Abstract: Due to the seasonality of its production and to its polluting characteristics, the management and disposal of large amounts of grape pomace (GP) produced worldwide every year can pose a significant economic and environmental challenge. The research on the possible exploitation of GP for various purposes has been constantly growing during the last years, due to the increased general sensibility on issues like sustainability of agro-industrial production and to the growing consumer demand for the use of natural versus synthetic compounds. The work concerned the determination of the polyphenolic profile and the dietary fiber content of skins and seeds from unfermented and fermented white and red grape pomace of different cultivars, sampled from local wineries in the Piedmont area (Italy) after winemaking. A double extraction was performed to maximize the extraction of polyphenols from grape pomace flours. The extractable polyphenols content (EPP) was determined in the extracts, while the non-extractable condensed tannins (NEPP) linked to the fiber were quantified in the residue after extraction. The total dietary fiber (TDF) was determined for skins and seeds; limited to skins, the analysis was extended to the distinction between soluble and insoluble dietary fiber (SDF and IDF). The polyphenolic and dietary fiber content was significantly higher in seeds than in skins. However, from a nutritional point of view, skins dietary fiber may be more interesting due to the higher NEPP content than seeds; moreover, the winemaking technique influenced the quantity and characteristics of skins fiber, which contained SDF, almost absent in seeds.

Abstract: A flexible paper base SERS substrate with hydrophobic surface was fabricated through a simple route. The Ag nanoparticle was modified on filter paper through in situ growth method. After optimizing the condition during the growth and surface modification process, the hydrophobic filter paper-Ag was prepared via soaking in 10-8 g/ml of 1-Dodecanethiol with 12 h growth time. The flexible SERS substrate exhibit excellent hydrophobic properties, the contact angle of water could achieve 130.2 °. When the solution of analyte was dropped onto the SERS substrate, the diffusion effect was limited. After evaporation, the target analyte was concentrated within a fixed area. The hydrophobic SERS substrate could simultaneously improve the SERS signal and fluorescence of the analyte. The paper base SERS substrate with hydrophobic surface was used for detecting thiram from edible oil, and the sensitivity was down to 10-7 M. We proposed a flexible, economical and green hydrophobic SERS substrate for the detection of harmful ingredient from hydrophobic phase.

Abstract:

Background: Food waste contains abundant (+)-catechin, but its efficient recovery remains challenging. This study aimed to prepare ionic liquid (IL)-modified sorbents and establish an efficient method for (+)-catechin recovery from chocolate waste via solid-phase extraction (SPE); Methods: Three serious of IL-modified sorbents (Sil-IL, ZIF67-IL, Sil@ZIF67-IL) were synthesized. Their adsorption performance was evaluated under different conditions; adsorption isotherms and kinetics were fitted to Langmuir/Freundlich and pseudo-first/second-order models, respectively. Sorbent stability and (+)-catechin recovery from chocolate waste extracts were tested; Results: Sil@ZIF67-Hmim showed the highest adsorption capacity (154.4 mg/g) at 25 °C within 120 min. Adsorption followed the Langmuir model (R²=0.99), indicating chemical adsorption. Sil@ZIF67-Hmim was subjected to repeated solid phase extraction (SPE) for five consecutive days, the recovery rate ranged from 98.1%-99.2%, and the relative standard deviation (RSD) was 3.2%-4.4%; Conclusion: Sil@ZIF67-Hmim is a high-efficiency sorbent for (+)-catechin recovery from chocolate waste, providing a novel approach for food waste valorization and highlighting the application potential of IL-modified MOF-silica composites.

