Negative differential response in chemical reactions

Reaction currents in chemical networks usually increase when increasing their driving affinities. But far from equilibrium the opposite can also happen. We find that such negative differential response (NDR) occurs in reaction schemes of major biological relevance, namely, substrate inhibition and autocatalysis. We do so by deriving the full counting statistics of two minimal representative models using large deviation methods. We argue that NDR implies the existence of optimal affinities that maximize the robustness against environmental and intrinsic noise at intermediate values of dissipation. An analogous behavior is found in dissipative self-assembly, for which we identify the optimal working conditions set by NDR.