Synthesis and Characterization of New Triazole-Bispidinone Scaffolds and Their Metal Complexes for Catalytic Applications.

Bispidines are a family of ligands that plays a pivotal role in various areas of coordination chemistry, with applications in medicinal chemistry, molecular catalysis, coordination polymers synthesis, and molecular magnetism. In the present work, triazole moieties were introduced using the CuAAC click-reaction, with the aim of expanding the number of coordination sites on the bispidine core. The 1,2,3-triazole rings were thus synthesized on propargyl-derived bispidines after reaction with different alkyl azides. The new class of triazole-bispidines was characterized, and their chelation capabilities were evaluated with different metals through NMR titration, ESI-MS spectrometry, and single-crystal X-ray diffraction (SC-XRD). Finally, the suitability of these molecules as metal ligands for the catalytic Henry reaction was demonstrated with copper and zinc.

Are natural deep eutectic solvents always a sustainable option? A bioassay-based study.

The traditional use of organic solvents in various branches of industry is being rethought as these compounds very often display high volatility, toxicity and lipophilicity (related to the ability to interact with biological membranes). More recently, developments in the field of Green Chemistry are focusing on the design of more sustainable and cost-effective solvent alternatives like Ionic Liquids (ILs), bio-based solvents and natural deep eutectic solvents (NADESs). The present study aimed at performing an ecotoxicological screening of 15 NADESs using an extensive set of marine and freshwater bioassays, based on different endpoints as the following: immobilization of the crustacean Daphnia magna, growth inhibition of Raphidocelis subcapitata and of Phaeodactylum tricornutum, larval development alterations on the serpulid Ficopomatus enigmaticus and bioluminescence inhibition of Aliivibrio fischeri. What emerged was a general absence of toxicity of all samples. However, both algal assays showed a certain degree of biostimulation, up to over 100% growth increase in respect to controls with 8 out of 15 compounds tested with Raphidocelis subcapitata. Despite NADESs-induced negligible toxicity effects to invertebrates, encouraging their labelling as "sustainable" solvents, the liability of their intentional or accidental release into aquatic systems may represent a serious risk in terms of ecosystem functioning impairments.

Deep Eutectic Solvents: Promising Co-solvents to Improve the Extraction Kinetics of CyMe4-BTBP.

In this communication, we report on the use of deep eutectic solvents (DESs) for processing nuclear waste, with a view to selectively recovering minor actinides (MA) from highly active raffinate solutions. DESs are an interesting new class of green and eco-sustainable solvents. Herein, a representative family of DES was tested as a co-solvent for MA/lanthanides partitioning based on Selective ActiNide EXtraction (SANEX)-like hydrometallurgical processes. The reference system exploits the CyMe4-BTBP lipophilic extractant for selective MA recovery, but the slow kinetics is the main limitation toward the industrial implementation. A selection of hydrophilic DESs has been proposed as a phase transfer catalyst and tested to improve the process performances. In this work, the radiochemical stability and the extraction behavior of these DESs have been ascertained. Moreover, a preliminary optimization of system composition has been achieved. This study underlines a catalytic effect of DES that can be proficiently exploited to enhance CyMe4-BTBP extraction and selectivity.

Deep eutectic solvent as solvent and catalyst: one-pot synthesis of 1,3-dinitropropanes via tandem Henry reaction/Michael addition.

The Henry reaction was performed using microwave heating within the deep eutectic solvent (DES) choline chloride/urea (ChCl/urea) which acted as both the catalyst and solvent for the reaction. The optimisation of the conditions (temperature, heating mode, time, DES) allowed 1,3-dinitropropane derivatives to be obtained via tandem Henry reaction/Michael addition, in one step from a range of different aromatic aldehydes in high yields and under mild reaction conditions.

Structural properties of the chelating agent 2,6-bis(1-(3-hydroxypropyl)-1,2,3-triazol-4-yl)pyridine: a combined XRD and DFT structural study.

The conformational isomerism of the chelating agent 2,6-bis(1-(3-hydroxypropyl)-1,2,3-triazol-4-yl)pyridine (PTD), exploited in fuel reprocessing in spent nuclear waste, has been studied by single crystal X-ray diffraction analysis in combination with an extensive DFT conformational investigation. In the solid-state, the elucidated crystal structure (i.e., not yet published) shows that by thermal treatment (DSC) no other phases are observed upon crystallization from the melt, indicating that the conformation observed by X-ray data is rather stable. Mapping of intermolecular and intramolecular noncovalent interactions has been used to elucidate the unusual arrangement of the asymmetric unit. Considerations relating to the stability of different conformational isomers in aqueous and non-aqueous solutions are also presented. The accurate structural description reported here might open various research topics such as the potential of PTD to act as an outer sphere ligand in the formation of second sphere coordination complexes and their interconversion by mechanochemical means.