The widespread use of controlled molecular-level motion in key natural processes suggests that great rewards could come from bridging the gap between the present generation of synthetic molecular systems, which by and large rely upon electronic and chemical effects to carry out their functions, and the machines of the macroscopic world, which utilize the synchronized movements of smaller parts to perform specific tasks. This is a scientific area of great contemporary interest and extraordinary recent growth, yet the notion of molecular-level machines dates back to a time when the ideas surrounding the statistical nature of matter and the laws of thermodynamics were first being formulated. Here we outline the exciting successes in taming molecular-level movement thus far, the underlying principles that all experimental designs must follow, and the early progress made towards utilizing synthetic molecular structures to perform tasks using mechanical motion. We also highlight some of the issues and challenges that still need to be overcome.

Synthetic molecular motors and mechanical machines.

Brownian motors: noisy transport far from equilibrium

The widespread use of molecular machines in biology has long suggested that great rewards could come from bridging the gap between synthetic molecular systems and the machines of the macroscopic world. In the last two decades, it has proved possible to design synthetic molecular systems with architectures where triggered large amplitude positional changes of submolecular components occur. Perhaps the best way to appreciate the technological potential of controlled molecular-level motion is to recognize that nanomotors and molecular-level machines lie at the heart of every significant biological process. Over billions of years of evolution, nature has not repeatedly chosen this solution for performing complex tasks without good reason. When mankind learns how to build artificial structures that can control and exploit molecular level motion and interface their effects directly with other molecular-level substructures and the outside world, it will potentially impact on every aspect of functional molecule and materials design. An improved understanding of physics and biology will surely follow.

The first steps on the long path to the invention of artificial molecular machines were arguably taken in 1827 when the Scottish botanist Robert Brown observed the haphazard motion of tiny particles under his microscope.1,2 The explanation for Brownian motion, that it is caused by bombardment of the particles by molecules as a consequence of the kinetic theory of matter, was later provided by Einstein, followed by experimental verification by Perrin.3,4 The random thermal motion of molecules and its implications for the laws of thermodynamics in turn inspired Gedankenexperiments (“thought experiments”) that explored the interplay (and apparent paradoxes) of Brownian motion and the Second Law of Thermodynamics. Richard Feynman’s famous 1959 lecture “There’s plenty of room at the bottom” outlined some of the promise that manmade molecular machines might hold.5,6 However, Feynman’s talk came at a time before chemists had the necessary synthetic and analytical tools to make molecular machines. While interest among synthetic chemists began to grow in the 1970s and 1980s, progress accelerated in the 1990s, particularly with the invention of methods to make mechanically interlocked molecular systems (catenanes and rotaxanes) and control and switch the relative positions of their components.7−24

Here, we review triggered large-amplitude motions in molecular structures and the changes in properties these can produce. We concentrate on conformational and configurational changes in wholly covalently bonded molecules and on catenanes and rotaxanes in which switching is brought about by various stimuli (light, electrochemistry, pH, heat, solvent polarity, cation or anion binding, allosteric effects, temperature, reversible covalent bond formation, etc.). Finally, we discuss the latest generations of sophisticated synthetic molecular machine systems in which the controlled motion of subcomponents is used to perform complex tasks, paving the way to applications and the realization of a new era of “molecular nanotechnology”.

1.1. The Language Used To Describe Molecular Machines
Terminology needs to be properly and appropriately defined and these meanings used consistently to effectively convey scientific concepts. Nowhere is the need for accurate scientific language more apparent than in the field of molecular machines. Much of the terminology used to describe molecular-level machines has its origins in observations made by biologists and physicists, and their findings and descriptions have often been misinterpreted and misunderstood by chemists. In 2007 we formalized definitions of some common terms used in the field (e.g., “machine”, “switch”, “motor”, “ratchet”, etc.) so that chemists could use them in a manner consistent with the meanings understood by biologists and physicists who study molecular-level machines.14

The word “machine” implies a mechanical movement that accomplishes a useful task. This Review concentrates on systems where a stimulus triggers the controlled, relatively large amplitude (or directional) motion of one molecular or submolecular component relative to another that can potentially result in a net task being performed. Molecular machines can be further categorized into various classes such as “motors” and “switches” whose behavior differs significantly.14 For example, in a rotaxane-based “switch”, the change in position of a macrocycle on the thread of the rotaxane influences the system only as a function of state. Returning the components of a molecular switch to their original position undoes any work done, and so a switch cannot be used repetitively and progressively to do work. A “motor”, on the other hand, influences a system as a function of trajectory, meaning that when the components of a molecular motor return to their original positions, for example, after a 360° directional rotation, any work that has been done is not undone unless the motor is subsequently rotated by 360° in the reverse direction. This difference in behavior is significant; no “switch-based” molecular machine can be used to progressively perform work in the way that biological motors can, such as those from the kinesin, myosin, and dynein superfamilies, unless the switch is part of a larger ratchet mechanism.14

