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.

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

Hydrogels for biomedical applications.

For several centuries fluid dynamics studies have relied upon the assumption that when a liquid flows over a solid surface, the liquid molecules adjacent to the solid are stationary relative to the solid. This no-slip boundary condition (BC) has been applied successfully to model many macroscopic experiments, but has no microscopic justification. In recent years there has been an increased interest in determining the appropriate BCs for the flow of Newtonian liquids in confined geometries, partly due to exciting developments in the fields of microfluidic and microelectromechanical devices and partly because new and more sophisticated measurement techniques are now available. An increasing number of research groups now dedicate great attention to the study of the flow of liquids at solid interfaces, and as a result a large number of experimental, computational and theoretical studies have appeared in the literature. We provide here a review of experimental studies regarding the phenomenon of slip of Newtonian liquids at solid interfaces. We dedicate particular attention to the effects that factors such as surface roughness, wettability and the presence of gaseous layers might have on the measured interfacial slip. We also discuss how future studies might improve our understanding of hydrodynamic BCs and enable us to actively control liquid slip.

https://iopscience.iop.org/article/10.1088/0034-4885/68/12/R05/pdf

Boundary slip in Newtonian liquids: a review of experimental studies

In the present review we try to give a comprehensive and most up to date view to the field, with an emphasis on the currently most investigated anodic TiO2 nanotube arrays. We will first give an overview of different synthesis approaches to produce TiO2 nanotubes and TiO2 nanotube arrays, and then deal with physical and chemical properties of TiO2 nanotubes and techniques to modify them. Finally, we will provide an overview of the most explored and prospective applications of nanotubular TiO2.

One-dimensional titanium dioxide nanomaterials: nanotubes.

Techniques for determining contact angle and wettability of powders

The adhesion strengths of a viscoelastic adhesive were measured on various substrates that were prepared by grafting silanes bearing organic functional groups to silicon wafers. Conventional theories predict that adhesion should be proportional to the surface free energy of the substrate; but adhesion on a fluorocarbon surface was significantly greater than on some of the hydrocarbon surfaces, although the fluorocarbon surface has the lowest surface free energy. This result could be explained by invoking a model of adhesion based on the slippage of the adhesive at the interface.

https://science.sciencemag.org/content/sci/269/5229/1407.full.pdf

Macroscopic evidence of the effect of interfacial slippage on adhesion.

We have developed a simple Marangoni flow-induced method for self-assembling nanoparticles (NPs) into both hexagonal and stripelike patterns. First, a NPs/ethanol suspension was spread on a slightly nonwettable and a wettable silicon oxide substrate. The Marangoni flow, induced by simultaneous evaporation of ethanol and condensation of water, leads to the formation of the corresponding hexagonal distributed circular NP rings and dotted stripes. The inter-ring spacing and ring size of the hexagonal patterns can be tuned by varying the relative humidity of the N2 stream blown over the slightly nonwettable substrate. Hexagonal patterns of circular NP patches can also be fabricated by lowering the evaporation of the condensed water droplets. On the wettable substrate, complex patterns result when the humidity of the N2 stream changes.

Marangoni flow-induced self-assembly of hexagonal and stripelike nanoparticle patterns.

Peeling of a viscoelastic adhesive from a solid substrate poses a wonderful problem of polymer flow. When the adhesive is peeled, it is also stretched in a direction normal to the substrate. The concomitant Poisson contraction creates a pressure gradient and thus induces a shear flow in the adhesive close to the delamination front. Earlier it was pointed out that the strength of viscoelastic adhesion would decrease if the shear stress in the adhesive is relaxed by a slip process at the interface. Here we report experimental results which confirm that viscoelastic adhesives do indeed slip on segmentally mobile organic surfaces at and near the crack tip regions. Evidence of slip was obtained from the interfacial displacements of small fluorescent particles when the adhesive was peeled from various substrates. While on most surfaces the slip distances were about 1−2 μm, a large slip (13 μm) was observed on segmentally mobile tethered chains of polydimethylsiloxanes (silicones). On the latter surface, slippag...

Effect of Interfacial Slippage on Viscoelastic Adhesion

Gradient surfaces are widely employed in biological studies for protein adsorption and cell attachment and growth. They also offer great potential in the areas of fluid flow and combinatorial experimental design for obtaining material properties and behaviors. Gradient surfaces are created with organosilanes by using the diffusion techniques proposed by Ewling and modified by Chaudhury. However, these techniques have limitations. They either generate a significant amount of organic waste or require well-controlled deposition conditions. In this paper, we propose a fast, convenient, reproducible, and inexpensive method that generates gradient surfaces with minimum waste generation. Particularly, we have adopted Whitesides's contact-printing technique to achieve a gradient by gradually varying the contact time over the contacted area using octadecyltrichlorosilane. Elastomeric stamps with different geometries and various radii of curvature are used to generate gradient surfaces at both millimeter and microm...

Bi-min Zhang Newby

Papers

Techniques for determining contact angle and wettability of powders

Macroscopic evidence of the effect of interfacial slippage on adhesion.

Marangoni flow-induced self-assembly of hexagonal and stripelike nanoparticle patterns.

Effect of Interfacial Slippage on Viscoelastic Adhesion

Micrometer-scaled Gradient Surfaces Generated Using Contact Printing of Octadecyltrichlorosilane