Abstract: The accumulation of polyethylene (PE) waste presents significant environmental and economic challenges, particularly in developing regions where plastic valorisation infrastructure remains limited. In this work, waste polyethylene was upgraded through coordination-catalyzed oxidative functionalization using earth-abundant Schiff base metal complexes of iron, cobalt, manganese, and copper with salen and salophen ligands. The process enables selective incorporation of oxygen-containing functional groups while largely preserving polymer molecular integrity, offering a material-oriented alternative to fuel-focused plastic recycling. Fourier transform infrared spectroscopy confirmed the formation of carbonyl and hydroxyl functionalities, with the carbonyl index (CI) increasing from 0.02 ± 0.01 for untreated polyethylene to 0.48 ± 0.04 and 0.42 ± 0.03 for Fe(salen)Cl and Co(salen) catalysts, respectively, under identical conditions. Salophen-based complexes consistently exhibited slightly higher oxidation efficiencies than their salen analogues. Gel permeation chromatography revealed controlled molecular weight reduction, with number-average molecular weight (Mₙ) decreasing from 62.4 × 10³ g•mol⁻¹ (untreated PE) to 56.8 × 10³ and 54.9 × 10³ g•mol⁻¹ for Fe- and Co-based systems, while dispersity remained within polymer-grade ranges. Differential scanning calorimetry and thermogravimetric analysis showed only minor changes in melting temperature and thermal stability. Surface-sensitive X-ray photoelectron spectroscopy confirmed oxidation localized primarily at the polymer surface, while atomic absorption spectroscopy indicated residual metal contents below 10 ppm. Catalyst reusability studies demonstrated sustained activity over multiple cycles. Overall, this coordination-catalyzed strategy provides a scalable and industrially relevant pathway for upgrading polyethylene waste into value-added functional polymers, with strong potential for integration into emerging circular polymer economies in Nigeria and other African regions.

Abstract: Photodynamic therapy (PDT) offers a promising complementary strategy for the treatment of glioblastoma multiforme (GBM); however, achieving selective activation in tumor tissue and maintaining efficacy under hypoxic conditions remain significant limitations. In this study, we present the synthesis and functional evaluation of Gal-SiX, an enzymatically activatable Si-xanthene photosensitizer designed to address these challenges. Prepared through an improved 10-step synthetic route, Gal-SiX displays a clear turn-on fluorescence and absorbance response upon β-galactosidase activation and generates reactive oxygen species efficiently in aqueous media. Mechanistic studies revealed that Gal-SiX enables both Type I and Type II PDT pathways, an advantageous feature for GBM, where oxygen availability is restricted. In vitro assays conducted on U87MG glioblastoma cells and L929 healthy fibroblasts demonstrated meaningful selectivity, with IC50 values of 3.30 μM and 7.19 μM, respectively. Gal-SiX also showed minimal dark toxicity (>80 μM) and potent light-induced cytotoxicity, yielding a phototoxicity index of 24.8 in glioblastoma cells. Confocal imaging and MTT assays consistently demonstrated its activation and PDT efficacy. Overall, this work introduces the first activatable Si-xanthene–based PDT agent for glioblastoma and provides the first evidence that the Si-xanthene scaffold can support dual Type I/II phototoxicity. These results underscore Gal-SiX’s potential as a selective PDT platform for addressing the unique constraints of GBM biology.

Abstract:

Archaea lipids are a source of new biomaterials for pharmaceutical and nanomedical applications; however, their classic extraction method relies on chloroform and methanol, toxic solvents that conflict with green chemistry principles. In this paper we explore the performance of an eco-friendly method for the extraction of total lipids from the haloarchaea Halorubrum tebenquichense. Using the bio-solvents ethyl acetate and ethanol in a two-step procedure, a fraction of total lipids (135 ± 41 mg phospholipids and 1.1 ± 0.4 mg bacterioruberin (BR) / 100 g cell paste) was obtained containing the same composition as that resulting from extraction with the classical solvents as confirmed by Electrospray Ionization Mass Spectrometry, although with lower phospholipid content, thus with a higher proportion of bacterioruberin. The extracted lipids were subsequently utilized for preparation of archaeosomes, which were characterized by uniform size distribution (406 ± 137 nm, 0.63 ± 0.13 polydispersity index), colloidal stability, and negative ζ potential (-38.2 ± 5.4 mV). The photoprotective potential of these archaeosomes was for the first time determined in human keratinocyte (HaCaT) cells exposed to UVB irradiation (270 mJ/cm²). Treatment with archaeosomes significantly (p< 0.05) enhanced cell viability (from ~43 to ~80 %), reduced intracellular ROS generation and proinflammatory cytokine release (TNF-α) and mitigated UVB-induced apoptosis compared to untreated controls, indicating effective cytoprotection. This study demonstrates that ethyl acetate–ethanol-based extraction offers an alternative for archaeal lipid recovery and highlights the potential of archaeosomes as natural photoprotective agents for skincare applications.

