ROOTS - Circular policies for changing the biowaste system.

The circular economy has a huge potential to make our societies more sustainable and decarbonised, with a reduced impact on the planet's resources. The deployment of innovative solutions in the field of urban biowaste valorisation and reuse is still hindered by numerous bottlenecks, such as technological readiness, funding and financing tools availability, quality and quantity of biowaste and regulatory barriers. The European Green Deal and associated legislative initiatives provide the opportunity to overcome the last ones. To promote innovative solutions for the European circular bioeconomy and help to overcome the barriers for the deployment of a circular bioeconomy, five Horizon 2020 projects working on biowaste valorisation have teamed up. This joint initiative is named ROOTS - circulaR pOlicies for changing the biOwasTe System. The projects HOOP, VALUEWASTE, SCALIBUR, WaysTUP! and CITYLOOPS are piloting new solutions to transform urban biowaste (food waste and green waste) and wastewater into valuable products like feed, fertilisers, bioplastics, biopesticides, proteins and bioethanol. They use different processes and technologies, but they all rely on high levels of recycling/upcycling and propose valorisation solutions relevant to the uptake of a truly circular bioeconomy. As a result of the work performed and experience acquired, a number of bottlenecks have been identified, on the following topics: biowaste prevention, recycling targets and treatment plants, waste and by-products, biopesticides, insects for animal feed, single cell protein, citizen behaviour, investment needs. For each identified bottleneck, this open letter proposes specifically 1) policy recommendations for each level of governance, and 2) information about solutions, good practices and concrete experiences from the participating projects.

Calcium environment in silicate and aluminosilicate glasses probed by 4³Ca MQMAS NMR experiments and MD-GIPAW calculations.

4³Ca MQMAS NMR spectra of three silica-based glasses in which Ca²âº ions play different structural roles have been collected and processed in order to extract the underlying NMR parameter distributions. The NMR parameters have been interpreted with the help of molecular dynamics simulations and DFT-GIPAW calculations. This synergetic experimental-computational approach has allowed us to investigate the Ca environment, to estimate Ca coordination numbers from MD-derived models, and to push further the discussion about 4³Ca NMR sensitivity to the first and second coordination spheres: 4³Ca δiso and Ca-O distance can be successfully correlated as a function of Ca coordination number.

Evidence of catalase mimetic activity in Ce(3+)/Ce(4+) doped bioactive glasses.

The ability of Ce-containing bioactive glasses to inhibit oxidative stress in terms of reduction of hydrogen peroxide, by mimicking the catalase enzyme activity is demonstrated here for the first time. The antioxidant properties of three bioactive glasses containing an increasing amount of CeO2 have been evaluated by following the degradation of hydrogen peroxide with time after immersion in H2O2 aqueous solutions with different concentration. XPS and UV-vis measurements allowed us to determine the Ce(3+)/Ce(4+) ratio in the bulk and on the glass surface, and to correlate it with the ability of the samples to show catalase mimetic activity. Interestingly, we have found that the bioactive glass with composition 23.2Na2O-25.7CaO-43.4SiO2-2.4P2O5-5.3CeO2 immersed in 0.1 M H2O2 aqueous solution is able to degrade 90% of it in 1 week. The reduction in bioactivity of the glasses with increasing CeO2 content is here rationalized in terms of a lower amount of phosphate groups available for the hydroxyapatite layer formation, after binding with cerium ions. In fact, classical molecular dynamics simulations revealed that the addition of CeO2 leads to the formation of cerium phosphate rich regions. The formation of an insoluble CePO4 crystalline phase is also observed by XRD analysis after thermal treatment of the glass samples.

On the structure of Ce-containing silicophosphate glasses: a core-shell molecular dynamics investigation.

Classical molecular dynamics simulations have been used to investigate the local and medium range structure of Ce-containing silicophosphate glasses widely used in optical and photonic devices because of their enhanced UV absorption and radiation damage resistance properties. New Ce(3+)-O and Ce(4+)-O parameters for a force-field based on the core-shell model were developed by fitting on the crystalline structures of Ce-containing crystal phases, and used to get insights into the structure of five silicophosphate glasses with increasing Ce2O3 and P2O5 content. An excellent agreement between experimental and computational data was found for the local environment around cerium ions and network former cations. The Ce(3+)-O bond lengths are generally longer than Ce(4+)-O, which shows higher coordination numbers. Both P and Si are four-fold coordinated; their allocation in the network is not uniform: the increasing Ce content leads to the formation of silica-rich domains and phosphate-rich domains, which entrap Ce cations increasing their solubility in the glass. We found that both the Q(n) distributions of phosphorous and Ce clustering depend on the Ce/P ratio in the glass. In particular, Ce clustering begins for Ce/P ratios between 0.17 and 0.29 in the glass series investigated.

Understanding the photophysical properties of coumarin-based Pluronic-silica (PluS) nanoparticles by means of time-resolved emission spectroscopy and accurate TDDFT/stochastic calculations.

The photophysical properties of two 7-aminocoumarin molecules with flexible and rigid alkyl moieties at the 7-nitrogen atom have been investigated in ethanol and in Pluronic-silica nanoparticles (PluS NPs) by means of time-resolved emission spectroscopy (TRES) and time-dependent density functional theory (TDDFT). Although the two coumarin derivatives have very different photophysical properties in solution, they show quite similar photophysical behaviour when embedded into the NPs, where an increase in the fluorescence quantum yield of about 10 times was observed for the more flexible molecule. TDDFT calculations employing long-range corrected functionals and with proper account of environmental effects reveal that the formation of an accessible twisted-intramolecular charge transfer state (TICT) is possible for 7-aminocoumarin molecules with flexible alkyl groups in fluid solution, where a conical intersection between the S1 and S0 states is observed at a dihedral angle of about 80°. The excited state dynamics of the population density of this reaction coordinate in ethanol and in silica NPs investigated through the resolution of a generalized Smoulochowsky equation shows that this deactivation mechanism is drastically hampered in a silica matrix, in good agreement with experimental evidence. Steady state and time resolved measurements also suggest that at high concentration for both the dyes intermolecular interactions into the silica matrix lead to fluorescence quenching. TDDFT/PCM calculations clearly indicate that the strong quenching and red shift observed is imputable to the formation of excimers with CT character after absorption of the monomeric species.