We report the first combined DFT and spectroscopic mechanistic investigation of a V(III)-chloride scorpionate complex, [VCl3{HC(pz)3}] (1), as a catalyst for the peroxidative oxidation of cyclohexane under mild conditions. DFT calculations reveal that 1 activates H2O2 through a multi-step oxidative mechanism following a V(III)-*V (IV)-*V(V) sequence, generating HOO center dot radicals as the primary oxidizing species. The catalytic activity emerges from a competition between productive radical generation and self-trapping processes whose balance is governed by the H2O2/1 ratio, providing a molecular-level explanation for the experimentally observed trends in TON and alcohol/ketone selectivity. Unlike previously studied V(IV)/V(V) systems, the productive catalytic cycle follows a V(IV)-*V(III)-*V(IV) redox sequence, representing a novel mechanistic feature of vanadium-catalysed peroxidative oxidations. The proposed mechanism is validated experimentally by CW-EPR, pulsed ESEEM, and UV-Vis spectroscopy. These findings establish a clear optimization principle for V(III)-scorpionate catalysts in selective alkane oxidation under environmentally benign conditions.

Abstract Understanding how fluorinated contaminants interact with porous carbonaceous materials requires to gain insights beyond macroscopic uptake metrics, particularly when heterogeneous pore networks and surface chemistries imply multiple mobility states. Here, we introduce a dynamic-signature approach to rank biochar-fluorinated liquid interactions based on molecular mobility states probed by 19F fast field-cycling (FFC) NMR relaxometry. Two fluorinated model systems, a perfluoropolyether mixture (Galden HT70) and the small-molecule perfluorodecalin (PFD), were investigated as neat liquids and after contact with two activated biochars (APN1 and LP39) characterized by diverse pore architectures and surface chemistries. Inverse Laplace transform (ILT) analysis of selected relaxation decays reveals the emergence of interfacial and confinement-related heterogeneity upon biochar contact, whereas quantitative analysis of 19F nuclear magnetic relaxation dispersion (NMRD) profiles using a two-term rotational–translational model yields effective dynamic parameters that encode these interactions. APN1, a predominantly microporous and alkaline carbon, induces moderate perturbations consistent with partial interfacial exchange and confinement, whereas LP39, a high-surface area, mesopore-richer and acidic carbon, produces strongly dispersive NMRD signatures indicative of restricted diffusion and enhanced surface-driven relaxation. These trends are consistent across both fluorinated probes, demonstrating that the observed dynamic signatures primarily reflect biochar physicochemical properties rather than probe-specific chemistry. Overall, the results show that activated biochars can be mechanistically typified by their ability to redistribute fluorinated molecules among bulk-like, interfacial, and confined dynamic states. The dynamic-signature approach presented here provides a complementary, mechanistically grounded perspective to conventional adsorption metrics and offers a pathway toward rational selection of biochars for fluorinated-contaminant retention.

The different functional portions present in the thiosemicarbazone (TSC) scaffold allow for a variety of non-covalent interactions while maintaining considerable conformational flexibility. This review gives an overview of how these weak interactions represent leading factors influencing the self-assembly and crystal packing behaviour of TSC-metal complexes, hence acting as building blocks for crystal engineering, leading to tailored 1D, 2D, and 3D architectures. Moreover, these systems represent a highly versatile class of compounds where non-covalent interactions also play a pivotal role in assessing their functions and the ensuing employment in diverse applications. In this context, we present a comprehensive survey concerning the use of TSC-metal complexes in catalysis, sensing, materials science, and environmental applications. Computational methodologies are presented as complementary tools to elucidate the nature and impact of these non-covalent forces. Overall, TSCs and their metal complexes represent a rich platform for designing advanced functional materials with precisely tunable properties through the strategic exploitation of non-covalent interactions.

