Novel eco-friendly and easily recoverable bismuth-based materials for capturing and removing polyphenols from water.

Olive oil production is one of the most developed Europe's sectors, producing olive oil and undesirable by-products, such as olive mill wastewater (OMWW) and organic waste. OMWW, containing large amounts of compounds (mainly polyphenols, phenols, and tannins), represents a problem. In fact, polyphenols have dual nature: i) antioxidant beneficial properties, useful in many industrial fields, ii) biorefractory character making them harmful in high concentrations. If not properly treated, polyphenols can harm biodiversity, disrupt ecological balance, and degrade water quality, posing risks to both environment and human health. From a circular economy viewpoint, capturing large quantities of polyphenols to reuse and removing their residuals from water is an open challenge. This study proposes, for the first time, a new path beyond the state-of-the-art, combining adsorption and degradation technologies by novel, eco-friendly and easily recoverable bismuth-based materials to capture large amounts of two model polyphenols (gallic acid and 3,4,5-trimethoxybenzoic acid), which are difficult to remove by traditional processes, and photodegrade them under solar light. The coupled process gave rise to collect 98% polyphenols, and to rapidly and effectively photodegrade the remaining portion from water.

Metamaterial architecture from a self-shaping carnivorous plant.

As meticulously observed and recorded by Darwin, the leaves of the carnivorous plant Drosera capensis L. slowly fold around insects trapped on their sticky surface in order to ensure their digestion. While the biochemical signaling driving leaf closure has been associated with plant growth hormones, how mechanical forces actuate the process is still unknown. Here, we combine experimental tests of leaf mechanics with quantitative measurements of the leaf microstructure and biochemistry to demonstrate that the closure mechanism is programmed into the cellular architecture of D. capensis leaves, which converts a homogeneous biochemical signal into an asymmetric response. Inspired by the leaf closure mechanism, we devise and test a mechanical metamaterial, which curls under homogeneous mechanical stimuli. This kind of metamaterial could find possible applications as a component in soft robotics and provides an example of bio-inspired design.

One pot synthesis of thio-glycosides via aziridine opening reactions.

A one-pot aziridine opening reaction by glycosyl thiols generated in situ from the corresponding anomeric thio-acetates affords thio-glycosides with a pseudo-disaccharide structure and an N-linked tether. The scope of the one-pot aziridine opening reaction was explored on a series of mono- and disaccharides, creating a class of pseudo-glycosidic compounds with potential for further functionalization. Unexpected anomerization of glycosyl thiols was observed under the reaction conditions and the influence of temperature, base and solvent on the isomerization was investigated. Single isomers were obtained in good to acceptable yields for mannose, rhamnose and sialic acid derivatives. The class of thio-glycomimetics synthesized can potentially be recognized by various lectins, while presenting hydrolytic and enzymatic stability. The nitrogen functionality incorporated in the glycomimetics can be exploited for further functionalization, including tethering to linkers, scaffolds or peptide residues.

Self-cleaning, photocatalytic films on aluminum plates for multi-pollutant air remediation: promoting adhesion and activity by SiO2interlayers.

In recent years, nanoparticles have come under close scrutiny for their possible health and environmental issues, making them less attractive for photocatalytic applications in air or water purification. Replacing free nano-powders with active and stable films is thus a fundamental step towards developing effective photocatalytic devices. Aluminum represents a cheap and technologically-relevant substrate, but its photocatalytic applications have been hampered by adhesion issues and metal ion diffusion within the photocatalytic layer. In this work, the use of silica interlayers is investigated as a strategy to promote adhesion, efficiency and reusability of TiO2films deposited on aluminum plates. Films were prepared from stable titania sols to avoid the use of nano-powders. Aluminum substrates with different surface morphology were investigated and the role of the silica interlayer thickness was studied. Films were extensively characterized, studying their structure, morphology, optical properties, adhesion and hardness. Self-cleaning properties were studied with respect to their superhydrophilicity and ability to resist fouling via alkylsilanes. Photocatalytic degradation tests were carried out using both volatile organic compounds and NOx, also in recycle tests. The presence of the silica interlayer proved crucial to promote the film robustness and photocatalytic activity. The substrate morphology determined the optimal interlayer thickness, especially in terms of the film reusability.

