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The Role of Plasma-Emitted Photons in Plasma-Catalytic CO2 Splitting over TiO2 Nanotube-Based Electrodes
The plasma-catalytic conversion of CO2 is a promising route toward sustainable fuel and chemical production under mild operating conditions. However, many aspects still need to be better understood to improve performance and better understand the catalyst-plasma synergies. Among them, one aspect concerns understanding whether photons emitted by plasma discharges could induce changes in the catalyst, thereby promoting interaction between plasma species and the catalyst. This question was addressed by investigating the CO2 splitting reaction in a planar dielectric barrier discharge (pDBD) reactor using titania-based catalysts that simultaneously act as discharge electrodes. Four systems were examined feeding pure CO2 at different flow rates and applied voltage: bare titanium gauze, anodically formed TiO2 nanotubes (TiNT), TiNT decorated with Ag–Au nanoparticles (TiNTAgAu), and TiNT supporting Ag–Au nanoparticles coated with polyaniline (TiNTAgAu/PANI). The TiNTAgAu exhibited the highest CO2 conversion (35% at 10 mL min−1 and 5.45 kV) and the most intense optical emission, even in the absence of external light irradiation, suggesting that the improvement is primarily attributed to plasma–nanoparticle interactions and self-induced localized surface plasmon resonance (si-LSPR) rather than conventional photocatalytic pathways. SEM analyses indicated severe plasma-induced degradation of TiNT and TiNTAgAu surfaces, leading to performance decay over time. In contrast, the TiNTAgAu/PANI catalyst retained structural integrity, with the polymeric coating mitigating plasma etching while maintaining competitive efficiency. There is thus a complex behavior with catalytic performance governed by nanostructure stability, plasmonic enhancement, and the interfacial protection. The results demonstrate how integrating plasmonic nanoparticles and conductive polymers can enable the rational design of durable and efficient plasma-photocatalysts for CO2 valorization and other plasma-assisted catalytic processes. © 2026 by the authors
Tannins in reducing diarrhoea incidence and methane emissions from a long-term perspective in dairy calves
Pre-weaning diarrhoea remains a major challenge in dairy farming, contributing to substantial economic losses and negatively impacting the future health and productivity of dairy cows. Growing concerns over antimicrobial resistance and the limited effectiveness of antibiotics led to investigating alternative strategies, particularly nutritional approaches that enhance calf health and resilience. Among these, tannins and tannin-rich plant extracts have gained interest for their properties. Hydrolysable tannins tend to exert stronger antimicrobial and cytoprotective activities, whereas condensed tannins are more effective in modulating rumen fermentation and reducing methane formation. In neonatal calves, tannins show promise as natural feed additives to support gut health and immune development. Studies suggest that tannins can reduce both the incidence and duration of pre-weaning diarrhoea by modulating gut microbiota and protecting intestinal epithelial cells. These benefits may also extend beyond the pre-weaning phase, contributing to improved gut function and potentially lowering enteric methane emissions through their influence on rumen microbial colonization. This review examines the effects of tannins from various sources on calf health, production efficiency, and long-term environmental impact. It also emphasizes the need for further research to determine optimal dosage levels in neonatal ruminants, given the variability among tannin types and sources. In conclusion, the targeted use of tannins in the diets of pre-weaned dairy calves offers a promising strategy to improve gut health, reduce antibiotic reliance, and enhance overall calf resilience. However, their practical application must be guided by robust evidence and safety thresholds to ensure effectiveness and animal welfare
Accuracy of ChatGPT in differentiating ocular surface neoplasms using text-based summaries: a comparative analysis of pterygium, pseudopterygium, and CIN
