Stability and thermophysical properties of PAO-Based nanofluids with MWCNTs, nano-MoS2 and their hybrid formulations for thermal applications

This study investigates the stability and thermophysical properties of polyalphaolefin (PAO)-based nanofluids formulated with molybdenum disulfide (MoS2), multi-walled carbon nanotubes (MWCNTs), and their hybrid combinations across concentrations ranging from 0.05 to 0.2 wt%. Two silane surfactants octadecyltrichlorosilane (OTS) and hexadecyltrimethoxysilane (HDTMS) were evaluated for dispersion stability, with OTS showing superior performance, particularly for MoS2-based nanofluids. OTS was therefore selected for hybrid nanofluid preparation. Thermophysical characterization revealed that PAO-MoS2 (0.05 %) achieved the highest thermal conductivity (∼0.203 W/m·K; 45 % enhancement) and thermal diffusivity (∼9.76 × 10−8 m2/s), while PAO-MWCNTs (0.1 %) demonstrated excellent diffusivity due to its low Cp. Hybrid nanofluids, especially PAO-Hybrid (0.2 %), offered a balanced performance with improved thermal conductivity (∼25.7 %), high specific heat (∼2.6 J/g·°C), and excellent viscosity index (VI = 132.77). These results highlight the synergistic effects of nanoparticle morphology and surfactant-assisted dispersion in enhancing thermal performance, confirming the potential of hybrid PAO-based nanofluids for high-efficiency heat transfer and lubrication applications

Development of MnOx base catalysts for the PROX process. Theoretical insights and practical application

The growing demand for sustainable energy carriers has positioned hydrogen at the center of the global energy transition. However, hydrogen produced by conventional hydrocarbon-reforming processes typically contains residual carbon monoxide (CO) hindering its direct use in proton exchange membrane fuel cells (PEM) due to the poisoning of Pt electrodes. Therefore, the abatement of CO represents a crucial purification step in hydrogen processing for PEM applications. Among the available H2 purification strategies, apart from methanation and membrane separation, the Preferential Oxidation of CO (PROX) has emerged over the past decades as a highly promising alternative, although the development of efficient, selective and low-cost catalysts represents the main scientific and technological challenge for the practical deployment of PEM technology. Therefore, aiming at bringing contribution in the field of H2 purification processes, this study offers a comprehensive investigation of the H2 and CO oxidation functionalities of a nanocomposite MnCeOx catalyst by a combined computational and experimental approach documenting its potential PROX behavior for PEM technology exploitation. The catalyst, synthesized by the redox-precipitation route, was extensively characterized, revealing the dominant role of surface Mn(IV) sites in governing a distinctive PROX behavior in the range of 293-423 K. In fact, catalytic tests reveal that this depends on the high CO oxidation activity of the MnCeOx catalyst at low temperature (∼293 K) and a substantial inactivity towards hydrogen oxidation at T<373 K. Complementary Density Functional Theory (DFT) calculations performed on a model Mn4O8 cluster provided theoretical support for the experimental observations, revealing different interaction pathways of Mn(IV) sites with CO and H2. These give rise to two separate oxidation cycles, characterized by a significant activation energy gap, which explains the observed selectivity toward CO oxidation. The experimental and theoretical insights were integrated into two simplified reaction mechanisms involving direct lattice oxygen abstraction and diatomic oxygen species respectively. The validity of these mechanistic interpretations was confirmed through the development of two kinetic models able to predict the CO and H2 oxidation activity of the MnCeOx catalyst in the range of 293-533K. Overall, this work contributes to the fundamental understanding of MnCeOx catalysts, elucidating the interplay between surface redox chemistry, oxygen mobility and catalytic selectivity. Beyond elucidating the molecular basis of PROX activity, the integration of computational and experimental insights establishes a robust methodological framework for the rational design of next-generation mixed-oxide catalysts for energy and environmental applications. Chapter 1 provides an overview of the global energy context highlighting the role of hydrogen as a sustainable energy carrier. It addresses the main hydrogen production routes, including Steam Methane Reforming (SMR), Partial Oxidation (POX) and Autothermal Reforming (ATR) of hydrocarbons and outlines the key purification strategies, namely Pressure Swing Adsorption (PSA), membrane separation and methanation required to meet hydrogen purity standards for hydrogen application. The chapter concludes with a review of recent advances in the preferential oxidation of CO describing the main classes of catalysts, their reaction mechanisms and the technological limitations that motivate further research. Chapter 2 focuses on materials and methods employed in this study. It describes the preparation of the MnCeOx catalyst and the suite of physico-chemical characterization techniques used to assess its properties, including X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), N2 physisorption, Laser Raman Spectroscopy (LRS), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), Temperature Programmed Reduction (TPR) and Temperature Programmed Desorption (TPD). The chapter also outlines the catalyst testing protocols, such as Temperature Programmed Catalytic Reaction (TPCR) experiments, and describes the computational approach adopted for Density Functional Theory (DFT) analysis. Chapter 3, devoted to results and discussion, begins with a detailed interpretation of the main physicochemical characterization data, providing a detailed interpretation of the structural, surface properties and redox behavior of the catalyst. Then, the second part of the chapter highlights the PROX performance of the catalyst under various conditions, in terms of activity, selectivity and stability under both kinetic regime and under real process conditions. Mechanistic insights from Density Functional Theory (DFT) calculations on a model Mn4O8 cluster and kinetic data of CO and H2 oxidation are then used to obtain simplified reaction mechanisms. Based on these evidences, finally, the chapter describes the development of suitable macrokinetic models able to predict the CO and H2 oxidation functionality of MnO2-based catalysts under a wide range of conditions, establishing quantitative correlations between structure, mechanism and reactivity and offering a rational basis for the interpretation and optimization of PROX performance

