Multigram Synthesis of Pure HMF and BHMF.

5-Hydroxymethylfurfural (HMF) is a bio-based platform chemical that can be used as a building block to produce several compounds with diverse applications. Even though HMF synthesis holds promise for a greener future, the current state of technology and the high production cost limit its competitiveness on an industrial scale. In this prospect, we have developed a multigram-scale procedure for HMF by reacting d-fructose with Purolite CT275DR-an acidic resin-in a dimethyl carbonate (DMC)/tetraethyl ammonium bromide (TEAB) biphasic system. Reactions performed in an autoclave for 2 h at 110 °C using up to 40 gram of d-fructose resulted in an overall HMF yield of 70%. HMF was purified by a custom-made procedure leading to ca 50% of the pure crystalline product; meanwhile, the residual HMF-rich oil was directly reduced to bis(hydroxymethyl)furan (BHMF). Green metrics and the Ecoscale algorithm were used to evaluate the sustainability of the herein-proposed procedure in comparison with previously reported works.

What do we know about the ecotoxicological implications of the rare earth element gadolinium in aquatic ecosystems?

Gadolinium (Gd) is one of the most commercially exploited rare earth elements, commonly employed in magnetic resonance imaging as a contrast agent. The present review was performed aiming to identify the Gd concentrations in marine and freshwater environments. In addition, information on Gd speciation in the environment is discussed, in order to understand how each chemical form affects its fate in the environment. Biological responses caused by Gd exposure and its bioaccumulation in different aquatic invertebrates are also discussed. This review was devoted to aquatic invertebrates, since this group of organisms includes species widely used as bioindicators of pollution and they represent important resources for human socio-economic development, as edible seafood, fishing baits and providing food resources for other species. From the literature, most of the published data are focused on freshwater environments, revealing concentrations from 0.347 to 80 µg/L, with the highest Gd anomalies found close to highly industrialized areas. In marine environments, the published studies identified a range of concentrations between 0.36 and 26.9 ng/L (2.3 and 171.4 pmol/kg), reaching 409.4 ng/L (2605 pmol/kg) at a submarine outfall. Concerning the bioaccumulation and effects of Gd in aquatic species, most of the literature regards to freshwater species, revealing concentration ranging from 0.006 to 0.223 µg/g, with high variability in the bioaccumulation extent according to Gd complexes chemical speciation. Conversely, no field data concerning Gd bioaccumulation in tissues of marine species have been published. Finally, impacts of Gd in invertebrate aquatic species were identified at different biological levels, including alterations on gene expression, cellular homeostasis, shell formation, metabolic capacity and antioxidant mechanisms. The information here presented highlights that Gd may represent an environmental threat and a risk to human health, demonstrating the need for further research on Gd toxicity towards aquatic wildlife and the necessity for new water remediation strategies.

How Ulva lactuca can influence the impacts induced by the rare earth element Gadolinium in Mytilus galloprovincialis? The role of macroalgae in water safety towards marine wildlife.

Rare earth elements (REEs) are gaining growing attention in environmental and ecotoxicological studies due to their economic relevance, wide range of applications and increasing environmental concentrations. Among REEs, special consideration should be given to Gadolinium (Gd), whose wide exploitation as a magnetic resonance imaging (MRI) contrast agent is enhancing the risk of its occurrence in aquatic environments and impacts on aquatic organisms. A promising approach for water decontamination from REEs is sorption, namely through the use of macroalgae and in particular Ulva lactuca that already proved to be an efficient biosorbent for several chemical elements. Therefore, the present study aimed to evaluate the toxicity of Gd, comparing the biochemical effects induced by this element in the presence or absence of algae. Using the bivalve species Mytilus galloprovincialis, Gd toxicity was evaluated by assessing changes on mussels' metabolic capacity and oxidative status. Results clearly showed the toxicity of Gd but further revealed the capacity of U. lactuca to prevent injuries to M. galloprovincialis, mainly reducing the levels of Gd in water and thus the bioaccumulation and toxicity of this element by the mussels. The results will advance the state of the art not only regarding the effects of REEs but also with regard to the role of algae in accumulation of metals and protection of aquatic organisms, generating new insights on water safety towards aquatic wildlife and highlighting the possibility for resources recovery.