Physical-chemical Characterization Research Articles

MEL DE ABELHAS TIÚBA (MELIPONA FASCICULATA) DO PARÁ: UM ESTUDO FÍSICO-QUÍMICO E COMPARATIVO

The State of Pará has a great diversity of flora and fauna, featuring several species of native stingless bees, especially the Melipona fasciculata bee, known as Tiúba or gray uruçu, which produces honey that is highly appreciated in the Amazon region. The present study focused on the physical-chemical characterization of honey samples of this species, from two municipalities in Pará and the distinction of the samples according to their location of origin. Physicochemical methods already established in the literature and multivariate analysis were used for the intended discrimination. The results demonstrated that the samples were of good quality, with some parameters that demonstrated dependence on the location of production, and it was possible to discriminate the samples according to the origin of the samples.

Dl-Limonene as an Alternative Sustainable Solvent to Xylenes for the Industrial Preparation of Release Formulations.

Many industrial processes use aromatic hydrocarbons as solvents, including benzene, toluene, ethylbenzene, and xylene (BTEX). However, their use is discouraged due to their toxicological profile. Research is ongoing to find alternative more sustainable solvents. This work explores the adoption of dl-limonene as an alternative to BTEX for the industrial preparation of release formulations containing carnauba wax to be employed in the peelable foils industry. A preliminary chemical-physical characterization of carnauba wax was carried out using spectroscopic (ATR-FTIR, NMR) and thermal analyses (DSC). Based on the chemical composition found for the carnauba wax used in the present study, different solvent mixtures and different concentrations of carnauba wax were tested to obtain a clear and stable solution. The most promising formulations were subjected to a coating test on a solid substrate (polyethylene terephthalate, PET) on a laboratory scale, followed by a peeling test to assess the resulting peeling strength. The dl-limonene/ethyl acetate mixture in the 9 : 1 ratio has been identified as the most suitable to completely solubilize carnauba wax (0.38 wt/vol %) and obtain an adequate release performance. The results of these experiments were then used to set up and successfully perform an industrial-scale coating test.

Synthesis and physical–chemical characterization of chitosan grafted with hyaluronic acid as potential application in biomaterials

Synthesis and physical–chemical characterization of chitosan grafted with hyaluronic acid as potential application in biomaterials

Ni-MOFs and lignin modified biochar: An environmentally-friendly and efficient catalyst for catalytic transfer hydrodeoxygenation of lignin derivatives

In this study, different kinds of lignin, including enzymatic hydrolysis of lignin (EHL), alkaline lignin (AL), kraft lignin (KL) and sodium lignosulfonate (LS) were investigated as precursor to prepare Ni@BTC@X (X= EHL, AL, KL, LS) catalysts using a traditional hydrothermal method with Ni-MOF for HDO upgrading of lignin derivative vanillin (VAN) to generate high value chemical 2-methoxy-4-methylphenol (MMP). The catalytic performance of these catalysts was investigated under different reaction conditions, and it was explored that the conversion of VAN was close to 100 % and the MMP yield was close to 90 % under the optimal conditions (Ni@BTC@LS catalyst, 220 ℃, 4 h, isopropanol, 2 MPa N2). Various physical-chemical characterization results verified that the effects of active sites Ni, porous structure of lignin biochar support and electronic properties of the catalysts played a significiant role in HDO of lignin derived VAN. Additionally, synergistic effect of the highly homogeneously dispersed oxygen vacancies and acidic sites also promoted the VAN conversion efficiency. This work developed a strategy combing the advantages of MOFs and biomass derived substrates for manufacturing novel lignin/MOFs materials in the catalytic field.

