A novel approach for adsorption of organic dyes from aqueous solutions using a sodium alginate/titanium dioxide nanowire doped with zirconium cryogel beads.

The presence of organic dyes in wastewater raises significant environmental and human health concerns, owing to their high toxicity. In light of this, a novel adsorbent material with porous cryogel architecture was developed and employed for the effective removal of organic dyes from an aqueous solution. Initially, a titanium dioxide nanowire doped with zirconium HZTO was synthesized by the hydrothermal process. Subsequently, the beads (SA/HZTO) of sodium alginate and HZTO were successfully prepared through a cross-linking process, employing Ca2+ ions as the crosslinking agent. Structural analysis of SA/HZTO beads was performed using FTIR, SEM, and EDX techniques. We systematically examined the impact of different conditions, including the initial dye concentration, pH, contact time, and adsorbent dosage, on the adsorption process. Batch experiments, both in signal and binary systems, were conducted to rigorously assess the dye adsorption capabilities. Kinetic modeling revealed that the adsorption process adhered to the pseudo-second-order kinetic model. Remarkably, the prepared beads exhibited impressive adsorption capacities of 26 and 29 mg/g toward methylene blue (MB) and safranin (SF), respectively. SA/HZTO beads have demonstrated excellent adsorption properties, offering a promising avenue for the development of low-cost, efficient, and reusable adsorbent to remove dyes from wastewater.

Design, synthesis, and molecular modeling studies of novel 2-quinolone-1,2,3-triazole-α-aminophosphonates hybrids as dual antiviral and antibacterial agents.

With the aim to identify new antiviral agents with antibacterial properties, a series of 2-quinolone-1,2,3-triazole derivatives bearing α-aminophosphonates was synthesized and characterized by 1H NMR, 13C NMR, 31P NMR, single crystal XRD and HRMS analyses. These compounds were examined against five RNA viruses (YFV, ZIKV, CHIKV, EV71 and HRV) from three distinct families (Picornaviridae, Togaviridae and Flaviviridae) and four bacterial strains (S. aureus, E. feacalis, E. coli and P. aeruginosa). The α-aminophosphonates 4f, 4i, 4j, 4k, 4p and 4q recorded low IC50 values of 6.8-10.91 µM, along with elevated selectivity indices ranging from 2 to more than 3, particularly against YFV, CHIKV and HRV-B14. Besides, the synthesized compounds were generally more sensitive toward Gram-positive bacteria, with the majority of them displaying significant potency against E. feacalis. Specifically, an excellent anti-enterococcus activity was obtained by compound 4q with MIC and MBC values of 0.03 µmol/mL, which were 8.7 and 10 times greater than those of the reference drugs ampicillin and rifampicin, respectively. Also, compounds 4f, 4p and 4q showed potent anti-staphylococcal activity with MIC values varying between 0.11 and 0.13 µmol/mL, compared to 0.27 µmol/mL for ampicillin. The results from DFT and molecular docking simulations were in agreement with the biological assays, proving the binding capability of hybrids 4f, 4i, 4j, 4k, 4p and 4q with viral and bacterial target enzymes through hydrogen bonds and other non-covalent interactions. The in silico ADME/Tox prediction revealed that these molecules possess moderate to good drug-likeness and pharmacokinetic properties, with a minimal chance of causing liver toxicity or carcinogenic effects.

Cellulose Acetate-Supported Copper as an Efficient Sustainable Heterogenous Catalyst for Azide-Alkyne Cycloaddition Click Reactions in Water.

