In the last decades, the impact of the emergent concept of sustainable development has driven the impressive evolution of catalytic methodologies, also stimulated by the breakthrough of new materials and nanotechnologies. Based on this evidence, we report herein the design of sustainable catalysts by addressing the unexploited potential of melanin, a class of pigments widely diffused in nature. By pursuing a straightforward and sustainable approach, we prepared a series of Pd@melanin hybrids inspired from mammalian eumelanin and fungal allomelanin. XPS analyses revealed that DHImel (DHI: 5,6-dihydroxyindole) can support palladium by promoting the reduction of Pd(II) to Pd(0) thanks to the catechol groups that can be converted into quinones. HR-TEM and XRD analyses revealed that palladium atoms are uniformly distributed, forming nanoaggregates in the face-centered cubic crystal structure with an average dimension of 8 nm. The catalytic activity of the hybrids was tested in the Sonogashira cross-coupling reaction. Overall, the collected data suggested that Pd@DHImel, with the highest product yields and lowest Pd loading, is the most efficient catalyst, even when working with deactivated aromatic iodides. Finally, stability tests indicated that the hybrid did not suffer leaching phenomena, leading to high yields for up to eight cycles.

In this study, LaFeO3/g-C3N4 (LFO/g-CN) hybrid materials with mass ratios of LFO and g-CN of 1/0.5, 1/1, and 1/1.5 were synthesized and evaluated for the visible light photocatalytic degradation of the azo-dye Orange G (OG). The composite materials were characterized to determine their textural, morphological, and optical properties. Preliminary photocatalytic results highlighted a significant synergistic interaction between LFO and g-CN. The LFO/g-CN (1/1.5) composite exhibits the highest activity, achieving 50% OG removal, representing a 2.7-fold improvement over pristine g-CN, with a rate constant of 0.0048 min-1 (3.7 times higher than bare g-CN). The degradation kinetics follow a pseudo-first-order model. The influence of key operational parameters, including catalyst loading, initial pH, pollutant concentration, and visible-light intensity, was systematically investigated using the optimized LFO/g-CN (1/1.5) composite. Optimal OG conditions (0.5 g L-1 catalyst, pH 2.0, 10 mg L-1 OG concentration, 0.95 W cm-2 visible light intensity) yielded a maximum rate constant of 0.0119 min-1 and 82% OG decolorization after 135 min. At higher catalyst or dye concentrations, the photocatalytic activity declined due to light scattering and surface saturation. Enhanced OG degradation under acidic conditions was attributed to favourable electrostatic attraction between the positively charged catalyst surface and anionic OG moieties. The composite also demonstrated excellent stability, retaining over 77% of its initial activity after four reuse cycles. These findings highlight the potential of LFO/g-CN heterojunctions as efficient visible-light photocatalysts for sustainable water remediation.

Mixed-phase TiO₂ systems offer unique opportunities for enhancing photocatalytic performance via interpolymorph junctions (homojunctions). While anatase/rutile interfaces have been extensively studied, anatase/brookite junctions remain comparatively underexplored. Here, we demonstrate that homojunctions between anatase and brookite, formed via a template-free, pH-controlled synthesis and low-temperature calcination (200 °C), significantly enhance photocatalytic activity under simulated solar light. High-resolution TEM reveals direct anatase/brookite junctions without isolated brookite crystallites. At the same time, IR spectroscopy detects the formation of CO2.− radical ions, suggesting that the homojunctions act as active defect sites, potentially contributing to visible light absorption or increasing photocatalytic performance. Notably, the surface generation of CO2.− under mild conditions could open new perspectives for CO₂ activation and solar fuel production, while also positioning this species as a valuable intermediate in organic synthesis for the formation of carboxylic acids. Compared to an anatase/brookite/rutile system obtained through calcination at 600 °C, the sample calcined at low temperature exhibits superior performance in degrading paracetamol, a model emerging contaminant in city water. Importantly, Surface-Enhanced Raman Spectroscopy (SERS) enables direct identification of paracetamol degradation intermediates, revealing a mechanistic pathway similar to that promoted by a commercial anatase/rutile TiO2. These findings underscore the potential of anatase/brookite homojunctions as efficient charge-separating interfaces, as further supported by electrochemical impedance spectroscopy.

