Synthesis of 3-(4-tert-butylphenyl)-2-propen-1-one, a precursor to Lilial (R), via an aldol condensation in an ionic liquid

An efficient synthesis of a precursor to Lilial(R), based on an aldol condensation in an ionic liquid, is described, utilising piperidine as the base catalyst. The yields obtained with this methodology are significantly increased in comparison with those reported in organic solvents to date. In the ionic liquid, the self-aldol condensation of propanal is suppressed and leads to an increased selectivity with respect to the cross-aldol condensation product without the need to use an excess of 4-tert-butylbenzaldehyde to obtain high selectivities.

Kassina senegalensis skin tachykinins: Molecular cloning of kassinin and (Thr2, Ile9)-kassinin biosynthetic precursor cDNAs and comparative bioactivity of mature tachykinins on the smooth muscle of rat urinary bladder

Tachykinins are among the most widely-studied families of regulatory peptides characterized by a highly-conserved C-terminal -Phe-X-Gly-Leu-Met.amide motif, which also constitutes the essential bioactive core. The amphibian skin has proved to be a rich source of these peptides with physalaemin from the skin of Physalaemus fuscomaculatus representing the archetypal aromatic tachykinin (X = Tyr or Phe) and kassinin from the skin of Kassina senegalensis representing the archetypal aliphatic tachykinin in which X = Val or Ile. Despite the primary structures of both mature peptides having been known for at least 30 years, neither the structures nor organizations of their biosynthetic precursors have been reported. Here we report the structure and organization of the biosynthetic precursor of kassinin deduced from cDNA cloned from a skin secretion library. In addition, a second precursor cDNA encoding the novel kassinin analog (Thr2, Ile9)-kassinin was identified as was the predicted mature peptide in skin secretion. Both transcripts exhibited a high degree of nucleotide sequence similarity and of open-reading frame translated amino acid sequences of putative precursor proteins. The translated preprotachykinins each consisted of 80 amino acid residues encoding single copies of either kassinin or its site-substituted analog. Synthetic replicates of each kassinin were found to be active on rat urinary bladder smooth muscle at nanomolar concentrations. The structural organization of both preprotachykinins differs from that previously reported for those of Odorrana grahami skin indicating a spectrum of diversity akin to that established for amphibian skin preprobradykinins.

Interaction of Room Temperature Ionic Liquid Solutions with a Cholesterol Bilayer

Water solutions of representative (IC(4)mim][Cl] and [C(4)mim][Tf2N] room temperature ionic liquids (ILs) in contact with a neutral lipid bilayer made of cholesterol molecules has been investigated by molecular dynamics simulations based on an empirical force field model. The results show that both ILs display selective adsorption at the water-cholesterol interface, with partial inclusion of ions into the bilayer. In the case Of [C(4)mim][Cl], the adsorption of ions at the water-cholesterol interface is limited by a sizable bulk solubility of the IL, driven by the high water affinity of [Cl](-). The relatively low Solubility Of [C(4)mim][Tf2N], instead, gives rise to a nearly complete segregation of the IL component on the bilayer, altering its volume, compressibility, and electrostatic environment. The computational results display important similarities to the results of recent experimental measurements for ILs in contact with phospholipid model membranes (see Evans, K. O. Int. J. Mol. Sci. 2008, 9, 498-511 and references therein).

Liquid-liquid miscibility and volumetric properties of aqueous solutions of ionic liquids as a function of temperature

The volumetric properties of seven {water + ionic liquid} binary mixtures have been studied as a function of temperature from (293 to 343) K. The phase behaviour of the systems was first investigated using a nephelometric method and excess molar volumes were calculated from densities measured using an Anton Paar densimeter and fitted using a Redlich-Kister type equation. Two ionic liquids fully miscible with water (1-butyl-3-methylimidazolium tetrafluoroborate ([CCIm][BF]) and 1-ethyl-3-methylimidazolium ethylsulfate ([CCIm][EtSO])) and five ionic liquids only partially miscible with water (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CCIm][NTf]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([CCIm][NTf]), 1-butyl-3-methylimidazolium hexafluorophosphate ([CCIm][PF]), 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([CCPyrro][NTf]), and butyltrimethylammonium bis(trifluoromethylsulfonyl)imide ([N][NTf])) were chosen. Small excess volumes (less than 0.5 cm · mol at 298 K) are obtained compared with the molar volumes of the pure components (less than 0.3% of the molar volume of the pure ionic liquid). For all the considered systems, except for {[CCIm][EtSO] + water}, positive excess molar volumes were calculated. Finally, an increase of the non-ideality character is observed for all the systems as temperature increases. © 2009 Elsevier Ltd. All rights reserved.

Assessment of Self-Compacting Concrete Immersed in Acidic Solutions

Ettringite and thaumasite can be found among the deterioration products of cementitious materials exposed to sulfate and hydrochloric attack. The results of a test program to investigate the acid resistance of self-compacting concrete (SCC) and conventional concrete (CC), immersed up to 18 weeks at 20°C in sulfuric and hydrochloric acid solutions, are described. The SCC was prepared with 47% carboniferous limestone powder, as a replacement for cement, and an ordinary portland cement. The CC was prepared with portland cement only. The water-binder ratios of the SCC and CC were 0.36 and 0.46, respectively. The parameter investigated was the time, in weeks, taken to cause 10% mass loss of fully immersed concrete specimens in a 1% solution of sulfuric acid and the same amount of loss in a 1% solution of hydrochloric acid. The investigation indicated that the SCC performed better than the CC in sulfuric solution but was slightly more vulnerable to hydrochloric acid attack compared to CC. The mode of attack between the two solutions was different.

1,3-dimethylimidazolium-2-carboxylate: the unexpected synthesis of an ionic liquid precursor and carbene-CO2 adduct

1,3-Dimethylimidazolium-2-carboxylate is formed in good yield, rather than the anticipated organic salt, 1,3-dimethylimidazolium methyl carbonate, as the reaction product resulting from both N-alkylation and C-carboxylation of 1-methylimidazole with dimethyl carbonate; the crystal structure of the zwitterion exhibits pi-stacked rings and two-dimensional sheets constructed by hydrogen-bonds from imidazolium-ring hydrogens to the carboxylate group.

Extraction of cesium ions from aqueous solutions using calix[4]arene-bis(tert-octylbenzo-crown-6) in ionic liquids

Solvent extraction of cesium ions from aqueous solution to hydrophobic ionic liquids without the introduction of an organophilic anion in the aqueous phase was demonstrated using calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) as an extractant. The selectivity of this extraction process toward cesium ions and the use of a sacrificial cation exchanger (NaBPh4) to control loss of imidazolium cation to the aqueous solutions by ion exchange have been investigated.