A new sustainable heterogeneous catalyst for copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC) was investigated. The preparation of the sustainable catalyst was carried out through the complexation reaction between the polysaccharide cellulose acetate backbone (CA) and copper(II) ions. The resulting complex [Cu(II)-CA] was fully characterized by using different spectroscopic methods such as Fourier-transform infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray (EDX), Ultraviolet-visible (UV-vis), and Inductively Coupled Plasma (ICP) analyses. The Cu(II)-CA complex exhibits high activity in the CuAAC reaction for substituted alkynes and organic azides, leading to a selective synthesis of the corresponding 1,4-isomer 1,2,3-triazoles in water as a solvent and working at room temperature. It is worth noting that this catalyst has several advantages from the sustainable chemistry point of view including no use of additives, biopolymer support, reactions carried out in water at room temperature, and easy recovery of the catalyst. These characteristics make it a potential candidate not only for the CuAAC reaction but also for other catalytic organic reactions.

Mechanistic Insights into the Selective Synthesis of 4H-Pyran Derivatives On-Water Using Naturally Occurring Alginate from Sargassum muticum: Experimental and DFT Study.

The naturally occurring sodium alginate (SA) biopolymer from the Sargassum muticum (Yendo) Fensholt was employed as a green organocatalyst for the synthesis of 4H-pyran derivatives. The naturally extracted macromolecule was fully characterized using different analyses, including nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and Energy Dispersive X-ray Analysis (EDX). The catalytic activity of SA was investigated in the one-pot reaction between aldehydes, malononitrile, and 1,3-dicarbonyl compounds in water at room temperature, and the corresponding 2-amino-3-cyano-4H-pyran derivatives were obtained with good to excellent yields. This organocatalyst was easily separated from the reaction mixture and reused for at least two consecutive cycles without a significant loss of its catalytic activity or selectivity. From the mechanistic point of view, density functional theory (DFT) and NCI analyses were performed for the first time to explain the regioselectivity outcomes for the synthesis of 2-amino-3-cyano-4H-pyran derivatives using SA as a green organocatalyst.

The Effect of Chitosan on Plant Physiology, Wound Response, and Fruit Quality of Tomato.

In agriculture, chitosan has become popular as a metabolic enhancer; however, no deep information has been obtained yet regarding its mechanisms on vegetative tissues. This work was conducted to test the impact of chitosan applied at different plant growth stages on plant development, physiology, and response to wounding as well as fruit shape and composition. Five concentrations of chitosan were tested on tomato. The most effective chitosan doses that increased leaf number, leaf area, plant biomass, and stomatal conductance were 0.75 and 1 mg mL-1. Chitosan (1 mg mL-1) applied as foliar spray increased the levels of jasmonoyl-isoleucine and abscisic acid in wounded roots. The application of this dose at vegetative and flowering stages increased chlorophyll fluorescence (Fv/Fm) values, whereas application at the fruit maturation stage reduced the Fv/Fm values. This decline was positively correlated with fruit shape and negatively correlated with the pH and the content of soluble sugars, lycopene, total flavonoids, and nitrogen in fruits. Moreover, the levels of primary metabolites derived from glycolysis, such as inositol phosphate, lactic acid, and ascorbic acid, increased in response to treatment of plants with 1 mg mL-1- chitosan. Thus, chitosan application affects various plant processes by influencing stomata aperture, cell division and expansion, fruit maturation, mineral assimilation, and defense responses.

Box-Behnken Design: Wet Process Optimization for Saponins Removal From Chenopodium quinoa Seeds and the Study of Its Effect on Nutritional Properties.

The pseudocereal grain, Quinoa (Chenopodium quinoa Willd.), has a great nutritional value due to its high contents of proteins, fiber, minerals, and vitamins. However, saponins naturally present outside the grains represent an obstacle to their consumption as human food. Before consumption, the grains are subjected to various treatments, which alter their nutritional value. In an attempt to eliminate the maximum of saponins using the wet process, while minimizing the washing conditions and preserving the nutritional quality, we explored the effects of several parameters, including volume of water, treatment time, soaking time, number of washing, and water temperature, followed by an optimization process using Box-Behnken Design, and finally, the impact of this process on the physicochemical and techno-functional properties of six quinoa genotypes seeds was evaluated. As a result, the variation of the treatment time, volume, and temperature of the water positively affected the saponins leaching. According to the quadratic model, the maximum percentages of eliminated saponins (96.53%-96.77%) were found at a temperature of 50°C, treatment times from 60 to 69 min, and water volumes from 6.99 to 7.50 mL per gram of seeds. The optimized method did not affect the proteins and microelements content (Zn, Mn, B, Mo), while a slight decrease of macro-elements (K, P, Ca, S, Mg) was noted in the level of some genotypes. On the other hand, a significant improvement of the techno-functional properties such as water and oil holding capacity was noted, with a sharp drop-in emulsifying activity in all genotypes without affecting the standard values of pH (6.4-6.8) and moisture content (10%-11%) of the seeds. Hence, the optimized method showed to be a more potential method for saponins removal than the currently used dry method.

