Modulating temperature for Cu2ZnSnS4 (CZTS) synthesis via hot injection method and studying the photocatalytic efficiencies for the degradation of Rhodamine 6G and Methylene blue pollutants.

Cu2ZnSnS4 (CZTS) was synthesized following hot injection method and the process was optimized by varying temperature conditions. Four samples at different temperatures viz., 200, 250, 300 and 350°C were prepared and analyzed using different characterization techniques. Based on the correlation between XRD, Raman and XPS, we conclude that the formation of ZnS and SnS2 occurs at 3500C but at 2000C there is no breakdown of the complex as per XRD. According to Raman and XPS analysis, as the temperature rises, the bonds between the metals become weaker, which is visibly seen in Raman and XPS due to the minor peaks of copper sulfide. Scanning electron microscopic analysis confirmed nanometric particles which increase in size with temperature. The photocatalytic evaluation showed that CZTS synthesized at 2000C performed efficiently in the removal of the two colorants, methylene blue and Rhodamine 6G, achieving 92.80% and 90.65%, respectively. The photocatalytic degradation efficiencies decreased at higher temperatures due to bigger sized CZTS particles as confirmed by SEM results. Computational simulations confirm that CZTS has a highly negative energy -25,764 Ry, confirming its structural stability and higher covalent than ionic character.

Water Quality Assessment and Decolourisation of Contaminated Ex-Mining Lake Water Using Bioreactor Dye-Eating Fungus (BioDeF) System: A Real Case Study.

The environmental conditions of a lake are influenced by its type and various environmental forces such as water temperature, nutrients content, and longitude and latitude to which it is exposed. Due to population growth and development limits, former mining lakes are being converted to more lucrative land uses like those of recreational zones, agriculture, and livestock. The fungus Ganoderma lucidum has the potential to be utilised as a substitute or to perform synergistic bacteria-coupled functions in efficient contaminated lake water treatment. The purpose of this paper is to evaluate the water quality and water quality index (WQI) of an ex-mining lake named Main Lake in the Paya Indah Wetland, Selangor. Furthermore, the current work simulates the use of a Malaysian fungus in decolourising the contaminated ex-mining lake by the BioDeF system in a 300 mL jar inoculated with 10% (v/v) of pre-grown Ganoderma lucidum pellets for 48 h. According to the results, the lake water is low in pH (5.49 ± 0.1 on average), of a highly intense dark brownish colour (average reading of 874.67 ± 3.7 TCU), and high in iron (Fe) content (3.2422 ± 0.2533 mg/L). The water quality index of the lake was between 54.59 and 57.44, with an average value of 56.45; thus, the water was categorized as Class III, i.e., under-polluted water, according to the Malaysian Department of Environment Water Quality Index (DOE-WQI, DOE 2020). The batch bioreactor BioDeF system significantly reduced more than 90% of the water's colour. The utilization of Ganoderma lucidum as an adsorbent material offers a variety of advantages, as it is easily available and cultivated, and it is not toxic.

Synthesis and Biodegradation Test of a New Polyether Polyurethane Foam Produced from PEG 400, L-Lysine Ethyl Ester Diisocyanate (L-LDI) and Bis-hydroxymethyl Furan (BHMF).

In this paper we produced a bio-based polyether-polyurethane foam PU1 through the prepolymer method. The prepolymer was obtained by the reaction of PEG 400 with L-Lysine ethyl ester diisocyanate (L-LDI). The freshly prepared prepolymer was extended with 2,5-bis(hydroxymethyl)furan (BHMF) to produce the final polyurethane. The renewable chemical BHMF was produced through the chemical reduction of HMF by sodium borohydride. HMF was produced by a previously reported procedure from fructose using choline chloride and ytterbium triflate. To evaluate the degradation rate of the foam PU1, we tested the chemical stability by soaking it in a 10% sodium hydroxide solution. The weight loss was only 12% after 30 days. After that, we proved that enzymatic hydrolysis after 30 days using cholesterol esterase was more favoured than hydrolysis with NaOH, with a weight loss of 24%, probably due to the hydrophobic character of the PU1 and a better adhesion of the enzyme on the surface with respect to water. BHMF was proved to be of crucial importance for the enzymatic degradation assay at 37 °C in phosphate buffer solution, because it represents the breaking point inside the polyurethane chain. Soil burial degradation test was monitored for three months to evaluate whether the joint activity of sunlight, climate changes and microorganisms, including bacteria and fungi, could further increase the biodegradation. The unexpected weight loss after soil burial degradation test was 45% after three months. This paper highlights the potential of using sustainable resources to produce new biodegradable materials.

