How Ionic Liquid Gels Work on the Removal of Bisphenol A from Wastewater.

The occurrence of emerging pollutants in water bodies is a pressing issue of modern society and identifying materials to remove them is the main target of current research. In this work, we prepared and characterized supramolecular gels of 1,3:2,4-dibenzylidene-d-sorbitol (DBS) in ionic liquids differing for the anion and the aliphatic or aromatic nature of the cation. We characterized our gels for their thermal stability and mechanical properties. We also found that all gels self-heal in 24 h after being cut by a razor blade. We then used our gels as sorbents to remove bisphenol A, an endocrine disruptor compound, from aqueous solutions. All gels adsorb BPA with high removal efficiencies, and those obtained in aliphatic ionic liquids act faster than their aromatic counterparts. The highest observed adsorption capacity was 314 mg/g. Gels were reused without loss in performance and need for intermediate washing, and the gel obtained in [bmpip][NTf2] could be reused 37 times, maintaining a removal efficiency higher than 96%. It was loaded in a sequential system of syringes to treat flowing aqueous phases, removing 60% of BPA in 30 min. We also embedded the gel in the dialysis membrane and observed a removal efficiency of 85% after 48 h.

Upcycling of Poly(lactic acid) Waste: A Valuable Strategy to Obtain Ionic Liquids.

With the aim to investigate new strategies for upcycling of plastic waste, we performed aminolysis of poly(lactic acid) (PLA), using N,N-dimethylethylenediamine (DMEDA), N,N-dimethylpropylenediamine (DMPDA), and 3-aminopropylimidazole (API) as nucleophiles. The N-substituted lactamides obtained were alkylated by using alkyl halides differing in alkyl chain length, obtaining organic salts that in most cases behaved as ionic liquids (ILs). Both aminolysis of PLA and alkylation of amides were carried out taking into consideration the basic principles of the holistic approach to green chemistry, applied at a laboratory scale, and carefully selecting the nature of the reaction solvent, temperature range, and amount of reagents. Organic salts obtained from the alkylation of N-substituted lactamides were investigated to determine their glass or solid-liquid transitions and their thermal stability. Furthermore, cytotoxicity toward normal lung fibroblasts was also assessed. Data collected show that the proposed strategy represents a valuable protocol to upcycle plastic waste, using it as starting material to obtain alternative solvents of potential industrial relevance.

Insights about the ability of folate based supramolecular gels to act as targeted therapeutic agents.

With the aim to obtain targeted chemotherapeutic agents, imidazolium and ammonium-based folate salts were synthesized. Their photophysical behavior was investigated both in buffer and buffer/DMSO solution as well as in solid phase, performing UV-vis and fluorescence investigations. Properties of the aggregates were also analyzed by dynamic light scattering. Gelation ability of the salts was analyzed in biocompatible solvents, and gel phases obtained were characterized by determining critical gelation concentrations and gel-solution transition temperatures. Insights about gelator interactions in the tridimensional network were also gained performing ATR-FTIR investigation. Properties of soft materials were further analyzed performing rheology measurements, scanning electron microscopy, fluorescence and resonance light scattering investigations. Antiproliferative activity of organic salts was tested towards two breast cancer cell lines, expressing different levels of folate receptor, namely MDA-MB-231 and MCF-7, and a normal epithelial cell line, like h-TER T-RPE-1, by using MTT assay. Dichlodihydrofluorescein acetate test was performed to verify the role of oxidative stress in cell death. Finally, antiproliferative activity was also evaluated in gel phase, to verify if salts were able to retain biological activity also after the entrapment in the gelatinous network. Results collected evidence that folate based organic salts were able to behave as targeted chemotherapeutic agents both in solution and gel phase, showing uptake mechanism and selectivity indexes that depend on both cancer cell line nature and salt structure.

Biochar Particles Obtained from Agricultural Carob Waste as a Suitable Filler for Sustainable Biocomposite Formulations.