Pesticides in fruits and vegetables from the Souss Massa region, Morocco.

This survey reports the monitoring of multi-pesticide residues of some fruits and vegetables sold in the local markets, sampled in 2018-2019, in the Souss Massa region in Morocco. A QuEChERS-LC-MS/MS method for 202 pesticides, belonging to different classes (carbamates, organophosphorus and organonitrogen pesticides) was applied and 51 samples were randomly bought from the local market, belonging to different products (tomato, cucumber, coriander, apricot, parsley, potato, zucchini, green bean, lettuce, strawberry and orange) and analysed for pesticide residues, which were detected in 69% of the samples, below the maximum residue limits (MRLs) for some pesticides which represent 14% of the targeted compounds. The most frequently detected compounds were acetamiprid, acibenzolar-s-methyl, abamectin, azoxystrobin, bifenazate, bitertanol, bromuconazole, butoxycarboxim, cyromazine, difenoconazole, epoxiconazole, fenbuconazole, fluometuron, linuron, metaflumizone, metconazole, metribuzin, myclobutanil, pirimicarb, pyraclostrobin, propamocarb, rotenone, trichlorfon, tebuconazole, tetraconazole, thiamethoxam and thiophanate-methyl. The obtained results provide a value to the situation of pesticide residues in Morocco.

A highly efficient chemical approach to producing green phosphorylated cellulosic macromolecules.

The introduction of phosphate groups into cellulosic fibers allows for the tuning of their fire resistance, chelating and metal-adhesion properties, enabling the development of flame-retardant adhesive and adsorbent materials. Toward that end, the major challenge is developing a novel efficient and environmentally friendly phosphorylation route that offers an alternative to existing methods, which can achieve the targeted properties. For this purpose, cellulosic fibers were chemically modified herein using solid-state phosphorylation with phosphoric acid and urea without causing substantial damage to the fibers. The morphological, physicochemical, structural and thermal characterisations were examined using FQA, SEM, EDX, FTIR, 13C/31P NMR, conductometric titration, zeta potential measurement and thermogravimetric analysis. All the characterisations converge towards a crosslinked polyanion structure, with about 20 wt% grafted phosphates, a nitrogen content of about 5 wt% and a very high charge density of 6608 mmol kg-1. Phosphate groups are linked to cellulose through a P-O-C bond in the form of orthophosphate and pyrophosphates. Furthermore, thermal properties of the phosphorylated cellulosic fibers were investigated and a new degradation mechanism was proposed.

An Insight into Saponins from Quinoa (Chenopodium quinoa Willd): A Review.

Saponins are an important group found in Chenopodium quinoa. They represent an obstacle for the use of quinoa as food for humans and animal feeds because of their bitter taste and toxic effects, which necessitates their elimination. Several saponins elimination methods have been examined to leach the saponins from the quinoa seeds; the wet technique remains the most used at both laboratory and industrial levels. Dry methods (heat treatment, extrusion, roasting, or mechanical abrasion) and genetic methods have also been evaluated. The extraction of quinoa saponins can be carried out by several methods; conventional technologies such as maceration and Soxhlet are the most utilized methods. However, recent research has focused on technologies to improve the efficiency of extraction. At least 40 saponin structures from quinoa have been isolated in the past 30 years, the derived molecular entities essentially being phytolaccagenic, oleanolic and serjanic acids, hederagenin, 3ß,23,30 trihydroxy olean-12-en-28-oic acid, 3ß-hydroxy-27-oxo-olean-12en-28-oic acid, and 3ß,23,30 trihydroxy olean-12-en-28-oic acid. These metabolites exhibit a wide range of biological activities, such as molluscicidal, antifungal, anti-inflammatory, hemolytic, and cytotoxic properties.