Abstract: All-inorganic metal halide perovskites exhibit excellent morphology-dependent pho-tophysical properties. Thus, detailed knowledge of photophysical behavior and mor-phological dependence of CsPbBr3 crystals is crucial for device engineering. However, the inability to directly control the morphology of CsPbBr3 crystals arises from a lim-ited understanding of their crystallization mechanism. Herein, we varied the prepara-tion parameters to investigate the perovskite growth mechanism and the impact of these parameters on size and shape of CsPbBr3 single crystals. By optimizing the solu-tion processing, the shape was tuned from the typical cubic microcrystals to more ir-regular ones. We have shown that three main factors favor the growth and formation of CsPbBr3 microcubes, namely high precursor concentration, high temperature and the use of DMSO solvent. The crystal size and density can be tuned by adjusting the precursor concentration, heating temperature, heating time and drop volume. The ob-tained crystals were of high quality and exhibited a strong photoluminescence at room temperature. This work not only introduces a distinct new morphology within the CsPbBr3 microcrystals family but also provides a fundamental understanding of the growth mechanism of these newly emerging functional materials.

Abstract:

This study investigates the application of Plasma Transferred Arc (PTA) surface treatment as an advanced method for the regeneration of railway wheels. Traditional wheel reprofiling, performed using semi-automatic lathes, involves the removal of at least 6 mm of metal from the running surface, leading to progressive rim thinning and eventual wheel replacement. Furthermore, the reprofiled surfaces lack any subsequent treatment to extend their operational lifespan. To address these limitations, PTA cladding was selected for its capability to produce enhanced surface layers with improved mechanical properties. Unlike commonly used diode laser treatments, PTA enables the deposition of alloying materials in wire form, providing a robust and controlled cladding process. The resulting surface structure comprises a heat-affected zone, a transition zone, and a remelted zone, all exhibiting significantly increased hardness compared to the untreated base metal. The cladding process allows for the incorporation of metal particles into the surface layer, facilitating the formation of a high-quality, wear-resistant top layer. These findings demonstrate the potential of PTA surface treatment to extend the service life of railway wheels by providing a durable and hard-wearing surface, thereby reducing maintenance frequency and costs [1–3].

Abstract: Pomegranate peel, accounting for 35-50% of the fruit's weight, is an underutilized by-product rich in ellagitannins and pectin. Although pomegranate juice has already been subjected to fermentation, this study aimed to demonstrate for the first time, that a simple fermentation process of pomegranate peel using Saccharomyces cerevisiae can yield tannin-rich extracts and enhance the potential prebiotic properties of pomegranate polysaccharides. Peels of ‘Wonderful’ and ‘G1’ cultivars, significantly differing in peel thickness, were used for fermentation applying three processes at room temperature monitored at 48 and 72 h. HPLC-DAD analysis showed that yeast-driven fermentation increased total tannin (up to 70% in dry extracts) compared with spontaneous fermentation (40-43%). A potential enhancement of prebiotic activity was associated with the reduction in the molecular weight of native polysaccharides (from a maximum of 705 kDa down to 26 kDa), as evaluated by DLS and DOSY-1H-NMR. Polysaccharides after fermentation were more effectively utilized by Bifidobacterium breve and Lactobacillus plantarum than those from control samples, as demonstrated by in vitro assays. These findings highlight a promising strategy for the valorization of pomegranate peel through the production of functional ingredients highly enriched in tannins and containing potentially prebiotic polysaccharides.

Abstract: The corrosion behavior and passive-film stability of a β-TiZrNbTa (β-TZNT) alloy were thoroughly examined in artificial seawater (ASW), with a focus on the effects of pH, temperature, immersion time, fluoride ion concentration, and potential scan rate. In addi-tion to electrochemical methods such as open-circuit potential (OCP), potentiodynamic polarization (PDP), and electrochemical impedance spectroscopy (EIS), scanning elec-tron microscopy (SEM) and X-ray diffraction (XRD) were used for surface characteriza-tion. The establishment of a stable and efficient passive layer enriched with Zr-, Nb-, and Ta-oxides was responsible for the β-TZNT alloy's superior corrosion resistance in fluo-ride-free ASW when compared to commercially pure titanium. Reduced passive-film re-sistance resulted from corrosion kinetics being greatly accelerated by decreasing the pH and increasing the temperature. Due to the chemical dissolution of TiO₂ through soluble fluoride complexes, the presence of fluoride ions significantly reduced passivity and in-creased corrosion current densities by more than an order of magnitude. A bilayer pas-sive structure with a compact inner barrier layer and a porous outer layer was identified by EIS analysis. The integrity of this structure gradually decreased as the fluoride con-centration and acidity increased. Over time, passive film degradation predominated in fluoride-free seawater, whereas prolonged immersion encouraged partial re-passivation in fluoride-containing media. Overall, the findings highlight the potential and constraints of β-TZNT alloy for advanced marine and offshore applications by offering new mecha-nistic insights into the synergistic effects of fluoride ions and environmental parameters on corrosion performance.

