.5% BAU-CE). By 2060, efficiencies approach ∼90%, with substantial reductions in aggregate inputs (fertilizer -30%, pesticides -50%, and irrigation water -34.4%). Under SDG-60, cropping greenhouse-gas emissions are ∼72% lower than under BAU-CE, while aggregate production across the nine crops declines by ∼50.5%. Spatial heterogeneity reveals trade-off zones where large mitigation gains and reduced chemical and water use coincide with output and income losses, particularly in rice-intensive provinces. Provinces with below-median labor productivity and income but above-median mitigation burdens are identified as structurally disadvantaged, highlighting where differentiated targets, incentives, and transition support are most needed to balance mitigation, food security, and rural livelihoods.
Space weathering causes physical and spectral changes on the surfaces of airless bodies. However, our understanding of how space weathering operates in the presence of volatile ices is in its early stages. Electron irradiation of ice-coated surfaces is expected in astrophysical environments including the early solar system, volatile ice-rich permanently shadowed regions of the Moon and Mercury, and other airless bodies like asteroids. A recent study suggests that anomalous oxygen isotope exchange occurs between water-ice and underlying surfaces when exposed to electron irradiation at extremely low temperatures (10 K). To delve deeper into the physical processes underlying isotopic exchange, we employ nanoscale atomic force microscopy-based infrared (AFM-IR) spectroscopy to identify Si-O bond formation resulting from the electron irradiation of H2O ice coated silicon targets. Experimental variables include electron energy, amount and timing of water-ice deposition, and surface area exposed to the electron beam. AFM-IR point spectra, surface topography and IR absorption mapping reveal that the degree of surface oxidation is dependent upon experimental conditions. Scanning electron microscopy and (scanning) transmission electron microscope imaging confirm the formation of thicker SiO x in regions of enhanced interaction between electron irradiation, water-ice, and the silicon substrate. In summary, we find that electron irradiation with energies as low as 1 keV/electron can break the chemical bonds of refractory solids like Si under these simulated cold astrophysical conditions. These results suggest that cosmic rays may play a more significant role than previously thought in the chemical evolution of dust grains in cold astrophysical and protoplanetary environments.
The extraction of rare earth elements (REE) from complex mineral matrices typically relies on hydrometallurgical routes involving strong inorganic acids, which pose significant environmental and operational challenges, including silica gel formation. In this study, a sustainable leaching approach was developed for the recovery of Ce, La, and Nd from calcined bastnasite ore using a nonaqueous type IV deep eutectic solvents (DES) composed of ethylene glycol (EG) and iron-(III) chloride (FeCl3). A systematic optimization was conducted using the Taguchi L32 orthogonal array design to evaluate the effects of temperature, solid-to-liquid (S/L) ratio, FeCl3 concentration, leaching time, and stirring speed. Statistical analysis and stepwise regression modeling identified temperature as the most critical parameter governing extraction efficiency, with the regression models exhibiting high predictive accuracy (R 2 > 0.87). Molarity and S/L ratio did not exhibit significant effects individually; however, their efficacy became pronounced in conjunction with temperature. The highest total light REE (LREE) extraction efficiency was found to be 62.8% under the conditions of 50 °C, 1 M FeCl3, S/L ratio of 0.05 g/mL, and 16 h. Furthermore, the dissolution mechanism was elucidated using FTIR spectroscopy, which provided direct evidence of an in-situ acidification process. Spectral analysis confirmed that ferric ions coordinate with ethylene glycol to form iron-glycolate complexes, releasing protons that drive the dissolution of REE oxides, with water generated as a stoichiometric byproduct. These findings demonstrate that the EG-FeCl3 system offers a competitive, simplified, and water-free alternative for processing REE ores, mitigating the limitations of conventional aqueous methods.
Rare-earth additions are widely used to mitigate harmful oxygen, nitrogen, and sulfur inclusions in high-Cr, high-Ti heat-resistant alloys, yet the interfacial mechanism governing rare-earth-inclusion interactions remains unclear. Here, density functional theory (DFT) calculations are used to systematically investigate yttrium adsorption on three representative inclusion phases: TiO2, TiN, and MnS. For each surface, we identify the most stable adsorption configurations and quantify the corresponding adsorption energetics. Differential charge density, electron localization function (ELF), and projected density of states (PDOS) analyses show that Y binding is characterized by pronounced charge redistribution and mixed ionic-covalent interactions with surface atoms, depending on inclusion chemistry. Y adsorption also stabilizes the inclusion surfaces by lowering the electronic energy and reducing high-energy surface states near the Fermi level, consistent with strengthened interfacial bonding. Together, these results provide an atomistic picture of how Y interacts with O/N/S inclusions and offer microscopic guidelines for rare-earth alloying strategies aimed at impurity control and processing optimization.
