Bio-based production of cis,cis-muconic acid as platform for a sustainable polymers production.

Production of the high industrial value cis,cis-muconic acid (ccMA) from renewable biomasses is of main interest especially when biological (green) processes are used. We recently generated a E. coli strain expressing five recombinant enzymes to convert vanillin (VA, from lignin) into ccMA. Here, we optimized a growing cell approach in bioreactor for the ccMA production. The medium composition, fermentation conditions, and VA addition were tuned: pulse-feeding VA at 1 mmol/h allowed to reach 5.2 g/L of ccMA in 48 h (0.86 g ccMA/g VA), with a productivity 4-fold higher compared to the resting cells approach, thus resulting in significantly lower E-factor and Process Mass Intensity green metric parameters. The recovered ccMA has been used as building block to produce a fully bioderived polymer with rubber-like properties. The sustainable optimized bioprocess can be considered an integrated approach to develop a platform for bio-based polymers production from renewable feedstocks.

Graphene Oxide and Oxidized Carbon Black as Catalyst for Crosslinking of Phenolic Resins.

Influence of different graphite-based nanofillers on crosslinking reaction of resorcinol, as induced by hexa(methoxymethyl)melamine, is studied. Curing reactions leading from low molecular mass compounds to crosslinked insoluble networks are studied by indirect methods based on Differential Scanning Calorimetry. Reported results show a catalytic activity of graphene oxide (eGO) on this reaction, comparable to that one already described in the literature for curing of benzoxazine. For instance, for an eGO content of 2 wt %, the exothermic crosslinking DSC peak (upon heating at 10 °C/min) shifted 6 °C. More relevantly, oxidized carbon black (oCB) is much more effective as catalyst of the considered curing reaction. In fact, for an oCB content of 2 wt %, the crosslinking DSC peak can be shifted more than 30 °C and a nearly complete crosslinking is already achieved by thermal treatment at 120 °C. The possible origin of the higher catalytic activity of oCB with respect to eGO is discussed.

Edge-Oxidation of Graphites by Hydrogen Peroxide.

A simple and eco-friendly procedure of edge oxidation of high-surface area graphites, based on hydrogen peroxide treatments at 60 °C, is presented. Already, short-term treatments lead to O/C weight ratios higher than 0.1, leaving unaltered interlayer spacing and correlation length. This clearly indicates that all oxidized groups are located on exposed sites (mainly on lateral edges) of the graphitic layers. Short-term H2O2 treatments, as expected, increase hydrophilicity and reduce thermal stability with respect to the starting graphite. Long-term treatments, on the contrary, reduce hydrophilicity and increase thermal stability with respect to the starting graphite, mainly due to surface area reduction associated with the oxidation procedure. Exfoliation of a substantial fraction of the obtained edge-oxidized graphite can be achieved by simple procedures of dispersion and sonication in water.