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Due to the pollution problem, the use of sustainable materials with a reduced environmental impact, such as biocompatible and biodegradable polymers, is growing worldwide in many fields, especially for Life Sciences applications.

Using a water-insoluble β-cyclodextrin-epichlorohydrin copolymer (β-EPI) as an adsorbent to remove carbamazepine (CBZ), an anti-epileptic drug often found both in hospital and urban wastewater, has been validated. The effect of several physicochemical parameters on CBZ retention onto β-EPI, such as contact time, adsorbent dosage, CBZ initial concentration, pH, salts, and temperature, was assessed. The adsorption process occurs in a very short time, less than 20 min, and depends on CBZ concentration and β-EPI amount used. Changes in pH and salt presence, regardless of the type of cation or anion used, do not significantly affect the system’s efficiency. Desorption experiments were also performed, and methanol has proven to be the best CBZ extraction medium; it was also found that the polymer can be recovered and reused for at least five cycles, which makes it cheap and environmentally friendly. Advanced oxidation processes were also tested for CBZ removal by synthesizing a β-EPI polymer bearing titanium dioxide for adsorption and consecutive photocatalytic degradation of the retained pollutant directly onto the material; the effect of TiO2 amount in the polymer on CBZ oxidation was evaluated. These experiments highlighted the system’s effectiveness, and it was also observed that the H2O2 presence in the solution enhanced the CBZ photodegradation.

Due to the negative effects of emerging contaminants on the environment, that can potentially induce deleterious effects in aquatic and human life, this paper focuses on the removal from the water of Furosemide, through the adsorption process. Indeed, only a few papers are available in the literature about the Furosemide adsorption and, chitosan films are thus proposed for this purpose as safe, sustainable, and recyclable adsorbent materials. In the present work, the effects on the adsorption process of several experimental parameters such as the pH values, ionic strength, amount of adsorbent/pollutant, and temperature values were investigated. The kinetics models, isotherms of adsorption, and the thermodynamic parameters were studied showing that the Furosemide physisorption occurred on the heterogeneous Chitosan surface, endothermically (ΔH° = +31.27 ± 3.40 kJ mol−1) and spontaneously (ΔS° = +150.00 ± 10.00 J mol−1 K−1), following a pseudo-second-order kinetic model. The 90% of the pollutant was adsorbed in 2 h, with a maximum adsorption capacity of 3.5 mg × g−1. Despite these relatively low adsorption capacities, experiments of desorption were performed and 100% of adsorbed Furosemide was recovered by using concentrated NaCl solutions, proposing a low-cost and green approach, with respect to the previous literature relative to the Furosemide adsorption, fundamental for the pollutant recovery and adsorbent reuse.

Treatment of wastewater pollution is a critical issue in the context of growing population and industrialization. Actual treatment methods are expensive and not fully effective and rely on fossil fuel-derived chemicals, thus calling for alternative adsorption methods on natural materials such as hemp. Industrial hemp (Cannabis sativa Linn) is a high-yielding annual industrial crop harvested for its fiber from the stem and its oil from the seeds. Hemp is a multi-purpose plant with great potential because of its many uses, such as building materials, textiles, paper, food and beverage, automotive, cosmetics, and medicine. Wastewater treatment is another innovative application. Indeed, the past decade has shown an explosion in the study of hemp-based materials for the biosorption of metal ions from effluents, demonstrating that industrial hemp is one of the most promising materials for environmental applications. Hemp products can be used as biosorbents in granular or felt forms or to prepare non-conventional activated carbons, both used in biosorption-oriented processes. In this chapter, after a brief description of biosorption, the use of different types of hemp-based materials that can be used as pollutant biosorbents is described.