Post-marketing safety profile of dengue vaccines CYD-TDV and TAK-003: analysis of adverse event reports from a European database

Introduction: Dengue is one of the major global public health burden, particularly in endemic regions. CYD-TDV and TAK-003 are the currently licensed live attenuated tetravalent dengue vaccines, differing in serostatus indication, age range, and immunogenic design. While efficacy has been demonstrated in clinical trials, post-marketing safety data are still limited, supporting the need for real-world pharmacovigilance analyses. Objective: This study characterize adverse reactions associated with CYD-TDV and TAK-003 reported in the European pharmacovigilance database and to compare their post-marketing safety profiles. Methods: A retrospective pharmacovigilance study was conducted using the EudraVigilance database. Individual Case Safety Reports (ICSRs) listing CYD-TDV or TAK-003 as suspected products were retrieved. Adverse drug reactions were coded using MedDRA® version 28.1 and classified by seriousness and outcome. Disproportionality analyses were performed using Reporting Odds Ratios (RORs) with 95% confidence intervals at the System Organ Class (SOCs) and Preferred Terms (PTs) levels. Sensitivity analyses included grouping clinically related PTs and restricting analyses to serious cases. Vaccine groups were compared using chi-square tests. Results: A total of 2,288 ICSRs were identified, including 1,768 (77.3%) related to TAK-003 and 520 (22.7%) to CYD-TDV. TAK-003-related reports mainly involved adults (49.8%) and females (57.9%). Although most ICSRs were classified as serious, serious reports were more frequent for CYD-TDV than for TAK-003 (81.1% vs. 76.4%; p = 0.04). Fatal outcomes were also more commonly reported for CYD-TDV (50.8% vs. 0.6%; p < 0.01). At the SOC level, TAK-003 showed lower disproportional reporting than CYD-TDV for infections and infestations (ROR = 0.07; 95% CI = 0.056–0.089), gastrointestinal disorders (ROR = 0.22; 95%CI = 0.18–0.27), general disorders and administration site conditions (ROR = 0.29; 95%CI = 0.23–0.36), nervous system disorders (ROR = 0.42; 95%CI = 0.34–0.51), cardiac disorders (ROR = 0.35; 95%CI = 0.23–0.51), and hepatobiliary disorders (ROR = 0.09; 95%CI = 0.04–0.19). Higher reporting for TAK-003 was observed for skin and subcutaneous tissue disorders (ROR = 1.98; 95%CI = 1.59–2.48). Conclusion: This real-world pharmacovigilance study suggests that TAK-003 is predominantly associated with non-serious, reactogenic adverse reactions, whereas CYD-TDV reports more frequently involve serious outcomes, likely reflecting differences in indications and epidemiological contexts. Continued post-marketing surveillance remains essential for both vaccines

