Zwitterionic "Solutions" for Reversible CO2 Capture.

The zwitterions resulting from the covalent attachment of 3- or 4-hydroxy benzene to the 1,3-dimethylimidazolium cation represent basic compounds (pKa of 8.68 and 8.99 in aqueous solutions, respectively) that chemisorb in aqueous solutions 0.58 mol/mol of carbon dioxide at 1.3 bar (absolute) and 40 °C. Equimolar amounts of chemisorbed CO2 in these solutions are obtained at 10 bar and 40 °C. Chemisorption takes place through the formation of bicarbonate in the aqueous solution using imidazolium-containing phenolate. CO2 is liberated by simple pressure relief and heating, regenerating the base. The enthalpy of absorption was estimated to be -38 kJ/mol, which is about 30 % lower than the enthalpy of industrially employed aqueous solutions of MDEA (estimated at -53 kJ/mol using the same experimental apparatus). The physisorption of CO2 becomes relevant at higher pressures (>10 bar) in these aqueous solutions. Combined physio- and chemisorption of up to 1.3 mol/mol at 40 bar and 40 °C can be attained with these aqueous zwitterionic solutions that are thermally stable and can be recycled at least 20 times.

Photocatalytic Reverse Semi-Combustion Driven by Ionic Liquids.

The simple photolysis of CO2 in aqueous solutions to generate CO and/or hydrocarbons and derivatives in the presence of a catalyst is considered to be a clean and efficient approach for utilizing CO2 as a C1 building block. Despite the huge efforts dedicated to this transformation using either semiconductors or homogeneous catalysts, only small improvements of the catalytic activity have been achieved so far. This article reports that simple aqueous solutions of organic salts-denominated as ionic liquids-can efficiently photo-reduce CO2 to CO without using photosensitizers or sacrificial agents. The system relies on the formation of the [CO2 ].- intermediate through homolytic C-C bond cleavage in a cation-CO2 adduct of imidazolium-based ionic liquids (ILs). The system continuously produced CO up to 2.88 mmol g-1 of IL after 40 h of irradiation by using an aqueous solution of 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIm.CO2 ) IL, representing an apparent quantum yield of 3.9 %. The organophotocatalytic principles of our system may help to develop more simple and efficient organic materials for the production of solar fuels from CO2 under mild conditions, which represents a real alternative to those based on semiconductors and homogeneous metal-based catalysts.

Imidazolium salt ion pairs in solution.

The formation, stabilisation and reactivity of contact ion pairs of non-protic imidazolium ionic liquids (ILs) in solution are conceptualized in light of selected experimental evidence as well theoretical calculations reported mainly in the last ten years. Electric conductivity, NMR, ESI-MS and IR data as well as theoretical calculations support not only the formation of contact ion pairs in solution, but also the presence of larger ionic and neutral aggregates even when dissolved in solvents with relatively high dielectric constants, such as acetonitrile and DMSO. The presence of larger imidazolium supramolecular aggregates is favoured at higher salt concentrations in solvents of low dielectric constant for ILs that contain shorter N-alkyl side chains associated with anions of low coordination ability. The stability and reactivity of neutral contact species are also dependent on the nature of the anion, imidazolium substituents, and are more abundant in ILs containing strong coordinating anions, in particular those that can form charge transfer complexes with the imidazolium cation. Finally, some ILs display reactivities as contact ion pairs rather than solvent-separated ions.

The formation of imidazolium salt intimate (contact) ion pairs in solution.

1-n-Butyl-2,3-dimethylimidazolium (BMMI) ionic liquids (ILs) associated with different anions undergo H/D exchange preferentially at 2-Me group of the imidazolium in deuterated solvents. This process is mainly related to the existence of ion pairs rather than the anion basicity. The H/D exchange occurs in solvents (CDCl3 and MeCN for instance) in which intimate contact ion pairs are present and the anion possesses a labile H in its structure, such as hydrogen carbonate and prolinate. In D2 O, separated ion pairs are formed and the H/D exchange does not occur. A plausible catalytic cycle is that the IL behaves as a neutral base in the course of all H/D exchange processes. NMR experiments, density functional calculations, and molecular dynamics simulations corroborate these hypotheses.

Self-assembly and structural characterization of Echinococcus granulosus antigen B recombinant subunit oligomers.

Echinococcus granulosus antigen B is an oligomeric protein of 120-160 kDa composed by 8-kDa (AgB8) subunits. Here, we demonstrated that the AgB8 recombinant subunits AgB8/1, AgB8/2 and AgB8/3 are able to self-associate into high order homo-oligomers, showing similar properties to that of parasite-produced AgB, making them valuable tools to study AgB structure. Dynamic light scattering, size exclusion chromatography and cross-linking assays revealed approximately 120- to 160-kDa recombinant oligomers, with a tendency to form populations with different aggregation states. Recombinant oligomers showed helical circular dichroism spectra and thermostability similar to those of purified AgB. Cross-linking and limited proteolysis experiments indicated different degrees of stability and compactness between the recombinant oligomers, with the AgB8/3 one showing a more stable and compact structure. We have also built AgB8 subunit structural models in order to predict the surfaces possibly involved in electrostatic and hydrophobic interactions during oligomerization.