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

Bull. Chem. Soc. Jpn. への投稿のすすめ

Flexible and wearable electronics are attracting wide attention due to their potential applications in wearable human health monitoring and care systems. Carbon materials have combined superiorities such as good electrical conductivity, intrinsic and structural flexibility, light weight, high chemical and thermal stability, ease of chemical functionalization, as well as potential mass production, enabling them to be promising candidate materials for flexible and wearable electronics. Consequently, great efforts are devoted to the controlled fabrication of carbon materials with rationally designed structures for applications in next-generation electronics. Herein, the latest advances in the rational design and controlled fabrication of carbon materials toward applications in flexible and wearable electronics are reviewed. Various carbon materials (carbon nanotubes, graphene, natural-biomaterial-derived carbon, etc.) with controlled micro/nanostructures and designed macroscopic morphologies for high-performance flexible electronics are introduced. The fabrication strategies, working mechanism, performance, and applications of carbon-based flexible devices are reviewed and discussed, including strain/pressure sensors, temperature/humidity sensors, electrochemical sensors, flexible conductive electrodes/wires, and flexible power devices. Furthermore, the integration of multiple devices toward multifunctional wearable systems is briefly reviewed. Finally, the existing challenges and future opportunities in this field are summarized.

Advanced Carbon for Flexible and Wearable Electronics.

Bio-integrated wearable systems can measure a broad range of biophysical, biochemical, and environmental signals to provide critical insights into overall health status and to quantify human performance. Recent advances in material science, chemical analysis techniques, device designs, and assembly methods form the foundations for a uniquely differentiated type of wearable technology, characterized by noninvasive, intimate integration with the soft, curved, time-dynamic surfaces of the body. This review summarizes the latest advances in this emerging field of “bio-integrated” technologies in a comprehensive manner that connects fundamental developments in chemistry, material science, and engineering with sensing technologies that have the potential for widespread deployment and societal benefit in human health care. An introduction to the chemistries and materials for the active components of these systems contextualizes essential design considerations for sensors and associated platforms that appear in f...

Bio-Integrated Wearable Systems: A Comprehensive Review

Carbon nanotubes (CNTs) promise to advance a number of real-world technologies. Of these applications, they are particularly attractive for uses in chemical sensors for environmental and health monitoring. However, chemical sensors based on CNTs are often lacking in selectivity, and the elucidation of their sensing mechanisms remains challenging. This review is a comprehensive description of the parameters that give rise to the sensing capabilities of CNT-based sensors and the application of CNT-based devices in chemical sensing. This review begins with the discussion of the sensing mechanisms in CNT-based devices, the chemical methods of CNT functionalization, architectures of sensors, performance parameters, and theoretical models used to describe CNT sensors. It then discusses the expansive applications of CNT-based sensors to multiple areas including environmental monitoring, food and agriculture applications, biological sensors, and national security. The discussion of each analyte focuses on the strategies used to impart selectivity and the molecular interactions between the selector and the analyte. Finally, the review concludes with a brief outlook over future developments in the field of chemical sensors and their prospects for commercialization.

Carbon Nanotube Chemical Sensors

For the next generation of wearable health monitors, it is essential to develop stretchable and conformable sensors with robust electrical performance. These sensors should, in particular, provide a stable electrical output without being affected by external variables such as induced strain. Here, we report circuit design strategies that can improve the accuracy and robustness of a temperature sensor based on stretchable carbon nanotube transistors. Using static and dynamic differential readout approaches, our circuits suppress strain-dependent errors and achieve a measured inaccuracy of only ±1 oC within a uniaxial strain range of 0–60%. We address device variability by using a one-time, single-point calibration approach. In contrast with previous approaches, which infer temperature change through a normalized measurement at two temperatures, our prototype devices provide an absolute output without temperature cycling. This is essential for practical deployment because heating and cooling the sensor is prohibitively slow and costly during real-time operation and production testing. Using carbon nanotube transistors, stretchable temperature sensor circuits can be designed that suppress strain-dependent errors and achieve a measured inaccuracy of only ±1 °C within a uniaxial strain range of 0–60%

