Green synthesis of metal nanoparticles from agro-food waste extracts offers environmental and economic advantages over conventional chemical methods, using natural phytochemicals as reducing and stabilizing agents. However, inherent variability in botanical feedstocks, arising from seasonal fluctuation, geographic origin, and extraction protocols, poses significant challenges to reproducibility and standardization. Current literature documents fewer than 300 systematically characterized synthesis studies using non-harmonized protocols, and botanical extract composition inherently varies 15–30 % seasonally and geographically, limiting the generalization of process parameters across waste sources. This review critically examines the materials science foundations of phytochemical-mediated nanoparticle formation, including the mechanistic roles of phenolic compounds, flavonoids, and terpenoids in metal-ion reduction, nucleation kinetics, and surface capping. We analyze how feedstock composition and extraction conditions influence particle size distribution, morphology, crystallinity, and surface chemistry properties, which ultimately determine biological identity and functional performance. We then evaluate the potential of Quality-by-Design (QbD) frameworks and artificial intelligence (AI) approaches to address these reproducibility challenges. However, we emphasize that significant prerequisites remain before AI deployment is viable: AI model performance reported in the literature ranges from 65 to 85 % accuracy across heterogeneous botanical waste sources, substantially lower than idealized estimates, and current models suffer from dataset-size limitations and the risk of overfitting. We propose a phased implementation roadmap: Phase 1 (18–24 months) requires establishing harmonized botanical characterization protocols and controlled extraction procedures; Phase 2 requires 300–500 documented synthesis experiments across multiple waste sources; Phase 3 can then build predictive AI models on this standardized foundation. Throughout, we distinguish between demonstrated evidence, emerging proof-of-concept results, and areas requiring substantial further validation before clinical or industrial translation becomes feasible.
Selective management of chemico-physical properties of l-polylactic acid (L-PLA) is pivotal to broaden the application range of this polymer. As a thermally and electrically insulating polymer, its application in energy field and electronic instruments requires innovative strategies capable of selectively tune thermal and electrical properties, safeguarding mechanical properties and thermal stability. Here, we propose a molecular approach to selectively enhance thermal conductivity of l-PLA, preserving electrical insulating capacity, by incorporating a benzoindolenine-based croconaine (CR-BI) as functional photothermal additive. l-PLA@CR-BI composite solid layers were prepared via solution casting, by combining different amounts of CR-BI and comprehensively characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), UV–vis and FTIR spectroscopy, electrical, photothermal and thermophysical measurements. l-PLA@CR-BI composites displayed homogeneous coloration and a uniform CR-BI molecular dispersion inner l-PLA, with a molecular-level thermal network resulting in a strong impact on its thermal properties. Remarkably, the inclusion of only 1wt% CR-BI led to an over threefold increase in thermal diffusivity and conductivity compared to neat l-PLA. TGA evidenced a CR-BI-induced enhancement of polymer chain mobility and the formation of new crystalline domains, improving heat transfer and suggesting thermal energy storage applications. Importantly, the electrical insulating nature of l-PLA remained unchanged across all compositions. To the best of our knowledge, this work provides the first demonstration of croconaines as molecular modulators of l-PLA’s chemico-physical properties, enabling selective and efficient enhancement of thermal transport while maintaining electrical insulation- an advance with significant implications for sustainable polymer-based electronic and energy materials.
This research employs advanced analytical techniques to explore the specific roles of Pomegranate Juice (PJ) phytochemicals in both the reduction and stabilization of gold nanoparticles (AuNPs) obtained by means of juice from wasted fruits. A level 3 for classes annotation, used for MALDI FT ICR-MS data, was useful to provide an immediate visualization of the main involved metabolites in AuNPs synthesis, through van Krevelen diagrams. More than 25 elemental formulae containing at least one Au atom were assigned to AuNPs sample, confirming the formation of organogold complexes. LC-MS/MS analysis allowed a level 2 annotation of polyphenols and carbohydrates involved in metal reduction and AuNPs surface coating. This work highlights the potential of PJ in green nanoparticles synthesis, providing insights into the bioactive compounds responsible for the tunable characteristics of AuNPs.