Development of a nanoemulsion containing Lippia origanoides essential oil with antifungal activity by low energy method: From extraction to formulation

The essential oil of Lippia origanoides is of great pharmacological interest because of a wide variety of attributes, in particular its antifungal action. Due to its low solubility in aqueous media, high volatility, and a high propensity for physicochemical degradation, the search for nanostructured systems to promote the stability of this phytocomplex is necessary. Nanoemulsion is an alternative method to stabilize and preserve this type of active ingredient, especially when generated by a low energy method and using Syagrus coronata (licuri) oil as an active carrier and stabilizer of this nanostructure. The objective of the present investigation was to formulate a stable nanoemulsion with Lippia origanoides essential oil carried through licuri oil with antifungal action by the low energy method. For this, we began with the extraction of the essential oil and the phytochemical characterization obtaining the chemotype B of this Lippia (carvacrol: 49.12%). Then, using the pseudoternary phase diagram, the optimal ratio of the oil phase 6:4 (essential oil: Syagrus coronata oil) was established, adding 15% of surfactant (polysorbate 80) and 75% of the aqueous phase. Then, with the formulated nanoemulsion, the physical-chemical characterization and evaluation of preliminary and accelerated stability were carried out. In addition, cytotoxicity, Franz cell permeation and antifungal activity against dermatophytes were evaluated. A stable nanoemulsion was obtained by the low energy method with the characteristic appearance of a nanoemulsion and a characteristic odor of essential oil. The average size of the nanoparticles was around 167.5 nm, narrow PDI (<0.2 nm), zeta potential below −10.0 mV, acidic pH (5.1), average conductivity 134.4 μSm/cm, refractive index characteristic of a translucent system and low viscosity (<6.0 mPa.S). Regarding cytotoxicity, it proved to be safe at dosages below 90 μg/mL, efficient in terms of permeation (76.7% in 24h) and effective in terms of antifungal activity as it had a minimum inhibitory concentration between 234.4/156.3 μg/mL and 11.2/7.5 μg/mL against the tested dermatophytes. In view of the results, a nanoemulsion containing the essential oil of L. origanoides carried by the oil of Syagrus coronata was shown to be a potential product for the topical treatment of fungal infections like dermatophytosis.

Toward a Plasmon-Based Biosensor throughout a Thermoresponsive Hydrogel.

This study investigates the potential of thermoresponsive hydrogels as innovative substrates for future in vitro diagnostic (IVD) applications using AVAC technology, developed and patented by the Mecwins biomedical company. In order to convert the hydrogel in a substrate compatible with AVAC technology, the following prerequisites were established: (1) the hydrogel layer needs to be permeable to gold nanoparticles (AuNPs), and (2) the optical properties of the hydrogel should not interfere with the detection of AuNPs with AVAC technology. These two key aspects are evaluated in this work. A silicon substrate (Sil) was coated with a layer of a thermosensitive hydrogel (TSH) based on poly(N-isopropylacrylamide-co-N,N'-methylene bis(acrylamide) (PNIPAAm-co-MBA). The TSH offers the advantage of easy modulation of its porosity through cross-linker adjustments, crucial for the plasmonic nanoparticle (NP) permeation. The platforms, denominated as (Sil)-g-(PNIPAAm-co-MBA), were fabricated by changing the cross-linker concentrations and exploring three deposition methods: drop casting (DC), spin coating (SC), and 3D printing (3D); the DC approach resulted in a very homogeneous and thin hydrogel layer, very suitable for the final application. Furthermore, after physical-chemical characterization, the TSH demonstrated its functionality in regulating nanoparticle absorption, and AVAC technology's capability to precisely identify such NPs through the hydrogel matrix was validated. The proposed hydrogel platform fulfills the initial requirements, opening the possibility for employing these hydrogels as dynamic substrates in sandwich immunoassay devices. The next step in the development of the hydrogel substrate would be its functionalization with biorecognition groups to allow for biomarker detection. By leveraging their enhanced capture efficiency and the ability to manipulate particle flow thermally, we anticipate a significant advancement in diagnostic methodologies, combining the spatial benefits of three-dimensional hydrogel structures with the precision of AVAC's digital detection.

Eudermic Properties and Chemical-Physical Characterization of Honeys of Different Botanical Origin.

