Conformational studies of Gram-negative bacterial quorum sensing acyl homoserine lactone (AHL) molecules: The importance of the n → π* interaction.

A 1H NMR study shows the presence of intermolecular hydrogen bonds for AHLs in CDCl3 solution. A detailed computational study of the structure of AHLs and the relative stability between the extended conformations (X) and those showing n → π* interactions (np) have been carried out by means of DFT calculations. Solvent effects have been shown to be very important when stabilising np conformations, particularly with polar solvents. This was shown by the shortening of C⋯O intramolecular distances and the increase in the relative energies favouring the np conformation with the dielectric constant of the solvent. The charge transfer between the O donor and the acceptor carbonyl group, assessed by second order perturbation energies, E(2), also shows an increase in the E(2) values with the dielectric constant of the solvent.

Conformational studies of Gram-negative bacterial quorum sensing 3-oxo N-acyl homoserine lactone molecules.

In their 1H NMR spectra in CDCl3 3-oxo-N-acyl homoserine lactones (OHLs) show significant downfield chemical shifts of the amide NH proton when compared to the parent N-acyl homoserine lactones (AHLs). NMR spectroscopic and DFT calculation studies have shown that this is most likely due to the presence of a stabilising intramolecular H-bond from the NH to the 3-oxo group. The 1H NMR spectra also show evidence for the enol tautomers and that the amount of enol present for a range of OHLs is 4.1-4.5% in CDCl3 and 6.5-7.2% in CD3CN. In contrast, DFT calculations show that the lowest energy enol tautomer and the keto tautomer are of equal energy in the gas phase, but that the keto tautomer is more stable in chloroform, acetonitrile and water solution. The calculations also show that there is no evidence for any n→π∗ or C5H-bonding interactions being present in either the lowest energy keto or enol tautomer of the OHLs in solution or the gas phase, which is in contrast to the reported solid-state structure.

Bioelectrical impedance analysis determination of water content and distribution in the horse.

A horse's hydration status is critical to its health. The accurate and quantitative determination of it has been problematic because of size, length and density of hair, and uneven topography. The objective of this study was to validate a bioelectrical impedance analysis (BIA) method for objectively quantifying hydration status. Monofrequency BIA values and simple biometric measurements were used to construct predictive equations for total body water, plasma, extracellular, and intra-cellular fluid volumes. These predictive equations were correlated with standard body fluid dilution reference methods. The result was an accuracy of ±0.64% for total body water, ±0.17% for plasma volume, ±1.91% for extra-cellular fluid, and ±0.57% for intra-cellular fluid compartments. Less than 5 min was required for all of the measurements and determinations. Therefore, it appears that an accurate measurement of body fluid distribution can be performed on horses using a fast, easy, non-invasive, inexpensive BIA method.