Coffee silver skin is reported as an adsorbent for treating water from Contaminants of Emerging Concern, focusing on the removal of Norfloxacin, an antibiotic. According to the sustainability principles, coffee silver skin before its use was washed with water, lowering the associated costs and the whole environmental impact. The proposed adsorbent was characterized by adopting synergistically ATR-FTIR, SEM, and TG techniques, inferring its main features before and after the pollutant removal. Specifically, the presence of the latter in water was monitored by using UV-Vis spectroscopy. Several experimental conditions were explored during the adsorption, and the roles of ionic strength, pH, adsorbent/pollutant amounts, and temperature were investigated. The thermodynamics, adsorption isotherms, and kinetics were also studied, revealing that the process was spontaneous and occurred on heterogeneous skin surfaces forming a pollutant multilayer, joining a maximum adsorption capacity of 50 mgxg(-1). Interestingly, the pH values and ionic strength strongly affected the process, denoting the main presence of reversible electrostatic interaction between the pollutant and coffee silver skin. Indeed, the recycling of the proposed adsorbent was demonstrated by adopting safe and green conditions of work in the presence of diluted salt solutions or water at 50 degrees C, also recovering the pollutant. So, this paper has the aim to present, for the first time, the kinetics and thermodynamics of an adsorption process referred to the removal of an emerging pollutant from water by using coffee silver skin, avoiding hard working conditions to pre-treat the material before its use, thus proposing an alternative way to reuse this by-product as recyclable adsorbent.
A composite material made of olive pomace biochar and chitosan sponges is presented during this work as a substrate for adsorbing Direct Blue-78, an anionic azo-textile dye from water. Moreover, the removal of other pollutants in mixture is demonstrated. The aim is to show the role of different physical and chemical parameters affecting the adsorption process attributed to the synergistic action of chitosan and biochar, such as pH, ionic strength, and temperature. Both pseudo-first and second order kinetic models were also successfully applied to achieve additional information; the Weber-Morris model was implemented to explore the role of intraparticle diffusion of dyes throughout the adsorbent that did not arise as the lone kinetic relevant step. Moreover, Langmuir, Freundlich, Temkin, and Dubinin-Raduschkevich isotherms were applied to better characterize the process that occurred on heterogeneous surfaces. Finally, the Van’t Hoff equation was adopted to calculate the thermodynamic parameters, showing the endothermic character and spontaneity of the adsorption process.
Water-stable crosslinked Metal Organic Frameworks alpha-Cyclodextrin-based are presented in this work for environmental applications as highly performant adsorbents. Specifically, hexamethylene diisocyanate was used as crosslinker, enhancing the high-water stability of the supramolecular assembly, otherwise not observed. The chemical and physical features of the adsorbent were thus investigated through the use of ATR-FTIR, DSC, TG, SEM, Z-potential and XRPD analyses. If alpha-Cyclodextrin and the corresponding Metal Organic Frameworks (assembled via K+ ion coordination), were highly soluble, the crosslinked structures occurred stable, exhibiting a Z-potential of -15 mV, a reduced crystalline order and thermal stability. The high performance of the adsorbent was demonstrated by testing Direct Blue-78, and its mixtures with Direct Red 83:1 and Direct Yellow 86. When Direct Blue-78 was in use, the role of different parameters affecting the adsorption process, such as pH, ionic strength, and temperature was assessed, demonstrating the key role of electrostatic attractions between the pollutant and adsorbent. The adsorption mechanism was multiple, involving also the salting out of the dye, much more evident in presence of salt-based solutions. The dye removal was endothermic and spontaneous, occurring with an increase of entropy. Langmuir, Freundlich, Temkin, and Dubinin-Raduschkevich isotherms described the process, demonstrating that a pollutants' multilayer should be considered, and the energy distribution of the adsorption sites was not uniform, changing during the process. Accordingly, pseudo-first and second order kinetic models described the dye removal, confirming the complex mechanism of adsorption, favoring the observed high maximum adsorption capacity that occurred 75 +/- 5 mg/g.
