Universidade Federal do Ceará

• In situ PXRD reveals anisotropic thermal expansion along the b and c axes • In situ Raman detects reversible local conformational changes near 523 K • Combined PXRD-Raman analysis links long-range stability to local vibrational dynamics In this work, Gd 2 (WO 4 ) 3 samples were synthesized by the hydrothermal method and subsequently calcined at 923 K, being characterized at room temperature by X-ray diffraction, UV-Vis spectrophotometry and Raman spectroscopy, in addition to in situ PXRD and Raman measurements under variable temperature conditions. Rietveld refinement confirmed the exclusive formation of the monoclinic phase (space group C2/c ). The in situ PXRD analyses, performed between 298 K and 773 K, revealed high long-range structural stability, evidenced by anisotropic thermal expansion that is more pronounced along the b (11.9(4) × 10 -6 K -1 ) and c (10.3(4) × 10 -6 K -1 ) axes than the a (2.2(6) × 10 -6 K -1 ) axis. The b/c ratio exhibited a non-linear trend: a continuous increase followed by an abrupt decrease around 523 K during both heating and cooling cycles, suggesting a subtle conformational modification within the crystal lattice. Consistently, in situ Raman spectroscopy indicated reversible local changes in the same temperature range (538 K), variation in intensity, as well as, shifts of vibrational modes associated with WO 4 2- tetrahedra. These effects were attributed to enhanced phonon-phonon anharmonicity and rearrangements of GdO 8 polyhedra. The results demonstrate that although the global structure of Gd 2 (WO 4 ) 3 remains monoclinic throughout the investigated temperature range, reversible local reorganizations occur, revealing an intrinsic thermal sensitivity of the lattice and supporting its potential use in thermally stable photonic and optoelectronic applications, such as Raman-based temperature sensors, high-temperature optical components, and rare-earth-doped laser host materials.

Green hydrogen, an emerging energy carrier that may help achieve national and global decarbonization goals, will reshape energy geographies. States are partnering with firms, offering subsidies and other incentives for developing hubs as agglomerations of green hydrogen producers, off-takers, and exporters, while new and incumbent firms are seeking new accumulation opportunities through the production of green hydrogen. Legitimation processes are key to the implementation and dissemination of new technological systems, but they are not well understood in the context of emerging green hydrogen hubs. We analyze the content of legitimization discourses supporting a green hydrogen hub in Ceará state, northeastern Brazil, seeking to determine the emerging space-making processes. We focus on the cognitive dimension of legitimacy through analysis of ∼ 500 news articles published between 2020 and 2023 in two major media outlets reporting on the proposed green hydrogen hub. The findings describe cognitive legitimation discourses on territorial characteristics, global leadership, breaking from the past, urgency, and essential state action. Legitimation mobilized ideas about landscape, territory, place, scale, and development through normative and technical arguments. Application of the cognitive dimension of legitimation advances economic geographies by highlighting how sub-national organizations represent their territories as adding value for investors, how stakeholders mobilize ideas for de-risking new technologies by overstating benefits and obscuring possible risks to producing states, and how elites justify processes leading to new spatial configurations of low-carbon energy systems. • Elite stakeholders legitimize green hydrogen through diverse arguments. • The cognitive dimension of legitimacy revealed space-making claims. • Legitimation deploys new scalar relationships and imaginations of landscape and territory.

Recent studies of marine sediments adjacent to the Parnaíba Basin, in northeastern Brazil, have been used for continental paleoenvironmental reconstructions of the glacial epoch. As the largest basin entirely located within the Northeast region, it spans a critical transition zone between the Cerrado and Caatinga biomes. To characterize the modern pollen rain within this ecotone, we analyzed 41 surface sediment samples and compared the pollen assemblages with published botanical surveys. First, pollen assemblages were characterized using three diagrams: vegetation type, geographical location, and depositional environment. The basin presents a unique mixed signature combining Cerrado elements (e.g., Astronium- type , Tapirira- type) with Caatinga taxa ( Mimosa -type). Spatially, the Upper and Lower sectors exhibited high heterogeneity, contrasting with arboreal consistency in the Mid-Parnaíba. Distinct hydrological markers also emerged: Cyperaceae was strictly linked to lacustrine environments, whereas Mauritia indicated permanently flooded soils within gallery forests and palm swamps. Landscape analysis subsequently confirmed that Arboreal Pollen (AP) frequencies accurately track woody cover, while Borreria -type and Poaceae serve as robust proxies for landscape openness. Multivariate analyses refined these patterns: Cluster Analysis identified six specific floristic groups ( Tapirira-Astronium , mixed, Melastomataceae-Combretaceae, Borreria-Aspidosperma , mixed woody-herbaceous, and Mimosa- type assemblages), while Redundancy Analysis (RDA) identified Mean Annual Temperature (MAT) as a significant environmental driver within the explained variance. Critically, comparison with paleoecological records reveals a sharp floristic shift from cooler, humid glacial periods to the current warmer climate, marked by the scarcity of montane taxa. This study establishes a crucial baseline for interpreting fossil records and understanding ecosystem dynamics in this transition zone. • Modern pollen rain reflects vegetation patterns along the Parnaíba River gradient. • Cerrado, Caatinga, and transitional zones show distinct pollen assemblages. • Analyses reveal floristic structure influenced by edaphoclimatic gradients. • Pollen assemblages are more related to local conditions than spatial location. • Anthropization and distinct grasslands strongly influence pollen assemblages.

Candidiasis, caused by yeasts of the Candida genus, is increasingly characterized by a high prevalence of clinical isolates resistant to conventional antifungals, rendering the development of novel therapeutic strategies paramount. Drug repurposing has emerged as a key strategy, utilizing established pharmaceuticals for indications beyond their original design; notably, haloperidol (HAL) has shown promising antimicrobial potential. In this context, the present study evaluates the activity of haloperidol, both as a monotherapy and in combination with conventional antifungals, against fluconazole-susceptible and fluconazole-resistant Candida spp. clinical strains. Furthermore, we investigate the underlying mechanisms of its antifungal action. Experimental approaches included broth microdilution assays to determine the Minimum Inhibitory Concentration (MIC), checkerboard assays for synergistic analysis, and cellular assessments via flow cytometry and fluorescence microscopy. Haloperidol displayed MIC values between 26.67 and 256 μg/mL. Synergistic interactions were identified between haloperidol and the azoles fluconazole and itraconazole, alongside a 2.5 % synergy rate with amphotericin B. Additionally, mechanistic assays confirmed that haloperidol induces programmed cell death (apoptosis) in C. albicans and C. auris strains. The oxidative stress caused by haloperidol altered Ca2+ homeostasis, followed by mitochondrial membrane depolarization, reduced ATP production, cytochrome c release into the cytosol and metacaspase activation, reduced viability, phosphatidylserine externalization, promoted fragmentation, damage and methylation of DNA. It also induced expression of genes related to oxidative stress. It reduced mitochondrial depolarization and decreased the reduction of glutathione (GSH), causing morphological alterations. The results suggest the apoptotic pathway as the main antifungal mechanism of haloperidol.