Caratterizzazione della distribuzione della coppia ergotioneina/ercinina e valutazione delle potenzialità dell’ercinina quale marker delle attività redox dell’ergotioneina

Given that redox activity of ergothioneine might explain the presence of hercynine in biological fluids, measurement of hercynine might serve to indirectly detect oxidative stress states or other biological processes involving ergothioneine. This could be particularly advantageous as the peculiar redox behavior of ergothioneine, which acts to rapidly restore ergothioneine concentrations, can minimize its potential fluctuations. Little is known about this betaine of the histidine in the body, which is in part due to the lack of reliable analytical methods and the difficulty in purchasing commercial standards. Following in-house chemical synthesis of hercynine and considering different analytical strategies, a LC-MS/MS method was developed for the measurement of hercynine levels in different animal and human specimens such as whole blood, plasma/serum, urine, and equine seminal plasma. The results of these analyses highlight the uncertain role of hercynine as an indirect marker of ergothioneine activities in humans. This was primarily due to the challenges with the identification of specific phenotypes where ergothioneine plays a clear biological role. Conversely, due to the unusual physiology of stallions’ sperm cells, who rely primarily on mitochondrial ATP production by oxidative phosphorylation rather than glycolysis, hercynine can serve as an indirect marker of ergothioneine in stallions’ seminal plasma.