Water pollution is a significant worldwide problem, and research studies in this field are still in progress to find strategies for removing pollutants from water. Among the others, adsorption process seems to exhibit several advantages, especially when biomasses are in use. This work proposes biochar from olive pomace pyrolysis for adsorbing contaminants from water, in synergistic combination with TiO2, for constituting water-stable and recyclable composite chitosan-based sponges. The photocatalyst and the biochar were embedded into the polymeric chitosan foam network. So, the employed materials were characterized from a physical and chemical point of view, revealing the nature of porous adsorbent substrates having irregular surfaces useful for sequestrating pollutants. UV-Vis spectroscopy was used to monitor the amount of pollutants in water, and the maximum adsorption capacities were calculated. Carbamazepine, was selected as a model contaminant to study the process features under different working conditions. A comparison with the removal of a textile dye was also performed to unveil the mechanism of adsorption. After the pollutant adsorption, its complete desorption was obtained, proposing a way to reuse the adsorbent material, lowering the environmental impact. An alternative to regenerate the adsorbent was also studied by exploiting the photocatalytic role of TiO2.
This work proposes the use of Coffee Silver Skin, a by-product of coffee production, as an adsorbent substrate for the removal of the antibiotic Norfloxacin from water and assesses the possibility of regenerating it through advanced oxidation processes. In detail, the study was developed by showing the best conditions for the pollutant removal, in which the adsorption process occurred with the main involvement of electrostatic interactions. A preliminary desorption approach in the presence of salt-based solutions, i.e., NaCl and 0.1 M MgCl2, was followed with the aim of desorbing the non-photodegraded Norfloxacin from the regenerated adsorbent. Therefore, indirectly, the quantitative evaluation of photodestroyed Norfloxacin was assessed according to selected working conditions: UV light, UV light/H2O2, UV light/TiO2, and UV light/TiO2/H2O2. Moreover, a comparison with the literature devoted to Norfloxacin photodegradation directly in water was accomplished. The use of UV light/TiO2 occurred as the best approach for the purpose of obtaining the complete degradation of Norfloxacin in 6 h. On the other hand, the use of H2O2 did not improve the process. Thus, to reduce the irradiation time, Norfloxacin degradation was evaluated simultaneously during its release from the adsorbent, in a 0.1 M MgCl2 solution, retrieving a similar and well-known behavior observed when the pollutant was degraded in water. In 3 h, the desorbed Norfloxacin was destroyed, enabling the recycling of Coffee Silver Skin for up to 3 cycles.
This study presents hybrid sponges composed of zinc oxide and chitosan, engineered via atomic layer deposition (ALD), as highly efficient adsorbents for the removal of textile dyes from aqueous environments, including complex dye mixtures. ALD is a vapor-phase strategy to conformally deposit photocatalytically active zinc oxide within the porous chitosan matrix, enabling enhanced water stability and improved structural integrity. The main aim is to elucidate the influence of key physicochemical parameters on the adsorption process using Direct Blue-78 as a model dye. The effects of the adsorbent amount, initial dye concentration, solution pH, ionic strength, and temperature were systematically investigated. The process occurred slightly influenced by changing pH values and ionic strength, revealing the contribution of both electrostatic forces and hydrophobic interactions. Interestingly, the increased amount of adsorbent and the reduced concentration of pollutants favored dye removal from water. A very high maximum adsorption capacity of 2000 ± 400 mg/g was observed, denoting the great performance of the proposed material that retained the same behavior if in the presence of azo-dye mixtures composed also by Direct Red 83:1 and Direct Yellow 86. Kinetic modeling was carried out, and several adsorption isotherm models, including Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, were used to fit to the experimental data. The results suggested that the proposed adsorbent had a heterogeneous adsorption surface and a single mathematical model cannot be able to fit experimental data. Furthermore, thermodynamic parameters were derived, highlighting the spontaneous and endothermic nature of the adsorption process.