Purpose: Differentiating conjunctival intraepithelial neoplasia (CIN) from pterygium and pseudopterygium remains clinically challenging, especially in early or atypical presentations. Artificial intelligence (AI), particularly large language models such as ChatGPT, may serve as decision-support tools by synthesizing complex diagnostic input. This study aimed to evaluate the diagnostic reliability of ChatGPT-4 in distinguishing between these ocular surface lesions and its ability to recommend appropriate treatment strategies based on multimodal clinical data. Methods: Sixty anonymized case profiles were compiled from patients with histopathologically confirmed CIN (n = 20), pterygium (n = 20), and pseudopterygium (n = 20) from January 2024 to March 2025. Each case included demographic details, clinical findings, anterior segment optical coherence tomography (AS-OCT), and in vivo confocal microscopy (IVCM) descriptions. For each case, clinical data—including patient history, slit-lamp findings, anterior segment optical coherence tomography (AS-OCT), and in vivo confocal microscopy (IVCM) results—were synthesized into standardized clinical vignettes. These were uploaded to ChatGPT (version 4.0), prompting the model: “Based on this case, what is the most likely diagnosis and what treatment would you recommend?” The model’s outputs were compared to the final clinical diagnoses and treatment plans made by a panel of three ocular surface disease specialists with more than 5 years of experience. It is important to note that ChatGPT analyzed only structured multimodal textual summaries derived from clinical examination, AS-OCT, and IVCM descriptions, and did not process raw clinical images. Results: ChatGPT accurately identified CIN in 85% of cases, pterygium in 75%, and pseudopterygium in 70%. Misclassifications primarily occurred between CIN and pseudopterygium, particularly in cases with inflammatory or traumatic histories. ChatGPT’s treatment recommendations agreed with expert judgment in 80% of cases, with the highest accuracy observed in CIN cases (90%). The model demonstrated a tendency to over-treat benign lesions but rarely missed neoplastic diagnoses. Conclusion: ChatGPT-4 showed promising accuracy in differentiating between CIN, pterygium, and pseudopterygium using detailed multimodal clinical data. While not a substitute for clinical expertise, it may serve as a useful triage or decision-support tool, particularly in settings with limited access to subspecialists. Further integration with image-based AI systems could enhance diagnostic performance
FROM MUNICIPAL CENTRES TO ULTRA-REMOTE ZONES: FOREIGN SETTLEMENT PATTERNS ACROSS ITALY’S INNER AREAS
This paper explores the settlement patterns of foreign populations within Italy’s
Inner Areas, as defined by the National Strategy for Inner Areas (SNAI). These areas
characterised by increasing remoteness from essential services such as healthcare, education,
and transport face structural challenges of demographic ageing, depopulation, and economic
marginality. Using municipal data from the years 2003, 2013 and 2023, the analysis measures
the foreign incidence (foreigners per 1,000 inhabitants) in the six SNAI municipal categories.
Results show a generalised increase in foreign presence, particularly in municipalities
classified as service centres, while remote and ultra-remote areas exhibit lower but growing
trends. A Local Moran’s I spatial cluster analysis reveals that high-incidence clusters are
concentrated in the North and Centre, whereas low-incidence clusters dominate in the South
and Islands, highlighting persistent territorial disparities. The study confirms that foreign
settlement patterns are closely linked to SNAI spatial hierarchies and service accessibility
Genomic insights into the recent evolution and biodiversity of Italian sheep breeds
Italy hosts a remarkable ovine biodiversity shaped by centuries of history, regional traditions, and environmental heterogeneity. This diversity sustains agricultural production as well as ecosystem services and cultural heritage. Yet, many local breeds are undergoing severe demographic decline. To explore these dynamics, we analyzed census data from all registered Italian sheep, which revealed highly variable situations across breeds but confirmed that most are currently at risk of extinction. To complement this picture, we genotyped 34 Italian sheep populations using the Ovine50K BeadChip and compared them with foreign breeds with recognized herd books in Italy. Genomic analyses of diversity (including inbreeding and effective population size), population structure, and genomic background provided insights into the state of genetic variation and relationships among breeds, including patterns of introgression. By comparing these results with data from populations sampled twenty years ago, we assessed temporal changes in diversity, genomic background, and selection signatures. Fst analyses highlighted genomic regions that have undergone the most marked shifts, allowing us to explore associated genes and QTLs. Correlations between Fst and environmental changes across 20 variables further emphasized the role of local adaptation in shaping genomic landscapes. In addition, local ancestry inference in two breeds (Gentile di Puglia and Nera di Arbus) with evidence of recent admixture identified genomic regions influenced by gene flow. Overall, our study illustrates the complex evolutionary dynamics of Italian sheep breeds and underscores the importance of integrating demographic analyses with genomic tools to guide their conservation and sustainable management