Ocean variability spans a wide range of scales, from centimeters to thousands of kilometers and from seconds to millennia. Turbulence and mixing occupy the smallest scales, with the Atlantic Meridional Overturning Circulation (AMOC) at the largest scales. However, small-scale processes can also affect the large-scale circulation. Past reviews have considered how mixing sets or affects the mean and structure of the AMOC. This review considers how mixing may affect the time variability of the AMOC. It first defines the AMOC, then discusses drivers of variability and how they are manifested in the observed overturning at the RAPID 26°N and Overturning in the Subpolar North Atlantic Program (OSNAP) arrays. It then considers how diabatic processes can change the large-scale overturning circulation.
Synthetic cells (SCs) are programmable biomimetic systems that reproduce selected cellular functions while offering high structural and functional controllability. A particularly attractive feature of SCs is their ability to respond to external stimuli, enabling regulated cargo release and communication with living cells. Here, we report a light-responsive SC platform capable of establishing chemically mediated communication with human cancer cells. Upon light stimulation, the SCs release signaling molecules, such as adenosine triphosphate (ATP) and histamine, that activate intracellular calcium signaling pathways in target cells. These results demonstrate the feasibility of remotely controlled communication between synthetic and living cells and highlight the potential of SCs as bio-hybrid interfaces for precise cellular modulation, therapeutic delivery, artificial organelles, and other biomedical applications.
Building compactness and construction epoch are relevant proxies of energy efficiency in buildings. By integrating building stock and Earth observation data, we characterize buildings globally and identify vulnerable areas dominated by old building age and unsuitable compactness in relation to climate conditions. Such areas are home to a population of 48 million persons that could increase by 10% to 30% by 2100 under likely socioeconomic pathways, shifting from cold regions of Eurasia to the heat-prone Sahel zone, Gulf countries and Pakistan. Results reveal stark disparities in building energy efficiency across income levels, urbanization patterns, and climate zones. Almost half of buildings globally (i.e., 43%) were built before 1980, when few to no energy efficiency measures existed, and these buildings are concentrated mainly in temperate and cold-climate urban areas in high-income countries. Low-income countries experienced more recent, lightweight and less compact urban expansion, which exposes them to the forecasted climate warming: this could increase their energy demand, hinder climate adaptation and imposes further challenges to ensure affordable thermal comfort for all.
Antimicrobial resistance (AMR) among Gram-negative bacteria represents a major global public health challenge, severely limiting therapeutic options and increasing morbidity and mortality. In particular, the widespread dissemination of extended-spectrum β-lactamase (ESBL)-producing Enterobacterales and the emergence of carbapenem-resistant organisms are critical concerns in both hospital and community settings. In Italy, particularly in southern regions, high rates of multidrug-resistant pathogens have been reported. A total of 145 non-duplicate Gram-negative isolates were collected from hospitalized patients in Calabria, Southern Italy, and analyzed by standard antimicrobial susceptibility testing and endpoint PCR for detection of carbapenemase genes (blaKPC, blaVIM, blaNDM, blaOXA-48) and ESBL genes (blaTEM, blaSHV, blaCTX-M). Carbapenem resistance was observed in 60.7% of isolates, predominantly in Klebsiella pneumoniae and Acinetobacter baumannii. Carbapenemase genes were detected in 84.1% of resistant isolates, with blaVIM being the most prevalent (53.4%), followed by blaKPC (34.1%), blaNDM (28.4%), and blaOXA-48 (14.8%); multiple genes were identified in 21.6% of cases. Among carbapenem-susceptible Enterobacterales, 81.3% were phenotypically ESBL producers. Genotypic analysis showed predominance of blaCTX-M (45.8%), followed by blaTEM (29.2%) and blaSHV (16.7%). Discrepancies between phenotypic and genotypic ESBL detection were observed. Also, sequence analysis of ompK35 and ompK36 in Klebsiella pneumoniae isolates revealed mutations and structural alterations potentially associated with reduced outer membrane permeability. This study documents the circulation of carbapenemase and ESBL determinants among Gram-negative clinical isolates in Southern Italy, highlighting the complexity of β-lactam resistance mechanisms. These findings reinforce the importance of integrating molecular surveillance with antimicrobial stewardship and infection control strategies to monitor the dissemination of multidrug-resistant pathogens.