Stretchable temperature-sensing circuits with strain suppression based on carbon nanotube transistors

ConspectusElectronics that are soft, conformal, and stretchable are highly desirable for wearable electronics, prosthetics, and robotics. Among the various available electronic materials, single walled carbon nanotubes (SWNTs) and their network have exhibited high mechanical flexibility and stretchability, along with comparable electrical performance to traditional rigid materials, e.g. polysilicon and metal oxides. Unfortunately, SWNTs produced en masse contain a mixture of semiconducting (s-) and metallic (m-) SWNTs, rendering them unsuitable for electronic applications. Moreover, the poor solubility of SWNTs requires the introduction of insulating surfactants to properly disperse them into individual tubes for device fabrication.Compared to other SWNT dispersion and separation methods, e.g., DNA wrapping, density gradient ultracentrifugation, and gel chromatography, polymer wrapping can selectively disperse s-SWNTs with high selectivity (>99.7%), high concentration (>0.1 mg/mL), and high yield (>20%). ...

Separation of Semiconducting Carbon Nanotubes for Flexible and Stretchable Electronics Using Polymer Removable Method

Semiconducting, single-walled carbon nanotubes (SWNTs) are promising candidates for applications in thin-film transistors, solar cells, and biological imaging. To harness their full potential, however, it is necessary to separate the semiconducting from the metallic SWNTs present in the as-synthesized SWNT mixture. While various polymers are able to selectively disperse semiconducting SWNTs, the subsequent removal of the polymer is challenging. However, many applications require semiconducting SWNTs in their pure form. Toward this goal, we have designed a 2-ureido-6[1H]-pyrimidinone (UPy)-based H-bonded supramolecular polymer that can selectively disperse semiconducting SWNTs. The dispersion purity is inversely related to the dispersion yield. In contrast to conventional polymers, the polymer described herein was shown to disassemble into monomeric units upon addition of an H-bond-disrupting agent, enabling isolation of dispersant-free, semiconducting SWNTs.

H-bonded supramolecular polymer for the selective dispersion and subsequent release of large-diameter semiconducting single-walled carbon nanotubes.

ConspectusWithin the framework of miniaturization of electromechanical devices, the development of a redox-switchable molecular gripper as a tool for nanorobotics is appealing both from an academic and from a practical perspective. Such a tool should be able to controllably grab a molecular cargo, translocate it over considerable distances and time scales, and release it.Resorcin[4]arene cavitands seem to be an ideal platform for the development of molecular grippers due to their ability to adopt two spatially well-defined conformations: an expanded kite and a contracted vase. Furthermore, they possess “legs” for functionalization and attachment to metal surfaces. While changes in temperature, pH, and metal-ion concentration were known to induce conformational switching, redox-switchable cavitands remained a challenge.In this Account, we describe our efforts toward the development of a new class of resorcin[4]arene cavitands that are redox-switchable. First, we introduced the naphthoquinone moiety as a re...

Development of Redox-Switchable Resorcin[4]arene Cavitands

Diquinone-based resorcin[4]arene cavitands that open to a kite and close to a vase form upon changing their redox state, thereby releasing and binding guests, have been prepared and studied. The switching mechanism is based on intramolecular H-bonding interactions that stabilize the vase form and are only present in the reduced hydroquinone state. The intramolecular H-bonds were characterized using X-ray, IR, and NMR spectroscopies. Guests were bound in the closed, reduced state and fully released in the open, oxidized state.

Igor Pochorovski

Papers

Stretchable temperature-sensing circuits with strain suppression based on carbon nanotube transistors

Separation of Semiconducting Carbon Nanotubes for Flexible and Stretchable Electronics Using Polymer Removable Method

H-bonded supramolecular polymer for the selective dispersion and subsequent release of large-diameter semiconducting single-walled carbon nanotubes.

Development of Redox-Switchable Resorcin[4]arene Cavitands

Redox-switchable resorcin[4]arene cavitands: molecular grippers.