Fabio Moretti

Introduction of oxygenated side chain into imidazolium ionic liquids: Evaluation of the effects at different biological organization levels

The biological effects of a class of oxygenated imidazolium ionic liquids were studied in comparison with alkyl imidazolium salts (BMIM BF4 and BMIM N(CN)2).The cellular and subcellular effects were evaluated on rat pheochromocytoma PC12 cell lines, through MTT test, lactate dehydrogenase release and acetylcholinesterase inhibition; the eco-toxicological responses were assessed through the acute toxicity tests towards Daphnia magna and Vibrio fischeri. The introduction of ethoxy moieties in the lateral chain of imidazolium cations reduced the biological effects in all the tests. The acute toxicity towards D. magna was not affected by the number of ethoxy units, but the crustacean seemed to be sensitive to the type of anion; on the contrary, a further addition of ethoxy moieties increased the toxicity towards V. fischeri, M(OE)4MIM N(CN)2 being the most toxic oxygenated ionic liquid. In the cytotoxicity assays the salts with oxygenated cations resulted ineffective compared to BMIMs, independently from the anion and the number of ethoxy units in the lateral chain. In order to estimate the influence on membrane fluidity, an analysis of fluorescence anisotropy was done and it indicated that BMIM BF4, the most toxic ionic liquid among the tested ones, led to a destabilization of the model membranes at any molarity.

Enzymatic acylation of levoglucosan in acetonitrile and ionic liquids

The regioselective acylation of carbohydrates is of great interest in many industrial fields. Levoglucosan (1,6-anhydroglucopyranose), an anhydro-sugar easily obtainable through the pyrolytic treatment of cellulose, can be used as an excellent alternative feedstock to get chemicals of interest from renewable resources. Levoglucosan has been acylated in good yields with diverse acyl donors, such as vinyl esters and carboxylic acids with long and short chains in alternative green solvents: CH3CN, a traditional organic solvent with low ecotoxicity, and ionic liquids. The surfactant properties of 4-O-lauryl-levoglucosan have been evaluated and resulted in the range of oil soluble emulsifiers.

Chemoselective Allylation of Ketones in Ionic Liquids Containing Sulfonate Anions

The chemoselective addition of tetraallyltin to dialkyl, alkenyl-alkyl, and alkynyl-alkyl ketones can be performed with high yields in N-methyl-N-butylpyrrolidinium trifuoromethansulfonate (MBP-Tf). Other room temperature ionic liquids (RTILs) can also be successfully employed if some sulfonic acid is added. The reaction is very sensitive to the electronic properties of the substrate. Aryl alkyl ketones bearing electron-withdrawing substituents behave like dialkyl ketones and react promptly; on the contrary, electron-rich aryl alkyl ketones react sluggishly, which allows selective competitive allylation of dialkyl substrates to occur. The ionic liquid solvent can be easily recycled, which meets the green chemistry principles of selectivity and reuse of chemicals. NMR spectroscopic data support the formation of tin-triflate catalysts in situ.

Characterization and quantification of racemic and meso-ethylenediamine-N,N'-bis(2-hydroxy-5-sulfophenylacetic) acid/iron (III) by ion-pair ultra-high performance liquid chromatography coupled with diode array detector and electrospray tandem mass spectrometry.

EDDHSA/Fe is a promising substitute of EDDHA/Fe to fight iron chlorosis. o,o-EDDHSA structure contains two chiral carbons giving the racemic and meso couples of stereoisomers. Ion-pair HPLC and UHPLC-UV/Vis-ESI-MS/MS methods were developed for the determination of racemic and meso-o,o-EDDHSA/Fe in commercial samples of chelates. The lack of a commercial EDDHSA standard was overcome by sulfonation of a commercial available o,o-EDDHA standard and subsequent quantification by (1)H-NMR. Assignment of configurations was carried out starting from racemic and meso-o,o-EDDHA/Fe by direct sulfonation to give the corresponding o,o-EDDHSA/Fe isomers. The performances of these methods were assessed in terms of intra and inter-day precision, linearity and selectivity. The high selectivity and lower detection limit (nanomolar) of the UHPLC-ESI-MS/MS method could allow to deepen the knowledge relative to meso and rac-o,o-EDDHSA/Fe interactions with plants, its fate in different soil conditions, its mobility and other environmental aspects.

Furan containing ammonium salts from furfural: synthesis and properties evaluation

Furan-containing quaternary ammonium iodides, bis(trifluoromethane)sulfonimides, and tetrafluoroborates are obtained in good overall yield with mild operation conditions starting from furfural, a cheap chemical substance obtainable from crop residue feedstocks. The application of these new ion pairs can be envisioned in the fields of ionic liquid solvents, of surfactants and of biocides in analogy with benzyl quaternary ammonium salts. In view of practical applications, the determination of the thermal properties of new ion pairs together with preliminary ecotoxicological evaluation of some representative products has also been performed.