Highly Diastereoselective Multicomponent Synthesis of Spirocyclopropyl Oxindoles Enabled by Rare-Earth Metal Salts.

The synthesis of polysubstituted spirocyclopropyl oxindoles using a series of rare-earth metal (REM) salts is reported. REMs, in particular Sc(OTf)3, allowed access to the target compounds by a multicomponent reaction with high diastereoselectivity (≤94:6:0:0). Density functional theory calculations on the model reaction are consistent with the observed selectivity and revealed that the special coordinating capabilities and the oxophilicity of the metal are key factors in inducing the formation of one main diastereoisomer.

Bio-Based Polyurethane Foams for the Removal of Petroleum-Derived Pollutants: Sorption in Batch and in Continuous-Flow.

In this paper, we evaluated the potential of two synthesized bio-based polyurethane foams, PU1 and PU2, for the removal of diesel and gasoline from water mixtures. We started the investigation with the experiment in batch. The total sorption capacity S (g/g) for the diesel/water system was slightly higher with respect to gasoline/water, with a value of 62 g/g for PU1 and 65 g/g for PU2. We found that the sorption follows a pseudo second-order kinetic model for both the materials. The experimental data showed that the best isotherm models were obtained with Langmuir and Redlich-Peterson models. In addition, to provide an idea of the process scalability for future industrial applications, we tested the sorption capacity of the foams using a continuous-flow of the same oil/water mixtures and we obtained performances even better with respect to the batch test. The regeneration can be performed up to 50 times by centrifuge, without losing efficacy.

Novel Regioselective Synthesis of 1,3,4,5-Tetrasubstituted Pyrazoles and Biochemical Valuation on F1FO-ATPase and Mitochondrial Permeability Transition Pore Formation.

An efficient, eco-compatible, and very cheap method for the construction of fully substituted pyrazoles (Pzs) via eliminative nitrilimine-alkene 1,3-dipolar cycloaddition (ENAC) reaction was developed in excellent yield and high regioselectivity. Enaminones and nitrilimines generated in situ were selected as dipolarophiles and dipoles, respectively. A deep screening of the employed base, solvent, and temperature was carried out to optimize reaction conditions. Recycling tests of ionic liquid were performed, furnishing efficient performance until six cycles. Finally, a plausible mechanism of cycloaddition was proposed. Then, the effect of three different structures of Pzs was evaluated on the F1FO-ATPase activity and mitochondrial permeability transition pore (mPTP) opening. The Pz derivatives' titration curves of 6a, 6h, and 6o on the F1FO-ATPase showed a reduced activity of 86%, 35%, and 31%, respectively. Enzyme inhibition analysis depicted an uncompetitive mechanism with the typical formation of the tertiary complex enzyme-substrate-inhibitor (ESI). The dissociation constant of the ESI complex (Ki') in the presence of the 6a had a lower order of magnitude than other Pzs. The pyrazole core might set the specific mechanism of inhibition with the F1FO-ATPase, whereas specific functional groups of Pzs might modulate the binding affinity. The mPTP opening decreased in Pz-treated mitochondria and the Pzs' inhibitory effect on the mPTP was concentration-dependent with 6a and 6o. Indeed, the mPTP was more efficiently blocked with 0.1 mM 6a than with 1 mM 6a. On the contrary, 1 mM 6o had stronger desensitization of mPTP formation than 0.1 mM 6o. The F1FO-ATPase is a target of Pzs blocking mPTP formation.

A model for the adsorption process of water dissolved elements flowing into reactive porous media: Characterization and sizing of water mining/filtering systems.