Chlamydomonas reinhardtii is a unicellular green alga long studied as a biological model system but rarely considered from the perspective of its own ecology, thus epitomizing the disconnection between reductionist biology in the laboratory and life in nature. Here we present insights into its ecology understood from field strains. We examined bacterial communities that coenriched with C. reinhardtii from the field, revealing specific associations. We then compared the biology of C. reinhardtii field strains to laboratory strains, illuminating strain level heterogeneity and adaptations to life in the field vs. laboratory. Field strains exhibited more robust photosynthesis, higher abundances of pherophorin proteins, a propensity for pallmeloid formation, and high cell wall permeability. Finally, we phenotyped cocultures of C. reinhardtii with a coenriched bacterial partner, demonstrating how differences between field and laboratory strains manifest in biotic interactions. Although the organisms in question are classically understood as unicellular, our observations of field strains highlighted their participation in multicellular units, challenging the utility of unicellular frameworks in extending our knowledge of model organism biology in the laboratory towards understanding microbial ecology.
Hippocampal pattern separation is a neural operation supporting mnemonic discrimination of highly similar memories by orthogonalizing neural inputs into nonoverlapping representations. In humans, pattern separation is thought to support the specificity of episodic memories. Recent neuroimaging studies suggest that the hippocampus can also access and manipulate semantic information. However, it is unclear whether the hippocampus can pattern separate highly similar semantic representations. Here, we tested multiple neural and behavioral signatures of pattern separation using high-resolution functional MRI during a well-established memory discrimination task where we manipulated semantic similarity in a multidimensional conceptual space using word-embeddings. Thirty young adults (Mage = 21.1, 16 females) saw adjective-noun phrases (e.g., "exotic zoo") that were later repeated exactly as before or modified with semantically similar adjectives (e.g., "strange zoo"). Crucially, we presented exact and modified repeats both during an incidental encoding and a two-choice recognition phase, where mnemonic discrimination was assessed. Consistent with pattern separation, we found attenuated repetition suppression for modified repeats in repetition sensitive clusters of the hippocampal head, which was evident at both high and low levels of similarity with no difference between two a priori defined similarity bins. In addition, within participants, the neural signature of pattern separation was associated with mnemonic discrimination at recognition. Finally, clusters sensitive to repetitions during encoding differentiated lures from foils at recognition. These results suggest that hippocampal pattern separation is triggered by fine-grained differences in meaning and supports the creation of highly specific representations of memories overlapping in semantic memory.
As coral reefs face declines driven by thermal stress and the breakdown of coral symbiosis (i.e., coral bleaching), restoration efforts rely on coral health and resilience rankings. However, seasonal plasticity in symbiosis and metabolism and the presence of cryptic species complicates data interpretation. Quantifying seasonal plasticity in coral physiology and incorporating genetic identification are essential for interpreting and drawing conclusions from trait-based and fitness-based analyses. To test the effect of seasonal and site variation on physiology, we sampled three ecologically dominant genera, Acropora, Pocillopora, and Porites across three lagoon sites (n = 15 tagged colonies genus-1 site-1) on the north shore of Mo'orea, French Polynesia in January, March, September, and December of 2020. We identified coral host and intracellular Symbiodiniaceae to the highest taxonomic resolution possible and quantified 13 physiological variables. Genetic analyses identified A. pulchra and cryptic lineages in Pocillopora (P. meandrina, P. tuahiniensis) and Porites (P. evermanni, P. lobata/lutea). Acropora pulchra hosted Durusdinium trenchii and Symbiodinium microadriaticum. Symbiont communities differed between cryptic congeners, with P. meandrina hosting Cladocopium latusorum and P. tuahiniensis hosting Cladocopium pacificum, whereas P. evermanni and P. lobata/lutea both hosted Cladocopium (C15), but each with unique C15 profiles. Acropora and Pocillopora displayed seasonal cycles of symbiont density and productivity ("boom and bust") in association with light and temperature, a pattern that may contribute to the greater environmental sensitivity previously reported in these taxa. In contrast, Porites exhibited greater symbiont stability, with temperature-rather than light-showing stronger associations with host physiology. Increased host biomass under cooler conditions, which may provide greater energy reserves, could represent one mechanism contributing to the comparatively greater stress tolerance observed in massive Porites. Collectively, our findings highlight the importance of integrating baseline physiological measurements with host and symbiont genetics when interpreting coral responses across seasons.