Surface modification of α-chitin using an acidic treatment followed by ultrasonication: Measurements of their sorption properties.

The biopolymer α-chitin is a promising raw source that can be used as a low-cost material for environmental applications. Nevertheless, its low surface properties and high crystallinity limit its use. Recent developments include surface modification as one of the most promising strategies for the application of α-chitin. To this end, we used an acidic treatment, followed by ultrasonication, to modify the α-chitin surface and improve its sorption characteristics to achieve the above goal. Structural analysis and measurement of the physicochemical properties (chemical structure and thermal degradation) of α-chitin, before and after surface modification, indicated no significant changes. However, specific surface area, morphology, surface charge, crystallinity and study of the sorption of methylene blue (MB) from aqueous solution demonstrated surface modification. It was established that the SBET of modified α-chitin increased to 110.7 m2/g and the crystallinity index decreased to 48%. Interestingly, the modified α-chitin could easily adsorb organic dye from an aqueous solution. The experimental adsorption capacity of the resulting α-chitin after surface modification reached the value of about 95 mg/g.

Foliar Application of Chitosan Increases Tomato Growth and Influences Mycorrhization and Expression of Endochitinase-Encoding Genes.

Nowadays, applying bio-organic fertilizer (e.g., chitosan, Ch) or integrating beneficial microorganisms (e.g., arbuscular mycorrhizal fungi, AMF) are among the successful strategies to promote plant growth. Here, the effect of two application modes of Ch (foliar spray or root treatment) and Ch-derived nanoparticles (NPs) on tomato plants colonized with the AMF Rhizophagus irregularis were analyzed, thereby focusing on plant biomass, flowering and mycorrhization. An increase of shoot biomass and flower number was observed in arbuscular mycorrhizal (AM) plants sprayed with Ch. The interaction with AMF, however, was reduced as shown by decreased mycorrhization rates and AM-specific gene expression. To get insights into Ch effect on mycorrhization, levels of sugars, jasmonates, abscisic acid, and the expression of two chitinase-encoding genes were determined in mycorrhizal roots. Ch had no effect on sugar and phytohormone levels, but the reduced mycorrhization was correlated with down- and upregulated expression of Chi3 and Chi9, respectively. In contrast, application of NPs to leaves and Ch applied to the soil did not show any effect, neither on mycorrhization rate nor on growth of mycorrhizal plants. Concluding, Ch application to leaves enhanced plant growth and flowering and reduced interaction with AMF, whereas root treatment did not affect these parameters.

Cu(ii)-alginate-based superporous hydrogel catalyst for click chemistry azide-alkyne cycloaddition type reactions in water.

A novel sustainable hydrogel catalyst based on the reaction of sodium alginate naturally extracted from brown algae Laminaria digitata residue with copper(ii) was prepared as spherical beads, namely Cu(ii)-alginate hydrogel (Cu(ii)-AHG). The morphology and structural characteristics of these beads were elucidated by different techniques such as SEM, EDX, BET, FTIR and TGA analysis. Cu(ii)-AHG and its dried form, namely Cu(ii)-alginate (Cu(ii)-AD), are relatively uniform with an average pore ranging from 200 nm to more than 20 µm. These superporous structure beads were employed for the copper catalyzed [3 + 2] cycloaddition reaction of aryl azides and terminal aryl alkynes (CuAAC) via click chemistry at low catalyst loading, using water as a solvent at room temperature and pressure. The catalytic active copper(i) species was generated by the reduction of copper(ii) by terminal alkyne via the oxidative alkyne homocoupling reaction. The prepared catalysts were found to be efficient (85-92%) and regioselective by affording only 1,4-disubstituted-1,2,3-triazoles. They were also recoverable and reused in their dried form for at least four consecutive times without a clear loss of efficiency. A mechanistic study was performed through density functional theory (DFT) calculations in order to explain the regioselectivity outcome of Cu(ii)-alginate in CuAAC reactions. The analysis of the local electrophilicity (ω k) at the electrophilic reagent and the local nucleophilicity (N k) at the nucleophilic confirms the polar character of CuAAC. This catalyst has the main advantage of being sustainably ligand-free and recyclable.