The anthropogenic environmental pollution generated during the last decades led to significant consequences for the aquatic ecosystems and to potential risks for human health. For this reason, the research has been focused on studying and develop pollutants-removing technologies. Nowadays, despite the presence of performing techniques applied in e.g. the potabilization and waste-water treatments, new strategies aimed to better meet the industrial needs and the environmental requirements are still widely investigated. In this frame, the pollution caused by the presence of anionic species in water, is still not completely solved. For this reason, this work is focused on studying novel cationic maltodextrin-based adsorbents obtained via sustainable approach, for water treatment applications. The adsorption performances towards nitrates-, sulphates- and phosphates-polluted water solutions have been tested and discussed.

The reactivity of the sulfur-containing nucleoside 4-thio-(2 '-deoxy)-thymidine usually abbreviated as 4-thio-thymidine, (S-4-TdR) under Fenton conditions, ie, in the presence of H2O2 and catalytic amounts of Fe(II), was investigated by UV-vis spectroscopy and electrospray ionization single and tandem mass spectrometry (ESI-MS and MS/MS). S-4-TdR hydroxylated on the S atom was found to be a key reaction intermediate, ultimately leading to (2 '-deoxy)-thymidine usually abbreviated as thymidine, (TdR) as the main reaction product. This finding was in accordance with the outcome of the reaction between S-4-TdR and H2O2, previously investigated in our laboratory. On the other hand, the additional presence of center dot OH radicals, induced by the Fe(II)/H2O2 combination, led to the increased generation of another interesting S-4-TdR product, already observed after its reaction with H2O2 alone, ie, the covalent dimer including a S-S bridge between two S-4-TdR molecules. More importantly, multihydroxylated derivatives of S-4-TdR and TdR were detected as peculiar products obtained under Fenton conditions. Among them, a product bearing an OH group both on the methyl group linked to the thymine ring and on the C5 atom of the ring was found to prevail. The results obtained during this study, integrated by those found previously in our laboratory, indicate 4-thiothymidine as a promising molecular probe for the recognition, through a careful characterization of its reaction products, of the prevailing species among reactive oxygen species (ROS) corresponding to singlet-state oxygen, hydrogen peroxide, and hydroxylic radical.

The very high adsorption efficiency of Direct Blue (DB), an anionic toxic azo dye, onto amino grafted mesoporous silica nanoparticles (MCM-41), was studied in this paper, for possible industrial applications. Interesting challenges and advances are proposed in this field, presenting an adsorbent able to efficiently and rapidly remove the anionic dye from water. The important added value of this work regards the system recycle, which allows both the DB and adsorbent material recover, with a global reduction of the environmental impact, in the viewpoint of the green economy. Indeed, this paper is the first example of very fast removal and recycle of great amounts of DB with adsorbent materials characterized by impressive adsorption/desorption capacities, at least of around 300 mg/g for each adsorption cycle, potentially increasable by performing consecutive cycles of DB adsorption/desorption. In detail, the MCM-41 amino functionalization (MCM-41-NH2) was obtained after (MCM-41-POST) and during (MCM-41-PRE) the synthesis of MCM-41, obtaining materials with different behavior towards the DB adsorption. The MCM-41-NH2 surface features and porous structure, before and after the dye adsorption, were carefully characterized. Considering the adsorption process, for investigating the nature of the DB/MCM-41-NH2 interaction, several parameters were studied: the contact time, the DB solutions pH values, adsorbent material and dye amount, with the additional analysis of how the adsorption process was influenced by the presence of electrolytes. The isotherms of adsorption were also considered. Although MCM-41-PRE exhibited a higher affinity towards DB molecules, the MCM-41-POST were able to rapidly desorb it, thus recycling both DB and the adsorbent material. (C) 2018 Elsevier B.V. All rights reserved.

