Department of Chemistry, State University of New York, Potsdam, NY 13676, USA.
Department of Molecular & Translational Medicine, University of Brescia, 25121 Brescia, Italy.
Int J Mol Sci. 2022 May 29;23(11):6100. doi: 10.3390/ijms23116100.
Most in vitro iron mobilization studies from ferritin have been performed in aqueous buffered solutions using a variety of reducing substances. The kinetics of iron mobilization from ferritin in a medium that resembles the complex milieu of cells could dramatically differ from those in aqueous solutions, and to our knowledge, no such studies have been performed. Here, we have studied the kinetics of iron release from ferritin in fresh yeast cell lysates and examined the effect of cellular metabolites on this process. Our results show that iron release from ferritin in buffer is extremely slow compared to cell lysate under identical experimental conditions, suggesting that certain cellular metabolites present in yeast cell lysate facilitate the reductive release of ferric iron from the ferritin core. Using filtration membranes with different molecular weight cut-offs (3, 10, 30, 50, and 100 kDa), we demonstrate that a cellular component >50 kDa is implicated in the reductive release of iron. When the cell lysate was washed three times with buffer, or when NADPH was omitted from the solution, a dramatic decrease in iron mobilization rates was observed. The addition of physiological concentrations of free flavins, such as FMN, FAD, and riboflavin showed about a two-fold increase in the amount of released iron. Notably, all iron release kinetics occurred while the solution oxygen level was still high. Altogether, our results indicate that in addition to ferritin proteolysis, there exists an auxiliary iron reductive mechanism that involves long-range electron transfer reactions facilitated by the ferritin shell. The physiological implications of such iron reductive mechanisms are discussed.
大多数来自铁蛋白的体外铁动员研究都是在水缓冲溶液中使用各种还原剂进行的。铁从类似于细胞复杂环境的介质中的铁蛋白动员的动力学可能与水溶液中的动力学有很大的不同,据我们所知,尚未进行过此类研究。在这里,我们研究了新鲜酵母细胞裂解物中铁蛋白中铁释放的动力学,并研究了细胞代谢物对该过程的影响。我们的结果表明,与缓冲液相比,在相同的实验条件下,铁蛋白在缓冲液中的铁释放速度极慢,这表明酵母细胞裂解物中存在某些细胞代谢物可促进铁蛋白核心中铁的还原释放。使用具有不同分子量截止值(3、10、30、50 和 100 kDa)的过滤膜,我们证明了分子量大于 50 kDa 的细胞成分参与了铁的还原释放。当用缓冲液洗涤细胞裂解液三次或从溶液中省略 NADPH 时,铁动员率会明显下降。添加生理浓度的游离黄素,如 FMN、FAD 和核黄素,可使释放的铁量增加约两倍。值得注意的是,所有的铁释放动力学都发生在溶液中的氧气水平仍然很高的时候。总的来说,我们的结果表明,除了铁蛋白蛋白水解作用外,还存在一种辅助的铁还原机制,该机制涉及由铁蛋白壳促进的长程电子转移反应。讨论了这种铁还原机制的生理意义。