Carbon nanomaterials have gained significant attention because of their unique tunable properties, including high surface area, excellent electrical conductivity, and chemical stability. These materials are classified by dimension, including 0D carbon quantum dots, 1D nanofibers, 2D nanosheets, and 3D hierarchical nanostructures such as hollow nanocages. Hollow carbon nanocages exhibit distinct characteristics, such as interior cavities and subnanometer channels, which enhance their structural stability and electrocatalytic efficiency. Furthermore, these structures, particularly when doped with heteroatoms like nitrogen, offer promising applications in energy storage, conversion, and sensing technologies. Nitrogen doping significantly influences the electronic properties, creating additional energy levels and active catalytic sites. Doping also facilitates extreme bending of the graphene planes, which improves electrocatalytic performance by enhancing oxygen reduction reactions and increasing active site density. This paper demonstrates, through both experimental and theoretical methods, that nitrogen atoms preferentially accumulate at the edges of carbon nanocages, inducing curvature in the graphitic structure. This finding provides insight into how heteroatom doping can be leveraged to tune the structural and electrochemical properties of carbon nanomaterials for advanced applications.

Ethanolamines are often added in the empirical formulation of commercial hard-surface cleaners and degreasers. Their use is usually justified by the fact they are anti-corrosive agents. However, their direct influence on cleaning performance is not well understood. In this work the cleaning performance of formulations with and without mono-ethanolamine (MEA) have been tested on standard polymerized grease baked on stainless steel plates. We demonstrate, for the first time, that even a small amount of MEA in water is crucial to obtain an efficient removal of burnt residues formed during baking processes. To rationalize this previously overlooked role, we have characterized the soil composition by infrared (IR) and X-ray photoelectron (XPS) spectroscopies and determined its Hansen solubility parameters. In parallel, the effect of MEA aqueous solutions on the soil was investigated by confocal microscopy, contact angle and IR measurements. IR measurements indicate that MEA modifies the baked soil softening it. Confocal imaging demonstrates that the MEA aqueous solution penetrates through the polymerized grease film wetting the substrate and inducing the softened soil retraction from the substrate (deweeeting).

Bacterial contamination in drinking water systems poses a serious health risk due to poor hygiene, human activities, and cross-contamination within the water supply. This study examines the potential of iron-doped titanium oxide nanometric powder (Fe-TiO2) for the photocatalytic disinfection of Gram-negative E. coli and Gram-positive S. aureus under visible light. The Fe-TiO2 photocatalyst, with an optimal nominal content of 2.5 wt % Fe, was synthesized using a surfactant-assisted sol-gel method, resulting in a mesoporous nanomaterial composed of anatase nanoparticles with a specific surface area of 123 m2/g. A sample of undoped anatase TiO2, obtained using the same sol-gel method and exhibiting a specific surface area of 116 m2/g, was utilized to confirm the role of Fe-doping in disinfection. The nanopowders were characterized using X-ray diffraction, N2 sorption at -196 °C, diffuse reflectance UV-vis spectroscopy, X-ray photoelectron spectroscopy, electrophoretic mobility measurements, high-resolution transmission electron microscopy combined with energy-dispersive X-ray spectroscopy, and field emission scanning electron microscopy. Photocatalytic disinfection tests were conducted using 1 and 0.5 g/L Fe-TiO2 with varying initial bacterial concentrations, with 1 g/L yielding the most promising results under the experimental conditions employed. After 240 min of treatment with 1 g/L Fe-TiO2, a 99.9% removal of both E. coli and S. aureus was achieved starting from a bacterial concentration of 1 × 106 CFU/mL. A 99.9% removal of E. coli and a 99.8% removal of S. aureus were achieved starting from 1 × 104 CFU/mL. The Fe-TiO2 nanomaterial was effective against high concentrations of both bacteria under visible light. Reusability was studied by recovering the Fe-TiO2 nanoparticles and assessing their performance over three cycles. The photocatalytic disinfection effectiveness of Fe-TiO2 nanoparticles under visible light was validated using an actual tap water sample containing 167 CFU/mL total coliforms and 8 CFU/mL E. coli . The bacteria were photocatalytically inactivated within 30 min.