This work aims to characterize the adsorption process of propranolol HCl, an emerging pollutant and a widely used β-blocker, onto kiwi peels, an agricultural waste. The use of UV-vis spectroscopy was considered to obtain information about the pollutant removal working in the in-batch mode. In a relatively short time, the adsorption process could remove the pollutant from water. A kiwi peel maximum adsorption capacity of 2 mg/g was obtained. With the perspective of scaling up the process, preliminary in-flux measurements were also performed. The investigation of the whole in-batch adsorption process was conducted by studying the effect of ionic strength (adopting salt concentrations from 0 to 0.4 M), pH values (from 2 to 12), adsorbent/pollutant amounts (from 25 to 100 mg and from 7.5 to 15 mg/L, respectively), and temperature values (from 289 to 305 K). The thermodynamics, the adsorption isotherms, and the kinetics of the adsorption process were also carefully investigated. The Langmuir model fitted the experimental data well, with an R2 of 0.9912, restituting KL: 1 L/mg and Q0: 1.8 mg/g. The temperature increase enhanced the pollutant removal due to the endothermic adsorption characteristics. Accordingly, a ΔH°298K of +70 KJ/mol was obtained. The pseudo-first-order kinetic model described the process. Due to the results observed during the study of the effects of pH and ionic strength, the prominent presence of electrostatic interactions, working in synergy with hydrophobic forces and H-bonds between the pollutant and kiwi peel surfaces, was successfully demonstrated. In particular, FTIR-ATR measurements confirmed the latter findings. Finally, desorption experiments for recycling 100% of propranolol for each cycle were performed using 0.1 M MgCl2. Ten cycles of adsorption/desorption were obtained and indicated that the percentage of propranolol removal was not affected during each run, increasing the maximum adsorption from 2 to 20 mg/g.

The present study describes an unprecedented approach to valorize potentially hazardous poly-(bisphenol A carbonate) (PC) wastes. In THF, under non-severe conditions (120 °C), the reaction of PC with long-chain diamines H2NRNH2 (2 equivalents) provided a tool to regenerate the monomer bisphenol A (BPA; 83–95%, isolated) and repurpose waste PC into [-NHRNHCO-]n polyureas (PUs; 78–99%, isolated) through a non-isocyanate route. Basic diamines (1,6-diaminohexane, 4,7,10-trioxa-1,13-tridecanediamine, meta-xylylenediamine, para-xylylenediamine) reacted with PC without any auxiliary catalyst; less reactive aromatic diamines (4,4’-diaminodiphenylmethane, 2,4-diaminotoluene) required the assistance of a base catalyst (1,8-diazabicyclo[5.4.0]undec-7-ene, NaOH). The formation of [-NHRNHCO-]n goes through a carbamation step affording BPA and carbamate intermediates H[-OArOC(O)NHRNHC(O)-]nOArOH (Ar=4,4’-C6H4C(Me)2C6H4-) that, in a subsequent step, convert into [-NHRNHCO-]n and more BPA. All the PUs were characterized in the solid state by CP/MAS 13C NMR (δ(C O) = 152–161 ppm) and IR spectroscopy. The positions of ν(N-H) and ν(C O) absorptions are typical of “hydrogen-bonded ordered” bands suggesting the presence of H-bonded groups in network structures characterized by some degree of order or regularity. DSC and TGA analyses showed that the PUs are thermally stable (Td,5%: 212–270 °C) and suitable for being processed since their degradation begins at temperatures about 100 °C higher than their Tg or Tm.

The aim of this paper is to present and characterize Polyamidoamine-based hydrogels (PAA) as scaffolds to host photoactive Chlorophyll a (Chl a) from Spirulina (Arthrospira platensis) sea-weed Extract (SE), for potential applications in Photodynamic Therapy (PDT). The pigment extracted from SE was blended inside PAA without further purification, according to Green Chemistry principles. A comprehensive investigation of this hybrid platform, PAA/SE-based, was thus performed in our laboratory and, by means of Visible absorption and emission spectroscopies, the Chl a features, stability and photoactivity were studied. The obtained results evidenced the presence of two main Chl a forms, monomeric and dimeric, interacting with hydrogel polyamidoamines network. To better understand the nature of this interaction, the spectroscopic investigation of this system was performed both before and after the solidification of the hydrogel, that occurred at least in 24 h. Then, focusing the attention on solid scaffold, the 1Chl a⁎ fluorescence lifetime and FTIR-ATR analyses of PAA/SE were carried out, confirming the findings. The swelling and Point Zero Charge (PZC) measurements of solid PAA and PAA/SE were additionally performed to investigate the hydrogel behavior in water. Chl a molecules blended in PAA were (photo) stable and photoactive, and this latter feature was demonstrated showing that the pigment induced, when swelled in water and under irradiation, the formation of singlet oxygen (1O2), measured by direct and indirect methods.