Abstract: Background: Boron Neutron Capture Therapy (BNCT) represents a highly selective therapeutic modality for recalcitrant cancers, leveraging the nuclear reaction initiated by thermal neutron capture in Boron-10 (10B) to deliver high-linear energy transfer radiation (α-particles and 7Li ions) directly within tumor cell boundaries. However, the widespread clinical adoption of BNCT is critically hampered by the pharmacological challenge of achieving sufficiently high, tumor-selective intracellular 10B concentrations (20-50 μg of 10B /g tissue). Conventional small-molecule boron carriers often exhibit dose-limiting non-specificity, rapid systemic clearance, and poor cellular uptake kinetics. Methods: To overcome these delivery barriers, we synthesized and characterized a novel dual-modality nanoplatform based on highly biocompatible, functionalized graphene oxide (GO). This platform was structurally optimized through covalent conjugation with high-boron content carborane clusters (dodecacarborane derivatives) to enhance BNCT efficacy. Crucially, the nanocarrier was further decorated with plasmonic gold nanostructures (AuNPs), thereby endowing the system with intrinsic surface-enhanced Raman scattering (SERS) properties, which enabled real-time, high-resolution intracellular tracking and quantification. Results: We evaluated the synthesized GO@Carborane@Au nanoplatforms for their stability, cytotoxicity, and internalization characteristics. Cytotoxicity assays demonstrated excellent biocompatibility against the non-malignant human keratinocyte line (HaCaT), while showing selective toxicity (upon irradiation, if tested) and high cellular uptake efficiency in the aggressive human glioblastoma tumor cell line (T98G). The integrated plasmonic component allowed for the successful, non-destructive monitoring of nanoplatform delivery and accumulation within both HaCaT and T98G cells using SERS microscopy, confirming the potential for pharmacokinetic and biodistribution studies in vivo. Conclusion: This work details the successful synthesis and preliminary in vitro validation of a unique Graphene Oxide-based dual-modality nanoplatform designed to address the critical delivery and monitoring challenges of BNCT. By combining highly efficient carborane delivery with an integrated photonic trace marker, this system establishes a robust paradigm for next-generation theranostic agents, significantly advancing the potential for precision, image-guided BNCT for difficult-to-treat cancers like glioblastoma.

Abstract: Green cosmetics are mainly based on plant-derived ingredients, using sustainable bio-technological tools for their preparation. The present research aimed to investigate the Usnea barbata extract in Jojoba oil (JO) enriched with 10% Vitamin E and 5% Pepper-mint oil (PEO), as a potential natural product for skin applications. Materials and Methods: The U. barbata extract (UBPJO) was obtained through cold maceration. Phytochemical screening was performed using Gas Chromatography/Mass Spectrometry (GC-MS), Folin Ciocalteu method, and Graphite-Furnace Atomic Absorption Spectro-photometry. The physicochemical properties were evaluated by Fourier Transform Infrared Spectroscopy and Atomic Force Microscopy. Then, rheological characteristics and oxidation stability (measuring the time required to reach the oxidation starting point, IP) of both oil samples (PJO and UBPJO), were investigated. Results: Total phenolic content in UBPJO was 2.5 times higher than in PJO (p < 0.05), while heavy metal levels (As and Pb) were slightly higher (p > 0.05). UBPJO has higher shear stress, viscosity, and spreadability than PJO, but without significant differences (p > 0.05). Finally, IP measurements indicated appreciable oxidative stability (UBPJO vs. PJO: 153.02 h vs 137.35 h, p > 0.05). Conclusions: The phytochemical composition and physicochemical properties support the inclusion of UBPJO in various skin-protective formulations.

