ABSTRACT
Whereas l-3-oxo-hexanoyl homoserine lactone (OHHL) is the active enantiomer of the of LuxR-regulated quorum sensing (QS) autoinducer, its d isomer is implicitly considered as inactive. The present work aims to clarify this l-specificity and investigate whether it extends to some analogues in the acyl homoserine lactone (AHL) family. For this purpose, OHHL and a series of AHL analogs were synthesized in racemic and enantiomerically pure d and l forms and their ability to induce or attenuate bioluminescence in the LuxR-dependent QS system was evaluated. In this study, l-isomers are confirmed as either the only, or as the most active, enantiomers. However, in several cases, especially for the natural ligand of LuxR (OHHL) and the very similar AHL agonist analogue 2, the d-isomer cannot be considered as totally inactive on QS. Molecular modelling suggests that when the lactone moiety of the d-isomer is able to twist, enabling the lactone carbonyl group and the amide function to interact with the key residues in the binding site, then the d-isomer can exhibit some activity.
Subject(s)
4-Butyrolactone/analogs & derivatives , 4-Butyrolactone/chemical synthesis , 4-Butyrolactone/chemistry , Dose-Response Relationship, Drug , Luminescent Measurements , Models, Molecular , Molecular Structure , Quorum Sensing , Stereoisomerism , Structure-Activity RelationshipABSTRACT
In this proof of concept study, the advantageous properties of both H(2)O(2)/NaHCO(3)/imidazole/Mn(TPP)OAc oxidation system and MOPyrroNTf(2) ionic liquid have been combined under ultrasonic irradiation to give an exceptionally favorable environment for Mn(TPP)OAc catalyzed olefin oxidations. The results reveal the crucial role played by the ultrasonic irradiations that influence drastically the oxidation process. In MOPyrroNTf(2) and under ultrasonic irradiation, the mechanism probably involves an oxo-manganyl intermediate at the expense of the classical bicarbonate-activated peroxide route.
Subject(s)
Alkenes/chemistry , Alkenes/radiation effects , Epoxy Compounds/chemistry , Epoxy Compounds/radiation effects , Ionic Liquids/chemistry , Ionic Liquids/radiation effects , Sonication/methods , High-Energy Shock Waves , Radiation DosageABSTRACT
Herein, we report the manganese complex with a novel trianionic ligand, the pentafluorophenyldipyrrinphenol ligand DPPH(3). The X-ray crystal structure reveals that the Mn(III) complex exists in a dimeric form in the solid state. Electrochemical studies indicate two quasi-reversible one electron oxidation processes. EPR data on the one electron oxidised species in solution support the formation of a monuclear Mn complex with an S = 3/2 spin system. Preliminary studies towards epoxidation reactions were tested in the presence of iodosylbenzene (PhIO) and are in favour of an oxygen-atom-transfer (OAT) reaction catalyzed by the Mn(III) complex.