In this work, for the first time, snail slime from garden snails "Helix Aspersa Müller", has been used to induce the formation of eco-friendly gold nanoparticles (AuNPs-SS) suitable for biomedical applications. An AuNPs-SS comprehensive investigation was performed and AuNPs with an average particle size of 14 ± 6 nm were observed, stabilized by a slime snail-based organic layer. Indeed, as recognized in high-resolution MALDI-MS analyses, and corroborated by FESEM, UV-Vis, ATR-FTIR, and XPS results, it was possible to assess the main presence of peptides and amino acids as the main components of the slime, that, combined with the AuNPs confers on them interesting properties. More specifically, we tested, in vitro, the AuNPs-SS safety in human keratinocytes and their potential effect on wound healing as well as their anti-inflammatory properties in murine macrophages. Moreover, the AuNPs-SS treatment resulted in a significant increase of the urokinase-type plasminogen activator receptor (uPAR), essential for keratinocyte adhesion, spreading, and migration, together with the reduction of LPS-induced IL1-? and IL-6 cytokine levels, and completely abrogated the synthesis of inducible nitric oxide synthase (iNOS). This journal is

An investigation of the thermal, electrical and dielectric properties of original nanocomposite materials based on the incorporation of carbon dots, synthesized in organic solvents, in a poly(methyl methacrylate) (PMMA) is presented. Thermal analysis was performed using differential scanning calorimetry. Electrical and dielectric measurements were carried out in the frequency range from 100 Hz to 1 MHz and at temperatures between 200 and 400 K. The data were analyzed using two formalisms: (i) AC conductivity that has been found to follow the Jonscher’s power law with double exponents, and (ii) electric modulus that permits to identify two dielectric relaxation processes. The first one, appearing at low-frequency, was attributed to the conduction effect which is consistent with the Havriliak-Negami model, and the second one, appearing at high-frequency was associated with the interfacial polarization effect. Furthermore, the analysis of the temperature dependence of AC conductivity using the Arrhenius representation indicated the existence of two mechanisms basically governing the conductivity.

The increased incidence of melanoma and other skin diseases induced by excessive sun exposure has led dermatologists to recommend a daily use of sunscreens to consumers. Interestingly, in the last few years, the formulation technology of these products has begun to employ nanomaterials to improve photoprotection and esthetic pleasantness. So, this chapter, among sunscreens, focuses the attention on the use of nanosunscreens, in particular, toward nano-TiO2 and nano-ZnO, taking into consideration their effectiveness and safety. In the first section of this chapter, an overview about sunscreens opens the discussion presenting their role, distinguishing them as organic and inorganic filters, giving information about their regulatory status. The sun protection factor and the characteristic of light are also defined. In the second section, the definition and use of nanomaterials in cosmetics, especially in sun-care products, their regulatory status, and nanotoxicology are deeply discussed.

Emerging pollutants are well-known chemicals without regulatory status that produce a significant environmental impact reaching aquatic and land ecosystems with a negative effect in the provision of ecosystem services. The aim of this work is the removal of tetracycline, through adsorption processes, from water by using alginate/chitosan microbeads enriched with TiO 2 . Through the photodegradation of the tetracycline, the recycle of the adsorbent is proposed under proper experimental conditions of work. While, by changing the ionic strength, a cleaner and low-cost approach is also presented to recover by desorption the adsorbed pollutant. The adsorption efficiencies observed for chitosan/alginate/TiO 2 composite materials indicate them as suitable for environmental applications, in the perspective of sustainable development and innovations in this field. Further, a detailed physical and chemical investigation is discussed assessing the kinetics and the isotherms of adsorption, along with the thermodynamic parameters.