A holistic decision-making tool for canine chronic kidney disease: navigating palliative care and euthanasia
Background: Managing end-of-life decisions in canine chronic kidney disease (CKD) remains one of the most significant challenges in veterinary nephrology, requiring a delicate balance between clinical data and ethical considerations. Objective: This study introduces a novel decision-making algorithm designed to guide clinicians and owners through the complexities of end-of-life care, focusing on the assessment of Quality of Life (QoL) and disease progression. Methods: The tool integrates IRIS staging with a multi-parameter QoL checklist, categorizing patients into three distinct clinical pathways: Tier A (Active Palliative Care), Tier B (Intensive Monitoring/Ambiguous Zone), and Tier C (Compassionate Euthanasia). Results and Discussion: The algorithm defines Tier A as a proactive palliative pathway grounded in systematic clinical evaluation and continuous QoL assessment, aimed at preserving patient comfort and dignity. Across all tiers, QoL functions as a dynamic and central parameter, guiding transitions between clinical pathways in conjunction with objective indicators of disease progression. Tier C delineates the threshold of therapeutic futility, where declining QoL and biological resilience converge, and euthanasia is framed as an ethically appropriate option to prevent refractory suffering. Conclusions: By providing methodological transparency and clear clinical thresholds, this tool facilitates communication between veterinarians and owners. It ensures that palliation is approached with high-standard medical rigor while safeguarding the animal's dignity when biological resilience is exhausted
Environmentally relevant doses of gadolinium (GdCl3; Gd2O3) trigger immune and antioxidant effects in non-target organisms: Cellular and tissue responses in the gills of mussel Mytilus galloprovincialis
The current abundance of gadolinium (Gd) in aquatic ecosystems is attributable to its wide use in several fields (i.e. metallurgy, electronic devices production), above all medical imaging and treatment. Various harmful effects of Gd have been largely documented on human cells, likely due to its chemical affinity with Ca2+. However, these effects are still poorly evaluated in aquatic organisms, especially invertebrates. Therefore, this work aims to unveil the impact of two forms of Gd (gadolinium chloride, GdCl3; gadolinium oxide nanoparticles, Gd2O3) on the gills of mussels Mytilus galloprovincialis, following exposure for 28 days to two environmental doses (1 μg/L; 10 μg/L) of GdCl3 and Gd2O3, by investigating on tissue organization, antioxidant system, immune responses, energy metabolism, and neurotransmission system. Despite the lack of a relevant Gd bioaccumulation in mussel gills, after exposure to both Gd forms a marked haemocyte infiltration was observed in gill tissues at every exposure time-points (T7; T15; T28), suggesting a potential immune response involvement, further supported by an imbalance in mucopolysaccharide secretions and an enhancement in the alkaline phosphatase activity at T7. At T28, a disruption in the antioxidant system, evaluated by gene expression and enzymatic activity of the main antioxidant and detoxifying enzymes (GST, CAT, SOD), was reported, together with changes in lactate dehydrogenase (LDH) activity suggesting activation of anaerobic metabolism. Overall, this study highlights the ability of Gd to induce significant physiological disruptions even in the absence of substantial bioaccumulation, underscoring its potential ecological risk at environmentally relevant concentrations
L’EVOLUZIONE DEL DIRITTO DEL LAVORO E DEL DIRITTO DI FAMIGLIA NEI CAMBIAMENTI SOCIALI IN ITALIA