During this work, the Bean Pods are reported as adsorbent to remove Contaminants of Emerging Concern from water. Specifically, the Bean Pods were washed before their use with 1 M NaOH and HCl solutions, for activating their surface and rendering the material porous with a larger surface area, as evidenced by BET and SEM analyses. Indeed, the pods were fully characterized by adopting different techniques, and UV–Vis spectroscopy was adopted to monitor, at several contact times, contaminated water. To pursue this aim, Ciprofloxacin, a largely used antibiotic, was selected as a model contaminant, exhibiting an high absorption in the UV–Vis spectrum. Moreover, the roles of the physical and chemical parameters such as ionic strength, pH, adsorbent/pollutant amounts, and temperature, during the adsorption, were assessed, obtaining interesting information on the whole process, that occurred efficiently with a maximum adsorption capacity of 45 mg/g. The increase of the adsorbent amount (from 3 to 25 mg) and decrease of pollutant concentration (from 30 to 10 mg/L) favored the Ciprofloxacin removal due to the large presence of active sites. The change of pH values (i.e. 3, 6 and 12) and ionic strength values (in the range 0.001–0.5 M by adopting NaCl) largely inhibited the adsorption, evidencing the presence of electrostatic interactions. The adsorption isotherms, thermodynamics and kinetics of the process were also studied. Specifically, the Freundlich and Temkin models well described the process, suggesting the heterogeneous character of the adsorption, with the formation of a pollutant multilayer onto the adsorbent surface; the process occurred spontaneously (ΔG < 0) with an increase of entropy (ΔS > 0), and it was favored by the increase of temperature (ΔH > 0). The pseudo-first-order kinetic equation described the process with the applicability of the Weber-Morris model, denoting the key role of active sites to host the pollutant, and intraparticle diffusion, respectively. The recycling of the proposed adsorbent was successfully demonstrated by means of a salt solution. New horizons in the use of Bean Pods, for water remediation, was thus successfully demonstrated during this work, proposing an environmentally friendly approach for decontaminating water.
According to circular bioeconomy principles, the use of kiwi peels to remove Direct Blue 78 (DB) from water is investigated during this work, proposing food waste as a recyclable adsorbent substrate.
Phthalates are the synthetic chemical plasticizers with the most varied uses and are a source of concern due to their toxicity and ubiquity, so much so that even plasticizer-free polymers can contain them as non-intentionally added substances (NIAS). Food packaging is among the materials with the greatest impact. In this study, a simple protocol is proposed for the location and identification of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, and dibutyl phthalate which is applicable to compliance studies of food packaging materials and for the associated risk assessment. Solid phase microextraction gas chromatography/mass spectrometry was used to evaluate the migration of four NIAS from food packaging to release media simulating food substrates. Three plasticizer-free polymers were used: two that were lab-made and based on sodium alginate and a commercial polyethylene film. Linearity ranged from the LOQ to 10 µg/mL; within-day and between-day precision values were between 12.3–25.7% and 21.9–35.8%, respectively; the LOD and LOQ were in the range 0.029–0.073 µg/mL and 0.122–0.970 µg/mL. Migration tests were conducted for different periods of time at room temperature and at 8 °C. Exposure to microwaves (MW) was also evaluated. All packaging materials tested had global migration limits lower than 10 mg/dm2 of material surface.