Chlorophyll a (Chl a), an amphipathic porphyrin, was employed as natural photosensitizer for photodynamic therapy applications. Due to its lacking solubility in water and high tendency to aggregate, Chl a was included into different modified cyclodextrins (CDs) to form stable water-soluble supramolecular complexes. To achieve this aim, 2-Hydroxypropyl-beta-cyclodextrin (2-HP-beta-CD), 2-Hydroxypropyl-gamma-cyclodextrin (2-HP-gamma-CD), Heptakis (2,6-di-o-methyl)-beta-cyclodextrin (DIMES) and Heptakis(2,3,6-tri-o-methyl)beta-cyclodextrin (TRIMEB) were used. The chemical physical properties of Chl a/CD complexes in cellular medium were studied by means of UV-Vis absorption spectroscopy. Results demonstrated the good aptitude of 2-HP-gamma-CD, and more particularly of 2-HP-beta-CD, to solubilize the Chl a in cell culture medium in monomeric and photoactive form. Then, Chl a/2-HP-beta-CD and Chl a/2-HP-gamma-CD complexes were evaluated in vitro on human colorectal adenocarcinoma HT-29 cell line, and cytotoxicity and intracellular localization were respectively assessed. Further tests, such as phototoxicity, ROS generation, intracellular localization and mechanism of cell death were then focused exclusively on Chl a/2-HP-beta-CD system. This complex exhibited no dark toxicity and a high phototoxicity toward HT-29 cells inducing cell death via necrotic mechanism. Therefore, it is possible to affirm that Chl a/2-HP-beta-CD supramolecular complex could be a promising and potential formulation for applications in photodynamic therapy.

The adsorption properties of two cyclodextrin-epichlorohydrin polymers to remove Direct Red 83:1 textile dye from wastewater solutions was evaluated. Adsorption studies were performed in a batch reactor, and the efficiency of the polymers under different parametric values such as contact time, adsorbent dosage, initial dye concentration, pH of initial solution and temperature was followed by spectrophotometry. Both Langmuir and Freundlich equations were used to fit the equilibrium isotherms and the kinetic data were analyzed by the pseudo-first-order and pseudo-second-order models. Adsorption process follows a pseudo-second-order kinetic and was influenced by intraparticle diffusion model, dye concentration and contact time, reaching equilibrium within the first 30 min. Experimental data were better fitted to Freundlich isotherm model than to Langmuir and Temkin isotherms. Since about 93% of dye removal was achieved under optimized conditions, the α-cyclodextrin-epichlorohydrin polymer seems to be a useful device for removing Direct Red 83:1 from aqueous solutions and industrial effluents. Ciencias Ambientales

This study is aimed to validate water-insoluble cyclodextrin-epichlorohydrin polymer (β-EPI) use to remove, by adsorption, sulfamethoxazole (SMX) from water and then release it via an environmentally friendly treatment so that the adsorbent can be recycled according to one of the objectives of the European Project Life “Clean up” (LIFE 16 ENV/ES/000169). SMX adsorption experiments on β-EPI polymer in-batch were performed, varying different experimental parameters of the process, such as contact time, pH values, and so on. The adsorption process, exothermic and driven by enthalpy, occurs both through the formation of inclusion and association complexes, involves mainly hydrophobic and hydrogen bonds, has a rate-controlling step depending on both pollutant concentration and adsorbent dose and can be described by the Freundlich and Dubinin-Radushkevich models which confirm the polymer surface heterogeneity and the physical nature of the adsorption. The presence of salts gives rise to a general decrease in the SMX sorption, mainly in the case of bromide, which was used to promote the SMX desorption and regenerate the adsorbent. The overall results indicate that β-EPI polymer is not only capable of removing SMX by adsorption with short contact times and a qmax = 10 mg/g but it is also easily regenerated using a 0.5 M solution of sodium bromide without any loss in the adsorption performance and with obvious economic and environmental advantages. The polymer as synthesized, with SMX adsorbed and regenerated was characterized by FT-IR, SEM and DSC.