In the context of sustainable and circular economy, the recovery of biowaste for sustainable biocomposites formulation is a challenging issue. The aim of this work is to give a new life to agricultural carob waste after glucose extraction carried out by a local factory for carob candy production. A pyrolysis process was carried out on bio-waste to produce biofuel and, later, the solid residual fraction of pyrolysis process was used as interesting filler for biocomposites production. In this work, biochar particles (BC) as a pyrolysis product, after fuels recovery of organic biowaste, specifically, pyrolyzed carobs after glucose extraction, were added on poly(butylene-adipate-co-terephthalate), (PBAT), at two different concentrations, i.e., 10 and 20 wt%. The BC have been produced using three pyrolysis processing temperatures (i.e., 280, 340 and 400 °C) to optimize the compositions of produced solid fractions and biofuels. The resulting particles from the pyrolysis process (BC280, BC340 and BC400) were considered as suitable fillers for PBAT. Firstly, the BC particles properties were characterized by elemental composition and spectroscopy analysis, particle size measurements and evaluation of radical scavenging activity and efficiency. Moreover, PBAT/BC composites were subjected to analysis of their rheological and thermal behavior, morphologies and mechanical properties. In addition, accelerated weathering, monitored by both tensile test and spectroscopic analysis, was carried out, and obtained results show that the biochar particles can exert a beneficial effect on photo-oxidation delay of PBAT matrix.

The Role Played by Ionic Liquids in Carbohydrates Conversion into 5-Hydroxymethylfurfural: A Recent Overview.

Obtaining industrially relevant products from abundant, cheap, renewable, and low-impacting sources such as lignocellulosic biomass, is a key step in reducing consumption of raw fossil materials and, consequently, the environmental footprint of such processes. In this regard, a molecule that is similar to 5-hydroxymethylfurfural (5-HMF) plays a pivotal role, since it can be produced from lignocellulosic biomass and gives synthetic access to a broad range of industrially important products and polymers. Recently, ionic liquids (ILs) have emerged as suitable solvents for the conversion of biomass and carbohydrates into 5-HMF. Herein, we provide a bird's-eye view on recent achievements about the use of ILs for the obtainment of 5-HMF, covering works that were published over the last five years. In particular, we first examine reactions involving homogeneous catalysis as well as task-specific ionic liquids. Then, an overview of the literature addressing the use of heterogeneous catalysts, including enzymes, is presented. Whenever possible, the role of ILs and catalysts driving the formation of 5-HMF is discussed, also comparing with the same reactions that are performed in conventional solvents.

Interplay of Acidity and Ionic Liquid Structure on the Outcome of a Heterocyclic Rearrangement Reaction.

The study of suitable probe reactions is a powerful tool to investigate the properties of nonconventional solvents such ionic liquids (ILs). In particular, we studied the acid-catalyzed mononuclear rearrangement of heterocycles (MHR) of the Z-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole into the relevant 1,2,3-triazole, in solution of ILs by means of kinetic measurements. We chose as solvents six ILs differing both in the cation and anion, in the presence of five carboxylic and sulfonic acids as catalysts. For a useful comparison, the reaction was also performed in 1,4-dioxane and methanol. In general, the reaction occurs faster in ILs, compared to conventional solvents, according to the weaker solvation interactions operating in the former media. The effect of IL anion and cation on the reactivity and on the acidic strength of the catalysts was analyzed. To this aim, we measured the acidic strength of the sulfonic acids in each IL, estimated by the equilibrium formation constant of each acid with 4-nitroaniline. We found that the trend of reactivity as a function of the IL anion mainly reflects the larger difference in acidic strengths of the catalyst. Conversely, acidic strength spans a narrower range as a function of the IL cation. As a result, other factors come into play, such as the π-π interactions involving aromatic IL cations, substrate, and transition states, leading to a more articulate trend.

Ionic liquids: "normal" solvents or nanostructured fluids?