Artificial Molecular Machines

In systems possessing spatial or dynamical symmetry breaking, Brownian motion combined with unbiased external input signals, deterministic and random alike, can assist directed motion of particles at submicron scales. In such cases, one speaks of ``Brownian motors.'' In this review the constructive role of Brownian motion is exemplified for various physical and technological setups, which are inspired by the cellular molecular machinery: the working principles and characteristics of stylized devices are discussed to show how fluctuations, either thermal or extrinsic, can be used to control diffusive particle transport. Recent experimental demonstrations of this concept are surveyed with particular attention to transport in artificial, i.e., nonbiological, nanopores, lithographic tracks, and optical traps, where single-particle currents were first measured. Much emphasis is given to two- and three-dimensional devices containing many interacting particles of one or more species; for this class of artificial motors, noise rectification results also from the interplay of particle Brownian motion and geometric constraints. Recently, selective control and optimization of the transport of interacting colloidal particles and magnetic vortices have been successfully achieved, thus leading to the new generation of microfluidic and superconducting devices presented here. The field has recently been enriched with impressive experimental achievements in building artificial Brownian motor devices that even operate within the quantum domain by harvesting quantum Brownian motion. Sundry akin topics include activities aimed at noise-assisted shuttling other degrees of freedom such as charge, spin, or even heat and the assembly of chemical synthetic molecular motors. This review ends with a perspective for future pathways and potential new applications.

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Artificial Brownian motors: Controlling transport on the nanoscale

Transport phenomena are fundamental in physics. They allow for information and energy to be exchanged between individual constituents of communication systems, networks or even biological entities. Environmental noise will generally hinder the efficiency of the transport process. However, and contrary to intuition, there are situations in classical systems where thermal fluctuations are actually instrumental in assisting transport phenomena. Here we show that, even at zero temperature, transport of excitations across dissipative quantum networks can be enhanced by local dephasing noise. We explain the underlying physical mechanisms behind this phenomenon and propose possible experimental demonstrations in quantum optics. Our results suggest that the presence of entanglement does not play an essential role for energy transport and may even hinder it. We argue that Nature may be routinely exploiting dephasing noise and show that the transport of excitations in simplified models of light harvesting molecules does benefit from such noise assisted processes. These results point toward the possibility for designing optimized structures for transport, for example in artificial nanostructures, assisted by noise.

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Dephasing-assisted transport: quantum networks and biomolecules

The manipulation of neutral atoms by light is at the heart of countless scientific discoveries in the field of quantum physics in the last three decades. The level of control that has been achieved at the single particle level within arrays of optical traps, while preserving the fundamental properties of quantum matter (coherence, entanglement, superposition), makes these technologies prime candidates to implement disruptive computation paradigms. In this paper, we review the main characteristics of these devices from atoms / qubits to application interfaces, and propose a classification of a wide variety of tasks that can already be addressed in a computationally efficient manner in the Noisy Intermediate Scale Quantum era we are in. We illustrate how applications ranging from optimization challenges to simulation of quantum systems can be explored either at the digital level (programming gate-based circuits) or at the analog level (programming Hamiltonian sequences). We give evidence of the intrinsic scalability of neutral atom quantum processors in the 100-1,000 qubits range and introduce prospects for universal fault tolerant quantum computing and applications beyond quantum computing.

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Quantum computing with neutral atoms

It was suggested recently that particles evolving in a bipotential that is macroscopically flat but locally asymmetric can be set into directed motion [J. Prost et al., Phys. Rev. Lett. 72, 2652 (1994)]. We show evidence of this effect using cold rubidium atoms in a grey optical lattice.

Ratchet for Cold Rubidium Atoms: The Asymmetric Optical Lattice

We present an experimental investigation of the local dynamics and spatial diffusion of atoms in a rubidium optical lattice using polarization-selective intensity correlation spectroscopy in both the time and frequency domains. Autocorrelations of the circularly polarized components of the fluorescence light are shown to give access to the atomic dynamics in a single optical potential well. By contrast, cross correlations between opposite circular components of the scattered light provide information about atomic transport in the lattice through escape and recapture between neighbor potential wells.

Atomic Transport in an Optical Lattice: An Investigation through Polarization-Selective Intensity Correlations.

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C. Jurczak

Papers

Quantum computing with neutral atoms

Ratchet for Cold Rubidium Atoms: The Asymmetric Optical Lattice

Atomic Transport in an Optical Lattice: An Investigation through Polarization-Selective Intensity Correlations.

Quantum computing with neutral atoms

Observation of intensity correlations in the fluorescence from laser cooled atoms