Abstract: Application of MXene-polymer composites in wearable and implantable medical devices requires the development of hydrophilic and biocompatible MXene-polymer hydrogel composites with high electromechanical response, flexibility, and durability. Here, we formulate low weight percentage MXene-hydrogel copolymer inks enabling direct light printing (DLP) of MXene-polyvinyl alcohol (PVA)-polyacrylic acid (PAA)-hydrogel composites. The low wt% MXene-PVA-PAA composites demonstrate high biocompatibility, mechanical flexibility, high sensitivity and high precision for sensing acute bending angles. The sub-millidegree angle resolution and sub-microradian stability of these electromechanical sensors demonstrates their suitability for applications such as high precision tracking of joint movements. In addition, the synthesized MXene membranes show promise for applications in osmotic energy conversion, with a harvested electric power density of 6.79 Wm-2.

Abstract: It has long been recognized that the oxygen reduction reaction occurs more readily on Pt(111) surfaces that include steps, both (111) and (100), than on near-perfect Pt(111). Theoretical models were developed involving the water structure in the electric double layer and its interactions with adsorbed OH, with the actual O₂ reduction occurring on the (111) terraces adjacent to the steps. However, the present density functional theory (DFT) calculations confirms that O₂ adsorbs strongly at the steps and can undergo dissociation aided by adjacent water molecules to produce adsorbed OH. OH produced at the steps can move to the (111) terraces, where it can be more readily reduced to H₂O and desorbed. This model avoids the scaling relation, which predicts that all oxygen-containing reactants and intermediates are proportional to each other on any given surface. Efforts to develop new O₂ reduction catalysts have been hampered by this assumption, which supposes that the reaction rate can be increased by decreasing OH adsorption strength, even though decreased OH adsorption strength is accompanied by decreased O₂ adsorption strength. This proposed model can explain the experimental results on stepped surfaces and may also be important for the development of Pt nanoparticle catalysts.

Abstract: Inter-row mulching with reflective film (RF) has been increasingly adopted in cool-climate vineyards to improve light availability and promote grape ripening. This study investigated the effects of ground-reflected light on the flavoromic profiles of wine grape berries (Vitis vinifera L.) over two consecutive vintages (2020–2021) in the Beijing Fangshan region of Eastern China, an area characterized by high precipitation and limited sunlight during ripening. Physicochemical analyses showed that RF treatment significantly increased total soluble solids (TSS) and decreased titratable acidity (TA) at harvest. Targeted metabolomic analyses using HPLC–MS and GC–MS identified 21 flavonoids and 35 volatile compounds responsive to altered light conditions. RF treatment markedly enhanced the accumulation of anthocyanins and flavonols, especially malvidin-based derivatives, and increased terpene and norisoprenoid concentrations, while C6/C9 compounds were more abundant in control berries. Multivariate analysis revealed that PC1 was mainly associated with anthocyanin accumulation, clearly separating RF-treated samples, whereas PC2 reflected differences in flavonols and flavan-3-ols, with higher flavonols under RF and higher skin- and seed-derived flavan-3-ols in controls. Overall, these findings demonstrate that ground-reflected light plays a critical role in modulating grape flavor composition and provides practical guidance for improving fruit quality in suboptimal climatic regions.

Abstract:

Polyphenols are a structurally diverse group of plant secondary metabolites widely recognized for their antioxidant, anti-inflammatory, antimicrobial, and chemoprotective properties, which have stimulated their extensive use in food, pharmaceutical, nutraceutical, and cosmetic products. However, their chemical heterogeneity, wide polarity range, and strong interactions with plant matrices pose major challenges for efficient extraction, separation, and reliable analytical characterization. This review provides a critical overview of contemporary strategies for the extraction, separation, and identification of polyphenols from plant-derived matrices. Conventional extraction methods, including maceration, Soxhlet extraction, and percolation, are discussed alongside modern green technologies such as ultrasound-assisted extraction, microwave-assisted extraction, pressurized liquid extraction, and supercritical fluid extraction. Particular emphasis is placed on environmentally friendly solvents, including ethanol, natural deep eutectic solvents, and ionic liquids, as sustainable alternatives that improve extraction efficiency while reducing environmental impact. The review further highlights chromatographic separation approaches—partition, adsorption, ion-exchange, size-exclusion, and affinity chromatography—and underlines the importance of hyphenated analytical platforms (LC–MS, LC–MS/MS, and LC–NMR) for comprehensive polyphenol profiling. Key analytical challenges, including matrix effects, compound instability, and limited availability of reference standards, are addressed, together with perspectives on industrial implementation, quality control, and standardization.