This study presents a mathematical model describing the adsorption-desorption process of water dissolved elements onto reactive porous materials during filtering operations performed under dynamic flow conditions. The developed model is based on a reversible second order adsorption kinetic featuring the progressive reduction of the purifying capacity of the filtering material due to the gradual exhaustion of the active sites available for solute retention. It enables the simulation of the performances of water filtering systems through the use of parameters having a clear chemical-physical significance or it can be used for the estimation of these parameters to characterize the adsorption properties of the reactive material. Starting from the same adsorptive conceptual model used for the filtering system marked by ongoing flowing conditions, an adaptation for static systems was performed on the mathematical framework in order to process the same chemical physical parameters in both schemes. Adsorption laboratory tests were carried out to validate the developed model. Results show that the kinetic constants and adsorption capacities (a maximum of about 45 mg g-1 was obtained for the tested material) are highly comparable, both within the same experimental system, and between different experimental setup. This confirms the validity of the developed model which is able to perfectly fit the observed concentration data in all tested configurations.

Regioselective Synthesis and Molecular Docking Studies of 1,5-Disubstituted 1,2,3-Triazole Derivatives of Pyrimidine Nucleobases.

1,2,3-triazoles are versatile building blocks with growing interest in medicinal chemistry. For this reason, organic chemistry focuses on the development of new synthetic pathways to obtain 1,2,3-triazole derivatives, especially with pyridine moieties. In this work, a novel series of 1,5-disubstituted-1,2,3-triazoles functionalized with pyrimidine nucleobases were prepared via 1,3-dipolar cycloaddition reaction in a regioselective manner for the first time. The N1-propargyl nucleobases, used as an alkyne intermediate, were obtained in high yields (87-92%) with a new two-step procedure that selectively led to the monoalkylated compounds. Then, FeCl3 was employed as an efficient Lewis acid catalyst for 1,3-dipolar cycloaddition between different aryl and benzyl azides and the N1-propargyl nucleobases previously synthesized. This new protocol allows the synthesis of a series of new 1,2,3-triazole derivatives with good to excellent yields (82-92%). The ADME (Absorption, Distribution, Metabolism, and Excretion) analysis showed good pharmacokinetic properties and no violations of Lipinsky's rules, suggesting an appropriate drug likeness for these new compounds. Molecular docking simulations, conducted on different targets, revealed that two of these new hybrids could be potential ligands for viral and bacterial protein receptors such as human norovirus capsid protein, SARS-CoV-2 NSP13 helicase, and metallo-ß-lactamase.

New Technologies to Decontaminate Pollutants in Water: A Report about the State of the Art.

The growing increase in the world population was accompanied by a massive development of industrialization [...].

Biochar-Supported TiO2-Based Nanocomposites for the Photocatalytic Degradation of Sulfamethoxazole in Water-A Review.

Sulfamethoxazole (SMX) is a frequently used antibiotic for the treatment of urinary tract, respiratory, and intestinal infections and as a supplement in livestock or fishery farming to boost production. The release of SMX into the environment can lead to the development of antibiotic resistance among the microbial community, which can lead to frequent clinical infections. SMX removal from water is usually done through advanced treatment processes, such as adsorption, photocatalytic oxidation, and biodegradation. Among them, the advanced oxidation process using TiO2 and its composites is being widely used. TiO2 is a widely used photocatalyst; however, it has certain limitations, such as low visible light response and quick recombination of e-/h+ pairs. Integrating the biochar with TiO2 nanoparticles can overcome such limitations. The biochar-supported TiO2 composites showed a significant increase in the photocatalytic activities in the UV-visible range, which resulted in a substantial increase in the degradation of SMX in water. The present review has critically reviewed the methods of biochar TiO2 composite synthesis, the effect of biochar integration with the TiO2 on its physicochemical properties, and the chemical pathways through which the biochar/TiO2 composite degrades the SMX in water or aqueous solution. The degradation of SMX using photocatalysis can be considered a useful model, and the research studies presented in this review will allow extending this area of research on other types of similar pharmaceuticals or pollutants in general in the future.

Synthesis, Characterization and Mechanical Properties of Novel Bio-Based Polyurethane Foams Using Cellulose-Derived Polyol for Chain Extension and Cellulose Citrate as a Thickener Additive.

A novel series of bio-based polyurethane composite foams was prepared, employing a cellulose-derived polyol for chain extension and cellulose-citrate as a thickener additive. The utilized polyol was obtained from the reduction reaction of cellulose-derived bio-oil through the use of sodium borohydride and iodine. Primarily, we produced both rigid and flexible polyurethane foams through chain extension of the prepolymers. Secondly, we investigated the role of cellulose citrate as a polyurethane additive to improve the mechanical properties of the realized composite materials. The products were characterized by FT-IR spectroscopy and their morphologies were analysed by SEM. Mechanical tests were evaluated to open new perspectives towards different applications.

