Artificial Molecular Motors Research Articles

A dynamical model for Brownian molecular motors driven by inelastic electron tunneling

In recent years, several artificial molecular motors driven and controlled by electric currents have been proposed. Similar to Brownian machines, these systems work by turning random inelastic tunneling events into a directional rotation of the molecule. Despite their importance as the ultimate component of future molecular machines, their modeling has not been sufficiently studied. Here, we develop a dynamical model to describe these systems. We illustrate the validity and usefulness of our model by applying it to a well-known molecular motor, showing that the obtained results are consistent with the available experimental data. Moreover, we demonstrate how to use our model to extract some difficult-to-access microscopic parameters. Finally, we include an analysis of the expected effects of current-induced forces (CIFs). Our analysis suggests that, although nonconservative contributions of the CIFs can be important in some scenarios, they do not seem important in the analyzed case. Despite this, the conservative contributions of CIFs could be strong enough to significantly alter the system's dynamics.

Tuning the Force, Speed, and Efficiency of an Autonomous Chemically Fueled Information Ratchet.

Autonomous chemically fueled molecular machines that function through information ratchet mechanisms underpin the nonequilibrium processes that sustain life. These biomolecular motors have evolved to be well-suited to the tasks they perform. Synthetic systems that function through similar mechanisms have recently been developed, and their minimalist structures enable the influence of structural changes on machine performance to be assessed. Here, we probe the effect of changes in the fuel and barrier-forming species on the nonequilibrium operation of a carbodiimide-fueled rotaxane-based information ratchet. We examine the machine’s ability to catalyze the fuel-to-waste reaction and harness energy from it to drive directional displacement of the macrocycle. These characteristics are intrinsically linked to the speed, force, power, and efficiency of the ratchet output. We find that, just as for biomolecular motors and macroscopic machinery, optimization of one feature (such as speed) can compromise other features (such as the force that can be generated by the ratchet). Balancing speed, power, efficiency, and directionality will likely prove important when developing artificial molecular motors for particular applications.

A DNA origami rotary ratchet motor

To impart directionality to the motions of a molecular mechanism, one must overcome the random thermal forces that are ubiquitous on such small scales and in liquid solution at ambient temperature. In equilibrium without energy supply, directional motion cannot be sustained without violating the laws of thermodynamics. Under conditions away from thermodynamic equilibrium, directional motion may be achieved within the framework of Brownian ratchets, which are diffusive mechanisms that have broken inversion symmetry1–5. Ratcheting is thought to underpin the function of many natural biological motors, such as the F1F0-ATPase6–8, and it has been demonstrated experimentally in synthetic microscale systems (for example, to our knowledge, first in ref. 3) and also in artificial molecular motors created by organic chemical synthesis9–12. DNA nanotechnology13 has yielded a variety of nanoscale mechanisms, including pivots, hinges, crank sliders and rotary systems14–17, which can adopt different configurations, for example, triggered by strand-displacement reactions18,19 or by changing environmental parameters such as pH, ionic strength, temperature, external fields and by coupling their motions to those of natural motor proteins20–26. This previous work and considering low-Reynolds-number dynamics and inherent stochasticity27,28 led us to develop a nanoscale rotary motor built from DNA origami that is driven by ratcheting and whose mechanical capabilities approach those of biological motors such as F1F0-ATPase.

Visiblelight-driven benzofuranone-based molecular motors: tuning rotary performance from solution phase to solid state

The advance of artificial molecular motors undoubtedly requires more versatile and tailored molecular scaffolds to achieve outstanding functions not only in the solution phase but also in the solid state. Herein, a novel type of light-driven unidirectional molecular motor based on benzofuranones was rationally designed and synthesized. Employment of the π-extension and electron donation strategies enabled several motors responsive to visible light with decent quantum yields and photoisomerizing efficiency at their photostationary states. In particular, one motor was responsive to 550 nm green light, representing the longest excitation wavelength up-to-now by one-photon excitation technique among the family of light-driven molecular motors. Moreover, the high biocompatibility and good performance under bio-environments hold these motors' enormous potential in biosciences. Importantly, these motors showed uncompromised rotary functions in condensed phases, such as soft supramolecular gel and solid polymeric films, laying a good foundation for the future design of motorized processible materials. The line of this work is assumed to promote the current focus of motor dynamics from the routine solution phase to the more practical condensed phase material systems. And the new motors explored here would offer a unique toolbox for motorists to perform the on-demand building of dynamic complexes.