Oxidative Inactivation of SARS-CoV-2 on Photoactive AgNPs@TiO2 Ceramic Tiles.

The current SARS-CoV-2 pandemic causes serious public health, social, and economic issues all over the globe. Surface transmission has been claimed as a possible SARS-CoV-2 infection route, especially in heavy contaminated environmental surfaces, including hospitals and crowded public places. Herein, we studied the deactivation of SARS-CoV-2 on photoactive AgNPs@TiO2 coated on industrial ceramic tiles under dark, UVA, and LED light irradiations. SARS-CoV-2 inactivation is effective under any light/dark conditions. The presence of AgNPs has an important key to limit the survival of SARS-CoV-2 in the dark; moreover, there is a synergistic action when TiO2 is decorated with Ag to enhance the virus photocatalytic inactivation even under LED. The radical oxidation was confirmed as the the central mechanism behind SARS-CoV-2 damage/inactivation by ESR analysis under LED light. Therefore, photoactive AgNPs@TiO2 ceramic tiles could be exploited to fight surface infections, especially during viral severe pandemics.

Emerging pollutant mixture mineralization by TiO2 photocatalysts. The role of the water medium.

Pharmaceutics and personal care products (PPCPs) are raising growing concern due to their widespread usage and resistance to conventional remediation techniques. Several of them raise significant health and environmental concerns, especially when present in complex mixtures. Due to their chemical resistance, Advanced Oxidation Processes (AOPs) are needed for their complete removal from surface and wastewaters. In the present work, photocatalysis by titanium dioxide (TiO2) under UV and simulated solar irradiation was adopted to degrade tetracycline hydrochloride, paracetamol, caffeine and atenolol, both as single pollutants and in mixtures. All molecules showed high removal and mineralization degrees. Moreover, no interference effects decreased the efficiency of the processes in the case of pollutant mixtures, achieving 60% of mineralization after 6 h. An immobilized TiO2 system was also developed by depositing titania on titanium meshes. A 50% mineralization degree of the pollutant mixture was obtained after 6 h, revealing a suitable efficiency for field applications. Eventually, the impact of the matrix composition on the photocatalytic efficiency was investigated by studying the reaction both in simulated drinking water and in commercial bottled mineral water. The scavenger role played by HCO3- species appears to be dominant in inhibiting the mineralization.

Clean Transformation of Ethanol to Useful Chemicals. The Behavior of a Gold-Modified Silicalite Catalyst.

Upon addition of gold to silicalite-1 pellets (a MFI-type zeolite), the vapor phase oxidation of ethanol could be addressed to acetaldehyde or acetic acid formation. By optimizing the catalyst composition and reaction conditions, the conversion of ethanol could be tuned to acetaldehyde with 97% selectivity at 71% conversion or to acetic acid with 78% selectivity at total conversion. Considering that unloaded silicalite-1 was found to catalyze the dehydration of ethanol to diethylether or ethene, a green approach for the integrated production of four important chemicals is herein presented. This is based on renewable ethanol as a reagent and a modular catalytic process.

Industrial Applications of Gold Catalysis.

Gold catalysis has recently found its first large-scale applications in the chemical industry. This Minireview provides a critical analysis of the success factors and of the main obstacles that had to be overcome on the long way from the discovery to the commercialization of gold catalysts. The insights should be useful to researchers in both academia and industry working on the development of tomorrow's gold catalysts to tackle significant environmental and economic issues.

Update on selective oxidation using gold.