Efficient and Fast Removal of Oils from Water Surfaces via Highly Oleophilic Polyurethane Composites.

In this study we evaluated the oil adsorption capacity of an aliphatic polyurethane foam (PU 1) and two of its composites, produced through surface coating using microparticles of silica (PU-Si 2) and activated carbon (PU-ac 3). The oil adsorption capacity in diesel was improved up to 36% using the composite with silica and up to 50% using the composite with activated carbon with respect to the initial PU 1. Excellent performances were retained in gasoline and motor oil. The adsorption was complete after a few seconds. The process follows a monolayer adsorption fitted by the Langmuir isotherm, with a maximum adsorption capacity of 29.50 g/g of diesel for the composite with activated carbon (PU-ac 3). These materials were proved to be highly oleophilic for oil removal from fresh water and sea water samples. Regeneration and reuse can be repeated up to 50 times by centrifugation, without a significant loss in adsorption capacity.

Cellulose citrate: a convenient and reusable bio-adsorbent for effective removal of methylene blue dye from artificially contaminated water.

In the present work, we proved the efficacy of cellulose citrate to remove methylene blue (MB) from artificially contaminated water. MB is a widely used dye, but because of its chemical aromatic structure, it is significantly stable with quite slow biodegradation, causing consequent serious health problems for people and significant environmental pollution. Cellulose citrate, the bio-adsorbent proposed and studied by us to remediate water polluted by MB, is produced by a green, cheap and fast procedure that makes use of two abundant natural products, cellulose and citric acid. The average of two citrate groups for each glucose unit of cellulose chains allows this material to have many carboxylic groups available for interaction with the cationic dye. The characterization was carried out through FT-IR, SEM, specific surface area, pore structure parameters and zeta potential. The negative value of the zeta potential at neutral pH is consistent with the affinity of this material for the adsorption of cationic compounds like MB. The activity of the adsorbent at different times, temperatures, pH and concentrations was investigated. The process followed monolayer adsorption typical of the Langmuir model, with a maximum adsorption capacity of 96.2 mg g-1, while for the kinetic studies the process followed a pseudo-second order model. The highest levels of adsorption were reported using solutions of dye with concentrations under 100 mg L-1. The adsorbent can be regenerated several times without a significant loss in the adsorption capacity, and it is not strongly affected by temperature and pH, giving rise to a simple and eco-sustainable procedure for water remediation. Therefore, we conclude that cellulose citrate can be considered as a promising bio-adsorbent for the removal of MB and other cationic pollutants from the environment.

Totally green cellulose conversion into bio-oil and cellulose citrate using molten citric acid in an open system: synthesis, characterization and computational investigation of reaction mechanisms.

The simultaneous transformation of crystalline or amorphous cellulose into a furan-based bio-oil and cellulose citrate was realized avoiding the use of strong inorganic acids, drastic conditions, enzymatic treatments or microorganism fermentation. This innovative method is very eco-friendly and involves the use of molten citric acid under solvent free conditions at atmospheric pressure. An accurate discussion on chemical composition of the bio-oil enriched in bioprivileged molecules as well as structural and morphological characterization of cellulose citrate was reported. Moreover, mechanistic hypotheses were formulated on the basis of experimental findings and detailed DFT quantum-mechanical simulations were carried out to confirm, step by step, the proposed reaction paths.

Synthesis and preliminary evaluation of the anti-cancer activity on A549 lung cancer cells of a series of unsaturated disulfides.

We synthesized a series of small symmetrical unsaturated disulfides by a multi-step reaction starting from organic alcohols, and we performed a preliminary test to evaluate the effect of these compounds on the viability of A549 lung cancer cells. The garlic-derived natural compound diallyl disulfide, known for its anticancer activity, was used as the lead compound in this study. We synthesized five DADS analogues having different carbon chain lengths and different positions of the double bonds. Two analogues exhibited a promising antitumor activity in vitro, and the allylic double bond did not seem to be the main driving force.