Background: Honey is a natural product that, thanks to its composition, particularly the high sugar content, is highly appreciated as an energy nourishment. In addition to sugars, it contains many other substances (carbohydrates, free amino acids, enzymatic proteins, organic acids, polyphenols) from which the therapeutic properties of honey arise: hydrating and osmotic activity, antimicrobial action, and antioxidant and anti-inflammatory power. Objectives: The present work aims to deepen our knowledge/understanding of the activity of skin protection exerted by honey, as a synergic result of its multiple therapeutic effects. Moreover, this study wants to find possible correlations between biological properties and the chemical-physical traits of honey. Methods: To carry out this research, five varieties of citrus honey, one of acacia honey, one of chestnut honey, and one of multifloral honey were used. The honeys were first characterized by chemical-physical analysis and then were subjected to qualitative melissopalynological analysis. Tests were also carried out to evaluate both their antioxidant power and the effect on collagenase, an enzyme involved in the degradation of collagen present in the extracellular matrix and, therefore, in the processes of skin aging. Finally, honey samples were then used in in vitro experiments to assess their action in stimulating cell viability and proliferation on human keratinocytes. Results: Chemical-physical analysis demonstrated a good water content (about 17%), an important sugar content (with the monosaccharides glucose and fructose being the most represented in all the honey samples), various amino acids (with proline remarkably being the highest in all honeys), and a high concentration of polyphenols and total flavonoids (the maximum in chestnut honey, 762 mg/kg and 514 mg/kg, respectively). Conclusions The results obtained in this work confirm the ethnopharmacological use of honey in wound care, bring new scientific knowledge on the use of honey in dermatology, and highlight two fields of excellence, particularly incitrus and chestnut honey.

Chitosan biomineralized with ions-doped nano-hydroxyapatite tunes osteoblasts metabolism and DNA damage

Hydroxyapatite (HA) is a bioceramic material widely used as a bone biomimetic substitute and can be synthesized by biomineralization, according to which HA nanoparticles are formed on a polymer template. Nevertheless, little is known about the effect of ion doping and biomineralization on cell metabolism, oxidative stress, and DNA damage. In the present contribution, we report on synthesizing and characterizing biomineralized chitosan as a polymer template with HA nanoparticles doped with magnesium (MgHA) and iron ions (FeHA). The physical-chemical and morphological characterization confirmed the successful synthesis of low crystalline ions-doped HA nanoparticles on the chitosan template, whereas the biochemical activity of the resulting nanoparticles towards human osteoblasts-like cells (MG63 and HOBIT) was investigated considering their effect on cell metabolism, proliferation, colony formation, redox status, and DNA damage extent. Data obtained suggest that particles enhance cell metabolism but partially limit cell proliferation. The redox status of cells was measured suggesting a slight increase in Reactive Oxygen Species production with chitosan biomineralized with iron-doped HA, whereas no effect with magnesium-doped HA and no effect of all formulations on the oxidation level of Peroxiredoxin. On the other hand, DNA damage was investigated by COMET assay, and expression and foci γH2AX. These latter tests indicated that HA-based nanoparticles promote DNA damage which is enhanced by chitosan thus suggesting that chitosan favors the nanoparticles’ internalization by cells and modulates their biological activity. The potential DNA damage should be considered – and potentially exploited for instance in anticancer treatment – when HA-based particles are used to devise biomaterials.

Screening of agroindustry residues for their usage as oxygen evolution reaction catalysts

The Oxygen Evolution Reaction (OER) is the limiting step of the water splitting process for the attainment of valuable hydrogen. A green and economic catalyst is hereby synthesized to reduce the OER overpotential. For the first time, a set of representative agroindustry residues were used and subjected to pyrolytic and hydrothermal treatments, fitting them into circular economy. Hydrothermally treated potato peels (PP-HC), particularly, reached 10, 50 and 100 mA/cm2 at overpotentials of 353, 408 and 431 mV, respectively. The novel material showed good electron-transfer and small Tafel slope (52.2±0.2 mV/dec) that is explained by the presence of electronic rich bonds as confirmed by physical-chemical and electrochemical characterization. PP-HC showed an astonishingly high stability for 90 h or 8000 cyclic voltammetries, with the hydrochar suffering only slight modifications, as measured by FTIR and XPS. This innovative study opens a path to efficient and environmentally friendly green hydrogen.