Abstract:

The family of N,N-dimethylaminomethylferrocenes is one of the most important in ferrocene chemistry. They serve as precursors for a range of anti-malaria and anti-tumour medicinal compounds in addition to being key precursors for ferrocene ligands in the Lucite alpha process. A brief discussion on the importance of, and the synthesis of N,N-dimethylaminomethyl-substituted ferrocenes preludes the synthesis of the new ligand 1,1´,2,2´-tetrakis-(N,N-dimethylaminomethyl)ferrocene. The crystal structure of this compound is reported and a comparison is made with its disubstituted analogue, 1,2-bis-(N,N-dimethylaminomethyl)ferrocene. The tetrahedral nickel dichloride complexes of both these ligands have been crystallographically characterised. Finally, a pointer to future research in the area is given which includes a discussion of a new method to extract ferrocenylmethylamines from mixtures using additives and a new synthetic avenue from substituted cyclopentadiene itself.

Abstract: Forensic ethanol gas standards are used for, among other, the calibration and metrological verification of evidential breath analysers as described in OIML-R126. A correction for the amount fraction ethanol in forensic gas standards due to cylinder wall adsorption is described. The correction was developed for both the national primary measurement standards as well as for derived primary reference materials. A novel method based on the well-known decanting principle was developed and assessed using two suites of gas mixtures with ethanol amount fractions between 50 μmol mol⁻¹ to 1000 μmol mol⁻¹ in nitrogen. From the results, it is inferred that the initial adsorption loss is a function of the amount fraction and an interpolation formula was developed accordingly. To account for differences in adsorption between cylinders, a mixed effects model was used to describe the adsorption loss data with an excess standard deviation to account for between-cylinder effects.

Abstract: A series of Fe-ZSM-5 catalysts with varying Fe loadings were synthesized via a hydrothermal method. Their catalytic performance was evaluated for the selective catalytic reduction (SCR) of NOx with ammonia. The catalyst with a Fe:Al molar ratio of 1:1 demonstrated the highest NOx conversion (99.9%) and exhibited a broader operating temperature window (240–390°C) compared to catalysts with other Fe/Al ratios. Characterization by X-ray diffraction (XRD),scanning electron microscopy(SEM), and X-ray photoelectron spectroscopy(XPS) confirmed that the incorporation of iron ions preserved the high crystallinity and MFI structure of the ZSM-5 zeolite. NH3-temperature-programmed desorption (NH3-TPD) profiles revealed the presence of two distinct acid sites at approximately 250 °C and 400 °C.

Abstract: The surface properties and electrical behavior of carbon-based materials can be effectively tailored by energetic ion irradiation. In this study, graphene oxide (GO), cyclic olefin copolymer foils (COC, Topas 112 and 011, respectively) were irradiated with 1 MeV Au ions using a 3 MV Tandetron accelerator at fluences of 1 × 10¹⁴, 1 × 10¹⁵, and 2.5 × 10¹⁵ ions/cm². The irradiation induced systematic modifications in surface chemistry, morphology, wettability, and electrical properties. Compositional changes before and after irradiation were investigated using Rutherford backscattering spectrometry (RBS) and elastic recoil detection analysis (ERDA), while surface morphology and roughness were characterized by atomic force microscopy (AFM), revealing a clear fluence-dependent evolution of nanoscale topography. The vibrational characteristics will be assessed through Raman spectroscopy. Surface wettability was evaluated by static contact angle measurements, and surface free energy was determined using the Owens–Wendt–Rabel–Kaelble (OWRK) method, showing a consistent decrease in water contact angle and an increase in surface free energy with increasing ion fluence in Topas 112/011 but not in GO. Electrical characterization demonstrated a pronounced fluence-dependent decrease in sheet resistivity across all investigated substrates. The results show that 1 MeV Au-ion irradiation enables controlled modification of both surface and electrical properties of carbon-based foils.