Spent coffee grounds were valorized as a renewable feedstock to prepare N-, P-, and O-codoped activated carbons via pyrolysis, targeting the development of metal-free electrocatalysts for the oxygen reduction reaction (ORR). Hexachlorocyclotriphosphazene (HCCP) was used as a doping agent, and the influence of different porosity activators such as NH4HCO3, KOH, and oxalic acid was studied. This work employs NH4HCO3 as a benign, metal-free activator and secondary nitrogen source compared against conventional porosity agents. Among the mild activators, NH4HCO3 simultaneously provided nitrogen and released NH3 and CO2, while oxalic acid generated a clean CO2 stream, both contributing to mesoporous structure formation. XPS confirmed the successful incorporation of N and P into the carbon matrix, with a high fraction of graphitic nitrogen enhancing the conductivity and catalytic activity. Raman spectroscopy, TEM, and XRD analyses revealed predominantly sp2-hybridized, turbostratic carbon, with higher structural order at 900 degrees C compared to 700 degrees C. The combined effect of pyrolysis temperature, HCCP, and NH4HCO3 produced mesoporous, nitrogen-rich graphitic carbon structures with promising ORR performance, demonstrating a green strategy that maximizes atom economy, minimizes energy input and waste, and transforms low-value biomass into high-performance metal-free electrocatalysts.

The coffee industry and landfill leachate treatment generate residual waste streams, known as spent coffee grounds (SCG) and landfill leachate membrane concentrate (LLMC). Current practices for managing these residues, including open burning, incineration, and landfilling as a final disposal method, represent a waste of resources and pose a challenge to sustainability. Due to the high pollution potential of solid waste SCG and LLMC, cost-effective management solutions are urgently needed. The present research investigates the slow pyrolysis of SCG using potassium hydroxide (KOH) (weight ratio of 1:1) and LLMC residue (weight ratio of 1:1) as activating agents. The high content of alkali and alkaline earth metals in LLMC could promote the activation of the resulting char and improve the quality of the carbon-based material produced in pyrolysis. The use of LLMC as an activating agent could be a sustainable alternative for valorizing SCG and landfill wastes, potentially replacing ingredients such as steam, CO2, and chemical additives used on an industrial scale. The SCG had a low specific surface area (4.5 m2 g-1), contrasting with the notable surface areas observed in both activated chars. In particular, the KOH-activated char exhibited a higher surface area than the LLMC-activated char, measuring 1,960 m2 g-1 compared to 1,138 m2 g-1 – a difference of about 72%. On the other hand, the combustion enthalpy of the LLMC-activated material was estimated at 22.04 MJ kg-1. The combustion enthalpy of LLMC-activated char was about 21.7% and 19.8% higher than that of SCG and KOH-activated chars, which had values of 18.11 and 18.40 MJ kg-1, respectively. Our findings confirm that pyrolysis of SCG with KOH produces a microporous material with a high specific surface area. In contrast, the resulting LLMC-activated char demonstrates a higher value of combustion enthalpy. This work showed that both activated chars had superior energetic and morphological properties compared to the non-activated char made from SCG biomass. Among the activating agents, KOH led to better performance in terms of char yield and morphological properties. Meanwhile, utilizing LLMC residue as an activating agent highlights its potential for converting landfill waste into high-value material.

Tetroxides of Group 4 elements are benchmark catalysts for aldol reactions and oxidation processes, achieving high yields and regio‐, diastereo‐, and enantioselectivities. Our computational analyses and experimental studies, performed in solution and solid, consistently reveal that these tetroxides form attractive interactions with lone pair compounds exhibiting distinctive σ‐hole bond features. We propose naming these novel bondings as titan bonds (TnBs). These new insights into Ti/Zr/Hf tetroxide interactions may significantly aid in designing more effective catalysts with enhanced selectivities.

Tetroxides of Group 4 elements are benchmark catalysts for aldol reactions and oxidation processes, achieving high yields and regio-, diastereo-, and enantioselectivities. Our computational analyses and experimental studies, performed in solution and solid, consistently reveal that these tetroxides form attractive interactions with lone pair compounds exhibiting distinctive σ-hole bond features. We propose naming these novel bondings as titan bonds (TnBs). These new insights into Ti/Zr/Hf tetroxide interactions may significantly aid in designing more effective catalysts with enhanced selectivities.

