Water-based processing of graphene-typically considered as physicochemically incompatible with water in the macroscale-emerges as the key challenge among the central postulates of green nanotechnology. These problematic concerns are derived from the complex nature of graphene in the family of sp2-carbon nanoallotropes. Indeed, nanomaterials hidden under the common "graphene" signboard are very rich in morphological and physicochemical variants. In this work, inspired by the adhesion chemistry of mussel biomaterials, we have synthesized novel, water-processable graphene-polylevodopa (PDOPA) hybrids. Graphene and PDOPA were covalently amalgamated via the "growth-from" polymerization of l-DOPA (l-3,4-dihydroxyphenylalanine) monomer in air, yielding homogeneously PDOPA-coated (23 wt %) (of thickness 10-20 nm) hydrophilic flakes. The hybrids formed >1 year stable and water-processable aqueous dispersions and further conveniently processable paints of viscosity 0.4 Pa·s at 20 s-1 and a low yield stress τ0 up to 0.12 Pa, hence exhibiting long shelf-life stability and lacking sagging after application. Demonstrating their applicability, we have found them as surfactant-like nanoparticles stabilizing the larger, pristine graphene agglomerates in water in the optimized graphene/graphene-PDOPA weight ratio of 9:1. These characteristics enabled the manufacture of conveniently paintable coatings of low surface resistivity of 1.9 kΩ sq-1 (0.21 Ω·m) which, in turn, emerge as potentially applicable in textronics, radar-absorbing materials, or electromagnetic interference shielding.
Nanostructured products are an actively growing area for food research, but there is little information on the sustainability of processes used to make these products. In this Review, we advocate for selection of sustainable process technologies during initial stages of laboratory-scale developments of nanofoods. We show that selection is assisted by predictive sustainability assessment(s) based on conventional technologies, including exploratory ex ante and "anticipatory" life-cycle assessment. We demonstrate that sustainability assessments for conventional food process technologies can be leveraged to design nanofood process concepts and technologies. We critically review emerging nanostructured food products including encapsulated bioactive molecules and processes used to structure these foods at laboratory, pilot, and industrial scales. We apply a rational method via learning lessons from sustainability of unit operations in conventional food processing and critically apportioned lessons between emerging and conventional approaches. We conclude that this method provides a quantitative means to incorporate sustainability during process design for nanostructured foods. Findings will be of interest and benefit to a range of food researchers, engineers, and manufacturers of process equipment.
1,4-Benzoxazines are important motifs in many pharmaceuticals and can be formed by a reaction sequence involving the oxidation of o-aminophenols to their corresponding quinone imine followed by an in situ inverse electron demand Diels-Alder (IEDDA) cycloaddition with a suitable dienophile. Reported herein is the development of a reaction sequence that employs horseradish peroxidase to catalyze the oxidation of the aminophenols prior to the IEDDA as a more sustainable alternative to the use of conventional stoichiometric oxidants. The synthesis of 10 example benzoxazines is demonstrated in this "one-pot, two-step" procedure with yields between 42% and 92%. The green chemistry metrics, including the E-factor and generalized reaction mass efficiency, for this biocatalytic reaction were compared against the conventional chemical approach. It was found that the reported biocatalytic route was approximately twice as green by these measures.