This critical review aims to update the recent development in the selective oxidation of organic compounds by gold catalysis, highlighting the progress in the last three years. Following the impressive developments in the last decades, several protocols for catalytic oxidation are today available, which are based on the extraordinary properties of gold in terms of catalytic activity, selectivity, reusability and resistance to poisons. Beside many other applications, gold can be recommended for green processes dedicated to fine chemicals, pharmaceuticals and the food industry owing to its recognized bio-compatibility. The collected literature is focused on experiments concerning the oxidation of different chemical groups and could be of interest, in the wide area of organic chemistry, for improving previous processes or for exploring new catalytic pathways (174 references).

A Green Lipophilization Reaction of a Natural Antioxidant.

A natural antioxidant, widely spread in plants, chlorogenic acid (CGA), can be lipophilized through a heterogeneous, non-enzymatic, catalytic process. Thus, sulfonic resins under no solvent conditions allow to obtain a series of esters in up to 93% yield through reaction of CGA with fatty alcohols of different chain length. The reaction takes place in one single step under mild conditions with conversions up to 96% and selectivity up to 99%. Product recovery in high purity was very easy and the esters obtained were fully characterized with spectroscopic techniques and through the DPPH test to verify the preservation of antioxidant activity. According to this test, all of them showed increased activity with respect to the parent acid and anyway higher than butylated hydroxyanisole. An in-silico method also suggested their very low toxicity. The increased lipophilicity of the esters allows their formulation in cosmetic and nutraceutic lipid-based products.

Ternary Polyaniline@Bi2O3-BiOCl Nanocomposites as Innovative Highly Active Photocatalysts for the Removal of the Dye under Solar Light Irradiation.

Ternary PANI@Bi2O3-BiOCl nanocomposites were successfully synthesized during the oxidative polymerization of aniline monomer in the presence of Bi2O3. PANI@Bi2O3-BiOCl nanocomposites were characterized by several analytical techniques, including X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), N2 physisorption, UV-Vis Diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). The effective PANI-semiconductor interaction promotes the fast separation and transfer of photogenerated electrons and holes, enhancing the photocatalytic efficiency of the materials towards methylene blue (MB) degradation under solar light irradiation. The best results were obtained by 0.5%PANI@Bi2O3-BiOCl, leading to 80% MB degradation in 2 h, four times higher than pristine Bi2O3-BiOCl. Moreover, 0.5%PANI@Bi2O3-BiOCl maintained stable photocatalytic performances for four cycles without significant activity loss. Various scavengers (isopropyl alcohol, formic acid, and benzoquinone) were used to identify the active species by trapping holes and radicals generated during the photocatalytic degradation process. Finally, a probable photocatalytic mechanism of PANI@Bi2O3-BiOCl photocatalyst was suggested.

Incidence of Potentially Toxic Elements and Perfluoroalkyl Substances Present in Canned Anchovies and Their Impact on Food Safety.

Fish plays a key role in a healthy and balanced Italian diet, but it is also subject to the bioaccumulation of different contaminants depending on the geographical or anthropogenic context from which it is derived. In recent years, the European Food Safety Authority (EFSA) has been focusing its attention on consumer toxicological risk, considering emerging contaminants such as perfluoroalkyl substances (PFASs) and potentially toxic elements (PTEs). Regarding fish, anchovies are among the five small pelagic main commercial species in the European Union and the top five fresh species consumed by households in Italy. Considering the lack of data on PFASs and PTEs in this species, our aim was to investigate the mentioned contaminants in salted and canned anchovies collected over 10 months from different fishing areas, even those far apart, to verify possible variations in bioaccumulation and to consider the risk for the consumer. According to our results, the assessed risk was very reassuring also for large consumers. The only concern, related to Ni acute toxicity, also dependent on the different consumers' sensitivity, was related to only one sample.

Efficient Day-and-Night NO2 Abatement by Polyaniline/TiO2 Nanocomposites.