Understanding how soil formation processes influence the microstructure and the dynamic behavior of clay-rich materials is essential for both pedological interpretation and technological assessment. In this study, we applied fast field cycling nuclear magnetic resonance (FFC NMR) relaxometry to investigate the microstructural heterogeneity of Moroccan clays developed under diverse pedogenetic conditions. Nuclear magnetic relaxation dispersion (NMRD) profiles were processed using a model-free inversion algorithm to retrieve the distribution of correlation times. The latter provides a phenomenological mapping of proton-surface interactions across distinct dynamic domains. Complementary indicators of micro-scale hydrological connectivity were, then, computed from the T₁ distributions, integrating both structural (SCI) and functional (FCI) heterogeneity. While the former indicates the breadth of molecular environments experienced by water across the system, the latter captures the dynamic contrast between fast- and slow-relaxing populations associated with variations in surface accessibility and magnetic heterogeneity. The results showed that the clay sample from Khemisset exhibited the greatest relaxation heterogeneity, consistent with advanced pedogenetic reorganization related to redox-driven redistribution of paramagnetic metals. In contrast, the clay samples from Berrechid and Tiflet displayed a more ordered architecture and lower magnetic heterogeneity, reflecting earlier-stage pedogenetic development. This study demonstrated that FFC NMR relaxometry reveals the microstructural memory encoded into water dynamics, offering a powerful tool to infer the pedogenetic pathways leading to soil formation. Beyond its relevance for pedological studies, the method also offers valuable insights into the technological behavior of clays, supporting the selection of raw materials for industrial purposes based on their microstructural properties.

As a corrosion inhibitor for mild steel in a molar hydrochloric acid medium, we investigated the potential of Eucalyptus globulus essential oil (EuEO). Through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, and theoretical methods, including DFT/B3LYP 6-31G (d, p) and Monte Carlo simulations, the interactions between the EuEO components and the steel surface were analyzed. D-Allose, Betulinaldehyde, and Uvaol were identified as the major active compounds in the GC-MS analysis. The experimental results showed that EuEO reached an inhibitory efficiency as high as 97% at a 1 g/L concentration. The findings suggest that EuEO operates as a mixed-type inhibitor, reducing both cathodic and anodic reactions, as well as building up a protective coating on the steel surface. Simulations also confirmed that EuEO molecules function as electron donors and acceptors, enhancing corrosion resistance.

In our continuing search for new polymer composites with antimicrobial activity, we observed that even unmodified epoxy resins exhibit significant activity. Considering their widespread use as starting materials for the realization of multifunctional nanocomposites with excellent chemical and mechanical properties, it was deemed relevant to uncover these unexpected properties that can lead to novel applications. In fact, in places where the contact with human activities makes working surfaces susceptible to microbial contamination, thus jeopardizing the sterility of the environment, their biological activity opens the way to their successful application in minimizing healthcare-associated infections. To this end, three commercial and widely used epoxy resins (DGEBA/Elan-TechW 152LR, 1; EPIKOTETM Resin MGS®/EPIKURETM RIM H 235, 2 and MC152/EW101, 3) have been investigated to determine their antibacterial and antiviral activity. After 24 h, according to ISO 22196:2011, resins 1 and 2 showed a high antibacterial efficacy (R value > 6.0 log reduction) against Staphylococcus aureus and Escherichia coli. Resin 2, prepared according to the ratio epoxy/hardener indicated by the supplier (sample 2a) and with 10% w/w hardener excess (sample 2b), exhibited an intriguing virucidal activity against Herpes Simplex Virus type-1 and Human Coronavirus type V-OC43 as a surrogate of SARS-CoV-2.

Three new coordination complexes of Cu(II) ions made from two hydrazone ligands, 7-chloro-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-2-furoyl-hydrazone (HL1) and 6-chloro-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-2-furoyl-hydrazone (HL2) have been synthesized and fully characterized by spectroscopic techniques. Their crystal and molecular structures revealed distorted square pyramidal mononuclear complexes: [(L1)Cu(H2O)2](NO3)·3H2O, 1(NO3), [(L2)Cu(H2O)2](NO3)·2H2O·CH3OH, 2(NO3), and [(L2)Cu(NO3)(CH3OH)]·2CH3OH, 3, comprising the ligand (L1 and L2) in tridentate fashion (ONO) with two water molecules in 1+ and 2+, and a single methanol molecule and a nitrate ion in 3 in their respective copper coordination spheres. EPR spectra in frozen methanol revealed the occurrence of several species arising from different coordination environments. A detailed DFT investigation on the energetics of solvents exchange (H2O, MeOH, and DMSO) and simulation of the EPR parameters showed that the exchange processes occur easily in solution. The value gz indicated the occurrence of a dimeric aggregate for 2+. The new copper complexes exhibited a noticeable antiproliferative activity with IC50 values in the micromolar range against HCT-15, H157, BxPC3, PNS-1, and A431 cell lines and they were found to be 3-fold more effective than cisplatin against pancreatic PSN-1 cell lines. Cross-resistance tests on A2780 and LoVo cancer cell lines and the corresponding multidrug or oxaliplatin resistant sublines showed that complexes 1(NO3) and 2(NO3) were equally cytotoxic to sensitive and resistant cells, thus overcoming multidrug and oxaliplatin resistance.