FINEAU (2021–2024) is a trans-disciplinary research project involving French, Serbian, Italian, Portuguese and Romanian colleagues, a French agricultural cooperative and two surface-treatment industries, intending to propose chènevotte, a co-product of the hemp industry, as an adsorbent for the removal of pollutants from polycontaminated wastewater. The first objective of FINEAU was to prepare and characterize chènevotte-based materials. In this study, the impact of water washing and treatments (KOH, Na2CO3 and H3PO4) on the composition and structure of chènevotte (also called hemp shives) was evaluated using chemical analysis, X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, X-ray computed nanotomography (nano-CT), attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy, solid state NMR spectroscopy and thermogravimetric analysis. The results showed that all these techniques are complementary and useful to characterize the structure and morphology of the samples. Before any chemical treatment, the presence of impurities with a compact unfibrillated structure on the surfaces of chènevotte samples was found. Data indicated an increase in the crystallinity index and significant changes in the chemical composition of each sample after treatment as well as in surface morphology and roughness. The most significant changes were observed in alkaline-treated samples, especially those treated with KOH.

The removal of Disperse Blue 73 from aqueous solutions, using olive pomace as adsorbent material, was investigated in a batch system with respect to contact time, pomace dosage, pH and temperature. SEM, FTIR-ATR, TG and XPS analyses appeared as powerful tools to characterize olive pomace, before and after the adsorption of dye, while UV-Visible analyses were used to quantify the amount of loaded dye on adsorbent material. The pseudo-second order kinetic model well fitted the experimental data and described the kinetic adsorption process. The dye desorption in glacial acetic acid was also obtained with the dye recovery enabling the recycle both of adsorbent material and dye itself. Five consecutive cycles of adsorption and desorption were performed and the absence of any degradation process affecting the dye after the adsorption/desorption cycles was observed. The recorded absorption spectrum, in acetic acid solution, before and after the desorption, confirmed such result. An environmentally friendly and a low cost material is thus presented, showing the excellent olive pomace potential both in disperse blue adsorption (with an efficiency of 100%) and desorption (with a mean value of 80% for each cycle). Additionally, an alternative environmental friendly use of olive oil solid residues is presented. (C) 2017 Elsevier Ltd. All rights reserved.

Alginate-chitosan beads were used as adsorbent to remove two azo anionic textile dyes, Direct Blue 78 and Direct Yellow 106, from aqueous solutions. Batch mode experiments of dyes adsorption were performed and the effects of various parameters such as contact time, adsorbent dosage, initial dye concentration, pH and temperature were examined. Successively, the dyes have been desorbed from the adsorbent and were recycled to dye a cotton fabric. The maximum efficiencies in dye removal, performed at pH 6, 298 K and with 0.5 g of adsorbent, were found to be about 97% for Direct Blue 78 and about 86% for Direct Yellow 106, respectively. The adsorption isotherms fitted the Freundlich’s model, the adsorption kinetics followed the pseudo-second order model and experimental data indicated an exothermic adsorption process. Moreover, the dyes desorption experiments from the alginate-chitosan beads demonstrated that about 50% of dyes were released in distilled water at high temperature (368 K) and the colored solutions obtained were so reused in dyeing tests. The results demonstrated that the alginate-chitosan beads are very efficient systems able not only to remove dyes from wastewater, but also to recycle and reuse them in further dyeing processes.