Finding innovative and highly performing approaches for NOx degradation represents a key challenge to enhance the air quality of our environment. In this study, the high efficiency of PANI/TiO2 nanostructures in the NO2 abatement both in the dark and under light irradiation is demonstrated for the first time. Heterostructures were synthesized by a "green" method and their composition, structure, morphology and oxidation state were investigated by a combination of characterization techniques. The results show that the unique PANI structure promotes two mechanisms for the NO2 abatement in the dark (adsorption on the polymeric chains and chemical reduction to NO), whereas the photocatalytic behavior prevails under light irradiation, leading to the complete NOx degradation. The best-performing materials were subjected to recycling tests, thereby showing high stability without any significant activity loss. Overall, the presented material can represent an innovative and efficient night-and-day solution for NOx abatement.

Herbal concoction Unveiled: A computational analysis of phytochemicals' pharmacokinetic and toxicological profiles using novel approach methodologies (NAMs).

Herbal medications have an extensive history of use in treating various diseases, attributed to their perceived efficacy and safety. Traditional medicine practitioners and contemporary healthcare providers have shown particular interest in herbal syrups, especially for respiratory illnesses associated with the SARS-CoV-2 virus. However, the current understanding of the pharmacokinetic and toxicological properties of phytochemicals in these herbal mixtures is limited. This study presents a comprehensive computational analysis utilizing novel approach methodologies (NAMs) to investigate the pharmacokinetic and toxicological profiles of phytochemicals in herbal syrup, leveraging in-silico techniques and prediction tools such as PubChem, SwissADME, and Molsoft's database. Although molecular dynamics, docking, and broader system-wide analyses were not considered, future studies hold potential for further investigation in these areas. By combining drug-likeness with molecular simulation, researchers identify diverse phytochemicals suitable for complex medication development examining their pharmacokinetic-toxicological profiles in phytopharmaceutical syrup. The study focuses on herbal solutions for respiratory infections, with the goal of adding to the pool of all-natural treatments for such ailments. This research has the potential to revolutionize environmental and alternative medicine by leveraging in-silico models and innovative analytical techniques to identify novel phytochemicals with enhanced therapeutic benefits and explore network-based and systems biology approaches for a deeper understanding of their interactions with biological systems. Overall, our study offers valuable insights into the computational analysis of the pharmacokinetic and toxicological profiles of herbal concoction. This paves the way for advancements in environmental and alternative medicine. However, we acknowledge the need for future studies to address the aforementioned topics that were not adequately covered in this research.

Advances in Polyaniline for Biomedical Applications.

Conducting polymers are an outstanding class of materials characterized by electroconductive properties that make them good candidates for applications in several sectors. Among them, polyaniline (PANI) is unique for its extraordinary ability to conduct electricity, biocompatibility, and low toxicity. In spite of its surprising features, to date, PANI has not found application in practical uses due to its low solubility and processability. In order to overcome these limitations, different approaches have been developed, such as polymer grafting processes, PANI-based composites, and blends preparation. The present review describes the most recent advances on PANI applications in biomedical fields, such as antioxidant, antimicrobial and antivirus activity, drug delivery, cancer therapy, etc. In this article, synthetic procedures are also reported which are crucial for the realization of more innovative materials in the future.

pH-Driven Selective Adsorption of Multi-Dyes Solutions by Loofah Sponge and Polyaniline-Modified Loofah Sponge.

In the last decades, sorbent materials characterized by low selectivity have been developed for the removal of pollutants (in particular dyes) from wastewater. However, following the circular economy perspective, the possibility to selectively adsorb and desorb dyes molecules today represents an unavoidable challenge deserving to be faced. Herein, we propose a sequential treatment based on the use of PANI-modified loofah (P-LS) and loofah sponge (LS) to selectively adsorb cationic (rhodamine, RHB, and methylene blue, MB) and anionic (methyl orange, MO) dyes mixed in aqueous solution by tuning the adsorption pH (100% MO removal by P-LS and 100% and 70% abatement of MB and RHB, respectively, by LS). The system maintained high sorption activity for five consecutive cycles. A simple and effective regeneration procedure for the spent adsorbents permits the recovery of the initial sorption capability of the materials (81% for MO, ca. 85% for both RHB and MB, respectively) and, at the same time, the selective release of most of the adsorbed cationic dyes (50% of the adsorbed MB and 50% of the adsorbed RHB), although the procedure failed regarding the release of the anionic component. This approach paved the way to overcome the traditional procedure based on an indiscriminate removal/degradation of pollutants, making the industrial wastewater a potential source of useful chemicals.

