RESUMEN
The free radical chemistry of lipoic acid (LA) and dihydrolipoic acid (DHLA) intersect at the point where DHLA loses hydrogen to a good hydrogen abstracting radical, while LA reacts with strongly reducing ketyl radicals capable of donating a hydrogen atom. While aliphatic thiyl radicals have an absorbance at ~ 330 nm, the resulting radical, formally also a thiyl radical has distinct spectroscopic properties with a maximum at 385 nm, suggesting that the two sulphur centres interact strongly with each other as part of the chromophore. The reactions that form these radicals were studied by laser flash photolysis that revealed DHLA as an excellent hydrogen donor, while LA is an excellent hydrogen acceptor. The results support earlier evidence that the real antioxidant is DHLA, while LA is not; yet, the reported facile interconversion of the two molecules suggests that LA may be a better supplement, given its shelf stability, compared with a far more difficult-to-handle DHLA.
RESUMEN
Given the current grave problems with antibiotic resistance, the discovery of novel, unconventional antibacterial drugs is not just important but also urgent. In this contribution, we report on the synthesis and testing of several composite nanomaterials that may find applications as therapeutic drugs or surface disinfectants. These materials are based on magnetic nanostructures coated with lignin, for example, lignin@FeCo. The magnetic properties of these nanocomposites facilitate removal or localization, whereas the lignin shell provides biocompatibility. These nanomaterials are mild antibacterials in the absence of light, but when illuminated become powerful antibacterial agents with typically ≥6 log units of bacterial reduction in 1-5 min of irradiation. These materials are strongly absorbing, including in the very useful NIR biological window, which we illustrate using 810 nm LED irradiation. We also show that in the short time required for antibacterial action, thermal changes are very small (≤5°C). Further, biocompatibility tests using fibroblasts show very limited cell damage and no enhanced adverse effect during 810 nm NIR illumination. As a surface coating for the active material, lignin provides a "trojan horse" strategy to facilitate the antibacterial action.