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Based on first-principles calculations with the DFT + U method, the couplings of lattice, charge, spin, and electronic behaviors underlying the Eu-Mn charge transfer in a strongly correlated system of EuMnO3 were investigated. The potential valence transition from Eu3+/Mn3+ to Eu2+/Mn4+ was observed in a compressed lattice with little distortions, which is achieved under hydrostatic pressure and external strain. The intraplane antiferromagnetism (AFM) of Mn is proved to be instrumental in the emergence of Eu2+. Furthermore, we calculated the magnetic exchange interactions within two equilibrium structures of Eu3+Mn3+O3 and Eu2+Mn4+O3. Mn-Mn ferromagnetic exchange in the ab-plane is enhanced strongly in the Eu2+Mn4+O3 structure, contributing to the existence of mixed states. The versatile electronic structures were obtained within the Eu2+Mn4+O3 phase by imposing different magnetic configurations on the Eu and Mn sublattice, attributed to the coupling of charge transfer and magnetic orderings. It is found that the intraplane ferromagnetic ordering of Mn leads to a metallic electronic structure with the coexistence of Eu2+ and Eu3+, while the intraplane AFM Mn spin ordering leads to insulating states only with Eu2+. Notably, a half-metallic characteristic emerges at the magnetic ground state of CF ordering (C-type AFM for the Eu sublattice and ferromagnetic for the Mn sublattice), which makes such a supposed phase more intriguing than the conventional experimental phase. Additionally, the mixture of delocalized 4f with 5d states of Eu in the background of Mn 3d and O 2p orbitals implies a pathway of Eu 4f 5d ↔ O 2p ↔ Mn 3d for charge transfer between Eu and Mn. Our calculation shows that the Eu-Mn charge transfer could be expected in compressed EuMnO3 and the introduction of Eu2+ 4f states near the Fermi level plays an important role in manipulating the interlinks of charge and spin together with electronic behaviors.Algal bloom microalgae are abundant in polluted water systems, but their biocrude oil production potential via hydrothermal liquefaction (HTL) is limited. This study proposed a novel process that combined biological (dark fermentation) and thermochemical (HTL) techniques aimed at changing the feedstock characteristics to be more suitable for thermochemical conversion, herein named integrated dark fermentation-hydrothermal liquefaction (DF-HTL). DF-HTL conversion of algae significantly enhanced the biocrude oil yield (wt %), carbon content (mol), energy content (MJ), and energy conversion ratios by 9.8, 29.7, 40.0, and 61.0%, respectively, in comparison to the control. Furthermore, DF-HTL processing significantly decreased the aqueous byproduct yield (wt %), carbon content (mol), nitrogen content (mol), and ammonia content (mol) by 19.0, 38.4, 25.0, and 13.2%, respectively, in comparison to the control. Therefore, DF-HTL reduced the environmental impact associated with disposing of the wastewater byproduct. However, DF-HTL also augmented the nitrogen content (mol) of the biocrude oil by 42.2% in comparison to the control. The benefits of DF-HTL were attributed to the increased acid content, the incorporation of H2 as a processing gas, and the enhancement of the Maillard reaction, which shifted the distribution of reaction products from the aqueous phase to the biocrude oil phase. This article provides insights into the efficacy of a novel integrated biological-thermochemical processing method with distinct environmental and energetic advantages over conventional HTL that heightens the biocrude oil yield for feedstocks with a high carbohydrate and a high protein content.Schistosomiasis is a chronic and painful disease of poverty caused by the flatworm parasite Schistosoma. Drug discovery for antischistosomal compounds predominantly employs in vitro whole organism (phenotypic) screens against two developmental stages of Schistosoma mansoni, post-infective larvae (somules) and adults. We generated two rule books and associated scoring systems to normalize 3898 phenotypic data points to enable machine learning. The data were used to generate eight Bayesian machine learning models with the Assay Central software according to parasite's developmental stage and experimental time point (≤24, 48, 72, and >72 h). The models helped predict 56 active and nonactive compounds from commercial compound libraries for testing. When these were screened against S. mansoni in vitro, the prediction accuracy for active and inactives was 61% and 56% for somules and adults, respectively; also, hit rates were 48% and 34%, respectively, far exceeding the typical 1-2% hit rate for traditional high throughput screens.Stable isotope tracers are applied for in vivo and in vitro studies to reveal the activity of enzymes and intracellular metabolic pathways. Most often, such tracers are used with gas chromatography coupled to mass spectrometry (GC-MS) owing to its ease of operation and reproducible mass spectral databases. Differences in isotope tracer performance of the classic GC-quadrupole MS instrument and newer time-of-flight instruments are not well studied. Here, we used three commercially available instruments for the analysis of identical samples from a stable isotope labeling study that used [U-13C6] d-glucose to investigate the metabolism of the bacterium Rothia mucilaginosa with respect to 29 amino acids and hydroxyl acids involved in primary metabolism. The prokaryote R. mucilaginosa belongs to the family of Micrococcaceae and is present and metabolically active in the airways and sputum of cystic fibrosis patients. Overall, all three GC-MS instruments (low-resolution GC-SQ MS, low-resolution GC-TOF MS, and high-resolution GC-QTOF MS) can be used to perform stable isotope