Advanced methods for characterizing battery interfaces: Towards a comprehensive understanding of interfacial evolution in modern batteries

Batteries are complex systems operating far from equilibrium, relying on intricate reactions at interfaces for performance. Understanding and optimizing these interfaces is crucial, but challenges arise due to the diverse factors influencing their development, making comprehensive characterization essential despite experimental difficulties. Recent advancements in characterization tools offer new opportunities to explore interfacial evolution, particularly in the solid electrolyte interphase (SEI).In this perspective article, leading experts in physical-chemical characterization techniques for electrochemical systems discuss the current state-of-the-art and emerging approaches to study interfaces and their evolution in batteries. The focus here is on the capabilities, technical challenges, limitations, and requirements that these techniques must meet to advance our understanding of battery interfacial evolution. The emphasis is placed on techniques that enable probing interfaces under realistic conditions, close to commercial battery systems, and on the integration of multiple approaches within a single measurement (multimodal) to minimise variable effects.This article focuses on the most promising techniques for characterizing all phases relevant to interfacial processes, as well as their integration with correlative analyses and computational modelling. We discuss solid phase characterization with X-ray spectroscopies and microscopies (XPS, XAS, STXM, X-PEEM & XCT), Raman spectroscopies (SERS, TERS & SHINERS), solid-state NMR and electron microscopies and spectroscopies (STEM, EDXS, EELS & 4D-STEM). The liquid phase characterization is discussed in terms of solution NMR spectroscopy, TEM and optical spectroscopies, while the gas phase can be characterized using OEMS, pressure monitoring and GCMS. Computational modelling and simulation (DFT, ReaxFF & MLIP) are also discussed

Multi-scale fatigue damage analysis in filament-wound carbon fiber reinforced epoxy composites for hydrogen storage tanks

This article presents the findings of a multi-scale experimental study on carbon fiber-reinforced epoxy composites (CFRP) used in lightweight hydrogen storage pressure vessels produced via filament winding. The research employs a combination of tension-tension load-controlled fatigue tests and high-resolution physical-chemical characterization and porosity quantification to assess the impact of porosity on mechanical performance. The findings demonstrate that porosity has a detrimental impact on mechanical properties, acting as nucleation sites for damage mechanisms such as crack initiation, fiber-matrix separation and fiber breakage. At the mesoscopic level, microdefects coalesce into transverse cracks and delamination, resulting in complex failure modes under cyclic loading. The results of the tensile tests demonstrated that the orientation of the fibers has a significant impact on the mechanical behavior of the material. The ±15° configuration demonstrated superior tensile strength and modulus, while the ±30° and multilayer configurations exhibited higher ductility. The results of the fatigue testing confirmed that fiber orientation has a significant impact on fatigue life, with the ±15° configuration proving to be the most resistant. Microscopic analysis indicated that pores act as damage initiation points, accelerating failure through matrix cracking, fiber-matrix debonding, and delamination. This study highlights the need for improved porosity control during manufacturing to enhance the durability of hydrogen storage systems. Additionally, it provides valuable insights for optimizing fiber orientation to improve fatigue performance in practical applications.

Effects on the antioxidant, physicochemical, microbiological, and sensory properties of bread when supplemented with Umbu flour

Umbu fruit is rich in vitamin C and presents excellent antioxidant activity, yet its industrial processing uses only the pulp, while the residues are discarded. The residues present important nutritional properties, able to fight free radicals in the human body, and in the form of flour, might contribute reduce food insecurity and environmental waste. In view of this, our objective was to develop bread using flour from the husks and seeds of Umbu fruit as a partial replacement for wheat flour, and to assess its physical, physical-chemical, bioactive, microbiological, and sensory properties. For this, flour was prepared from Umbu wastes and used in the production of breads in concentrations of 0, 10, 20, and 30%. Respectively, the control at 0% = PC, 10% = P10, 20% = P20, and 30% = P30. Physical-chemical characterization, determination of total phenolic compounds and vitamin C, instrumental colorimetry, microbiological and sensory analyses were performed. The P20 and P30 breads presented lower humidity and pH, with higher ash, protein, lipids, acidity, total phenolic compounds, and vitamin C than the control. By instrumental color, the P20 and P30 breads were both darker and greener than the controls (PC). For microbiological analysis, all formulations were within norms established for human consumption. By sensory analysis, the breads supplemented with the Umbu residues flour were well received, yet with lower test values than the controls for all attributes and for intentions purchase. Yet in view of the above, flour made from Umbu residues remains a promising ingredient for incorporation into both breads and other bakery industry products.