Intrinsically unidirectional chemically fuelled rotary molecular motors.

Biological systems mainly utilize chemical energy to fuel autonomous molecular motors, enabling the system to be driven out of equilibrium1. Taking inspiration from rotary motors such as the bacterial flagellar motor2 and adenosine triphosphate synthase3, and building on the success of light-powered unidirectional rotary molecular motors4-6, scientists have pursued the design of synthetic molecular motors solely driven by chemical energy7-13. However, designing artificial rotary molecular motors operating autonomously using a chemical fuel and simultaneously featuring the intrinsic structural design elements to allow full 360° unidirectional rotary motion like adenosine triphosphate synthase remains challenging. Here we show that a homochiral biaryl Motor-3, with three distinct stereochemical elements, is a rotary motor that undergoes repetitive and unidirectional 360° rotation of the two aryl groups around a single-bond axle driven by a chemical fuel. It undergoes sequential ester cyclization, helix inversion and ring opening, and up to 99% unidirectionality is realized over the autonomous rotary cycle. The molecular rotary motor can be operated in two modes: synchronized motion with pulses of a chemical fuel and acid-base oscillations; and autonomous motion in the presence of a chemical fuel under slightly basic aqueous conditions. This rotary motor design with intrinsic control over the direction of rotation, simple chemical fuelling for autonomous motion and near-perfect unidirectionality illustrates the potential for future generations of multicomponent machines to perform mechanical functions.

Singular optimal driving cycles of stochastic pumps

The investigation of optimal processes has a long history in the field of thermodynamics. It is well-known that finite-time processes which minimize dissipation often exhibit discontinuities. We use a combination of numerical and analytical approaches to study the driving cycle that maximizes the output in a simple model of a stochastic pump: a system driven out of equilibrium by a cyclic variation of external parameters. We find that this optimal solution is singular, with an infinite rate of switching between sets of parameters. The appearance of such singular solutions in thermodynamic processes is surprising, but we argue that such solutions are expected to be quite common in models whose dynamics exhibit exponential relaxation, as long as the driving period is not externally fixed and is allowed to be arbitrarily short. Our results have implications to artificial molecular motors that are driven in a cyclic manner.

Through the Eyes of Creators: Observing Artificial Molecular Motors.

Inspired by molecular motors in biology, there has been significant progress in building artificial molecular motors, using a number of quite distinct approaches. As the constructs become more sophisticated, there is also an increasing need to directly observe the motion of artificial motors at the nanoscale and to characterize their performance. Here, we review the most used methods that tackle those tasks. We aim to help experimentalists with an overview of the available tools used for different types of synthetic motors and to choose the method most suited for the size of a motor and the desired measurements, such as the generated force or distances in the moving system. Furthermore, for many envisioned applications of synthetic motors, it will be a requirement to guide and control directed motions. We therefore also provide a perspective on how motors can be observed on structures that allow for directional guidance, such as nanowires and microchannels. Thus, this Review facilitates the future research on synthetic molecular motors, where observations at a single-motor level and a detailed characterization of motion will promote applications.

Effect of charge-transfer enhancement on the efficiency and rotary mechanism of an oxindole-based molecular motor.

