Exercising demons: how to drive a chemical system away from equilibrium

Abstract

The concept of tiny machines capable of selectively transporting particles between two compartments by Brownian motion dates back to the 19th century when James Clerk Maxwell pondered the significance of a hypothetical ‘sorting demon’ being able to perform such a task adiabatically. This thesis report the design, synthesis and operation of a compartmentalized molecular machine in which the distribution of a Brownian particle, the macrocycle in a rotaxane, is controlled by using the lightinduced transmission of information to lower a kinetic barrier according to the location of the particle. For an ensemble of such machines the particle distribution is driven further and further away from equilibrium, providing a non-adiabatic realization of Maxwell’s pressure demon in molecular form. The nanomachine does not break the Second Law of Thermodynamics because the energy cost of the information transfer is met by externally supplied photons. As the molecular structure can be understood in chemical terms, it is possible in this experimental system to pin-point precisely how information is traded for energy. Intriguingly, the chemical mechanism can also be understood in terms of game theory. This is the first example of a synthetic molecular machine designed to operate via an information ratchet mechanism, where knowledge of the object’s position is used to control its transport away from equilibrium.