Reductive Stress of Sulfur-Containing Amino Acids within Proteins and Implication of Tandem Protein–Lipid Damage

Reductive radical stress represents the other side of the redox spectrum, less studied but equally important compared to oxidative stress. The reactivity of hydrogen atoms (H•) and hydrated electrons (e–aq) connected with peptides/proteins is summarized, focusing on the chemical transformations of methionine (Met) and cystine (CysS–SCys) residues into α-aminobutyric acid and alanine, respectively. Chemical and mechanistic aspects of desulfurization processes with formation of diffusible sulfur-centered radicals, such as methanethiyl (CH3S•) and sulfhydryl (HS•) radicals, are discussed. These findings are further applied to biomimetic radical chemistry, modeling the occurrence of tandem protein–lipid damages in proteo-liposomes and demonstrating that generation of sulfur-centered radicals from a variety of proteins is coupled with the cis–trans isomerization of unsaturated lipids in membranes. Recent applications to pharmaceutical and pharmacological contexts are described, evidencing novel perspectives in the stability of formulations and mode of action of drugs, respectively.

Effect of Different Running Exercise Modalities on Post-Exercise Oxidative Stress Markers in Trained Athletes

The aim of this study was to examine the effect of running exercise modality on oxidative stress. Thirteen endurance athletes (age: 21.46 ± 0.66 years) performed three different running exercise modalities (Continuous running exercise (CR): continuous running exercise at 75% of VO2max for 25 min; intermittent running exercise #1 (15/15): intermittent running protocol, 15 s running at 75% of VO2max, 15 s passive recovery, performed for 50 min; intermittent running exercise #2 (30/30): intermittent running protocol, 30 s running at 75% of VO2max, 30 s passive recovery, performed for 50 min) in a randomized order. Blood samples were drawn at rest and immediately after each running exercise and assessed for malondialdehyde (MDA), advanced oxidation protein products (AOPP), superoxide dismutase(SOD), and glutathione peroxidase (GPX) activities. MDA increased by 55% following 30/30 exercise (p < 0.01), while it remained unchanged with CR and15/15 exercise. SOD increased after CR (+13.9%, p < 0.05), and also remained unchanged after 15/15 (p > 0.05) and decreased after 30/30 (−19.7% p < 0.05). GPX and AOPP did not change after exercise in all experimental sessions (p > 0.05). In conclusion, 30/30 intermittent running induced higher lipid damages than the 15/15 and CR exercise. 15/15 intermittent exercise promoted a better balance between free radicals production and antioxidant defense compared to continuous exercise and intermittent 30/30 exercise.