Harvesting energy and converting it into mechanical motion forms the basis for both natural and artificial molecular motors. Overcrowded alkene-based light-driven rotary motors are powered through sequential photochemical and thermal steps. The thermal helix inversion steps are well characterised and can be manipulated through adjustment of the chemical structure, however, the insights into the photochemical isomerisation steps still remain elusive. Here we report a novel oxindole-based molecular motor featuring pronounced electronic push–pull character and a four-fold increase of the photoisomerization quantum yield in comparison to previous motors of its class. A multidisciplinary approach including synthesis, steady-state and transient absorption spectroscopies, and electronic structure modelling was implemented to elucidate the excited state dynamics and rotary mechanism. We conclude that the charge-transfer character of the excited state diminishes the degree of pyramidalisation at the alkene bond during isomerisation, such that the rotational properties of this oxindole-based motor stand in between the precessional motion of fluorene-based molecular motors and the axial motion of biomimetic photoswitches.

Mechanisms, Methods of Tracking and Applications of DNA Walkers: A Review.

The front cover artwork is provided by Julián Valero and Marko Škugor from Aarhus University and University of Bonn. The image shows an ad libitum representation of a new class of artificial molecular motors, coined as DNA walkers, on an athletic track testing their performance i.e. speed, directionality and progressivity. Read the full text of the Review at 10.1002/cphc.202000235.

A Chemically Driven Rotary Molecular Motor Based on Reversible Lactone Formation with Perfect Unidirectionality

Summary Among the amazing variety of ingenious molecular machines present in living organisms, enabling motility, responsiveness, and out-of-equilibrium behavior among others, rotary motors, such as the ATPase and bacterial flagellar motors, hold a special position. While these biological machines are mainly powered by chemical conversion and artificial light-driven rotary molecular motors have been well established, genuine chemically driven rotary motor systems are very limited. Here, we report a chemically powered rotary molecular motor based on biaryl structures that allows complete 360° unidirectional rotation i.e., >99% based on simple esterification chemistry. All the stereoisomers involved in the 4-stage rotary process have been characterized using X-ray crystallography confirming the relative stereochemistry of each isomer in accordance with the sequential and complete stereoselective operation of the rotary system. Having established the basic principles of this novel molecular rotary motor, it will facilitate the design of more sophisticated future artificial machine systems driven solely by chemical energy.

Switching of Self-Assembly to Solvent-Assisted Assembly of Molecular Motor: Unveiling the Mechanisms of Dynamic Control on Solvent Exchange.

Natural biological molecular motors are capable of performing several biological functions, such as fuel production, mobility, transport, and many other dynamic features. Inspired by these biological motors, scientists effectively synthesized artificial molecular motors to mimic several biological functionalities. Several molecular systems, from sensitive materials to molecular motors, are essential for controlling dynamic processes in larger assemblies. In this work, we discuss the self-assembly of molecular motors in water and how this self-assembly switches to the solvent-assisted assembly as solvent changes to a water-THF (tetrahydrofuran) mixture. We present an elaborate description of the morphological changes of molecular motor assemblies from pure water to a water-THF mixture to pure THF. Under the influence of THF solvent, molecular motors form an assembled structure by taking a sufficient number of THF molecules in between themselves, resulting in an assembled molecular motor with a softened core. So, molecular motor assembly swells in the water-THF mixture, and in pure water, it shrinks. This solvent-assisted assembled structure has a specific shape. We have confirmed this assembly as a solvent-assisted assembly with the help of molecular dynamics simulation and quantum chemical analysis. Molecular motor-THF and THF-THF interactions are the main responsible interactions for solvent-assisted assembly over self-assembly. This work is a perfect example of conversion between self-assembly (shrinking) and solvent-assisted assembly (swelling) of molecular motors by adding THF into water or vice versa. A spectacular check on the shrinking and swelling by merely altering solvents illustrates so many intriguing possibilities for an alteration of dynamic processes at the nanoscale.

Reorientation behavior in the helical motility of light-responsive spiral droplets

The physico-chemical processes supporting life’s purposeful movement remain essentially unknown. Self-propelling chiral droplets offer a minimalistic model of swimming cells and, in surfactant-rich water, droplets of chiral nematic liquid crystals follow the threads of a screw. We demonstrate that the geometry of their trajectory is determined by both the number of turns in, and the handedness of, their spiral organization. Using molecular motors as photo-invertible chiral dopants allows converting between right-handed and left-handed trajectories dynamically, and droplets subjected to such an inversion reorient in a direction that is also encoded by the number of spiral turns. This motile behavior stems from dynamic transmission of chirality, from the artificial molecular motors to the liquid crystal in confinement and eventually to the helical trajectory, in analogy with the chirality-operated motion and reorientation of swimming cells and unicellular organisms.