Tumour Burden Score as a Predictor of Extrahepatic Progression After Transarterial Chemoembolizationfor Hepatocellular Carcinoma: An Observational Multicenter Study

Background: In patients with hepatocellular carcinoma (HCC), extrahepatic progression (EHP) has a known dismal meaning. We evaluated the incidence and risk factors of EHP in HCC patients treated with transarterial chemoembolization (TACE), and the predictive role of tumour burden. Methods: From the ITA.LI.CA database, 890 HCC patients undergoing first-line TACE were included. Tumour burden score (TBS) was calculated and, after identification of the best cut-point value, incidence and predictors of EHP were compared be- tween TBS-low and TBS-high groups. Independent predictors of EHP at the first progression episode or at any time during fol- low-up were identified through multivariable Cox analysis. Results: After TACE, 7.2% of patients experienced EHP at the first progression episode, while the overall EHP rate during the follow-up was 26.1%. The best cut-point for TBS was 3.66. TBS-high group (> 3.66) showed a significantly higher proportion of EHP both at first progression (10.4% vs. 3.6%; p < 0.001) and overall (32.6% vs. 18.7%; p < 0.001) compared to the TBS-low group. Moreover, TBS-high patients had shorter progression-free survival and overall survival. TBS-high and AFP levels emerged as in- dependent predictors of EHP at the first progression episode and during the follow-up, and their combined evaluation accurately stratified patients for their risk of EHP

Neodymium and Yttrium Adsorption on Citrate-Modified Cellulose: Experimental and Computational Insights

Neodymium (Nd) and yttrium (Y), two rare earth elements, play a crucial role in a wide range of technologies, and their separation is a challenging process. Adsorption-based approaches offer a sustainable and cost-efficient substitute for the most widely used solvent extraction procedure. Here, we assess the potential of cellulose citrate (CC) as an adsorbent for the removal of Y and Nd through both experimental and computational approaches. CC was successfully synthesized by reacting raw cellulose extracted from Spartium junceum (Spanish broom) with molten citric acid using a green approach that does not require any solvent. The final goal is to shed light on the mechanism of adsorption by citrate-functionalized cellulose by interpreting the adsorption measurements through kinetics and isotherm adsorption models, as well as Density functional theory (DFT) calculations and molecular mechanics (MM) simulations. Adsorption properties of the sorbent are investigated at different contact times, pH values, and metal concentrations. Cellulose citrate has proven to be a highly effective material for the adsorption of the two metals, exhibiting a slight preference for Y at low-to-medium concentrations and for Nd at higher concentrations, suggesting a different binding stoichiometry of the two cations. The adsorption process is found to be pH-dependent, with equilibrium being reached after approximately 60 min. Interestingly, a certain degree of selectivity toward Nd is observed, which becomes more pronounced at pH values below 3 and at higher metal concentrations. DFT and MM modeling confirm the experimental results and allow an adsorption mechanism to interpret the measured performance of this material

Redefining sovereignty: the rise of artificial authority and the crisis of constitutional values

