Opportunities for the Use of Brazilian Biomass to Produce Renewable Chemicals and Materials.

This Review highlights the principal crops of Brazil and how their harvest waste can be used in the chemicals and materials industries. The Review covers various plants; with grains, fruits, trees and nuts all being discussed. Native and adopted plants are included and studies on using these plants as a source of chemicals and materials for industrial applications, polymer synthesis, medicinal use and in chemical research are discussed. The main aim of the Review is to highlight the principal Brazilian agricultural resources; such as sugarcane, oranges and soybean, as well as secondary resources, such as andiroba brazil nut, buriti and others, which should be explored further for scientific and technological applications. Furthermore, vegetable oils, carbohydrates (starch, cellulose, hemicellulose, lignocellulose and pectin), flavones and essential oils are described as well as their potential applications.

Structural analysis of five-coordinate aluminium(salen) complexes and its relationship to their catalytic activity.

The crystal structure of [Al(tBu-salen)]2O·HCl shows major changes compared to that of [Al(tBu-salen)]2O. The additional proton is localized on the bridging oxygen atom, making the aluminium atoms more electron deficient. As a result, a water molecule coordinates to one of the aluminium atoms, which becomes six-coordinate. This pushes the salen ligand associated with the six-coordinate aluminium ion closer to the other salen ligand and results in the geometry around the five-coordinate aluminium atom becoming more trigonal bipyramidal. These results experimentally mirror the predications of DFT calculations on the interaction of [Al(tBu-salen)]2O and related complexes with carbon dioxide. Variable temperature NMR studies of protonated [Al(tBu-salen)]2O complexes revealed that the structures were dynamic and could be explained on the basis of an intramolecular rearrangement in which the non-salen substituent of a five-coordinate aluminium(tBu-salen) unit migrates from one face of a square based pyramidal structure to the other via the formation of structures with trigonal bipyramidal geometries. Protonated [Al(tBu-salen)]2O complexes were shown to have enhanced Lewis acidity relative to [Al(tBu-salen)]2O, coordinating to water, dioxane and 1,2-epoxyhexane. Coordinated epoxyhexane was activated towards ring-opening, to give various species which remained coordinated to the aluminium centers. The protonated [Al(tBu-salen)]2O complexes catalysed the synthesis of cyclic carbonates from epoxides and carbon dioxide both in the presence and absence of tetrabutylammonium bromide as a nucleophilic cocatalyst. The catalytic activity was principally determined by the nature of the nucleophilic species within the catalyst structure rather than by changes to the Lewis acidity of the metal centers.

Evaluating the Viability of Successive Ring-Expansions Based on Amino Acid and Hydroxyacid Side-Chain Insertion.

The outcome of ring-expansion reactions based on amino/hydroxyacid side-chain insertion is strongly dependent on ring size. This manuscript, which builds upon our previous work on Successive Ring Expansion (SuRE) methods, details efforts to better define the scope and limitations of these reactions on lactam and ß-ketoester ring systems with respect to ring size and additional functionality. The synthetic results provide clear guidelines as to which substrate classes are more likely to be successful and are supported by computational results, using a density functional theory (DFT) approach. Calculating the relative Gibbs free energies of the three isomeric species that are formed reversibly during ring expansion enables the viability of new synthetic reactions to be correctly predicted in most cases. The new synthetic and computational results are expected to support the design of new lactam- and ß-ketoester-based ring-expansion reactions.

Unprecedented reductive cyclisation of salophen ligands to tetrahydroquinoxalines during metal complex formation.

The synthesis of novel tetrahydroquinoxalines by a metal induced one-electron reductive cyclisation of salophen ligands was found to occur when a salophen ligand was treated with chromium(ii) chloride or decamethylcobaltocene.

Capacitance-Assisted Sustainable Electrochemical Carbon Dioxide Mineralisation.

An electrochemical cell comprising a novel dual-component graphite and Earth-crust abundant metal anode, a hydrogen producing cathode and an aqueous sodium chloride electrolyte was constructed and used for carbon dioxide mineralisation. Under an atmosphere of 5 % carbon dioxide in nitrogen, the cell exhibited both capacitive and oxidative electrochemistry at the anode. The graphite acted as a supercapacitive reagent concentrator, pumping carbon dioxide into aqueous solution as hydrogen carbonate. Simultaneous oxidation of the anodic metal generated cations, which reacted with the hydrogen carbonate to give mineralised carbon dioxide. Whilst conventional electrochemical carbon dioxide reduction requires hydrogen, this cell generates hydrogen at the cathode. Carbon capture can be achieved in a highly sustainable manner using scrap metal within the anode, seawater as the electrolyte, an industrially relevant gas stream and a solar panel as an effective zero-carbon energy source.