Seafood, a delight for many people, is sold in the market as a wide variety of products. However, seafood industries produce many by-products, for example, during the processing, the heads and shells of shellfish are generated as waste. This results in the generation of a large amount of shell waste that is accumulated over time, inducing a major environmental concern. Effective solutions for recycling shell waste should be taken into consideration, and the extraction of commercially useful substances like chitin and its derivates, such as chitosan, could be a valid solution for reducing the seafood waste&rsquo, s environmental impact. Thus, during this work, we propose the use of chitosan as biowaste, to induce the formation of solid films useful for decontaminating water from emerging pollutants. In particular, ketoprofen was used as a model contaminant, and a high percentage of removal, at least 90%, was obtained in a short time under our experimental conditions. Thus, a comprehensive investigation into the adsorption of ketoprofen onto chitosan film was performed, detailing the nature of the adsorption by studying the effects of pH, temperature changes, and electrolyte presence in the solutions containing the pollutant. The process was found to be pH-dependent, involving meanly electrostatic interactions between the pollutant molecules and chitosan. The endothermic character of the adsorption was inferred. The kinetics of the process was investigated, showing that the pseudo second-order kinetic model best fit the experimental data. A recycling process of the adsorbent was proposed, therefore, the adsorbed pollutant can be recovered by reusing the same adsorbent material for further consecutive cycles of adsorption without affecting the efficiency for ketoprofen removal from water.

This paper reported the first example on the use of chitosan films, without further modification, to remove and recover, through bio-sorption processes, the emerging pollutant Diclofenac from water. The latter was adopted as a model, among non-steroidal anti-inflammatory drugs, by obtaining a maximum adsorption capacity, qmax, on chitosan of about 10 mg/g, under the applied experimental conditions of work. The literature gap about the use of chitosan films, which was already used for dyes and heavy metals removal, to adsorb emerging pollutants from water was covered, claiming the wide range application of chitosan films to remove a different class of pollutants. Several parameters affecting the Diclofenac adsorption process, such as the pH and ionic strength of solutions containing Diclofenac, the amount of the bio-sorbent and pollutant, and the temperature values, were investigated. The kinetics and the adsorption isotherms, along with the thermodynamic parameters (&Delta, G&deg, &Delta, H&deg, and &Delta, S&deg, ) were also evaluated. The process occurred very efficiently, and Chitosan/Diclofenac amounts dependent, remove about the 90% of the pollutant, in 2 h, from the tested solutions, through electrostatic interaction involving the carboxylic moiety of Diclofenac and Chitosan amino groups. This finding was confirmed by the pH and salt effects on the bio-sorption process, including swelling measurements of Chitosan films and by FTIR-ATR analysis. In detail, the maximum adsorption was observed at pH 5, when pollutant and Chitosan were negatively and positively charged, respectively. By reducing or increasing the pH around this value, a reduced affinity was observed. Accordingly, the presence of salts retarded the Diclofenac removal screening its charges, which hinders the interaction with Chitosan. The sorption was spontaneous (&Delta, &lt, 0) and endothermic (&Delta, &gt, 0) following the pseudo-second order kinetic model. The process was Diclofenac and Chitosan amount dependent. In addition, the Freundlich and Temkin isotherms well described the process, which showed the heterogeneous character of the process. Experiments of the complete desorption were also performed by using NaCl solutions 0.25 M (like sea water salt concentration) proposing the reuse of the pollutant and the recycling of the bio-sorbent lowering the associated costs. The versatility of the adsorbent was reported by exploring the possibility to induce the Diclofenac light-induced degradation after the adsorption and by-products adsorption onto chitosan films. To emphasize the chitosan capacity of treating water, the removal of another pollutant such as Ketoprofen and the mixture of Diclofenac and Ketoprofen were investigated. In this way, a green and eco-friendly production-pollution prevention technology for removing emerging pollutants from water was presented, which reduced the overall environmental impact. This illustrated experiments both in static and dynamic conditions for potential industrial applications.