Annatto (Bixa orellana)-Based Nanostructures for Biomedical Applications-A Systematic Review.

Plants are a source of valuable organic chemical compounds with complex structures rich in therapeutic activities. The encapsulation of compounds in nanostructured systems is an alternative to avoid limitations, such as instability and low solubility, and to promote therapeutic use. The objective of the present review was to summarize the data in the literature on the physicochemical characteristics, biomedical efficacy, and toxicity of nanostructures containing extracts and oils obtained from annatto (Bixa orellana). For this, searches were conducted in the CINAHL, LILACS, Embase, FSTA, MEDLINE, ProQuest, PubMed, ScienceDirect, Scopus, and Web of Science databases. Studies that carried out the development, physical-chemical characterization, and evaluation of therapeutic efficacy and/or in vitro, in vivo, or clinical toxicity of nanostructures containing extracts and oils derived from annatto were included in the review. Of the 708 articles found, nine met the inclusion criteria. The included studies developed different nanostructures (nanofibers, nanocochleates, chitosan, lipid, polymeric, and metallic nanoparticles). These nanostructures showed leishmanicidal, photoprotective, antioxidant, antimicrobial, and immunomodulatory efficacy, and tissue regeneration potential with no or low toxic effects in the tested models. Thus, the present work supports the nanostructuring of annatto extracts and oils as a relevant approach to the development of new technologies for biomedical applications.

Physical-chemical characterisation of an alum-based water treatment sludge in different raw water turbidity scenarios

Characterisation of the water treatment sludge (WTS) generated in drinking water treatment plants (DWTPs) is crucial to define alternatives for its adequate management, including potential reuse options. To define these alternatives, it is necessary to evaluate rainfall seasonality effect on WTS production and its physical and chemical characteristics. This study assessed the production and characterisation of four types of alum-based WTS. The WTS was generated in a pilot-scale system from different raw water turbidities (i.e., low: <5 NTU, medium: 5–10 NTU, high: ≥10 NTU, and very high turbidity: ∼300 NTU) and coagulant doses. To estimate WTS production, mathematical models based on variables such as raw water turbidity, coagulant dosage, and organic matter removed were used. The WTS characterisations included physical (solids and particle size distribution), chemical (metallic oxides, pH, mineral phases), and surface properties (functional groups and zero-charge point pH). The modified Kawamura model presented the best fit (R2 = 1.0, RMSE = 0.1062 and the lower Akaike Information Criterion) for the estimation of WTS production, indicating that at the DWTPs, it is possible to make sludge production projections using only two simple variables: coagulant dose and the raw water turbidity. The four types of WTS consist mainly of amorphous materials (45–65 %), featuring some mineral phases and exhibiting high contents of Al (Al2O3: 30–34 %), Si (SiO2: 21–26 %) and Fe (Fe2O3: 11–13 %). Nevertheless, very high turbidity WTS shows variations in its characteristics, notably a heightened content of clays. As a result of the high concentrations of Al and Fe, the WTS has the potential to be used as coagulants or for the recovery of coagulants, especially low turbidity WTS, which is produced from water with low turbidity and organic matter. The presence of aluminium–silicate clays and the surface functional groups of the silica network suggest that WTS, particularly very high turbidity WTS, also has the potential to be raw materials for generating adsorbents. The potential applications of WTS in coagulation and adsorption can be leveraged in wastewater treatment, promoting the circular economy in the water sector.