Ionic liquids (ILs) are a class of non-conventional solvents, which, for almost two decades, have continued to generate burgeoning interest in different fields of present-day chemical research with few similar precedents. Among the various aspects related to ILs, a topic worthy of in-depth analysis is their influence on organic reactivity and reaction rates. In light of this, the present short review aims to provide an overview of the literature from 2010 to the present day that addresses this issue. In particular, we herein present two main different viewpoints by which the solvent effect of ILs is explained: the first is mainly based on considering the bulk polarity of ILs and linear solvation energy relationships, while the other treats ILs as nanostructured fluids. In both cases, studies dealing with IL mixtures are also covered. Finally, literature addressing the area of supramolecular catalysis "by" or "in" ILs is also reported. This is one of the few reviews covering these specific aspects, aiming to provide a useful framework to guide future research into the effects of ILs on organic reactivity.

End-of-life and waste management of disposable beverage cups.

Different human activities have caused and currently cause catastrophic environmental phenomena, and unfortunately, a significant negative contribution to these catastrophic phenomena can be attributed to uncontrolled plastic production, use and release everywhere. On the other hand, the plastics offer numerous comforts and advantages, and for this reason, the modern life is unthinkable without plastic. Currently, numerous scientific papers and large audience advertisings, related to the production and use of polymers made by natural sources, i.e. bio-based polymers, as a valid alternative to the petroleum-based counterparts, have been published. Therefore, for production of daily disposables and usages, the choice of petroleum-based polymers, coming from fossil-based resources, or bio-based polymers, coming from renewable resources, can be correctly understood and evaluated taking into account different issues concerning resources supplying, production technology and costs, application properties and performance, and finally, waste management. Current paper is focused on a reflection point related to waste management through burning/incineration (i.e. oxidation) of disposable beverage cups (volume 200 ml). The simple calculations of oxidation process of petrol-based or bio-based materials, which is the theoretical basis of waste management through burning/incineration, highlights that none of cup materials, can be considered better than the others to produce daily disposables and usages.

Naphthalimide Imidazolium-Based Supramolecular Hydrogels as Bioimaging and Theranostic Soft Materials.

1,8-Naphthalimide-based imidazolium salts differing for the alkyl chain length and the nature of the anion were synthesized and characterized to obtain fluorescent probes for bioimaging applications. First, their self-assembly behavior and gelling ability were investigated in water and water/dimethyl sulfoxide binary mixtures. Only salts having longer alkyl chains were able to give supramolecular hydrogels, whose properties were investigated by using a combined approach of fluorescence, resonance light scattering, and rheology measurements. Morphological information was obtained by scanning electron microscopy. In addition, conductive properties of organic salts in solution and gel state were analyzed. Imidazolium salts were successfully tested for their possible application as bioimaging and cytotoxic agents toward three cancer cell lines and a nontumoral epithelial cell line. Characterization of their behavior was performed by MTT and cell-based assays. Finally, the biological activity of hydrogels was also investigated. Collectively, our findings showed that naphthalimide-based imidazolium salts are promising theranostic agents and they were able to preserve their biological properties also in the gel phase.

Natural Compounds as Sustainable Additives for Biopolymers.

In the last few decades, the interest towards natural compounds, coming from a natural source and biodegradable, for biopolymers is always increasing because of a public request for the formulation of safe, eco-friendly, and sustainable materials. The main classes of natural compounds for biopolymers are: (i) naturally occurring fillers (nFil), such as nano-/micro- sized layered alumino-silicate: halloysite, bentonite, montmorillonite, hydroxyapatite, calcium carbonate, etc.; (ii) naturally occurring fibers (nFib), such as wood and vegetable fibers; (iii) naturally occurring antioxidant molecules (nAO), such as phenols, polyphenols, vitamins, and carotenoids. However, in this short review, the advantages and drawbacks, considering naturally occurring compounds as safe, eco-friendly, and sustainable additives for biopolymers, have been focused and discussed briefly, even taking into account the requests and needs of different application fields.

Environmentally Friendly Eutectogels Comprising l-amino Acids and Deep Eutectic Solvents: Efficient Materials for Wastewater Treatment.