Quercetin (QU), a bioactive flavonoid with significant nutritional and antioxidant properties, plays a vital role in the quality and stability of wine. This study presents the development of a molecularly imprinted polymer (MIP)-based optical sensor for the selective and sensitive detection of quercetin in red and white wines. The sensor combines the selective molecular recognition capabilities of MIPs with the optical properties of nanostructured porous silica (PSiO2) scaffolds, which serve as the transducer. MIP synthesis was achieved through a novel room-temperature vapor-phase polymerization method using pyrrole as the functional monomer. Computational simulations were used to optimize pyrrole interactions with QU and at the polymer level, to explore the binding interactions of QU with the resulting polypyrrole (PPy) matrix. Comprehensive characterization including UV-vis reflectance spectroscopy and advanced surface analyses confirmed successful MIP formation. The sensor exhibited high sensitivity in a dual linear response range (2.5-80 μM and 80-200 μM), with a detection limit of 0.7 μM. Selectivity tests against structurally similar flavonoids and antioxidants demonstrated a significantly higher response to quercetin, with an imprinting factor of 3.6. The sensor was validated using real wine samples, demonstrating the ability to detect quercetin without prior sample preparation. Results showed strong agreement with high-performance liquid chromatography (HPLC), confirming the sensor reliability. Additionally, the sensor exhibited excellent reusability with minimal signal variation (RSD = 2.6%) and good stability over 60 days (RSD = 3%). This work highlights the potential of MIP-based optical sensors for the real-time monitoring of bioactive compounds in complex food matrices, such as wine, offering a robust and cost-effective alternative for quality control applications.

This study deals with the reduction reaction of nitroarenes using hydrazine monohydrate as the reducing agent and iron‐supported steel slag as a novel green heterogeneous catalyst. Steel slag is a byproduct of the steel industry, which, due to its alkalinity, can act as a reactive support that can trigger the formation of catalytically active iron oxides/hydroxides. A systematic study is conducted to evaluate the catalytic activity of steel slags modified with the following salts (or mixtures): FeSO 4 ·7H 2 O, FeCl 3 ·6H 2 O, and FeCl 2 ·4H 2 O. The modified steel slags are characterized by X‐ray powder diffraction, Mössbauer spectroscopy, scanning electron microscopy, scanning transmission electron microscopy, energy dispersive X‐ray spectroscopy, nitrogen sorption analysis, and X‐ray photoelectron spectroscopy. All iron‐supporting steel slags demonstrate active behavior in the hydrogenation of nitrobenzene at 80 °C with the best results, in terms of activity, selectivity, and recyclability achieved with the catalyst prepared from FeCl 3 ·6H 2 O ( Fe3 ). The scalability of the reaction is confirmed by carrying out a test on 12.5 mmol of substrate. The superiority of Fe3 compared with the other studied materials is ascribed to its morphology and the remarkably high surficial area. The iron species active in the Fe3 catalyst are noncrystalline oxo–hydroxo species of Fe(III) (2L‐ferrihydrite).

This study investigates the molecular mechanisms underlying the antiproliferative effects of the platinum(IV) complex trans-[Pt(OBz)2(O,C-10-BzODA)(1R,2R-DACH)] (complex 1; OBz = benzoate, 10-BzODA = 10-benzoyloxy-2-decenoate, DACH = diaminocyclohexane) in pancreatic cancer cell models. Initial findings revealed that complex 1 exhibits substantial antiproliferative activity, positioning it as a promising therapeutic agent for pancreatic cancer, where effective treatment options remain limited. Notably, complex 1 demonstrates significantly greater efficacy compared to platinum(II) drugs, such as cisplatin and oxaliplatin, with IC50 values in the low micromolar range across various pancreatic cancer cell lines. Mechanistic studies suggest that complex 1's enhanced activity is attributed to the axial benzoate ligands, which differentiate it from its platinum(II) analog. Complex 1 accumulates intracellular platinum without undergoing reduction in the extracellular environment, and it induces mitochondrial hyperpolarization. This effect is reminiscent of free sodium benzoate but occurs at a much lower extracellular concentration, indicating the crucial role of the benzoate ligands in modulating mitochondrial function. Furthermore, complex 1 triggers caspase-dependent apoptosis in cancer cells and is also effective in 3D tumor cell models, highlighting its potential as an effective anticancer agent. Thus, this work presents a Pt(IV) prodrug bearing benzoate axial ligands that exhibit distinctive chemical and biological behavior compared with previously reported Pt(IV) prodrugs. In conclusion, the unique properties of complex 1, driven by its benzoate ligands, suggest that Pt(IV) complexes represent a promising approach for the development of targeted chemotherapeutic agents for the treatment of pancreatic cancer.