Abstract Introduction Hospital surfaces play an important role in the transmission of pathogens responsible for healthcare-associated infections (HAIs). In addition to patients, although less frequently, doctors, nurses and other health professionals may also be affected by these infections. The aim of this study is to assess the antibacterial activity of new epoxy resin-based materials (NM1 and NM2) for their possible use as collective protection measures in healthcare settings. Methods To evaluate the in vitro bactericidal activity of NM1 and NM2, the tests were carried out according to ISO 22196:2011. Known concentrations of E. coli ATCC® 8739 and S. aureus ATCC® 6538P were deposited on NM samples. Bactericidal activity was evaluated by calculating the average reduction (R) of the colony forming units (CFU) per cm2 in NM samples compared to controls. Results The results show that the NM1 is effective (R=2.36 Log CFU/cm2) against E. coli but not against S. aureus. As for the NM2, this has bactericidal activity both against E. coli (R=6.68 Log CFU/cm2) and against S. aureus (R=3.75 Log CFU/cm2). Discussion Our preliminary data are extremely promising, particularly those obtained from NM2 tests. Other experimental assays are currently underway on bacteria (Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter Baumanii) responsible for nosocomial infections. Conclusion Several pathogens can persist on hospital surfaces for a long time causing serious infections and epidemic outbreaks. The research in the field of advanced materials could make a significant contribution to the fight against HAIs also limiting the spread of multidrug resistant bacteria.

The pyrolysis process has emerged as an attractive option for waste treatment. In this technology, inorganic compounds play catalytic effects in the pyrolytic reaction of organic materials, increa-sing the char's yield, porosity, and physicochemical properties. The present research investigates and compares the slow pyrolysis of spent coffee grounds (SCG) using potassium hydroxide (KOH) (weight ratio of 1:1) and landfill leachate membrane concentrate (LLMC) residue (weight ratio of 1:1) as pyrolitic additives. We hypothesized that the high content of alkali and alkaline earth metals in LLMC could enhance the yield or improve the quality of the carbon-based material produced in pyrolysis. This strategy could be a sustainable alternative for valorizing SCG and landfill wastes, replacing catalyzing agents such as steam, CO2, and chemical additives used on an industrial scale. The char yields in slow pyrolysis ranged from 18 to 24%. The SCG had a low specific surface area (4.5 m2 g-1), contrasting with the notable surface areas observed in both ac-tivated chars. In particular, the KOH-activated char displayed a higher surface area than the LLMC-activated char (1960 vs. 1130 m2 g-1). On the other hand, the combustion enthalpy of the LLMC-activated material was estimated at 22 MJ kg-1. This value was 22% higher than the energy enthalpy of SCG and KOH-activated char used for comparison. Our findings confirm that pyrolysis of SCG with KOH produces a microporous material with a high specific surface area. In contrast, the resulting LLMC-activated char demonstrates a higher calorific value. Our findings could contribute to establishing potential industrial applications for SCG and LLMC residues to produce energy and high-value materials.

Platinum complexes used in catalysis were the first to utilize hydrogen peroxide in oxidation reactions, resulting successful in epoxidation, sulfoxidation, and Baeyer-Villiger oxidations. This are due to the soft Lewis acidic character of these complexes along with some peculiar properties of Pt that make it unique among late transition metals. Among these properties is the full compatibility of some phosphine containing Pt complexes with water, opening the way to the use of aqueous micellar media to perform oxidations. Improved activities and selectivities at any level (chemo-, regio-, and enantio-) were observed because of specific complex/micelle interactions capable of decreasing the activation energy of certain pathways involved in oxidation processes. Additional advantages observed in micellar media were substrate selectivity and reduction of the E-factor in a series of reactions, ultimately leading to industrial applications.

