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

Calixarene-derived fluorescent probes.

There is an enormous demand for chemical sensors for many areas and disciplines. High sensitivity and ease of operation are two main issues for sensor development. Fluorescence techniques can easily fulfill these requirements and therefore fluorescent-based sensors appear as one of the most promising candidates for chemical sensing. However, the development of sensors is not trivial; material science, molecular recognition and device implementation are some of the aspects that play a role in the design of sensors. The development of fluorescent sensing materials is increasingly captivating the attention of the scientists because its implementation as a truly sensory system is straightforward. This critical review shows the use of polymers, sol–gels, mesoporous materials, surfactant aggregates, quantum dots, and glass or gold surfaces, combined with different chemical approaches for the development of fluorescent sensing materials. Representative examples have been selected and they are commented here.

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Design of fluorescent materials for chemical sensing

Noble metal nanoparticles for water purification: A critical review

Sensors based on self-assembled monolayers (SAMs) are the topic of this article. First an overview of the analytical techniques used for the characterization of monolayers is given. This is followed by details of the use of functional SAMs to study interactions with analytes, for example, the complexation of metal ions by crown ether adsorbates.

Sensor functionalities in self-assembled monolayers

Self-assembled monolayers (SAMs) of 2-[(6-mercaptohexyl)oxy]methyl-12-crown-4 (1) and 2-[(6-mercaptohexyl)oxy]methyl-15-crown-5 (2) on gold are able to bind cations reversibly from aqueous solutions. This binding of the electrochemically inactive cations is monitored by cyclic voltammetry and impedance spectroscopy using the redox couple Ru(NH3)62+/3+ as "reporter ion". Gold electrodes modified with 1 detect Na+ even in the presence of a 100-fold excess of K+; SAMs of 2 are K+ selective. As a result of the high surface density of crown ethers, sandwich complexes are formed. Reduced surface concentrations of receptors in mixed monolayers of 2 with heptanethiol prevent the sandwich complexation and decreases the K+/Na+ selectivity of the SAM.

Electrochemical detection of electrochemically inactive cations by self-assembled monolayers of crown ethers

Functionalization of self-assembled monolayers on glass and oxidized silicon wafers by surface reactions

Monolayer of a Na+-Selective Fluoroionophore on Glass: Connecting the Fields of Monolayers and Optical Detection of Metal Ions

Self-assembled monolayers (SAMs) of crown ether adsorbates on gold reversibly bind metal ions from aqueous solutions. The resulting changes of the electrochemical properties of the monolayers were monitored by impedance spectroscopy. The increased dielectric constant of the layer due to the complexation of ions results in an increase of the monolayer capacitance (CML). Analysis of the response curves with a Langmuir isotherm enables the determination of association constants of the SAMs with various metal ions. The cation binding also influences the charge-transfer resistance (RCT) of a redox couple Ru(NH3)62+/3+ in the electrolyte. Comparison of both responses allows an accurate interpretation of the origin of the resistive response. Furthermore, the association constants enable the quantitative determination of interactions between SAMs and metal ions, using either capacitive or resistive responses.

Simon Flink

Papers

Sensor functionalities in self-assembled monolayers

Electrochemical detection of electrochemically inactive cations by self-assembled monolayers of crown ethers

Functionalization of self-assembled monolayers on glass and oxidized silicon wafers by surface reactions

Monolayer of a Na+-Selective Fluoroionophore on Glass: Connecting the Fields of Monolayers and Optical Detection of Metal Ions

Recognition of Cations by Self-Assembled Monolayers of Crown Ethers