Recently, the presence of Contaminants of Emerging Concern (CECs) and other pollutants, such as textile dyes, in the environment, particularly in water bodies, is representing a problem of global interest [1].To face this issue, this work proposes the use of a material able to absorb pollutants from water with high efficiency.Specifically, by following the Circular Economy principles, the preparation of an adsorbent material using wastes coming from ichthyic and foodagricultural industries was attained, for finally obtaining chitosan sponges in which biochar from olive pomace and TiO2 were added.The sponges were used for removing of two pollutants: Carbamazepine (CBZ), a psychoactive drug belonging to the class of iminostilbenes used in the treatment of bipolar disorder and schizophrenia for its anticonvulsant activity, and Direct Blue-78 (DB-78), a non-biodegradable [2] azo dye used in textile processes.To investigate the adsorption process, the effects of various chemical-physical parameters were studied.Additionally, the kinetic models of PFO (Pseudo-First Order), PSO (Pseudo-Second Order) and Webber-Morris were applied, along with Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models.The thermodynamic parameters were also obtained to evaluate the endothermic character and to verify the spontaneity of the adsorption process.Furthermore, under suitable conditions of work, the desorption and the solid-state photodegradation of contaminants were proposed to recycle the adsorbent for several cycles attending its lifetime.For the purpose, TiO2 was added as a photocatalyst [3] for promoting Advanced Oxidation Processes (AOPs) to photodegrade the pollutants after their adsorption.
AbstractLow‐cost, millimeter‐thick chitosan‐based sponges are engineered with zinc oxide (ZnO) using atomic layer deposition (ALD) to create a multifunctional nanocomposite for the potential application in water remediation and self‐regeneration via solid‐state photocatalysis. Initially, non‐porous chitosan films served as control samples to study the ZnO growth mechanism and its impact on the biopolymer's optical and chemical properties. Subsequently, porous chitosan sponges are engineered to further explore the photocatalyst growth and infiltration into the porous matrix. The characterization of the chitosan/ZnO hybrid material is performed using spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, UV–vis, photoluminescence, and infrared spectroscopy, analyzing the effect of varying the number of ALD cycles, resulting in different ZnO thicknesses in the range of 5–30 nm on the chitosan matrix. A reaction‐limited growth model is found and strong interactions between ZnO and chitosan amino groups significantly enhance the stability in water and impart photocatalytic features. Adsorption tests using Direct Blue 78 dye demonstrated high removal efficiency, with capacities up to 2000 mg g−1, surpassing pristine chitosan sponges, which degrade in water. Electrostatic interactions between dye sulfonate groups and protonated chitosan amino moieties are identified as key to this performance. Preliminary photocatalytic experiments using Naproxen confirms the ZnO‐coated sponges' ability to degrade pollutants, showcasing ALD as a key technology for producing bio‐based, photoactive materials for sustainable water treatment.
Due to the pollution problem, the use of more sustainable materials with a reduced environmental impact, spanning across biocompatible and biodegradable polymers, is growing worldwide in many different fields, particularly when referring to applications in Life Sciences. Accordingly, with the aim of developing multifunctional materials for potential cosmetic/biomedical purposes, this work reports the physical and chemical characterization of chitosan-based films blended with snail slime, exhibiting antioxidant and sunscreen features. A suitable formulation for preparing free-standing chitosan platforms, mixing low molecular weight chitosan, lactic acid, glycerol, and snail slime into an appropriate ratio, is thus described. The results obtained by morphological analysis and ATR-FTIR spectroscopy, XRD, swelling analysis (also when varying pH, ionic strength, and temperature), and WVTR measurements evidence a uniform distribution of snail slime inside the chitosan network, forming more compacted structures. At first, the UV-Vis analysis is used to investigate the theoretical Sun Protection Factor, finding that these innovative platforms can be used for preventing sunburn. Then, the antioxidant features are investigated using the ABTS assay, displaying a snail slime-mediated and dose-dependent boosted activity.