Cerium oxide nanoparticles (CeO2NPs) have been widely investigated for numerous applications due to their redox activity, free radical scavenging property, and biofilm inhibition. Here we describe a new antibiofilm system based on CeO2NPs protected and stabilised by PLGA micelles embedded in two different biodegradable and biocompatible films. CeO2NPs were synthesised following the W/O microemulsion method and subsequently encapsulated in PLGA micelles according to the single emulsion/solvent procedure. All formulations (free NPs, empty micelles and loaded micelles) were incorporated in gelatine and starch films aimed at food packaging use. The chemical and physical characterizations of the NPs and micelles solutions were carried out by Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). Blank films and films incorporating micelles and NPs were also characterized by Scanning Electron Microscopy (SEM) and by XPS. Antibacterial experiments were also performed to investigate the system viability for the final use.

Abstract Herein, this work reports the first example of second‐generation wearable biosensor arrays based on a printed electrode technology involving a water‐based graphite ink, for the simultaneous detection of l‐lactate and d‐glucose. The water‐based graphite ink is deposited onto a flexible polyethylene terephthalate sheet, namely stencil‐printed graphite (SPG) electrodes, and further modified with [Os(bpy)2(Cl)(PVI)10] as an osmium redox polymer to shuttle the electrons from the redox center of lactate oxidase from Aerococcus viridans (LOx) and gluocose oxidase from Aspergillus niger (GOx). The proposed biosensor array exhibits a limit of detection as low as (9.0 ± 1.0) × 10−6 m for LOx/SPG‐[Os(bpy)2(Cl)(PVI)10] and (3.0 ± 0.5) × 10−6 m for GOx/SPG‐[Os(bpy)2(Cl)(PVI)10], a sensitivity as high as 1.32 μA mm−1 for LOx/SPG‐[Os(bpy)2(Cl)(PVI)10] and 28.4 μA mm−1 for GOx/SPG‐[Os(bpy)2(Cl)(PVI)10]. The technology is also selective when tested in buffer and artificial sweat and is endowed with an operational/storage stability of ≈80% of the initial signal retained after 20 days. Finally, the proposed array is integrated in a wristband and successfully tested for the continuous monitoring of l‐lactate and d‐glucose in a healthy volunteer during daily activity. This is foreseen as a real‐time wearable device for sport‐medicine and healthcare applications.

The present study employs X-ray photoelectron spectroscopy (XPS) to analyze plastic samples subjected to degradation processes with the aim to gain insight on the relevant chemical processes and disclose fragmentation mechanisms. Two model plastics, namely polystyrene (PS) and polyethylene (PE), are selected and analyzed before and after artificial UV radiation-triggered weathering, under simulated environmental hydrodynamic conditions, in fresh and marine water for different time intervals. The object of the study is to identify and quantify chemical groups possibly evidencing the occurrence of hydrolysis and oxidation reactions, which are the basis of degradation processes in the environment, determining macroplastic fragmentation. Artificially weathered plastic samples are analyzed also by Raman and FT-IR spectroscopy. Changes in surface chemistry with weathering are revealed by XPS, involving the increase in chemical moieties (hydroxyl, carbonyl, and carboxyl functionalities) which can be correlated with the degradation processes responsible for macroplastic fragmentation. On the other hand, the absence of significant modifications upon plastics weathering evidenced by Raman and FT-IR spectroscopy confirms the importance of investigating plastics surface, which represents the very first part of the materials exposed to degradation agents, thus revealing the power of XPS studies for this purpose. The XPS data on experimentally weathered particles are compared with ones obtained on microplastics collected from real marine environment for investigating the occurring degradation processes.

