There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

In this chapter, we will restrict our attention to the ferrites and a few other closely related materials. The great interest in ferrites stems from their unique combination of a spontaneous magnetization and a high electrical resistivity. The observed magnetization results from the difference in the magnetizations of two non-equivalent sub-lattices of the magnetic ions in the crystal structure. Materials of this type should strictly be designated as “ferrimagnetic” and in some respects are more closely related to anti-ferromagnetic substances than they are to ferromagnetics in which the magnetization results from the parallel alignment of all the magnetic moments present. We shall not adhere to this special nomenclature except to emphasize effects, which are due to the existence of the sub-lattices.

Ferromagnetic materials

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.

Interpretation of X-ray Powder Diffraction Patterns . By H. Lipson and H. Steeple. Pp. viii + 335 + 3 plates. (Mac-millan: London; St Martins Press: New York, May 1970.) £4.

X-Ray Diffraction

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

The increasing understanding of the advantages offered by fish and insect-like locomotion is creating a demand for muscle-like materials capable of mimicking nature's mechanisms. Actuator materials that employ voltage, field, light, or temperature driven dimensional changes to produce forces and displacements are suggesting new approaches to propulsion and maneuverability. Fundamental properties of these new materials are presented, and examples of potential undersea applications are examined in order to assist those involved in device design and in actuator research to evaluate the current status and the developing potential of these artificial muscle technologies. Technologies described are based on newly explored materials developed over the past decade, and also on older materials whose properties are not widely known. The materials are dielectric elastomers, ferroelectric polymers, liquid crystal elastomers, thermal and ferroelectric shape memory alloys, ionic polymer/metal composites, conducting polymers, and carbon nanotubes. Relative merits and challenges associated with the artificial muscle technologies are elucidated in two case studies. A summary table provides a quick guide to all technologies that are discussed.

Artificial muscle technology: physical principles and naval prospects

Oriented conducting polymer actuators are produced via stretching electrodeposited polypyrrole films to high elongations. An anisotropic electroactive strain response (e⊥/e∥ = 38) is observed due t...

Anisotropy of Electroactive Strain in Highly Stretched Polypyrrole Actuators

In situ observation of dynamic elastic modulus in polypyrrole actuators

We seek to improve polypyrrole and other conducting polymer actuators by discovering and exploiting the connection between nanoscale transport events and macroscale active strain. To this end we have used diffraction and electron microscopy to investigate the microstructure of polypyrrole. and propose a new description consisting of disordered polypyrrole chains held together by small crystalline bundles, around which solvent and counterions are randomly distributed. We utilize different modes of deformation to impart orientational texture to polypyrrole films, and show that by controlling polymer chain conformation and packing at a sub-micron level a conducting polymer actuator can be engineered that shows a significantly larger macroscopic electroactive response. We also alter the synthesis and doping conditions to produce films with widely varying surface morphologies, allowing us to control the rate of electroactive response. Our detailed understanding of polypyrrole morphology at different lengthscales provides valuable insight to the mechanisms of polypyrrole actuation, and has helped us process polypyrrole more intelligently for improved electroactive devices. Thesis Supervisor: Edwin L. Thomas Title: Morris Cohen Professor of Materials Science and Engineering Thesis Supervisor: Ian W. Hunter Title: Hatsopoulos Professor of Mechanical Engineering Thesis Supervisor: Timothy M. Swager Title: John D. MacArthur Professor of Chemistry

Rachel Z. Pytel

Papers

Artificial muscle technology: physical principles and naval prospects

Anisotropy of Electroactive Strain in Highly Stretched Polypyrrole Actuators

In situ observation of dynamic elastic modulus in polypyrrole actuators

Artificial muscle morphology : structure/property relationships in polypyrrole actuators

Anisotropic actuation of mechanically textured polypyrrole films