Artificial intelligence has begun to deeply penetrate the States decision-making processes and power is also shifting from state to non-state actors. The traditional concept of sovereignty is consequently under transition. Originally, it was conceived as the highest power of the State within a legal and political order, rooted in the Westphalian model of absolute State authority and fixed territorial borders. In the modern era, this view has moved towards the best sovereignty ideal of power of values, a paradigm that is now undergoing a profound crisis. States are losing their exclusive capacity to legislate, administer justice and enforce rights and order because their own power goes through AI systems able to increasingly distribute, automate and minimize such that power. Governments now rely on algorithmic tools for border control, welfare distribution, judicial sentencing and even predictive policing. At the same time, citizens are subject to continuous profiling, classifications and behavioural targeting, often without their own knowledge and control. In this scenario, it is necessary to question the value of constitutional principles and the resilience of the system of protections, even of the fundamental human rights. To do so, this essay proposes the pattern of «artificial authority» to design a new notion of sovereignty arguing that the traditional State sovereignty is no longer a human state-centric construct rather it is increasingly shaped and exercised by private transnational entities through algorithmic and opaque computational systems. Analysing the doctrinal framework, the contribution examines these developments. Conclusions will focus on the tension between Artificial intelligence authority and the normative foundations of constitutional democracies

Mapping Memory and Legitimating Heritage: The Case of Two Italian Parks

Building upon in-depth interviews, surveys, participant observation and an extensive body of documentary material gathered in the last ten years, this chapter will shed light upon the variables that can influence heritage construction processes and the way conflicts over memory can evolve when that memory is used to condition political choices on the present. The authors submit that the urban fabric has always been characterized by a duality between past and present, but it is only when this becomes a recognized heritage, for example, a UNESCO World Heritage Site, that the urban fabric is enhanced as such, i.e., becoming a historic centre. The chapter will rely upon a comparative theoretical framework and focus on two Italian Parks: The Archaeological Park of Tindari (Sicily) and the National Park of the Colline Metallifere (Tuscany). The two authors of the chapter are deeply involved in the life of the two Parks for sharing or having shared professional or institutional positions related to them

Positioned and primary positioned C\mathcal {C}-semigroups

Let C be a positive integer cone and k \in C. A C-semigroup S is k-positioned if for every h \in C\S we have that k-h belongs to S. In this work, we focus on this family of semigroups and introduce primary positioned C-semigroups, characterizing a subfamily of them through the perspective of irreducibility. Furthermore, we provide some procedures to compute all such semigroups, describing a family of graphs containing all the primary positioned C-semigroups for a fixed k \in C

From Cure to Complexity: Post-SVR Liver and Metabolic Trajectories in Diabetic Patients

ABSTRACT Background and Aims: The long-term impact of HCV cure on hepatic and metabolic outcomes in patients with type 2 diabetes (T2D) remains insufficiently defined. This study evaluated T2D-related vascular complications, liver disease progression and overall survival over 9 years of follow-up, also exploring genetic variability contribution. Methods: Consecutive T2D patients with HCV-related chronic liver disease or cirrhosis treated with direct-acting antivi- rals (DAAs) between 2015 and 2018 at the University Hospital of Messina were prospectively followed until September 2024. Demographic, biochemical, and clinical data were collected at baseline and throughout follow-up. Regression models were ap- plied to identify predictors of metabolic and hepatic outcomes. Genetic variants—PNPLA3 rs738409, TM6SF2 rs58542926 and rs641738 at the MBOAT7/TMC4 locus—were also assessed. Results: A total of 183 patients (52% males, median age 67 years; 56% cirrhotic) were followed for a median of 48 months (range 24–84). Despite significant improvements in HbA1c (p = 0.006), liver-stiffness (p < 0.001), gamma-globulins (p < 0.001), and ami- notransferases (p < 0.001), only 27.3% maintained clinical stability. Liver disease progression occurred in 20.8% of patients and was related to cirrhosis (p = 0.021), prior decompensation (p = 0.07), and the MBOAT7 variant (p = 0.025). Macrovascular and mi- crovascular complications developed in 50.8% and 33.9% of patients, respectively, mostly within 2 years after SVR. In multivariate models, higher TyG index (p = 0.038) predicted the composite progression endpoint, while elevated LDL cholesterol (p = 0.048), mortality