The Acidity of the HBr/AlBr3 System: Stabilization of Crystalline Protonated Arenes and Their Acidity in Bromoaluminate Ionic Liquids.

Bulk protonated mesitylene, toluene, and benzene bromoaluminate salts were stabilized and characterized in the superacidic system HBr/n AlBr3 with NMR spectroscopy and X-ray analysis of [HC6 H3 (CH3 )3 ](+) [AlBr4 ](-) (1), [HC6 H5 (CH3 )](+) [AlBr4 ](-) (2), and [C6 H7 ](+) [Al2 Br7 ](-) ⋅C6 H6 (3). Protonation attempts in bromoaluminate ILs led to a complete protonation of mesitylene, and a protonation degree of up to 15 % for toluene in the IL BMP(+) [Al2 Br7 ](-) . Benzene could only be protonated in the more acidic IL BMP(+) [Al3 Br10 ](-) , with a degree of 25 %. Protonation attempts on aromatics provide evidence that the bromoaluminate ILs tolerate superacidic environments. On the basis of the absolute Brønsted acidity scale, quantum chemical calculations confirmed the superacidic properties, and rank the acidities in ILs down to a pHabs value of 164 with an error of less than one pH unit compared with experimental findings. The neat AlBr3 /HBr system even may reach acidities down to pHabs 163.

Absolute Brønsted Acidities and pH Scales in Ionic Liquids.

Although receiving large interest over the last years, some fundamental aspects of Brønsted acidity in ionic liquids (ILs) have up to now been insufficiently highlighted. In this work, standard states, activity, and activity coefficient definitions for IL solvent systems were developed from general thermodynamic considerations and then extended to a general mixed solvent standard state. By using the bromide/bromoaluminate systems as representative ILs, formulae for thermodynamically consistent pH scales for ILs with simple (Br(-) ) and complex ([Aln Br3n+1 ](-) ) anions were derived on the basis of the chemical potential of the proton. Supported by quantum chemical [ccsd(t)/MP2/DFT/COSMO-RS] calculations, Gibbs solvation energies of the proton were calculated, which allowed the ILs to be ranked in absolute acidity, that is, pHabs or µabs (H(+) , IL), and additionally allowed their acidity to be compared with molecular Brønsted acid systems. It was shown that bromoaluminate ILs are suited for reaching superacidic conditions. The complexity of autoprotolysis processes in C6 MIM(+) [AlBr4 ](-) (C6 MIM=1-hexyl-3-methylimidazolium) with or without the addition of basic (i.e. Br(-) ) or acidic (AlBr3 and/or HBr) solutes was examined in detail by model calculations, and they indicated a large thermodynamic influence of small deviations from the exact stoichiometric composition.

The superacid HBr/AlBr(3) : protonation of benzene and ordered crystal structure of [C(6)H(7)](+)[Al(2)Br(7)](-).

Crystalline and properly ordered protonated benzene as the [C6 H7 ](+) [Al2 Br7 ](-) ⋅(C6 H6 ) salt 1 are obtained by the combination of solid AlBr3 , benzene, and HBr gas. Compound 1 was characterized and verified by NMR, Raman and X-Ray spectroscopy. This unexpected simple and straight forward access shows that HBr/AlBr3 is an underestimated superacid that should be used more frequently.

Superacidic or not ? Synthesis, characterisation, and acidity of the room-temperature ionic liquid [C(CH3)3]+ [Al2Br7]-.

The room-temperature ionic liquid (RT-IL) [C(CH(3))(3)](+)[Al(2)Br(7)](-) (m.p. 2 °C) was generated by bromide abstraction from tert-butyl bromide with the Lewis acid aluminum bromide in the absence of solvent. The crystal structure of the tert-butyl cation salt was determined by X-ray diffraction. NMR, IR, and Raman spectroscopy, as well as quantum-chemical and thermodynamic calculations, confirm the composition of this RT-IL. Thus, one may consider this RT-IL to be a readily accessible (and on a large scale) cationic Brønsted acid (protonated isobutene) with the potential for further reactivity. Based on the new absolute Brønsted acidity scale, we calculated an absolute pH(abs) value of 171 for liquid bulk [C(CH(3))(3)](+)[Al(2)Br(7)](-). This value is about as acidic as 100 % sulfuric acid (pH(abs) = 171) and, thus, on the edge of superacidity.

Comparative study of biphasic calcium phosphate with beta-tricalcium phosphate in rat cranial defects--A molecular-biological and histological study.

The aim of this study was to evaluate the in vivo biocompatibility of a biphasic calcium phosphate (BCP) bone graft substitute consisting of 60% hydroxyapatite and 40% ß-tricalcium phosphate (ß-TCP) in comparison to a pure ß-TCP of identical shape and porosity. The materials were evaluated using an established rat cranial defect model in 24 animals. One bone defect with a diameter of 5mm was created per animal. The defects were filled with either BCP or ß-TCP and left to heal for 4 weeks. Twelve samples (6 per material) were processed for histological evaluation and immunohistochemistry. The remaining 12 samples were processed for mRNA expression analysis. No signs of inflammation or adverse material reactions were detected. New bone formation in the former defect site did not differ between the two groups (BCP: 49.2%; ß-TCP: 52.4%). Osteoblast-like and TRAP-positive osteoclast-like cells were found at the surface of the bone graft substitute granules. The ß-TCP group showed significantly higher mRNA levels for the bone resorption marker Acp5 and osteogenic differentiation marker Runx2. The expression of IGF1, IGF2, VEGF, Phex, Alpl, Col1, Col2, Bglap and MMP8 did not differ between the groups. The in vivo biocompatibility of BCP is to a large part identical to those of TCP. Within the limitation of the animal model, the implantation study shows that BCP can be used as bone graft substitute, due to the fact that the material integrates into tissue, remains stable in the implantation bed and serves as an osteoconductive scaffold.