A new nitrogen-rich triazolo-triazole compound, (3-(6-methyl-1H-[1,2,4]-triazolo-[4,3-b]-[1,2,4]-triazol-3-yl)-1H-1,2,4-triazol-5-amine), TTT1, has been prepared, and its acid-base and tautomeric behavior has been investigated. In the pH range of 0.3-12, TTT1 can accept up to two protons, forming a monocation and a dication, and can deliver one proton, forming a monoanion. The tautomeric behavior is particularly rich for the monocation, for which computational analysis predicts four different tautomers in a narrow energy range of 2 kcal/mol. Two of these tautomers (2H-7H-8H and 3H-7H-8H) have been isolated in salts of the monocation with suitable counterions (chloride, bromide, perchlorate). Surprisingly, the most stable predicted tautomer, 1H-3H-7H, has not been found in the four crystallized salts of the monocation. The energetic perchlorate salt of the monocation (3H-7H-8H tautomer) shows good thermal stability and good stability to impact, friction, and electric discharge. The packing of this compound shows the formation of H-bonded dimers with interactions between N8-H···N1. The crystal structure of this energetic salt was studied experimentally up to 2.8 GPa; no phase change or decomposition was observed.
Isidoidae Heestand Saucier, France & Watling, 2021 is a rare octocoral family currently represented by a single genus and species, Isidoides armata Nutting, 1910 recorded in the western Pacific Ocean. The taxonomic status and diversity of Isidoides is unclear, due to the lack of diagnostic taxonomic features and limited taxon sampling. Based on 23 Isidoides specimens obtained from the northwestern to southwestern Pacific, we carried out morphological and phylogenetic analyses to reveal the taxonomic status of new species and develop reliable features for species identification. The 23 specimens could be classified into four well-supported clades by the phylogenomic analysis of ultraconserved elements (UCEs), four groups by 28S rDNA, and two groups by mtMutS-cox1. Integrating morphology and molecular data, we uncovered unexpected diversity of Isidoides composed of the known species Isidoides armata and three new species, viz., I. elegans sp. nov., I. gracilis sp. nov. and I. pseudarmata sp. nov. The morphological analysis showed high intraspecific morphological variation in colony color and the size, shape and arrangement of polyps. By contrast, sclerite forms with their surface sculpturing are more diagnostic features for species identification. Our phylogenetic and species delimitation analyses indicate that UCEs have higher resolution than the nuclear 28S rDNA and the mitochondrial genes mtMutS and cox1 for species discrimination within Isidoidae. ZooBank: urn:lsid:zoobank.org:pub:392485F5-502E-4383-B153-45B167571190.
Wacker-type oxidation is a cornerstone catalytic transformation for alkene-to-carbonyl conversion in organic synthesis, with immense industrial and academic impact over six decades. However, the classic Wacker-Tsuji system suffers from inherent limitations, including corrosive chloride reliance, poor regiocontrol, noble metal dependence, catalyst deactivation, and sustainability issues, which severely restrict its synthetic utility. Ligand engineering has emerged as the central strategy to revolutionize this field, yet no comprehensive review dedicated to ligand-controlled Wacker-type oxidation has been reported to date. Herein, we systematically dissect the fundamental regulatory mechanisms of ligands in Wacker-type oxidation, and provide a holistic overview of state-of-the-art advances in ligand-modulated palladium catalysis, including chloride/copper-free systems, switchable Markovnikov/anti-Markovnikov regioselectivity, and asymmetric catalysis. We further summarize ligand-enabled palladium-free oxidation based on earth-abundant metals (Fe, Co, Ru, Cu), which achieves unprecedented anti-Markovnikov selectivity inaccessible to traditional Pd catalysts. Finally, we critically outline the key unresolved challenges and future perspectives in this field, aiming to provide rational guidance for the development of next-generation efficient, selective, and sustainable Wacker-type oxidation systems.