Synthetic Systems Powered by Biological Molecular Motors

Biological molecular motors (or biomolecular motors for short) are nature's solution to the efficient conversion of chemical energy to mechanical movement. In biological systems, these fascinating molecules are responsible for movement of molecules, organelles, cells, and whole animals. In engineered systems, these motors can potentially be used to power actuators and engines, shuttle cargo to sensors, and enable new computing paradigms. Here, we review the progress in the past decade in the integration of biomolecular motors into hybrid nanosystems. After briefly introducing the motor proteins kinesin and myosin and their associated cytoskeletal filaments, we review recent work aiming for the integration of these biomolecular motors into actuators, sensors, and computing devices. In some systems, the creation of mechanical work and the processing of information become intertwined at the molecular scale, creating a fascinating type of "active matter". We discuss efforts to optimize biomolecular motor performance, construct new motors combining artificial and biological components, and contrast biomolecular motors with current artificial molecular motors. A recurrent theme in the work of the past decade was the induction and utilization of collective behavior between motile systems powered by biomolecular motors, and we discuss these advances. The exertion of external control over the motile structures powered by biomolecular motors has remained a topic of many studies describing exciting progress. Finally, we review the current limitations and challenges for the construction of hybrid systems powered by biomolecular motors and try to ascertain if there are theoretical performance limits. Engineering with biomolecular motors has the potential to yield commercially viable devices, but it also sharpens our understanding of the design problems solved by evolution in nature. This increased understanding is valuable for synthetic biology and potentially also for medicine.

Photo- and Redox-Driven Artificial Molecular Motors.

Directed motion at the nanoscale is a central attribute of life, and chemically driven motor proteins are nature's choice to accomplish it. Motivated and inspired by such bionanodevices, in the past few decades chemists have developed artificial prototypes of molecular motors, namely, multicomponent synthetic species that exhibit directionally controlled, stimuli-induced movements of their parts. In this context, photonic and redox stimuli represent highly appealing modes of activation, particularly from a technological viewpoint. Here we describe the evolution of the field of photo- and redox-driven artificial molecular motors, and we provide a comprehensive review of the work published in the past 5 years. After an analysis of the general principles that govern controlled and directed movement at the molecular scale, we describe the fundamental photochemical and redox processes that can enable its realization. The main classes of light- and redox-driven molecular motors are illustrated, with a particular focus on recent designs, and a thorough description of the functions performed by these kinds of devices according to literature reports is presented. Limitations, challenges, and future perspectives of the field are critically discussed.

Life-like motion driven by artificial molecular machines

Essentially, all motion in living organisms emerges from the collective action of biological molecular machines transforming chemical energy, originally harvested from light, into ordered activity. As a man-made counterpart to nature’s biomolecular machines, chemists have created artificial molecular machines that display controlled and even directional motion in response to light. However, to be of practical value, the motion of these light-fuelled molecular machines will have to be coupled to the rest of the world. Inspired by the complex functional movement seen in the plant and animal world, chemists have undertaken the challenge to harness molecular motion and, so, they have set artificial molecular motors and switches to work and perform useful mechanical action at the macroscopic level. Here, we review these recent developments. We show how modern research has embraced the full complexity of the molecular world by aiming at the design of autonomous, and sometimes adaptive, molecular systems that work continuously under the effect of illumination. We report evidence that molecular motion can be engineered into highly sophisticated movements and that, from a fundamental point of view, continuous movement can only emerge when man-made molecules cooperate, in space and time. Eventually, unravelling the rules of molecular motion will support the creation of molecular materials that produce work continuously under a constant input of energy. The natural world has long provided inspiration for the production of artificial, adaptive materials. This Review discusses how unravelling the rules of molecular motion has enabled integration of the cooperative, and sometimes synchronized, operation of light-responsive molecular machines, across length scales, into responsive and autonomous matter.