Current concerns for sustainability and the environment make low-impact materials desirable for environmental remediation and, in particular wastewater treatment. We obtained supramolecular gels of l-amino acids in the deep eutectic solvent formed by choline chloride and phenylacetic acid. After gel characterization, and investigating gel-sol transition temperatures, gelation kinetics, rheological properties, and morphology, the gels were applied as sorbents to remove cationic dyes from aqueous solutions. The effects of the pH, dye nature, volume, and concentration of wastewater were analyzed, and the best result was obtained with a l-phenylalanine-based eutectogel. It can be reused for at least 9 times without losing efficiency, also with dye mixtures. Interestingly, this gel can be loaded onto columns to decolorize flowing solutions, achieving 85 % of removal efficiency in only 10 minutes and allowing its reuse for at least 4 cycles. In terms of adsorption capacity, this eutectogel is competitive with efficient gel-based dye sorbent systems, with a value 1930 mg/g reached at a high concentration of rhodamine B 479 mg/L.

Improvement of oxidation resistance of polymer-based nanocomposites through sonication of carbonaceous nanoparticles.

The work aim is focused on two different aspects: first, the investigation of the effect of extended ultra-sound-assisted treatment (us) of carbonaceous nanoparticles, such as carbon nanotubes (CNTs) and carbon black (CB), on their radical scavenging activity, and second, the investigation of the oxidative resistance of polymer-based nanocomposites, containing us-treated CNTs and CB. Particularly, the CNTs and CB have been subjected to us sonication for different time intervals and the performed analysis reveals that both kinds of nanoparticles show decreased average hydrodynamic diameters and large content of surface defects. Really, the increased content of CNTs and CB defects, achieved during the sonication time, leads to an increased reactivity toward 1,1-diphenyl-2-pycryl (DPPH) radicals and an enhanced anti-oxidant activity toward macro-radicals, coming from the photo-degradation of the host polymer matrix. The studies of photo-oxidative behavior of the nanocomposites, based on Ultra High Molecular Weight (UHMWPE), reveal that the us treatment of the nanoparticles has a benefic effect on the oxidative resistance of the nanocomposites, especially at long exposure times. Overall, the ultra-sound-assisted treatment can be considered twofold powerful tool: (i) for disruption of the nanoparticles aggregations, and (ii) for capitalization of surface defects, amplifying and tuning in a controlled way the radical scavenging activity of the carbonaceous nanoparticles.

Ionic liquid gels and antioxidant carbon nanotubes: Hybrid soft materials with improved radical scavenging activity.

HYPOTHESIS: Performances of materials are frequently affected by the action of radicals that can induce their degradation. To overcome the above issue, natural antioxidants (AOs) can be added during manufacturing. Considering the high instability of AOs, they have been adsorbed on carbon nanomaterials surface. However, the inclusion of functionalized carbon nanomaterials into gel matrix could enhance the antioxidant efficiency and represent an easy way to disperse and handle the active species. EXPERIMENTS: Carboxypropyl functionalized carbon nanotubes (f-CNT), pure or with physically adsorbed α-tocopherol (f-CNT-VE) and quercetin (f-CNT-Q), were incorporated in some ionic liquid gels (ILGs) formed by 1,3-didodecylimidazolium-based salts. Temperature of gel-sol transition, morphology, response to external stimuli and rheology of hybrid ILGs (HILGs) were investigated before their use as radical scavengers. To this purpose a free radical test was performed on gels. FINDINGS: The properties of HILGs significantly differ from the ones of pure ILGs, as CNTs appreciably improved gel rheological response. Besides, the gel network is able to enhance radical scavenging activity of both natural AOs and f-CNTs, achieving a complete radical reduction in less than 1 h. Furthermore, the activity is also preserved in thin films obtained from HILGs, opening the way to the application of these systems as material coatings.

Carbon Nanomaterial Doped Ionic Liquid Gels for the Removal of Pharmaceutically Active Compounds from Water.

