Organic Cages as Building Blocks for Mechanically Interlocked Molecules: Towards Molecular Machines (original) (raw)

A platform approach to mechanically caged molecules

2024

Inspired by interlocked oligonucleotides, peptides and knotted proteins, synthetic systems where a macrocycle cages a bioactive species that is "switched on" by breaking the mechanical bond have been reported. However, to date, each example uses a bespoke chemical design. Here we present a platform approach to mechanically caged structures wherein a single macrocycle precursor is diversified at a late stage to include a range of trigger units that control ring opening in response to enzymatic, chemical, or photochemical stimuli. We also demonstrate that our approach is applicable to other classes of macrocycles suitable for rotaxane and catenane formation.

Controlling Motion at the Nanoscale: Rise of the Molecular Machines

ACS Nano, 2015

As our understanding and control of intra-and intermolecular interactions evolve, ever more complex molecular systems are synthesized and assembled that are capable of performing work or completing sophisticated tasks at the molecular scale. Commonly referred to as molecular machines, these dynamic systems comprise an astonishingly diverse class of motifs and are designed to respond to a plethora of actuation stimuli. In this Review, we outline the conditions that distinguish simple switches and rotors from machines and draw from a variety of fields to highlight some of the most exciting recent examples of opportunities for driven molecular mechanics. Emphasis is placed on the need for controllable and hierarchical assembly of these molecular components to display measurable effects at the micro-, meso-, and macroscales. As in Nature, this strategy will lead to dramatic amplification of the work performed via the collective action of many machines organized in linear chains, on functionalized surfaces, or in three-dimensional assemblies.

Molecular Motors, Actuators, and Mechanical Devices

Atomically precise manufacturing systems, such as those described in Nanosystems [1], will utilize molecular motors and actuators 1 that drive components to perform useful work. The conversion of electrical and chemical energy into mechanical motion is facilitated by the use of gears, bearings, drive shafts, springs, and so forth, to direct the motion of components and minimize energy losses. Thus, research efforts dedicated to produce these sorts of components are considered to be both a direct pathway in our Roadmap and an enabler of other pathways that can take advantage of these molecular mechanical devices and the fabrication techniques developed to produce them. This section summarizes the state-of-the-art in the construction of these devices and describes their relevance to the Roadmap. Table 3 at the end of this section provides a summary of representative molecular motors, actuators, and mechanical devices.

Artificial nanomachines based on interlocked molecular species: recent advances

Chemical Society Reviews, 2006

The bottom-up construction and operation of nanoscale machines and motors, that is, supramolecular systems wherein the molecular components can be set in motion in a controlled manner for ultimately accomplishing a function, is a topic of great interest in nanoscience and a fascinating challenge of nanotechnology. The field of artificial molecular machines and motors is growing at an astonishing rate and is attracting a great deal of interest. Research in the last decade has shown that species made of interlocked molecular components like rotaxanes, catenanes and related systems are most attractive candidates. In recent times, the evolution of the structural and functional design of such systems has led to the construction and operation of complex molecular machines that, in some cases, are able to do specific tasks.

Artificial Molecular Motors and Machines: Design Principles and Prototype Systems

Topics in Current Chemistry

A molecular machine can be defined as an assembly of a discrete number of molecular components (that is, a supramolecular structure) designed to perform a function through the mechanical movements of its components, which occur under appropriate external stimulation. Hence, molecular machines contain a motor part, that is a device capable of converting energy into mechanical work. Molecular motors and machines operate via nuclear rearrangements and, like their macroscopic counterparts, are characterized by the kind of energy input supplied to make them work, the manner in which their operation can be monitored, the possibility to repeat the operation at will, i.e., establishing a cyclic process, the time scale needed to complete a cycle of operation, and the performed function. Owing to the progress made in several branches of Chemistry, and to the better understanding of the operation mechanisms of molecular machines of the biological world, it has become possible to design and construct simple prototypes of artificial molecular motors and machines. The extension of the concept of machine to the molecular level is of great interest not only for basic research, but also for the growth of nanoscience and the development of nanotechnology. We will illustrate some basic features and design principles of molecular machines, and we will describe a few recent examples of artificial systems, based on rotaxanes, catenanes and related species, taken from our own research. 2 V. Balzani et al. Keywords Catenane • Electron transfer • Photochemistry • Rotaxane • Supramolecular chemistry Abbreviations AMH ammonium center BPM 4,4-bipyridinium unit CT charge transfer DB24C8 dibenzo[24]crown-8 DON 1,5-dioxynaphthalene unit SCE saturated calomel electrode TTF tetrathiafulvalene unit 1 Basic Principles 1.1

A nanomechanical device based on linear molecular motors

Applied Physics Letters, 2004

An array of microcantilever beams, coated with a self-assembled monolayer of bistable, redox-controllable [3]rotaxane molecules, undergoes controllable and reversible bending when it is exposed to chemical oxidants and reductants. Conversely, beams that are coated with a redox-active but mechanically inert control compound do not display the same bending. A series of control experiments and rational assessments preclude the influence of heat, photothermal effects, and pH variation as potential mechanisms of beam bending. Along with a simple calculation from a force balance diagram, these observations support the hypothesis that the cumulative nanoscale movements within surface-bound "molecular muscles" can be harnessed to perform larger-scale mechanical work.

Controlled Rotary Motion in a Monolayer of Molecular Motors

Angewandte Chemie International Edition, 2007

Rotary molecular motors are ubiquitous in natural systems where they are used for diverse tasks including molecular transport, cellular translocation, and ATP synthesis, and are considered key components of future synthetic nanomechanical devices. In many of these systems, such as ATPase or the bacterial flagella motor, immobilization into the cellular membrane allows their rotary action to be harnessed. Attaching biological or synthetic molecular rotary motors to solid substrates is considered to be a key step toward the fabrication of devices that exploit the collective rotational mechanical motion generated by these systems. Although linear synthetic and biological motors have been mounted on surfaces, examples of surface-bound rotary motors are scarce. Preliminary work to this end includes the successful characterization of functioning ATPase while immobilized on quartz and recently, a single example of synthetic rotary molecular motors functioning on gold nanoparticles in solution. Although the latter is a significant step toward future applications, the nanoparticles in solution are still overwhelmed by Brownian rotation and translation, and the motor function might to some extent suffer from excitedstate quenching by the gold, making it difficult to harness work from the system.

Optomechanical control of molecular motors

SPIE Proceedings, 2010

The majority of mechanisms that can be deployed for optical micromanipulation are not especially amenable for extension into the nanoscale. At the molecular level, the rich variety of schemes that have been proposed to achieve mechanical effect using light commonly exploit specific chemical structures; familiar examples are compounds that can fold by cis-trans isomerization, or the mechanically interlocked architectures of rotaxanes. However, such systems are synthetically highly challenging, and few of them can realistically form the basis for a true molecular motor. Developing the basis for a very different strategy based on programmed electronic excitation, this paper explores the possibility of producing controlled mechanical motion through optically induced modifications of intermolecular force fields, not involving the limitations associated with using photochemical change, nor the high intensities required to produce and manipulate optical binding forces between molecules. Calculations reveal that significant, rapidly responsive effects can be achieved in relatively simple systems. By the use of suitable laser pulse sequences, the possibilities include the generation of continuous rotary motion, the ultimate aim of molecular motor design.