The development of food packaging materials that reduce the production of plastic, preserving at the same time the quality of food, is a topic of great interest today for the scientific community. Therefore, this article aims to report the effectiveness of an eco-friendly packaging material based on alginic acid and grape pomace extract from Vitis vinifera L. (winemaking by-products) for storing red meat in a domestic refrigerator. Specifically, biogenic amines are considered “sentinels” of the putrefactive processes, and their presence was thus monitored. For this purpose, an experimental analytical protocol based on the use of solid-phase microextraction coupled with gas chromatography–mass spectrometry was developed during this work for the determination of six biogenic amines (butylamine, cadaverine, isobutylamine, isopentylamine, putrescine, and tyramine). Moreover, by combining the analytical results with those of pH and weight loss measurements, differential scanning calorimetry, and microbiological analysis, it was proved that the studied materials could be proposed as an alternative packaging material for storing foods of animal origin, thus lowering the environmental impact according to sustainability principles.
Following a green approach, kiwi peels (a waste) were washed in hot water to obtain a water-based polyphenolic extract (KPWW) used to reduce Au 3+ (coming from a HAuCl 4 water-based solution) for forming gold nanoparticles (AuNPs). Indeed, KPWW, as shown after performing high-performance liquid chromatography-mass spectrometry (HPLC/MS-MS) analysis, is mainly composed by different polyphenols acting as reductant agents, accomplishing a red-ox reaction and decorating the AuNPs-KPWW surface. Spectroscopic and morphologic techniques were used in synergy for investigating the AuNPs-KPWW main features. Polyhedral-shaped plasmonic nanoparticles with a mean size of 30±10 nm and a negative charge of −40 mV were thus obtained. The AuNPs’ stability was assessed under different working conditions, investigating the role of ionic strength, pH, and temperature. The photostability was also assessed by irradiating AuNPs-KPWW with a solar simulator lamp. Both temperature and solar light did not perturb AuNPs-KPWW. Thanks to the presence of polyphenols, the antioxidant and skin-lightening properties were positively demonstrated. Moreover, the protective role of AuNPs in scavenging H 2 O 2 and ·OH was also investigated by inhibiting the oxidation of a biomolecule. The sunscreen ability of AuNPs-KPWW was also estimated, and the theoretical calculation of the sun protection factor (SPF) was determined. Finally, the AuNPs-KPWW biocompatibility was tested on endothelial colony-forming cells and normal dermal fibroblasts as human cell lines, revealing that AuNPs-KPWW did not affect cell viability and did not alter cell morphology, demonstrating their safety and their potential application in nanomedicine.
In this work, the great performance of chitosan-based films blended with TiO2 (CH/TiO2) is presented to adsorb the hazardous pollutant 2,4-dinitrophenol (DNP) from water. The DNP was successfully removed, with a high adsorption %: CH/TiO2 exhibited a maximum adsorption capacity of 900 mg/g. For pursuing the proposed aim, UV–Vis spectroscopy was considered a powerful tool for monitoring the presence of DNP in purposely contaminated water. Swelling measurements were employed to infer more information about the interactions between chitosan and DNP, demonstrating the presence of electrostatic forces, deeply investigated by performing adsorption measurements by changing DNP solutions’ ionic strength and pH values. The thermodynamics, adsorption isotherms, and kinetics were also studied, suggesting the DNP adsorption’s heterogeneous character onto chitosan films. The applicability of pseudo-first- and pseudo-second-order kinetic equations confirmed the finding, further detailed by the Weber–Morris model. Finally, the adsorbent regeneration was exploited, and the possibility of inducing DNP desorption was investigated. For this purpose, suitable experiments were conducted using a saline solution that induced the DNP release, favoring the adsorbent reuse. In particular, 10 adsorption/desorption cycles were performed, evidencing the great ability of this material that does not lose its efficiency. As an alternative approach, the pollutant photodegradation by using Advanced Oxidation Processes, allowed by the presence of TiO2, was preliminary investigated, opening a novel horizon in the use of chitosan-based materials for environmental applications.