Uptake of Pb(II) onto nanochitosan/sodium alginate hybrid beads: Mechanism and kinetics study.

Nanochitosan/sodium alginate (NCS/SA) beads were prepared using nanochitosan and alginate as a high-performance absorbent for Pb(II) removal from aqueous solution. The morphology, structure, thermal stability, surface area, and elements present in the NCS/SA beads before and after adsorption were characterized using instrumental techniques like SEM, FTIR, TGA, BET, and EDX analysis, respectively. Various adsorption parameters were studied. The results indicated that the equilibrium adsorption data were fitted to Langmuir isotherms and the maximum Langmuir monolayer capacity of Pb(II) was 178.57 mg/g at 45°C. The adsorption process was in good agreement with pseudo-first-order kinetic model. Mechanism studies showed that electrostatic interaction and ion exchange were the major mechanisms for lead (II) removal by the NCS/SA beads. The results of this study indicate that NCS/SA beads could be used as an effective adsorbent for the elimination of lead (II) present in aqueous solution. PRACTITIONER POINTS: Nanochitosan/sodium alginate beads were synthesized using Ca2+ as a crosslinking agent. NCS/SA beads were used to remove Pb(II) for the first time and working parameters were optimized. Adsorption monolayer capacity of NCS/SA adsorbent towards Pb (II) was found to be 178.57 mg/g.

Bioinspired Synthesis of Pygmaeocins and Related Rearranged Abietane Diterpenes: Synthesis of Viridoquinone.

A bioinspired synthesis of rearranged abietane diterpenes, related to pygmaeocins, is described. In this process, the key step is the 1,2-migration of the C-20 angular methyl to the C-5 position of the abietane skeleton, which occurs when a C6-C7 unsaturated dehydroabietane derivative is treated with SeO2 in dioxane under reflux (19 examples for this rearrangement are described). Utilizing this reaction, an enantiospecific synthesis of pygmaeocin C and the first synthesis of viridoquinone, starting from the abietane phenol ferruginol, are reported. A tentative mechanism for this reaction and a possible biosynthetic pathway for this family of metabolites are postulated.

Dihydropyrimidinone/1,2,3-triazole hybrid molecules: Synthesis and anti-varicella-zoster virus (VZV) evaluation.

By combining the structural features of dihydropyrimidinone and 1,2,3-triazole heterocycles, novel hybrid compounds were synthesized using a simple and convenient method. A series of novel mono and bis 1,2,3-triazole was synthesized via copper-catalyzed Huisgen azide-alkyne cycloadditions (CuAAC) under microwave irradiation. The newly synthesized compounds were evaluated for their antiviral activity against varicella-zoster virus (VZV). Compounds 6aa, 7ab, 6ba and 6da showed valuable antiviral activities, with EC50 values ranging from 3.6 to 11.3 µM against TK+ and TK- VZV and without measurable cell-growth inhibition.

Design, Synthesis, and Antiviral Activity of Novel Ribonucleosides of 1,2,3-Triazolylbenzyl-aminophosphonates.