Doped-polyaniline based sorbents for the simultaneous removal of heavy metals and dyes from water: Unravelling the role of synthesis method and doping agent.

Recently, the engineering of alternative adsorbents with better functional and sorbing ability towards the purification of wastewaters has received much attention from the scientific community. Currently polymers, in particular, are regarded as attractive soft materials in the field of environmental remediation due to their several unique properties. In this regard, the synthesis method is key point to fabricate polymer-based adsorbent with targeted characteristics. In the present work, four polyaniline (PANIs) samples were synthesized by two alternative chemical approaches, a traditional one and an eco-friendly one, and two different dopants were used, HCl and H2SO4, respectively. All PANIs were characterized for their thermal, optical, morphological, and structural properties and their capability to remove simultaneously dyes and heavy metals from water have been investigated. It was deduced that the sorption ability is dependent on the as-synthesized PANI using different procedures and dopants. All the PANIs from traditional method showed high levels of pollutants removal (from 89 to 97%). Even though the materials obtained from the green way are overall less active, H2SO4-doped corresponding polymer showed high sorption capability (75-97%). Finally, the most performing PANIs were selected for recycling tests exhibiting high sorption efficiency retention up to four runs without any regeneration treatment. Most important, the cycling tests were stopped well before the sample sorption limit could be reached.

A review of advances in multifunctional XTiO3 perovskite-type oxides as piezo-photocatalysts for environmental remediation and energy production.

Over more than three decades, the field of engineering of photocatalytic materials with unique properties and enhanced performance has received a huge attention. In this regard, different classes of materials were fabricated and used for different photocatalytic applications. Among these materials, recently multifunctional XTiO3 perovskites have drawn outstanding interest towards environmental remediation and energy conversion thanks to their unique structural, optical, physiochemical, electrical and thermal characteristics. XTiO3 perovskites are able to initiate different surface catalytic reactions. Under ultrasonic vibration or heating, XTiO3 perovskites can induce piezo-catalytic reactions due to the titling of their conduction and valence bands, resulting in the formation of separated charge carriers in the medium. In addition, under light irradiation, XTiO3 perovskites are considered as a new class of photocatalysts for environmental and energy related applications. Herein, we addressed the recent advances on variously synthesized, doped and formulated XTiO3 perovskite-type oxides showing piezo- and/or photocatalytic exploitation in environmental remediation and energy conversion. The control of structural crystallite size and phase, conductivity, morphology, oxygen vacancy control, doping agents and ratio has a significant role on the photocatalytic and piezocatalytic activities. The different piezo or/and photocatalytic processes mechanistic pathways towards varying applications were discussed. The current challenges facing these materials and future trends were addressed at the end of the review.

q value and parent energy optimization using a low-voltage ionization approach increases resolution in linear ion trap mass spectrometry.

In this work, the isolation step in the linear ion trap was performed using different "q values" conditions at a low collision-induced dissociation (CID) energy leading to the parent ion resolution improvements, reasonably due to better ion energy distribution. According to the results, we obtained a greater resolution and mass accuracy operating in both traditional electrospray and low voltage ionization near the q value = 0.778 and with a CID energy of 10%. This effect was evaluated with low-molecular-mass compounds (skatole and arginine). The proposed optimization yielded a superior instrument performance without adding technological complexity to mass spectrometry analyses.