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The aim of this Doctoral Thesis is the development of new catalytic synthetic methodologies in the context of the modern organic chemistry setting, with special focus on the use of cheap, sustainable catalytic materials. Specifically, during the course my PhD, I focused my research on two main distinct catalytic strategies, namely: the use of carbonaceous materials as catalysts (carbocatalysis) and nickel catalysis, also investigating a synergistic combination of the two. These methodologies were explored as means for the manipulation of (hetero)aromatic cores, representing ubiquitous, easily accessible and privileged scaffolds in medicinal or natural products chemistry. Both polar and radical reaction manifolds were engaged as complementary reactivities, capitalizing on metal- as well as organo-based activation modes. Particular attention has been devoted to addressing modern synthetic challenges or highly sought- after methodologies. Specifically, protocols for direct substitution of alcohols, dearomatization of arene nuclei, formation of C-S bonds, carbon dioxide fixation, C-C bond activation and fluoroalkylation were successfully achieved under carbo- or nickel catalyzed conditions.

The tandem catalytic functionalization/carboxylation of double as well as triple carbon-carbon bonds with CO2 represent an emerging research area in synthetic organic methodology. In particular, the combination of mild reaction conditions, stoichiometric acceptor/donorless conditions (visible light photoredox catalysis) and chiral catalysts contributed to a rapid development of this intriguing research area capable of creating chemical diversity/ complexity from readily available unsaturated hydrocarbons and CO2 as a C1-buinding block. The most recent developments in the field have been collected in the present review article and organized, based on the different sets of π-systems/intermediates/reactive partners employed (i.e., nickelalactones, organo-halides) as well as synthetic strategies (i.e., visible-light photo redox catalysis).

Insights into the effect of die swell on extrusion foam of thermoplastic polymers are presented. The die swell or Barus effect is the swelling of a viscoelastic material due to a fast elastic recovery after being subjected to stress. The elastic recovery is proportional to the energy stored in the material during the deformation that is released immediately when the material is free to expand. In extrusion foam, the elastic recovery happens at the die exit together with the foaming process (i.e., bubble nucleation and growth). Previous reports on extrusion have focused on modeling the die swell or foaming individually. We investigated the existence of a link between the die swell and foaming that is fundamental in designing the geometry of a die for extrusion foam. Simple and complex dies were used to measure the expansion ratio of a polyethylene blown with isobutane and CO2. It was found that the expansion ratio is anisotropic, the anisotropy in the expansion of the foam is due to the die swell strongly affecting the final shape of the product, and it cannot be neglected in standard application for extrusion foam. Surprisingly, it was found that the foam density changes at a high level of die swell because it is affected by the elastic recovery of the material.