Due to large drug consumption, pharmaceutically active compounds (PhACs) can be found as water contaminants. The removal of PhACs is a significant issue, as they can easily overtake traditional purification methods. Because of their surface properties, carbon nanomaterials are among the most efficient materials able to adsorb PhACs. However, their limitation is their recovery after use and their possible leakage into the aquatic system. Consequently, new hybrid supramolecular ionic liquid gels (HILGs) have been designed for the adsorption of some antibiotic drugs (ciprofloxacin and nalidixic acid) from water. The chemical-physical properties of gels, such as the temperature of the gel-sol transition, morphology, and rheology, have been studied for their use as sorbents. These properties influence the gel removal efficiency of PhAC, i.e., the best system is the gel that presents weaker colloidal forces. A fast removal (RE = 51%) is obtained in 3 h for ciprofloxacin, while a slower adsorption process is observed for nalidixic acid (RE = 88% in 24 h). HILGs can be recycled up to seven cycles and regenerated. In addition, they can be used with higher concentrations or volumes of PhAC and in a realistic apparatus like dialysis membranes. These peculiarities suggest that HILGs can be competitive with more complex sorbent systems.

Task-Specific Organic Salts and Ionic Liquids Binary Mixtures: A Combination to Obtain 5-Hydroxymethylfurfural From Carbohydrates.

The increase in energy demand and depletion of fossil fuels are among major issues of modern society. Valorization and transformation of raw materials in products of industrial value represent a challenge. This justifies the growing interest of scientific research toward the identification of suitable media and methodologies able to pursue above goals, paying attention to matter of sustainability. On this subject, we studied sulfonic-acid functionalized diimidazolium salts as catalysts for the conversion of fructose and sucrose to 5-hydroxymethylfurfural (5-HMF) in an ionic liquid mixture. In general, using these salts allowed us to obtain 5-HMF in good yields from both substrates in mild conditions. Indeed, at 60°C and in the presence of 20 mol% of catalyst, 5-HMF yields of 60 and 30% were obtained from fructose and sucrose, respectively. The catalytic system was recycled and used up to six times observing no appreciable loss in yield for the first four cycles. Moreover, we gathered mechanistic information by in situ 1H NMR monitoring the dehydration of fructose. To dissect the role of acidity on the reaction, we determined the Hammett acidity function of each salt. Comparison of these results with yields and reactivity observed in the presence of related monocationic salts and with a dicationic salt bearing only one sulfonic acid group, allowed stating that the reactivity observed is the result of the combined action of acidity and structural features of the catalysts. Overall, the approach proposed here could contribute to pave the way to increase sustainability in the raw material valorization processes.

Ionic Liquid Gels: Supramolecular Reaction Media for the Alcoholysis of Anhydrides.

The search of new enantioselective catalysts, able to promote synthetically useful organic reactions with high levels of asymmetric induction, should be associated with the attention to the suitable reaction medium able to achieve the best efficiency in chemical processes. We have investigated the enantioselective desymmetrization of cyclic meso-anhydrides in nonconventional reaction media such as ionic liquids and supramolecular gels. With this aim, we examined several variables in the reacting system: the nature of ionic liquid used as the reaction medium, the gelation solvent, the structure of the anhydrides, the structure of alcohols, the chiral catalysts, and the reaction conditions, i.e., temperature and time. The different components of the system differently influence the reaction outcome, and to understand the interactions existing among them, 1H NMR investigation was carried out. In general, the nonconventional reaction media demonstrated better performance than conventional ones, applying only a small amount of solvent. Good results in terms of yield and enantiomeric excess have been obtained in ionic liquid gels that seem promising media in the catalytic field. Furthermore, to the best of our knowledge, this is one of the first examples for the study of asymmetric alcoholysis of anhydrides in ionic liquid solution and gel phase.

Carbohydrate-supramolecular gels: Adsorbents for chromium(VI) removal from wastewater.

