Synthesis of Purine-Based Ionic Liquids and Their Applications.

Bio-based ionic liquids (ILs) are being increasingly sought after, as they are more sustainable and eco-friendly. Purines are the most widely distributed, naturally occurring N-heterocycles, but their low water-solubility limits their application. In this work, four purines (theobromine, theophylline, xanthine, and uric acid) were combined with the cation tetrabutylammonium to synthesize bio-based ILs. The physico-chemical properties of the purine-based ILs were characterized, including their melting and decomposition temperatures and water-solubility. The ecotoxicity against the microalgae Raphidocelis subcapitata was also determined. The ILs show good thermal stability (>457 K) and an aqueous solubility enhancement ranging from 53- to 870-fold, in comparison to their respective purine percursors, unlocking new prospects for their application where aqueous solutions are demanded. The ecotoxicity of these ILs seems to be dominated by the cation, and it is similar to chloride-based IL, emphasizing that the use of natural anions does not necessarily translate to more benign ILs. The application of the novel ILs in the formation of aqueous biphasic systems (ABS), and as solubility enhancers, was also evaluated. The ILs were able to form ABS with sodium sulfate and tripotassium citrate salts. The development of thermoresponsive ABS, using sodium sulfate as a salting-out agent, was accomplished, with the ILs having different thermosensitivities. In addition, the purine-based ILs acted as solubility enhancers of ferulic acid in aqueous solution.

Natural and Biomimetic Antitumor Pyrazoles, A Perspective.

The present review presents an overview of antitumor pyrazoles of natural or bioinspired origins. Pyrazole compounds are relatively rare in nature, the first ones having been reported in 1966 and being essentially used as somniferous drugs. Cytotoxic pyrazoles of natural sources were first isolated in 1969, and a few others have been reported since then, most of them in the last decade. This paper presents a perspective on the current knowledge on antitumor natural pyrazoles, organized into two sections. The first focuses on the three known families of cytotoxic pyrazoles that were directly isolated from plants, for which the knowledge of the medicinal properties is in its infancy. The second section describes pyrazole derivatives of natural products, discussing their structure-activity relationships.

Repurposing Kraft black Liquor as Reductant for Enhanced Lithium-Ion Battery Leaching.

The economic advantages of H2SO4 make it the acid of choice for the hydrometallurgical treatment of waste lithium-ion batteries (LIBs). However, to facilitate the full dissolution of the higher valency metal oxides present in the cathode black mass, a suitable reducing agent is required. Herein, the application of industrial black liquor (BL) obtained from the Kraft pulping for papermaking is investigated as a renewable reducing agent for the enhanced leaching of transition metals from LIB powder with H2SO4. The addition of acidified BL to H2SO4 significantly improved the leaching efficiency for a range of LIB cathode chemistries, with the strongest effect observed for manganese-rich active material. Focusing on NMC111 (LiMnxCoyNizO2) material, a linear correlation between the BL concentration and the leaching yield of Mn was obtained, with the best overall leaching efficiencies being achieved for 2.0 mol L-1 H2SO4 and 50 vol % of BL at 353 K. A quasi-total degradation of oxygenated and aromatic groups from the BL during NMC111 dissolution was observed after leaching, suggesting that these chemical groups are essential for LIB reduction. Finally, the leached transition metals could be easily recovered by pH adjustment and oxalic acid addition, closing the resource loop and fostering resource efficiency.

The role of biomass elemental composition and ion-exchange in metal sorption by algae.

The use of macroalgae, microalgae and cyanobacteria for metal sorption has been widely reported. Still, there are no studies allowing a direct comparison of the performance of these biomasses, especially while evaluating metal competition. The simultaneous sorption of Co2+, Cu2+, Ni2+ and Zn2+ present in a multi-elemental solution by six macroalgae, two microalgae and three cyanobacteria was evaluated. Brown macroalgae were shown to be the most promising biosorbent, with Undaria pinnatifida having a total metal sorption capacity of 0.6 mmol g-1. Overall, macroalgae performed better than microalgae, followed by cyanobacteria. Carboxyl groups were identified as being the main functional groups involved in metal sorption, and all biomass samples were found to be selective to Cu2+. This was linked not only to its higher complexation constant value with relevant functional groups when compared to the remaining metals, but also the Irving-Williams series. The release of K+ and Ca2+ to the aqueous solution during the metal sorption was followed. The obtained results suggest they are readily exchanged with metals in the solution, indicating the occurrence of an ion-exchange mechanism in metal sorption by most biomass. Red macroalgae are an exception to the reported trends, suggesting that their metal sorption mechanism may differ from the other biomass types.