tracing studies for glycolytic intermediates, tricarboxylic acid (TCA) metabolites, and amino acids, yielding similar biological results, with high-resolution GC-QTOF MS offering additional capabilities to identify the chemical structures of unknown compounds that might show significant isotope enrichments in biological studies.Two new antimonous phosphates, namely Ba3Sb2(PO4)4 and Cd3Sb2(PO4)4(H2O)2, have been successfully prepared through mild hydrothermal reactions. Ba3Sb2(PO4)4 features a 1D [Sb(PO4)2]3- chain structure separated by Ba2+ cations while Cd3Sb2(PO4)4(H2O)2 presents a 2D [Sb(PO4)2]3- layered structure with Cd2+ located at the interlayer space. The [Sb(PO4)2]3- chain in Ba3Sb2(PO4)4 is the first example of 1D antimonous phosphate structure, and Cd3Sb2(PO4)4(H2O)2 represents the first d10 transition metal antimonous phosphate. Based on UV-vis-NIR spectra, both Ba3Sb2(PO4)4 and Cd3Sb2(PO4)4(H2O)2 can display large optical band gaps (4.30 and 4.36 eV, respectively). But their transparent ranges are quite different because of the coordination water of Cd3Sb2(PO4)4(H2O)2 (500-2000 and 500-1300 nm for Ba and Cd compounds). The anhydrous Ba3Sb2(PO4)4 shows high thermal stability in the nitrogen atmosphere (900 °C). Because of the incorporation of the lone pair cation of Sb(III), the birefringence of Ba3Sb2(PO4)4 and Cd3Sb2(PO4)4(H2O)2 has been enhanced to 0.086 and 0.053 at 532 nm, respectively.The linkage of molecular components into functional heterogeneous framework materials has revolutionized modern materials chemistry. Here, we use this principle to design polyoxometalate-based frameworks as high affinity adsorbents for drugs of abuse, leading to their application in solid-phase extraction analysis. The frameworks are assembled by the reaction of a Keggin-type polyanion, [SiW12O40]4-, with lanthanoids Dy(III), La(III), Nd(III), and Sm(III) and the multidentate linking ligand 1,10-phenanthroline-2,9-dicarboxylic acid (H2PDA). Their reaction leads to the formation of crystalline 1D coordination polymers. Because of the charge mismatch between the lanthanoids (+3) and the dodecasilicotungstate (-4), we observe incorporation of the PDA2- ligands into crystalline materials, leading to four polyoxometalate-based frameworks where Keggin-type heteropolyanions are linked by cationic Lnn(PDA)n groups (Ln = Dy (1), La (2), Nd (3), and Sm (4)). Structural analysis of the polyoxometalate-based frameworks suggested that they might be suitable for surface binding of common drugs of abuse via supramolecular interactions. To this end, they were used for the extraction and quantitative determination of four model drugs of abuse (amphetamine, methamphetamine, codeine, and morphine) by using micro-solid-phase extraction (D-μSPE) and high-performance liquid chromatography (HPLC). The method showed wide linear ranges, low limits of detection (0.1-0.3 ng mL-1), high precision, and satisfactory spiked recoveries. Our results demonstrate that polyoxometalate-based frameworks are suitable sorbents in D-μSPE for molecules containing amine functionalities. this website The modular design of these networks could in the future be used to expand and tune their substrate binding behavior.ConspectusChemically induced transformations are postsynthetic processing reactions applied to first generation (as-synthesized) nanomaterials to modify property-defining factors such as atomic structure, chemical composition, surface chemistry, and/or morphology. Compared with conditions for direct synthesis of colloidal nanocrystals, postsynthetic chemical transformations can be conducted in relatively mild conditions with a more controllable process, which makes them suitable for the precise manipulation of nanomaterials and for trapping metastable phases that are typically inaccessible from the conventional synthetic routes. Each of the chemically induced transformations methods can result in substantial restructuring of the atomic structure, but their transformation pathways can be very different. And the converse is also true the atomic structure of the parent material plays a large role in the pathway toward and the resulting chemically transformed product. Additionally, the characteristic length of thing this processing for functional materials.As the global threat of plastic pollution has grown in scale and urgency, so have efforts to find sustainable and efficient solutions. Research conducted over the past few years has identified gut environments within insect larvae, including Tenebrio molitor (yellow mealworms), as microenvironments uniquely suited to rapid plastic biodegradation. However, there is currently limited understanding of how the insect host and its gut microbiome collaborate to create an environment conducive to plastic biodegradation. In this work, we provide evidence that T. molitor secretes one or more emulsifying factor(s) (30-100 kDa) that mediate plastic bioavailability. We also demonstrate that the insect gut microbiome secretes factor(s) ( less then 30 kDa) that enhance respiration on polystyrene (PS). We apply these insights to culture PS-fed gut microbiome enrichments, with elevated rates of respiration and degradation compared to the unenriched gut microbiome. Within the enrichment, we identified eight unique gut microorganisms associated with PS biodegradation including Citrobacter freundii, Serratia marcescens, and Klebsiella aerogenes. Our results demonstrate that both the mealworm itself and its gut microbiome contribute to accelerated plastic biodegradation. This work provides new insights into insect-mediated mechanisms of plastic degradation and potential strategies for cultivation of plastic-degrading microorganisms in future investigations and scale-up.
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