Burning effects on the soils of the Mexican Maya Lowlands: Current evidence for understanding past events

The slash-and-burn cultivation system is a millenarian practice still used in many countries today, with significant environmental impacts. However, identifying evidence of this agricultural method in soil records is challenging due to natural and human factors that can obscure or alter fire signals. This challenge is particularly evident in the Yucatán Peninsula, where the ancient Maya practiced slash-and-burn agriculture in a dynamic tropical karst environment, making it difficult to pinpoint the origins and consequences of this practice. In this study, we use a recent agricultural burning in a karstic landscape in Chiapas as a model to understand alterations in soil properties. We then apply these insights to identify similar features at a Maya site on the Yucatán Peninsula, specifically at Coyote Quarry. For both cases, we conducted micromorphological analysis, soil physical-chemical characterization, thermogravimetry and differential scanning calorimetry analysis, and radiocarbon dating of mollusk shells, soil organic carbon, and charcoal fragments (the latter exclusively at Coyote Quarry). Our findings reveal significant effects on the soils from the Chiapas site post-burning, including changes in grain size distribution, pH, and total organic and inorganic carbon. These results were compared to those obtained from the Coyote Quarry soils and pedosediments. Key findings include micromorphological features, the presence of charcoal and other burned materials, and pyrogenic carbon identified through thermal analyses. The preservation of these burned features was facilitated by the typical karstic vertical soil erosion and redeposition as pedosediments in karstic depressions. The intrinsic association of the fire signals found in these karstic sinkholes and their radiocarbon dates enables us to link this evidence to the initiation of slash-and-burn agriculture by the Maya in the Yucatán Peninsula during the transition between the Archaic and Early Pre-Classic periods.

Electrochemical and surface characterisation of poly(3,4-ethylenedioxythiophene) dodecylbenzenesulfonate layers

Poly(3,4-ethylenedioxythiophene) (PEDOT) films were electrochemically synthesised with sodium dodecylbenzenesulfonate (DBS) and chloride acting as dopant anions within the polymer matrix. Upon redox switching of the PEDOT/DBS film between conducting and non-conducting states, the DBS anion remained within the polymer and cation insertion and expulsion occurred, as confirmed by Electrochemical Quartz Crystal Microbalance (EQCM) measurements. Electrolytes composed of alkali metal cations of varying masses (Li+, Na+, K+) were employed to investigate the cation insertion/expulsion processes, thereby resulting in varying mass changes being observed upon film redox switching. The charging and discharging of bulky anion doped polymer films presented higher capacitance upon charging and lower capacitance when discharging, which is expected during doping and de-doping as confirmed by AC impedance. In this work, the main results obtained by chemical-physical characterisation are presented and critically discussed, with regard to the possible use of a viable conducting polymer as a drug delivery vehicle.

Exploiting Deep Eutectic Solvents in LiFePO4 Battery Recycling: From Cathode Leaching to Resynthesis