HYPOTHESIS: To overcome the contamination of water by heavy metals the adsorption of the pollutant on gel phases is an attractive solution since gels are inexpensive, potentially highly efficient and form a distinct phase while allowing diffusion of the contaminated water throughout the material. This work tests the chromium(VI) adsorbent capacity of new supramolecular gels for Chromium(VI) removal from wastewater. EXPERIMENTS: First hydrophobic imidazolium salts of carbohydrate anions were synthesised as new gelators. Subsequently, they were dissolved in a solvent by heating and, after cooling overnight, to give the formation of supramolecular gels. The properties of the resulting gels, such as thermal stability, mechanical strength, morphology, rheology, and kinetics of gel formation, were studied as a function of gelator structure, gelation solvent and pollutant removal efficiency. FINDINGS: Carbohydrate-derived gels showed the best removal capacity, i.e. 97% in 24 h. Interestingly, in one case, the reduction of chromium(VI) to chromium(III) also occurred after the adsorption process, and this phenomenon has been analysed using 1H NMR spectroscopy, IR spectroscopy, and SEM. The most efficient gel can reach an adsorption capacity of 598 mg/g in contrast to a value of 153 mg/g for the most effectively best hydrogels reported to date. The new gel can be also recycled up to 4 times. These findings suggest that these new, supramolecular hydrogels have potential applications in environmental remediation.

Multifunctional Carrier Based on Halloysite/Laponite Hybrid Hydrogel for Kartogenin Delivery.

A novel carrier system based on halloysite nanotubes (HNT), for the potential intraarticular delivery of kartogenin (KGN) by means laponite (Lap) hydrogel (HNT/KGN/Lap), is developed. The drug was first loaded into HNT, and the hybrid composite obtained was used as filler for laponite hydrogel. Both the filler and the hydrogel were thoroughly investigated by several techniques and the hydrogel morphology was imaged by transmission electron microscopy. Furthermore, the gelating ability of laponite in the presence of the filler and the rheological properties of the hybrid hydrogel were also investigated. The kinetic release of kartogenin from HNT and HNT/Lap hybrid hydrogel was studied both in physiological conditions and in ex vivo synovial fluid. In the last case, the kinetic results highlighted that HNT carrier can effectively release KGN in a sustained manner for at least 38 days. Finally, a preliminary biological assays showed that the HNT/KGN/Lap hybrid hydrogel did not exhibit any cytotoxic effect.

Ionic liquids gels: Soft materials for environmental remediation.

HYPOTHESIS: Nanostructured sorbents and, in particular, supramolecular gels are emerging as efficient materials for the removal of toxic contaminants from water, like industrial dyes. It is also known that ionic liquids can dissolve significant amounts of dyes. Consequently, supramolecular ionic liquids gels could be highly efficient sorbents for dyes removal. This would also contribute to overcome the drawbacks associated with dye removal by liquid-liquid extraction with neat ionic liquids which would require large volumes of extractant and a more difficult separation of the phases. EXPERIMENTS: Herein we employed novel supramolecular ionic liquid gels based on diimidazolium salts bearing naturally occurring or biomass derived anions, to adsorb cationic and anionic dyes from wastewaters. We also carried out a detailed investigation of thermal, structural, morphological and rheological features of our gels to identify which of them are key in designing better sorbents for environmental remediation. FINDINGS: The most effective gels showed fast and thorough removal of cationic dyes like Rhodamine B. These gels could also be reused up to 20 times without any loss in removal efficiency. Overall, our ionic gels outperform most of gel-based sorbents systems so far reported in literature.

Nitrogen-Doped Carbon Nanodots-Ionogels: Preparation, Characterization, and Radical Scavenging Activity.

Hybrid diimidazolium-based ionogels were obtained by dispersing nitrogen-doped carbon nanodots (NCNDs) in ionic liquid (IL) solutions and by using dicationic organic salts as gelators. The properties of the NCND-ionogels were studied in terms of thermal stability, mechanical strength, morphology, rheological, and microscopic analyses. Insights into the formation of the hybrid soft material were attained from kinetics of sol-gel phase transition and from estimating the size of the aggregates, obtained from opacity and resonance light-scattering measurements. We demonstrate that, on one hand, NCNDs were able to favor the gel formation both in the presence of gelating and nongelating ILs. On the other hand, the gelatinous matrix retains and, in some cases, improves the properties of NCNDs. The NCND-ionogels showed the typical fluorescence emission of the carbon dots and a notable antiradical activity, with higher efficiency as compared to the single components. The presented hybrid materials hold great promise for topical applications in antioxidant fields.