A novel series of ribonucleosides of 1,2,3-triazolylbenzyl-aminophosphonates was synthesized through the Kabachnik-Fields reaction using I2 as catalyst followed by copper-catalyzed cycloaddition of the azide-alkyne reaction (CuAAC). All structures of the newly prepared compounds were characterized by (1) H NMR, (13) C NMR, and HRMS spectra. The structures of 2e, 2f, 3d, and 3g were further confirmed by X-ray diffraction analysis. These compounds were tested against various strains of DNA and RNA viruses; compounds 4b and 4c showed a modest inhibitory activity against respiratory syncytial virus (RSV) and compound 4h displayed modest inhibitory activity against Coxsackie virus B4.

Crystal structure of 2-benzamido-N-(2,2-di-eth-oxy-eth-yl)benzamide.

In the title compound, C20H24N2O4, both peptide bonds adopt a trans configuration with respect to the -N-H and -C=O groups. The dihedral angle between the aromatic rings is 53.58 (4)°. The mol-ecular conformation is stabilized by an intra-molecular N-H⋯O hydrogen bond. The crystal packing is characterized by zigzag chains of N-H⋯O hydrogen-bonded mol-ecules running along the b-axis direction.

Benzimidazole-1,2,3-triazole hybrid molecules: synthesis and evaluation for antibacterial/antifungal activity.

A novel series of hybrid molecules 4a-i and 5a-i were prepared by condensation of 4-(trimethylsilylethynyl)benzaldehyde 1 with substituted o-phenylenediamines. These in turn were reacted with 2-(azidomethoxy)ethyl acetate in a Cu alkyne-azide cycloaddition (CuAAC) to generate the 1,2,3-triazole pharmacophore under microwave assistance. The newly synthesized compounds were examined for their in vitro antimicrobial activities against Gram-positive and Gram-negative bacteria and the phytopathogenic fungi Verticillium dahliae and Fusarium oxysporum f. sp. albedinis. 2-((4-(4-(5-Trifluoromethyl benzimidazol-2-yl)phenyl)-1,2,3-triazol-1-yl)methoxy)ethanol 5e showed a moderate inhibition of 30% in the Foa sporulation test.

Synthesis of new 1,2,3-triazol-4-yl-quinazoline nucleoside and acyclonucleoside analogues.

In this study, we describe the synthesis of 1,4-disustituted-1,2,3-triazolo-quinazoline ribonucleosides or acyclonucleosides by means of 1,3-dipolar cycloaddition between various O or N-alkylated propargyl-quinazoline and 1'-azido-2',3',5'-tri-O-benzoylribose or activated alkylating agents under microwave conditions. None of the compounds selected showed significant anti-HCV activity in vitro.

Four related diethyl [(arylamino)(4-ethynylphenyl)methyl]phosphonates.

Crystal structures are reported for four related diethyl [(arylamino)(4-ethynylphenyl)lmethyl]phosphonate derivatives, namely diethyl [(4-bromoanilino)(4-ethynylphenyl)methyl]phosphonate, C19H21BrNO3P, (I), diethyl ((4-chloro-2-methylanilino){4-[2-(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate, C23H31ClNO3PSi, (II), diethyl ((4-fluoroanilino){4-[2-(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate, C22H29FNO3PSi, (III), and diethyl [(4-ethynylphenyl)(naphthalen-2-ylamino)methyl]phosphonate, C23H24NO3P, (IV). The conformation of the anilinobenzyl group is very similar in all four compounds. The P-C bond has an approximately staggered conformation, with the aniline and ethynylphenyl groups in gauche positions with respect to the P=O double bond. The two six-membered rings are almost perpendicular. The sums of the valence angles about the N atoms vary from 344 (2) to 351 (2)°. In the crystal structures, molecules of (I), (III) and (IV) are arranged as centrosymmetric or pseudocentrosymmetric dimers connected by two N-H···O=P hydrogen bonds. The molecules of (II) are arranged as centrosymmetric dimers connected by C(methyl)-H···O=P hydrogen bonds. The N-H bond of (II) is not involved in hydrogen bonding.