Nowadays, the increasing demand for electronic devices and electric vehicles influences the request for Lithium-Ion Batteries (LIBs), which are worldwide the most exploited electrochemical energy storage systems for portable devices and are expected to completely dominate also the sector of transportation soon. In particular, the use of LIBs with ordered-olivine structure LiFePO4 (LFP) cathodes stands out ever since their invention in 1997, being a valid solution in terms of durability, reliability, and safety, essential characteristics in the electric mobility application combined with the benefit of low content of critical raw materials, CRMs. Considering that the average life of LFP cathodes is about 5-8 years, the management of these materials as waste becomes essential: the growing number and volumes of LIBs that are currently produced is inevitably intended to correspond to the number of LIBs that will reach the end of their life, becoming waste that are accumulating, posing a staggering danger. [1,2] An also important consideration concerns the conditions required to synthesize LFP for electrochemical purposes, as it is necessary to coat the surface with conductive species, controlling the morphology and reducing the particle size, thus complicating the synthesis and making it economically more impactful. [3]In such a context, recycling combines the necessity to produce new LIBs with the need to cope with the increase in batteries’ waste accumulation: this can limit the disposal of waste batteries into landfills, thus decreasing the inevitable hazardous environmental consequences, while reducing the demand for new mining, re-assigning value to raw materials, in an attempt to minimize the costs that would be required to synthesize pristine LFP-based cathodes. Today, recycling is already implemented at the industrial level, exploiting the pyrometallurgy approach, which involves thermal treatments at very high temperatures (>1000°C) allowing for the recovery of only a fraction of valuable metals; nevertheless, this approach has a strong environmental impact due to the high energy demand and high carbon footprint. The hydrometallurgical approach is also employed, exploiting the leaching process with strong inorganic acids; however, this brings problematic issues, because producing such acids is itself a polluting process, and acidic wastewater management is a demanding problem. Moreover, today these processes involve the recycling of the most diffused cathode, LiCoO2, Li(Ni/Mn/Co)O2, LiMn2O4, and the sustainability of recycling relies on the possibility to recover valuable CRMs such as Co and Ni.In the proposed work we are currently investigating the degradation properties of Deep Eutectic Solvents (DESs), cheap and greener mixtures of compounds forming a eutectic system, liquid at room temperature. [4] In particular, the focus is on the leaching of LFP with a DES obtained by mixing different molar ratios of hydrogen bond acceptor and various hydrogen bond donors, in order to assess the best combination to leach the elements out of LFP structure. The key point of such approach is the design of a degradation system that can enable the conditions for the direct re-synthesis of new LFP material. Indeed, here the sustainability of the process cannot be driven by the recovery of CRMs, thus must rely on the close-loop recycling scheme. For this reason, we specifically designed DES compositions that allow for this process.The proposed DESs, which have been easily prepared at mild heating conditions, have been investigated through different techniques; the results obtained on the chemical-physical characterization (via FTIR spectroscopy, Solid-State NMR, viscosity, thermal analysis) will be presented. Among the different DESs, those with the best combination of properties (e.g. low viscosity, high thermal stability) have been explored for the leaching of LFP cathode. The leaching process has been optimized with respect to the temperature, duration, and cathode-to-DES ratio for different DESs, and the leaching yields have been evaluated through ICP-OES analysis. The obtained leached solution has been considered as the starting point for a sol-gel-like synthesis of new LFP material, finally characterized through XRD, TGA, ICP-OES, and SEM-EDX analysis. Tuning the parameters of the synthesis (temperature and duration of the heat treatment, ratio between LFP mass and conductive species to realize the coating) enables to control the morphology and the dimension of the synthesized particles, to find the best condition for the electrochemical application. The electrochemical performances of the resynthesized materials will also be presented.[1] Sun et al., J. Alloys Compd., 818 (2020)[2] Lv et al. ACS Sustain. Chem. Eng., 6 (2018)[3] Yuan et al., Energy Environ. Sci, 4 (2010)[4] Zhu et al., Resour. Conserv. Recycl., 188 (2023)

(Invited) Solvometallurgy as a Sustainable Approach for Lithium-Ion Batteries Recycling

