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Renewal in the world production of plastics with growing amounts of building blocks from biomass is a pressing demand among society. Adipic acid is one of the monomers of nylon 6,6, and, traditionally, is obtained from fossil sources, but it is possible to reduce the muconic acids, deriving it from biomass, to obtain adipic acid. However, these catalyzed reactions use commonly hazardous conditions or reagents; in this study, a pathway to obtain a bio-adipic acid, following the Green Chemistry, is reported. Metal nanoparticles (M NPs; M = Pd, Pt, Ru, Rh) were synthesized in water at 80 °C using sodium lignosulphonate as a reducing and stabilizing agent. They were characterized by TEM and XRD techniques: Pd NPs were larger (21 nm) and spherical in shape; Pt NPs were irregular; Ru and Rh NPs were smallest (1.9 and 5.3 nm, respectively). M NPs were tested as catalyst in the hydrogenation reactions of dicarboxylic acids (fumaric, malonic, trans,trans- and cis,cis-muconic acids) in water at room pressure and temperature. The NPs transformed selectively fumaric and malonic acids to succinic acid, although with different yields. Ru and Pt NPs were moderately active while with Pd NPs, 80% of succinic acid was obtained and with Rh NPs, 100% was observed. Carrying out the hydrogenations on muconic acids at pH 5, the formation of adipic acid was observed with all NPs but selectivities in the presence of Ru, Pt and Pd NPs were not excellent. The selectivity with Rh NPs was remarkable (86% from cis,cis- and about 100% from trans,trans-muconic acid) considering the mild conditions; furthermore, it is attractive that the adipic acid was obtained also from the cis,cis isomer which can be produced from biomass.

Cellulose Nanocrystals, CNC, opportunely functionalized are proposed as reactive fillers in bio-based flexible polyurethane foams to improve, mainly, their mechanical properties. To overcome the cellulose hydrophilicity, CNC was functionalized on its surface by linking covalently a suitable bio-based polyol to obtain a grafted-CNC. The polyols grafted with CNC will react with the isocyanate in the preparation of the polyurethane foams. An attractive way to introduce functionalities on cellulose surfaces in aqueous media is silane chemistry by using functional trialkoxy silanes, X-Si (OR)3. Here, we report the synthesis of CNC-grafted-biopolyol to be used as a successful reactive filler in bio-based polyurethane foams, PUFs. The alkyl silanes were used as efficient coupling agents for the grafting of CNC and bio-polyols. Four strategies to obtain CNC-grafted-polyol were fine-tuned to use CNC as an active filler in PUFs. The effective grafting of the bio polyol on CNC was evaluated by FTIR analysis, and the amount of grafted polyol by thermogravimetric analysis. Finally, the morphological, thermal and mechanical properties and hydrophobicity of filled PUFs were thoughtfully assessed as well as the structure of the foams and, in particular, of the edges and walls of the cell foams by means of the Gibson–Ashby model. Improved thermal stability and mechanical properties of PU foams containing CNC-functionalized-polyol are observed. The morphology of the PU foams is also influenced by the functionalization of the CNC.

The combination of metal nanoparticles (Pd or Pt NPs) with NAD-dependent thermostable alcohol dehydrogenase (TADH) resulted in the one-flask catalytic double reduction of 3-methyl-2-cyclohexenone to 3-(1S,3S)-methylcyclohexanol. In this article, some assumptions about the interactions between a chemocatalyst and a biocatalyst have been proposed. It was demonstrated that the size of the NPs was the critical parameter for the mutual inhibition: the bigger the NPs, the more harmful for the enzyme they were, even if the NPs themselves were only moderately inactivated. Conversely, the smaller the NPs, the more minimal the TADH denaturation, although they were dramatically inhibited. Resuming, the chemocatalysts were very sensitive to deactivation, which was not related to the amount of enzyme used, while the inhibition of the biocatalyst can be strongly reduced by minimizing the NPs/TADH ratio used to catalyze the reaction. Among some methods to avoid direct binding of NPs with TADH, we found that using large Pd NPs and protecting their surfaces with a silica shell, the overall yield of 3-(1S,3S)-methylcyclohexanol was maximized (36%).

Nowadays, the chemical industry is looking for sustainable chemicals to synthesize nanocomposite bio-based polyurethane foams, PUs, with the aim to replace the conventional petrochemical precursors. Some possibilities to increase the environmental sustainability in the synthesis of nanocomposite PUs include the use of chemicals and additives derived from renewable sources (such as vegetable oils or biomass wastes), which comprise increasingly wider base raw materials. Generally, sustainable PUs exhibit chemico-physical, mechanical and functional properties, which are not comparable with those of PUs produced from petrochemical precursors. In order to enhance the performances, as well as the bio-based aspect, the addition in the polyurethane formulation of renewable or natural fillers can be considered. Among these, walnut shells and cellulose are very popular wood-based waste, and due to their chemical composition, carbohydrate, protein and/or fatty acid, can be used as reactive fillers in the synthesis of Pus. Diatomite, as a natural inorganic nanoporous filler, can also be evaluated to improve mechanical and thermal insulation properties of rigid PUs. In this respect, sustainable nanocomposite rigid PU foams are synthesized by using a cardanol-based Mannich polyol, MDI (Methylene diphenyl isocyanate) as an isocyanate source, catalysts and surfactant to regulate the polymerization and blowing reactions, H2O as a sustainable blowing agent and a suitable amount (5 wt%) of ultramilled walnut shell, cellulose and diatomite as filler. The eect of these fillers on the chemico-physical, morphological, mechanical and functional performances on PU foams has been analyzed.

Continuous flow processes have recently emerged as a powerful technology for performing chemical transformations since they ensure some advantages over traditional batch procedures. In this work, the use of commercially available and affordable PEEK (Polyetheretherketone) and PTFE (Polytetrafluoroethylene) HPLC (High Performance Liquid Chromatography) tubing as microreactors was exploited to perform organic reactions under continuous flow conditions, as an alternative to the commercial traditional glass microreactors. The wide availability of tubing with different sizes allowed quickly running small-scale preliminary screenings, in order to optimize the reaction parameters, and then to realize under the best experimental conditions a reaction scale up for preparative purposes. The gram production of some Active Pharmaceutical Ingredients (APIs) such as (S)-Pregabalin and (S)-Warfarin was accomplished in short reaction time with high enantioselectivity, in an experimentally very simple procedure.

One-pot combinations of sequential catalytic reactions can offer practical and ecological advantages over classical multi-step synthesis schemes. In this context, the integration of enzymatic and chemo-catalytic transformations holds particular potential for efficient and selective reaction sequences that would not be 10 possible using either method alone. Here we report the one-pot combination of alcohol dehydrogenasecatalysed asymmetric reduction of 2-azido ketones and Pd nanoparticle-catalysed hydrogenation of the resulting azido alcohols, which gives access to both enantiomers of aromatic 1,2-amino alcohols in high yields and excellent optical purity (ee >99%). Furthermore, we demonstrate the incorporation of an upstream azidolysis and a downstream acylation step into the one-pot system, thus establishing a highly 15 integrated synthesis of the antiviral natural product (S)-tembamide in 73% yield (ee >99%) over 4 steps. Avoiding the purification and isolation of intermediates in this synthetic sequence leads to an unprecedentedly low ecological footprint, as quantified by E-factor and solvent demand.