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.

Over the 100 years since its discovery, liquid crystals have been the intriguing subject for both academia and industries. The textbook of de Gennes The Physics of Liquid Crystals published in 1974 is still the bible for many LC researchers, but new subjects unmentioned in the book have also risen for these years. This chapter describes the story of the recent developments and the future perspectives in physics of liquid crystals, especially focusing on the contributions by Japanese research groups for the last decade.

Physics of Liquid Crystals

Miniaturizing a simple photomechanical system could expand its range of applications. Polymer solutions and solids that contain light-sensitive molecules can undergo photo-contraction, whereby light energy is converted into mechanical energy1,2,3,4,5,6,7,8. Here we show that a single film of a liquid-crystal network containing an azobenzene chromophore can be repeatedly and precisely bent along any chosen direction by using linearly polarized light. This striking photomechanical effect results from a photoselective volume contraction and may be useful in the development of high-speed actuators for microscale or nanoscale applications, for example in microrobots in medicine or optical microtweezers.

/pdf/photomechanics-directed-bending-of-a-polymer-film-by-light-3gibe37tkj.pdf

Photomechanics: directed bending of a polymer film by light.

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

A number of materials have been explored for their use as artificial muscles Among these, dielectric elastomers (DEs) appear to provide the best combination of properties for true muscle-like actuation DEs behave as compliant capacitors, expanding in area and shrinking in thickness when a voltage is applied Materials combining very high energy densities, strains, and efficiencies have been known for some time To date, however, the widespread adoption of DEs has been hindered by premature breakdown and the requirement for high voltages and bulky support frames Recent advances seem poised to remove these restrictions and allow for the production of highly reliable, high-performance transducers for artificial muscle applications

Advances in dielectric elastomers for actuators and artificial muscles.

A range of monodomain nematic liquid-crystal elastomers containing differing proportions of photoisomerizable mesogenic moieties, which turn from a rodlike to a kinked shape upon ultraviolet (uv) irradiation, was studied. Depending on the proportion and positional role of the photosensitive groups in the crosslinked polymer network, different types and magnitudes of response were found. The principle consequence of such photoisomerization is the destabilization of the nematic phase, whose order parameter depends on temperature in a near-critical fashion. Accordingly, the effect of uv irradiation is dramatically enhanced near the critical temperature, with the associated reduction in the nematic order parameter manifesting as a change in the macroscopic shape of the elastomer samples, producing a large uniaxial contraction. Theoretical analysis of this phenomenon gives a good quantitative agreement with experiment.

https://people.bss.phy.cam.ac.uk/~emt1000/uv1.pdf

UV manipulation of order and macroscopic shape in nematic elastomers.

Liquid-crystalline elastomers have demonstrated their unique material properties and potential for applications in a number of areas. They also present challenging problems for fundamental science, ranging from applied mathematics of elastic media with microstructure, to physical effects of shape memory, soft elasticity, and pattern formation, and to new synthetic routes and concepts. One of the most remarkable properties of nematic elastomers formed with the director aligned in a monodomain fashion is uniaxial spontaneous deformation in response to any external factor changing the underlying order parameter. The resulting shape memory is very different from all other shape-memory effects reported in the literature in that it is a fully reversible, equilibrium phenomenon (other shape-memory systems act only in a one-stroke way and require a reset afterwards). It also has astonishingly large amplitude, with deformation exceeding 200–300%, and can be stimulated by temperature change, irradiation by light, and exposure to solvents. An overview of these effects, related materials, and the history of publications is available in the literature. [1] One of the difficulties that still restricts the broad range of application of nematic-elastomer actuators is the problem of forming the network with a particular alignment of the nematic director. The most common method currently in use is the technique of two-step crosslinking, pioneered by Kupfer and Finkelmann. [2] It is based on first forming a partially crosslinked gel network with no specified director orientation, then mechanically stretching it, thus inducing an aligning internal stress, and then fully crosslinking the network to record the imposed orientation. Most of the (highly successful) work on monodomain nematic elastomers in the last decade has been

Self-Assembled Shape-Memory Fibers of Triblock Liquid-Crystal Polymers**

We study the monodomain (single-crystal) nematic elastomer materials, all side-chain siloxane polymers with the same mesogenic groups and crosslinking density, but differing in the type of crosslinking. Increasing the proportion of long di-functional segments of main-chain nematic polymer, acting as network crosslinking, results in dramatic changes in the uniaxial equilibrium thermal expansion on cooling from the isotropic phase. At higher concentration of main chains their behaviour dominates the elastomer properties. At low concentration of main-chain material, we detect two distinct transitions at different temperatures, one attributed to the main-chain, the other to the side-chain component. The effective uniaxial anisotropy of nematic rubber, r(T) = /
 proportional to the effective nematic order parameter Q(T), is given by an average of the two components and thus reflects the two-transition nature of thermal expansion. The experimental data is compared with the theoretical model of ideal nematic elastomers; applications in high-amplitude thermal actuators are discussed in the end.

Spontaneous thermal expansion of nematic elastomers

We demonstrate, for the first time, the large electromechanical response in nematic liquid-crystalline elastomers filled with a very low ( ~ 0.01%) concentration of carbon nanotubes, aligned along the nematic director at preparation. The nanotubes create a very large effective dielectric anisotropy of the composite. Their local field-induced torque is transmitted to the rubber elastic network and is registered as the exerted uniaxial stress of order ~ 1 kPa in response to a constant field of order ~ 1 MV/m. We investigate the dependence of the effect on field strength, nanotube concentration and reproducibility under multiple field-on and -off cycles. The results indicate the potential of the nanotube-nematic elastomer composites as electrically driven actuators.

http://people.bss.phy.cam.ac.uk/~emt1000/nano1.pdf

Nematic elastomers with aligned carbon nanotubes: New electromechanical actuators

The macroscopic shape of liquid-crystalline elastomers strongly depends on the order parameter of the mesogenic groups. This order can be manipulated if photo-isomerisable groups, e.g. containing N=N bonds, are introduced into the material. We have explored the large photo-mechanical response of such an azobenzene-containing nematic elastomer at different temperatures, using force and optical birefringence measurements, and focusing on fundamental aspects of population dynamics and the related speed and repeatability of the response. The characteristic time of “on” and “off” regimes strongly depends on temperature, but is generally found to be very long. We were able to verify that the macroscopic relaxation of the elastomer is determined by the nematic order dynamics and not, for instance, by the polymer network relaxation.

A. R. Tajbakhsh

Papers

UV manipulation of order and macroscopic shape in nematic elastomers.

Self-Assembled Shape-Memory Fibers of Triblock Liquid-Crystal Polymers**

Spontaneous thermal expansion of nematic elastomers

Nematic elastomers with aligned carbon nanotubes: New electromechanical actuators

UV isomerisation in nematic elastomers as a route to photo-mechanical transducer.