Lithium-Ion Batteries, LIBs, are the core devices that made possible the diffusion of portable consumer electronics and, more recently, the booming of the electric vehicle market. [1] Their ubiquitous use and diffusion led to the well-known and urgent problem of spent LIBs management. Indeed, spent LIBs represent a complex and hazardous kind of waste for which specific regulation, disposal, and recycling routes are still missing. At the same time the continuous and growing production of LIBs involves the mandatory use of specific elements such as Li, Co, Ni, Cu, Al that are considered strategic or critical raw materials due to their limited availability, high costs, monopoly, and geological distribution. [2] The development of efficient and sustainable procedures for recycling of spent LIBs is the answer to these two main challenges as in enable to properly manage the LIBs waste and allow for the recovery of critical raw materials. While at industrial scale the high temperature pyrometallurgy and hydrometallurgy are the methods in use today, in the very last years, many approaches have been explored at research level, among them low temperature pyrometallurgy, soft hydrometallurgy, solvometallurgy, bioleaching. [3] Among them, the solvometallurgical approach exploiting Deep Eutectic Solvents (DESs) as leaching agents is particularly appealing thank to some specific features such as the low volatility, low flammability, low costs, ease of preparation combined with high leaching efficiencies.DESs are mixture of based on the presence of a hydrogen bond donors and acceptors forming a eutectic mixture at ambient temperature; although their first conceptualization is recent, several compositions have been already appeared in literature for this specific application. [4] At the same time, a rationalization of the role of the mixture components and a specific design of the composition, tailored for the application in LIBs recycling is still missing. We here present the results of our work on the development of new DESs compositions enabling the close-loop recycling of different spent cathodes. The DES compositions have been designed considering the overall recycling process, the effect of the DES compositions in terms of hydrogen bond donors and acceptors has been evaluated and rationalized through a preliminary chemical-physical characterization through thermal, NMR, FTIR, viscosity analysis. The leaching of the most common cathode has been optimized against the dominant parameters (temperature, treatment duration, cathode-to-DES ratio) opening the ways for two possibilities: the recovery of critical raw materials and the direct resynthesis of new cathodes. All the steps and products have been fully characterized with a multi-technique approach including structural and chemical investigation through the electrochemical testing of the re-synthetized materials. Finally, these two options have been assessed through LCA analysis, being able to provide an overview of the global sustainability of the proposed processes.[1] Ji et al., Chem Soc. Rev. (2023) doi 10.1039/d3cs00254c[2] Global Supply Chains of EV Batteries report, International Energy Agency[3] Yasa et al. J. En. Stor. 73 (2023) 109073[4] Padwal et al. Adv. En. Sus. Res. 3 (2022) 2100133

Hyaluronic Acid-Based Nanoparticles Loaded with Rutin as Vasculo-Protective Tools against Anthracycline-Induced Endothelial Damages.

Anthracycline-based therapies exert endothelial damages through peroxidation and the production of proinflammatory cytokines, resulting in a high risk of cardiovascular complications in cancer patients. Hyaluronic acid-based hybrid nanoparticles (LicpHA) are effective pharmacological tools that can target endothelial cells and deliver drugs or nutraceuticals. This study aimed to prepared and characterized a novel LicpHA loaded with Rutin (LicpHA Rutin), a flavonoid with high antioxidant and anti-inflammatory properties, to protect endothelial cells against epirubicin-mediated endothelial damages. LicpHA Rutin was prepared using phosphatidylcholine, cholesterol, poloxamers, and hyaluronic acid by a modified nanoprecipitation technique. The chemical-physical characterization of the nanoparticles was carried out (size, zeta potential, morphology, stability, thermal analysis, and encapsulation efficiency). Cytotoxicity studies were performed in human endothelial cells exposed to epirubicin alone or in combination with Free-Rutin or LicpHA Rutin. Anti-inflammatory studies were performed through the intracellular quantification of NLRP-3, MyD-88, IL-1β, IL-6, IL17-α, TNF-α, IL-10, and IL-4 using selective ELISA methods. Morphological studies via TEM and image analysis highlighted a heterogeneous population of LicpHA particles with non-spherical shapes (circularity equal to 0.78 ± 0.14), and the particle size was slightly affected by Rutin entrapment (the mean diameter varied from 179 ± 4 nm to 209 ± 4 nm). Thermal analysis and zeta potential analyses confirmed the influence of Rutin on the chemical-physical properties of LicpHA Rutin, mainly indicated by the decrease in the surface negative charge (from -35 ± 1 mV to -30 ± 0.5 mV). Cellular studies demonstrated that LicpHA Rutin significantly reduced cell death and inflammation when compared to epirubicin alone. The levels of intracellular NLRP3, Myd-88, and proinflammatory cytokines were significantly lower in epirubicin + LicpHA Rutin-exposed cells when compared to epirubicin groups (p < 0.001). Hyaluronic acid-based nanoparticles loaded with Rutin exerts significant vasculo-protective properties during exposure to anthracyclines. The overall picture of this study pushes towards preclinical and clinical studies in models of anthracycline-induced vascular damages.

Physical and Elementary Chemistry Characterization of Particles PM2.5 through Scanning Electron Microscopy equipped with X-ray Scattering

Physical and Elementary Chemistry Characterization of Particles PM2.5 through Scanning Electron Microscopy equipped with X-ray Scattering