Herein we report on a novel enzymatic fuel cell (EFC) based on stencil printed electrodes modified with pyrrolo quinoline quinone glucose dehydrogenase and bilirubin oxidase, which are assembled by considering two different configurations: (i) normal assembling in liquid electrolyte and (ii) six EFCs connected in series, each one comprising both bioanode and biocathode, coupled through a hydrogel-based electrolyte in a stack-like mode similar to a Voltaic pile. After a deep electrodes characterization, they are assembled according to the first configuration obtaining an open circuit voltage (OCV) of 0.562 +/- 0.002 V. Moreover, the EFC performance are substantially improved by using the second configuration (six EFCs connected in series) obtaining an OCV of 2.36 +/- 0.22 V with a maximum power output of 22.9 +/- 0.9 mu Wat a cell voltage of 1.95 V (operating in 10 mM D-glucose). This innovative approach represents a proof-of-concept towards the development of renewable power sources and could serve as acritical step in powering implantable bioelectronics, such as pacemakers

The Carbon Capture and Utilization (CCU) option can be an efficient solution for CO2 emission mitigation. To this end, we have investigated the carbon dioxide methanation at low temperatures. Highly active, selective, stable, low-cost catalysts are required for energy and carbon balance benefits. Supported nickel-based catalysts result as the most studied and promising candidates showing a good compromise between performance and low preparation costs. The catalyst design role is key to obtaining the best performance, requiring many experiments and optimisation procedures. Herein, the enhanced Montmorillonite MK10-supported Ni(0)Ce(III) catalyst, prepared by consecutive hydrothermal and electrostatic adsorption methods followed by reduction under hydrogen flow, was used in batch CO2 methanation, exhibiting 76 % of CO2 conversion with 100 % CH4 selectivity after 3 h. The catalytic system reveals very high robustness preserving the same activity and selectivity for at least 5 reaction cycles if compared with gamma-Al2O3-supported Ni(0)Ce(III) catalyst, the latter showing the same activity but only in the first cycle. EDX, XPS, SEM, TPD, TPR, and BET characterisation techniques were used to elucidate and evaluate the potential synergistic effect of the active metal centre-promoter-support interfaces, highlighting their role in the activity and robustness of the catalyst, comparing the same effect using different alumina and silicate solid supports. The effects of the reaction conditions on the methane yield and selectivity were also evaluated.

Herein, we report an ultrasensitive and highly selective analytical methods to detect 2,4-dichlorophenoxyacetic acid (2,4-D) using an o-phenylenediamine based molecularly imprinted polymer (o-PD-MIP) sensor. Electrochemical Quartz Crystal Microbalance (EQCM) is used to investigate both the kinetics and the mass of the electropolymerized o-phenylenediamine. Additionally, successful removal of the template from the imprinted cavities is confirmed by comparing the XP spectra of imprinted and o-PD-MIPs after various template removal procedures. The most effective method involves a 70:30 mixture of MeOH:H2O for 15 min under stirring. The o-PD-MIP sensor exhibits high sensitivity with a LoD of (3 +/- 1) x 10(-12) M, which is below the EU regulation limits for drinking water by six orders of magnitude, a linear range between 10 and 100pM, and an excellent selectivity. These results proved the effectiveness of template removal procedure by using a 70:30 MeOH:H2O mixture and are a proof-of-concept for ultrasensitive and selective 2,4-D detection in real samples.

The photocatalytic degradation of the emerging contaminant paracetamol in aqueous solution has been studied under 1 SUN (~1000 W m−2) in the presence of four commercial TiO2 powders, namely sub-micrometric anatase and rutile, and nanometric brookite and P25 (the popular anatase/rutile mixture used as a benchmark in most papers). The rutile powder showed low activity, whereas, interestingly, the anatase and the brookite powders outperformed P25 in terms of total paracetamol conversion to carboxylic acids, which, according to the literature, are the final products of its degradation. To explain such results, the physicochemical properties of the powders were studied by applying a multi-technique approach. Among the physicochemical properties usually affecting the photocatalytic performance of TiO2, the presence of some surface impurities likely deriving from K3PO4 (used as crystallization agent) was found to significantly affect the percentage of paracetamol degradation obtained with the sub-micrometric anatase powder. To confirm the role of phosphate, a sample of anatase, obtained by a lab synthesis procedure and having a “clean” surface, was used as a control, though characterized by nanometric particles and higher surface area. The sample was less active than the commercial anatase, but it was more active after impregnation with K3PO4. Conversely, the presence of Cl at the surface of the rutile did not sizably affect the (overall poor) photocatalytic activity of the powder. The remarkable photocatalytic activity of the brookite nanometric powder was ascribed to a combination of several physicochemical properties, including its band structure and nanoparticles size.

