Małgorzata E. Zakrzewska

Ionic liquid-mediated formation of 5-hydroxymethylfurfural-a promising biomass-derived building block.

The reduction of fossil fuels dependence in a framework of shifts in oil prices and geopolitical instability1 is one of the major interests of the current world. It can be achieved by using lignocellulosic biomass. However, there is also growing concern about its overall sustainability, especially regarding land use change, intensified use of agricultural inputs, and possible limitations on food security. Furthermore, the global energy demand is projected to grow over 50% by 2030. This will have an additional impact on the climate and, hence, on our planet. The recent United Nations Framework Convention on Climate Change in Copenhagen, Denmark, has ratified the Kyoto Protocol and is intended to reduce global emissions by at least 20% by 2020 and by 50%-60% by 2050 relative to the emission level in 2006.2 To achieve these ambitious goals in the near future, the next generation of chemicals and fuels from the biorefinery of lignocellulosic biomass has to be used sustainably, since the competition for raw materials between the food and energy industries prevents further (significant) increase of the current first-generation biofuels already on the market. Biomass, especially that which exists in the form of nonedible lignocellulosic materials such as grasses, woods (hard and soft), and crop residues (corn stover, wheat straw, sugar cane, bagasse, etc.), serves as renewable feedstock and could be considered as an alternative source of the chemicals and energy currently derived from petroleum. There are a number of technological breakthroughs necessary to reach a mature and cost-effective commercial technology for biomass utilization. Cost reductions in biological and chemical conversion are to be found in the improvement of individual process steps, far-reaching integration, the development of new efficient methods of carbohydrate conversions by alternative solvents or by robust microbial cell fermentation and by integration of all residues (e.g., spent lignins) and wastewaters into a one-pot process. Lignocellulosic biomass is composed of cellulose, hemicellulose, and lignin. The compositions of these materials vary, and their structures are very complex. Biomass requires many hydrolytic technologies and biological as well as chemical pretreatments to be reduced in size and have its physical structure opened.3 Various methods such as acid hydrolysis, hydrothermal or alkaline treatments, organosolv, solid (super)acids, ionic liquids, or subcritical or supercritical fluids can be employed.4 Carbohydrates constitute up to 75% of the annual production of biomass, estimated at 170 × 109 tons.5 Carbohydrates are an abundant, diverse, and reusable source of carbon. They find many industrial applications in such diverse areas as the chemistry, fermentation, petroleum production, food, paper, and pharmaceutical industries.6 Unfortunately, the * Fax: +351217163636. Telephone: +351210924600ext 4224. E-mail: rafal.lukasik@lneg.pt. † Universidade Nova de Lisboa. ‡ Laboratório Nacional de Energia e Geologia. Małgorzata Ewa Zakrzewska received her two M.Sc. B.Sc. degrees in Environmental Protection Technology and in Biotechnology from the Gdańsk University of Technology, Poland. Currently, at REQUIMTE, Universidade Nova de Lisboa, she has been gaining experience in highpressure work under the supervision of Doctor Rafał Bogel-Łukasik and Professor Manuel Nunes da Ponte. Her research is focused on the application of supercritical CO2 in reaction and extraction. Chem. Rev. 2011, 111, 397–417 397

Insight into the phase equilibrium phenomena of systems containing dienes and dicyanamide ionic liquids as a new potential application.

This work presents a systematic investigation into liquid-liquid phase equilibria for systems containing three various ionic liquids and four dienes as they have not been reported yet. The systems employed in this study containing dicyanamide based ionic liquids and dienes reveal the phase envelopes that have a similar shape to binodal curves with the upper critical solution temperature. Generally, 1-methyl-3-octylimidazolium dicyanamide ([C(8)mim][DCA]) was found to be a better solvent for nonpolar dienes. The 1-butyl-3-methylimidazolium dicyanamide ([C(4)mim][DCA]) ionic liquid is a much worse solvent for 1,5-cyclooctadiene, 1,3-cyclooctadiene, 1,5-hexadiene, and 1,7-octadiene compared to other ionic liquids studied. The miscibility gaps shrink for a less polar [C(8)mim][DCA] or even more for 1-dodecyl-3-methylimidazolium dicyanamide ([C(12)mim][DCA]). In the range of the studied temperatures, the solubility of dienes is significantly higher compared to the solubility of the ionic liquids containing the shorter alkyl chain in the cation. The solubility of the presented dienes in ([C(4)mim][DCA]) ionic liquid is also relatively high and may reach up to 0.19 mol fraction of the diene. The attained results demonstrate that nonpolar compounds can be dissolved to some extent in highly charged and polar solvents such as ionic liquids.

Intramolecular C–H insertion catalyzed by dirhodium(II) complexes using CO2 as the reaction media

Abstract In this work, the intramolecular C–H insertion of diazoacetamides catalyzed by dirhodium(II) complexes and using CO2 as solvent is disclosed. The expected lactams were obtained in yields over 97%. The asymmetric intramolecular C–H insertion was also achieved and the β-lactam 14 was obtained in >97% yield and 65% ee using the chiral dirhodium(II) catalyst Rh2(S-PTTL)4. Finally, the dirhodium(II) complex Rh2(OAc)4 was used in two consecutive cycles in which complete conversion to the lactam was observed.

Solubility of Bioactive, Inorganic and Polymeric Solids in Ionic Liquids — Experimental and Prediction Perspectives

This work was supported by Fundacao para a Ciencia e a Tecnologia through projects (PEstC/LA0006/2013, PTDC/CTM/103664/2008, EXPL/QEQ ERQ/2243/2013) one contract under Investigador FCT (L.C. Branco); two Postdoctoral fellowships (G.V.S.M. Carrera - SFRH/BPD/72095/2010 and A. V. M. Nunes - SFRH/BPD/74994/2010) and one doctoral fellowship (M. E.Zakrzewska SFRH/BD/74929/2010).