This paper accounts the first example about the development of a self-assembled supramolecular system based on the use of green-synthetized gold nanoparticles (AuNPs) and chitosan (CH), for solubilizing ellagic acid (EA) in water. AuNPs were synthetized by using Punica granatum Juice (PGJ) and, after their synthesis, in order to adsorb ellagic acid on the nanoparticles surface (AuNPs/CH/EA), the chitosan wrapping was performed (AuNPs/CH). For this purpose, chitosan having high viscosity, low and medium molecular weights were used and compared to check the best condition of work. The stability of the proposed system, before and after the addition of ellagic acid, under different conditions of work, i.e. solution pH, temperature and light irradiation were investigated demonstrating the stability of the proposed functional ingredient. The supramolecular system exhibited wide ranging properties such as antioxidant, skin lightening and sunscreen. More specifically, the % of antioxidant activity occurred around 80% and 60% from the DPPH and ABTS assays respectively; the tyrosinase inhibition was around of 50% and the Sun Protection Factor was found to be 20. Thanks to the multi-properties of the proposed functional ingredient it should exhibit several advantageous in cosmetic applications. The ingredient could be a valid alternative to the traditional nanostructured TiO2 and ZnO offering the possibility to have at the same time several properties due to the use of AuNPs (having light absorption and scattering ability, are biocompatible showing low toxicity) and EA. If these positive aspects are associated with the use of an eco-friendly and low-cost protocol for AuNPs synthesis, according to the Green Chemistry principles, a great interesting space is opened towards the study of PGJ-based AuNPs, as multifunctional platform in cosmetic.

This paper focuses on the removal of tetracycline from polluted water by chitosan-olive pomace adsorbing films. More specifically, both raw olive solid wastes (olive pomace) and the olive solid wastes/chitosan composite were compared and used for this purpose. Adsorption capacities values of 16 mg x g(-1) and 1.6 mg x g(-1) were obtained for the two adsorbents respectively. However, chitosan/olive pomace is proposed as suitable for environmental applications avoiding the dispersion of the pomace blocked inside the chitosan film. To detail the adsorption process, the effect of several experimental parameters such as the pH values, ionic strength, amount of adsorbent and pollutant and temperature values was investigated. The results showed that the adsorption process improved increasing the pH values, with a maximum at pH 8, and it was negatively affected by the presence of salts that retarded the adsorption. Indeed, the desorption of tetracycline was obtained in a MgCl2 2 M solution. So, a low-cost and cleaner approach, fundamental for the pollutant recovery and for an adsorbent safe reuse, for several cycles of adsorption/desorption, transforming a waste in resource is presented. The kinetics, isotherms models of adsorption and the thermodynamic parameters (Delta G degrees, Delta H degrees and Delta S degrees) were also evaluated observing that the physisorption of the pollutant occurred with and an endothermic character (Delta H degrees > 0) with Delta G degrees < 0 and Delta S degrees > 0. The use of Advanced Oxidation Processes was proposed as possible alternative to the tetracycline recovery, obtaining its degradation after the desorption. With the present paper, the alternative reuse of olive pomace is reported avoiding its disposal in the environment claiming its potential in the removal/recover of emerging contaminants from water. (C) 2019 Elsevier B.V. All rights reserved.

Melanogenesis is a biosynthetic pathway that produces the pigment melanin in human skin. The catalyzation of the key enzyme tyrosinase is the first step in melanogenesis, and the downregulation of tyrosinase enzyme activity is the most reported method for inhibiting melanogenesis. Hyperpigmentation is an important issue in the cosmetic industry, and there is great demand for melanogenesis inhibitors. In the present study, we demonstrated the anti-melanogenic effect of Inonotus obliquus in alpha-melanocyte-stimulating hormone (&alpha, MSH)-induced B16F10 mouse melanoma cells and identified it as a new melanogenesis inhibitor. Comparing the B16F10 cells treated with the control and the Inonotus obliquus extract, we identified the melanin contents, mRNA and protein expression of tyrosinase, tyrosinase activity, and microphthalmia-associated transcription factor (Mitf) activity using a constructed plasmid. Through these experiments, we confirmed that Inonotus obliquus extract inhibits melanin synthesis by downregulating the activity and expression of tyrosinase. Furthermore, we revealed that tyrosinase expression is regulated by Inonotus obliquus extract via the repression of Mitf transcriptional activity. Thus, in this study, we found that Inonotus obliquus extract has anti-melanogenic effects via the suppression of melanin synthesis. Taken together, we demonstrated that Inonotus obliquus extract is a good potential candidate for use as a natural source for the therapeutic treatment of hyperpigmentation and for applications in whitening cosmetic products.