Università degli studi di Modena e Reggio Emilia

This work is focused on performing a quantitative assessment of the environmental impacts associated with an organic synthesis reaction, optimized using an experimental design approach. A nucleophilic substitution reaction was selected, employing vanillin as the substrate, a phenolic compound widely used in the food industry and of pharmaceutical interest, considering its antioxidant and antitumoral potential. To carry out the reaction, three different solvents have been chosen, namely acetonitrile (ACN), acetone (Ace), and dimethylformamide (DMF). The syntheses were planned with the aid of a multivariate experimental design to estimate the best reaction conditions, which simultaneously allow a high product yield and a reduced environmental impact as computed by Life Cycle Assessment (LCA) methodology. The experimental results highlighted that the reactions carried out in DMF resulted in higher yields with respect to ACN and Ace; these reactions were also the ones with lower environmental impacts. The multilinear regression models allowed us to identify the optimal experimental conditions able to guarantee the highest reaction yields and lowest environmental impacts for the studied reaction. The identified optimal experimental conditions were also validated by experimentally conducting the reaction in those conditions, which indeed led to the highest yield (i.e., 93%) and the lowest environmental impacts among the performed experiments. This work proposes, for the first time, an integrated approach of DoE and LCA applied to an organic reaction with the aim of considering both conventional metrics, such as reaction yield, and unconventional ones, such as environmental impacts, during its lab-scale optimization.

This work is focused on the application of Life Cycle Assessment (LCA) methodology for the quantification of the potential environmental impacts associated to the obtainment of three glucosyl derivatives of genistein. Genistein is known to possess the ability in vitro to contribute to control signaling of some molecules like Angiopoietin-2 that has a key role in angiogenesis and fibrosis from which Hepatocellular cancer can arise. Therefore, a fine tuning of genistein uptake and bioavailability (e.g., through glycosylation) may provide innovative anti-angiogenic therapies with benefits for cancer chemoprevention and treatment.The production of pharmaceutical quality genistein, from which the derivatives are obtained, was modelled considering a recently optimized published procedure. The preparation of 7-O-(beta-Dglucosyl)genistein (or genistin) was experimentally conducted by exploiting a two-step synthetic protocol. During the work-up procedure, two further derivatives were isolated.In order to also comprise the potential human health benefits of the synthesized compounds, this work also proposes for the first time a potential damage assessment factor for genistein and its derivatives.

This paper represents the first attempt to quantitatively and reliably assess the environmental sustainability of solution combustion synthesis (SCS) with respect to other soft chemistry strategies, which are more conventionally employed in the preparation of engineered oxide nanomaterials, namely hydrolytic and non-hydrolytic sol-gel syntheses (i.e., HSGS and NHSGS). Indeed, although SCS is well known to rely on significant reduction in the energy as well as time required for the obtainment of the desired nanocrystals, its quantitative environmental assessment and a detailed comparison with other existing synthetic pathways represents an absolute novelty of high scientific desirability in order to pursue a more sustainable development in the inorganic chemistry as well as materials science research fields. TiO2 nanoparticles were selected as the material of choice, for the production of which three slightly modified literature procedures were experimentally reproduced and environmentally evaluated by the application of the comprehensive Life Cycle Assessment (LCA) methodology. Particularly, SCS was compared from an environmental perspective with sol-gel approaches performed both in water and in benzyl alcohol. The results of the present study were also framed among those recently obtained in a systematic study assessing seven further chemical, physical and biological routes for the synthesis of TiO2 nanoparticles, comprising also flame spray pyrolysis (typically used in industrial productions), highlighting and quantifying the excellent environmental performances of SCS.