Treatment of primary bone malignancies comprises surgery, radiotherapy, chemotherapy, and analgesics. Platinum-based chemotherapeutics, such as cisplatin, are commonly used for the treatment of bone cancer but, despite their success, outcomes are limited by toxicity and resistance. Recently, dinuclear Pt complexes with a bridging geminal bisphosphonate ligand proved to be endowed with selective accumulation in bone tumors or metastases leading to improved efficacy and reduced systemic toxicity. Further improvement could be expected by the use of a bisphosphonate ligand with intrinsic pharmacological activity such as zoledronic acid (ZL). In the present work is reported the synthesis and full characterization of the dinuclear Pt(II) complex [{cis-Pt(NH3)2}2(ZL)]HSO4 which combines two drugs with antitumor activity, cisplatin and zoledronic acid. Both drugs, individually, are already approved by the U.S. Food and Drug Administration and the European Medicinal Agency for clinical use. The in vitro cytotoxicity of the new Pt(II)-ZL complex has been tested against a panel of human tumor cell lines.

One of the crucial challenges of our time is to effectively use metal and metal oxide nanoparticles (NPs) as an alternative way to combat drug-resistant infections. Metal and metal oxide NPs such as Ag, Ag2O, Cu, Cu2O, CuO, and ZnO have found their way against antimicrobial resistance. However, they also suffer from several limitations ranging from toxicity issues to resistance mechanisms by complex structures of bacterial communities, so-called biofilms. In this regard, scientists are urgently looking for convenient approaches to develop heterostructure synergistic nanocomposites which could overcome toxicity issues, enhance antimicrobial activity, improve thermal and mechanical stability, and increase shelf life. These nanocomposites provide a controlled release of bioactive substances into the surrounding medium, are cost effective, reproducible, and scalable for real life applications such as food additives, nanoantimicrobial coating in food technology, food preservation, optical limiters, the bio medical field, and wastewater treatment application. Naturally abundant and non-toxic Montmorillonite (MMT) is a novel support to accommodate NPs, due to its negative surface charge and control release of NPs and ions. At the time of this review, around 250 articles have been published focusing on the incorporation of Ag-, Cu-, and ZnO-based NPs into MMT support and thus furthering their introduction into polymer matrix composites dominantly used for antimicrobial application. Therefore, it is highly relevant to report a comprehensive review of Ag-, Cu-, and ZnO-modified MMT. This review provides a comprehensive overview of MMT-based nanoantimicrobials, particularly dealing with preparation methods, materials characterization, and mechanisms of action, antimicrobial activity on different bacterial strains, real life applications, and environmental and toxicity issues.

The development of ultrasensitive analytical detection methods for organophosphorus pesticides such as dimethoate (DMT) plays a key role in healthy food production. DMT is an inhibitor of acetylcholinesterase (AChE), which can lead to the accumulation of acetylcholine and result in symptoms related to the autonomous and central nervous systems. Herein, we report the first spectroscopic and electrochemical study on template removal after an imprinting process from a polypyrrole-based molecularly imprinted polymer (PPy-MIP) film for the detection of DMT. Several template removal procedures were tested and evaluated using X-ray photoelectron spectroscopy. The most effective procedure was achieved in 100 mM NaOH. The proposed DMT PPy-MIP sensor exhibits a limit of detection of (8 ± 2) × 10-12 M.

The chemical surface composition of a nanomaterial is fundamental to determine its properties. In this paper different nanomaterials will be discussed in terms of surface speciation and related properties and peculiarities.