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Thiol reactivity: lost in the crowd?
Eduardo Fuentes-Lemus1, Michael J Davies2
1Departamento de Química Física, Escuela de Química, Facultad de Química y de Farmacia, Pontificia Universidad Católica de Chile, Santiago, Chile; Department of Biomedical Sciences, Panum Institute, University of Copenhagen, Blegdamsvej 3, 2200 Copenhagen, Denmark.
Trends in Biochemical Sciences
|October 12, 2026
Abstract:
Predictions of cysteine reactivity rely heavily on acidity (pKa) data from dilute solutions. However, the intracellular milieu is crowded and dynamic, with substrates, cofactors, and metabolites that modulate reactivity, thereby affecting cell signaling and metabolic adaptation. This forum argues that Cys pKa values are necessary but insufficient, proposing an integrated, microenvironment-dependent framework.