Negative differential response in chemical reactions

TL;DR

This paper demonstrates the occurrence of negative differential response in key biological chemical reactions, revealing optimal conditions for robustness and dissipation through large deviation analysis.

Contribution

It introduces a theoretical framework showing NDR in biological reactions and identifies optimal affinities for robustness and dissipation.

Findings

NDR occurs in substrate inhibition and autocatalysis models.

Optimal affinities maximize robustness against noise.

NDR is also observed in dissipative self-assembly.

Abstract

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.