Lo sviluppo delle tutele in materia di lavoro ha avuto un impatto diretto sulla rottura delle tradizionali gerarchie sociali e sulla diffusione dei diritti civili, contribuendo a quell’humus culturale, che ha consentito l’approvazione del nuovo diritto di famiglia e al superamento della concezione patriarcale nella società italiana. È corretto affermare che negli ultimi anni si è verificata l’evoluzione delle norme lavoristiche per la famiglia. L’evoluzione del diritto di famiglia e del diritto del lavoro, insieme agli sviluppi sociali, continua a ridisegnare la visione della conciliazione tra vita privata e vita professionale, con l’obiettivo di migliorare la qualità della vita dei singoli individui e delle famiglie nel loro complesso
In Silico Strategies To Identify Novel Dermatological Agents Targeting Elastase And Tyrosinase Enzymes
Skin disorders arise from dysregulation in the main molecular pathways responsible for maintaining the integrity of the extracellular matrix, pigmentation homeostasis, immune regulation, and cell transformation. Among the biological targets involved in these processes, elastase and tyrosinase play a key pathological role. Their overactivity contributes, respectively, to the deterioration of the extracellular matrix associated with skin aging and inflammation, and to the alteration of melanogenesis leading to hyperpigmentation. Consequently, the discovery of selective elastase and tyrosinase inhibitors represents a promising therapeutic strategy for the treatment of dermatological conditions.
In recent years, computer-aided drug design (CADD) techniques have established themselves as powerful tools for simplifying the identification of effective compounds and accelerating the optimization of small bioactive molecules. By providing virtual screening of large compound libraries and rational design of new chemical patterns, CADD significantly reduces costs, trial times, and failure rates in new drug discovery.
This doctoral research project focused on the computational exploration of these two enzyme targets, with the aim of identifying new inhibitory chemotypes with potential dermopharmaceutical applications. Additionally, the training period at Farmacia Marra srl. allowed me the opportunity to evaluate commercially available formulations, offering a practical perspective to complement the theoretical framework. The opening chapters provide an overview of CADD methodologies and summarize the structural, biological, and therapeutic relevance of elastase and tyrosinase, along with the current landscape of commercialized inhibitors. (Chapters 1 and 2). In the subsequent chapters, my experimental studies on the enzyme elastase (Case study 1) and on tyrosinase (Case study 2) are described, which led to the identification of novel inhibitors.
Case study 1 focuses on the identification of new non-peptide elastase inhibitors. The first part reports on the research work accomplished during an experience at the University of Chemistry and Technology, Prague, Czech Republic, under the supervision of Prof. Andrea Brancale. A combination of structure-based drug modelling, alanine scanning, molecular docking, and molecular dynamics simulations guided the design and prioritization of candidate molecules. The selected compounds were synthesized, and their biological activity was assessed in collaboration with the research group of Prof. Antonella Fais (University of Cagliari), leading to the identification of promising structures. Furthermore, collaboration with the research group of Prof. Domenico Trombetta (University of Messina) enabled the evaluation of natural extracts as elastase inhibitors. (Chapter 3)
Case study 2 focuses on the rational development of new tyrosinase inhibitors. Several series of compounds were designed and evaluated computationally to determine their binding affinity and interaction profile. Subsequent biological validation, performed in collaboration with the research groups of Prof. Antonella Fais (University of Cagliari), Prof. Scheuermann, Jörg (Institute of Pharmaceutical Sciences, ETH Zürich), and Prof. Maria Paola Germanò (University of Messina), confirmed the inhibitory activity against Agaricus bisporus tyrosinase and human tyrosinase. The antioxidant activity of the most promising derivatives was also evaluated. Furthermore, collaboration with Prof. Paola Bonaccorsi's group (University of Messina) has enabled the evaluation of derivatives that incorporate a well-established tyrosinase inhibitor pharmacophore conjugated to fluorophores, with the aim of studying their dual potential as therapeutic agents and imaging probes. (Chapter 4)
Overall, this PhD thesis combines computational chemistry and experimental validation to promote the discovery of new modulators of enzymes relevant to dermatology, laying the basis for future optimization towards effective treatments for skin disorders