Resource depletion and climate change have fostered sustainable initiatives in the waste management sector. Pyrolysis (Py) has emerged as an option for valorizing spent coffee grounds (SCG). In addition, inorganic compounds can have catalytic effects on the pyrolytic reaction of organic materials, increasing the char yield and porosity of biochar. This study investigates the slow pyrolysis of SCG using concentrated landfill leachate residue (CLLR) (1:1 wt%) as a pyrolitic additive due to its high salinity. Biochars were characterized based on their thermal behavior to discuss environmental benefits and potential applications. Slow-py experiments were conducted using a lab-scale pyrolizer, and thermal characterization was performed using TA Instruments, specifically the SDTQ600 model. Biochars were characterized by higher water contents and heating rates than those experienced by their feedstocks. It is suggested that the high metal content of CLLR could change the biochar’s thermal stability, decreasing its decomposition temperature. Values were 9.18 wt% and 18.11 MJ kg−1 and 23.25 wt% and 22.05 MJ kg−1 for biochars produced using SCG and SCG and CLLR (1:1 wt%), respectively. Future studies will include biochar ecotoxicity analyses and measure carbon–energy balance.

The present study aims to investigate the adsorption behavior of methylene blue (MB) using purified Moroccan clay/alginate beads and optimize the process conditions using Response Surface Methodology (RSM). Composite alginate beads were synthesized via the drop method, and their performance as adsorbents for MB removal was assessed under varying pH levels, adsorbent dosage, and initial MB concentration using the Box-Behnken design. The results revealed that the optimal conditions for achieving 100% MB removal were pH 11.8, adsorbent mass of 4.9 g, and MB concentration of 191 ppm. The adsorption process was well described by the pseudo-second-order kinetic model and Langmuir isotherm model, suggesting that the process involves monolayer adsorption. Moreover, the regenerated adsorbent exhibited satisfactory adsorption performance after five cycles. These findings demonstrate the potential of purified Moroccan clay/alginate beads as an efficient, reusable adsorbent for MB removal from water solutions, contributing to the development of sustainable solutions for dye removal in wastewater treatment applications.

The paper aims to compare different methods able to estimate the specific loss power (SLP) generated by three different types of magnetic nanoparticles, MNPs, dispersed in a suspension fluid, e.g., octane or water. The nanoparticles were characterized morphologically in terms of shape and size, chemically for composition and their physical properties like magnetization and SLP were studied. We evidenced the differences in SLP evaluation due to the applied method, particularly in the presence of thermally induced phenomena such as aggregation or precipitation of MNPs that can affect the heating curve of the samples. Then, the SLP determination methods less sensible to this phenomenon appear to be the ones that use the initial slope when the sample is in quasi-adiabatic condition. Finally, we propose a comparison of those methods based on the pros and cons of their use for the SLP determination of magnetic nanofluids. In particular, the analysis of the behavior of the heating curve is useful to evaluate the useful amplitude of the interval analysis for the initial slope methods.

Population Medicine considers the following types of articles:• Research Papers -reports of data from original research or secondary dataset analyses.• Review Papers -comprehensive, authoritative, reviews within the journal's scope.These include both systematic reviews and narrative reviews.• Short Reports -brief reports of data from original research.• Policy Case Studies -brief articles on policy development at a regional or national level.• Study Protocols -articles describing a research protocol of a study.• Methodology Papers -papers that present different methodological approaches that can be used to investigate problems in a relevant scientific field and to encourage innovation.• Methodology Papers -papers that present different methodological approaches that can be used to investigate problems in a relevant scientific field and to encourage innovation.

Two nanomicas of similar composition, containing muscovite and quartz, but with different particle size distributions, have been used to prepare transparent epoxy nanocomposites. Their homogeneous dispersion, due to the nano-size, was achieved even without being organically modified, and no aggregation of the nanoparticles was observed, thus maximizing the specific interface between matrix and nanofiller. No exfoliation or intercalation has been observed by XRD, despite the significant dispersion of the filler in the matrix which produced nanocomposites with a loss in transparency in the visible domain of less than 10% in the presence of 1% wt and 3% wt of mica fillers. The presence of micas does not affect the thermal behavior of the nanocomposites, which remains similar to that of the neat epoxy resin. The mechanical characterization of the epoxy resin composites revealed an increased Young’s modulus, whereas tensile strength was reduced. A peridynamics-based representative volume element approach has been implemented to estimate the effective Young’s modulus of the nanomodified materials. The results obtained through this homogenization procedure have been used as input for the analysis of the nanocomposite fracture toughness, which has been carried out by a classical continuum mechanics–peridynamics coupling approach. Comparison with the experimental data confirms the capability of the peridynamics-based strategies to properly model the effective Young’s modulus and fracture toughness of epoxy-resin nanocomposites. Finally, the new mica-based composites exhibit high values of volume resistivity, thus being excellent candidates as insulating materials.