Light-driven molecular switch for reconfigurable spin filters

Artificial molecular switches and machines that enable the directional movements of molecular components by external stimuli have undergone rapid advances over the past several decades. Particularly, overcrowded alkene-based artificial molecular motors are highly attractive from the viewpoint of chirality switching during rotational steps. However, the integration of these molecular switches into solid-state devices is still challenging. Herein, we present an example of a solid-state spin-filtering device that can switch the spin polarization direction by light irradiation or thermal treatment. This device utilizes the chirality inversion of molecular motors as a light-driven reconfigurable spin filter owing to the chiral-induced spin selectivity effect. Through this device, we found that the flexibility at the molecular scale is essential for the electrodes in solid-state devices using molecular machines. The present results are beneficial to the development of solid-state functionalities emerging from nanosized motions of molecular switches.

Photoefficient 2nd generation molecular motors responsive to visible light.

Molecular motors that operate with high efficiency using visible light are attractive for numerous applications. Here the synthesis and characterisation of three novel visible light switchable 2nd generation molecular motors is presented. Two of them are based on push-pull systems with the third one possessing an extended π-system. With a maximum effective excitation wavelength of 530 nm we designed the most red-shifted artificial rotary motor known to date. All three motors benefit from efficient switching to the metastable isomer, high quantum yields and excellent photostability setting them apart from visible light switchable motors reported previously. The activation barriers of the rate-determining thermal helix inversion could be accurately predicted using DFT calculations and differences between the motors can be explained by distinct transition state structures. Enantiomers of push-pull motors were successfully separated and their helical twisting power in E7 liquid crystals was determined.

Bacteriorhodopsin-Inspired Light-Driven Artificial Molecule Motors for Transmembrane Mass Transportation.

In nature, biological machines and motors can selectively transport cargoes across the lipid membranes to efficiently perform various physiological functions via ion channels or ion pumps. It is interesting and challengeable to develop artificial motors and machines of nanodimensions to controllably regulate mass transport in compartmentalized systems. In this work, we show a system of artificial molecular motors that uses light energy to perform transmembrane molecule transport through synthetical nanochannels. After functionalizing the polymer nanochannels with azobenzene derivatives, these nanomachines exhibit autonomous selective transport behavior over a long distance upon simultaneous irradiation with UV (365 nm) and visible (430 nm) light. With new strategies or suitable materials for directed molecular movement, such device can be regarded as a precursor of artificial light-driven molecular pumps.

Bacteriorhodopsin‐Inspired Light‐Driven Artificial Molecule Motors for Transmembrane Mass Transportation

AbstractIn nature, biological machines and motors can selectively transport cargoes across the lipid membranes to efficiently perform various physiological functions via ion channels or ion pumps. It is interesting and challengeable to develop artificial motors and machines of nanodimensions to controllably regulate mass transport in compartmentalized systems. In this work, we show a system of artificial molecular motors that uses light energy to perform transmembrane molecule transport through synthetical nanochannels. After functionalizing the polymer nanochannels with azobenzene derivatives, these nanomachines exhibit autonomous selective transport behavior over a long distance upon simultaneous irradiation with UV (365 nm) and visible (430 nm) light. With new strategies or suitable materials for directed molecular movement, such device can be regarded as a precursor of artificial light‐driven molecular pumps.

Light-Driven ATP Transmembrane Transport Controlled by DNA Nanomachines.

In nature, biological machines can perform sophisticated and subtle functions to maintain the metabolism of organisms. Inspired from these gorgeous works of nature, scientists have developed various artificial molecular motors and machines. However, selective transport of biomolecules across membrane has remained a great challenge. Here, we establish an ATP transport system by assembling photocontrolled DNA nanomachines into the artificial nanochannels. With alternant light irradiation, these ATP transport lines can selectively shepherd cargoes across the polymer membrane. These findings point to new opportunities for manipulating and improving the mass transportation and separation with light-controlled biomolecular motors, and can be used for other molecules and ions transmembrane transport powered by light.