Two switchable, palindromically constituted bistable [3]rotaxanes have been designed and synthesized with a pair of mechanically mobile rings encircling a single dumbbell. These designs are reminiscent of a "molecular muscle" for the purposes of amplifying and harnessing molecular mechanical motions. The location of the two cyclobis(paraquat-p-phenylene) (CBPQT 4+ ) rings can be controlled to be on either tetrathiafulvalene (TTF) or naphthalene (NP) stations, either chemically ( 1 H NMR spectroscopy) or electrochemically (cyclic voltammetry), such that switching of inter-ring distances from 4.2 to 1.4 nm mimics the contraction and extension of skeletal muscle, albeit on a shorter length scale. Fast scan-rate cyclic voltammetry at low temperatures reveals stepwise oxidations and movements of one-half of the [3]rotaxane and then of the other, a process that appears to be concerted at room temperature. The active form of the bistable [3]rotaxane bears disulfide tethers attached covalently to both of the CBPQT 4+ ring components for the purpose of its self-assembly onto a gold surface. An array of flexible microcantilever beams, each coated on one side with a monolayer of 6 billion of the active bistable [3]rotaxane molecules, undergoes controllable and reversible bending up and down when it is exposed to the synchronous addition of aqueous chemical oxidants and reductants. The beam bending is correlated with flexing of the surfacebound molecular muscles, whereas a monolayer of the dumbbell alone is inactive under the same conditions. This observation supports the hypothesis that the cumulative nanoscale movements within surface-bound "molecular muscles" can be harnessed to perform larger-scale mechanical work.
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.
From analyses of pressure−area isotherms and X-ray photoelectron spectra, we have demonstrated that redox-controllable molecular shuttles, in the shape of amphiphilic, bistable rotaxanes, are mechanically switchable in closely packed Langmuir films with chemical reagents. Additionally, mechanical switching has been proven to occur in closely packed Langmuir−Blodgett bilayers while mounted on solid substrates. The results not only constitute a proof of principle but they also provide the impetus to develop solid-state nanoelectromechanical systems that have the potential to reach up to the mesoscale.
By applying atomic force microscope (AFM)-based force spectroscopy together with computational modeling in the form of molecular force-field simulations, we have determined quantitatively the actuation energetics of a synthetic motor-molecule. This multidisciplinary approach was performed on specifically designed, bistable, redox-controllable [2]rotaxanes to probe the steric and electrostatic interactions that dictate their mechanical switching at the single-molecule level. The fusion of experimental force spectroscopy and theoretical computational modeling has revealed that the repulsive electrostatic interaction, which is responsible for the molecular actuation, is as high as 65 kcal⅐mol ؊1 , a result that is supported by ab initio calculations.computational modeling ͉ force spectroscopy ͉ molecular motors ͉ switchable rotaxanes M olecular motors have recently garnered considerable interest within the domains of microsciences and nanosciences (1, 2). Harnessing the ability to selectively, cooperatively, and repeatedly induce structural changes in molecules may hold the promise of engineered systems that operate with the same complexity, elegance, and efficiency as biological motors function in the human body. In natural systems, it has become apparent that both macro and micro processes are initiated and controlled by nanoscale molecular motors (3). For example, myosin and kinesin are associated with muscle contraction and intracellular trafficking, respectively, and have recently found their ways into engineered devices (4, 5). Moreover, initial work has been performed that demonstrates the ability of natural nanoscale molecular motors to power microfabricated systems (6).Synthetic motor-molecules (7-11), which are designed to excel where their biological counterparts fall short, also have been investigated. Whereas devices powered by biological molecules require (4-6) chemical diffusion for actuation stimulus, synthetic molecules have been shown (2, 9) to operate with a variety of different stimuli, thereby lending much greater flexibility to a particular system's design. Moreover, a synthetic nanoscale actuating molecule carries with it an inherent ability to be modified and optimized precisely for a specific task.Switchable, bistable rotaxanes (2, 9), compounds comprised of a dumbbell-shaped component containing two different recognition sites for an encircling ring-shaped component, show particular promise as molecular actuators, given their ability to undergo controllable, reversible mechanical switching with the appropriate chemical, electrochemical, or photochemical stimulus in solution. Toward the goal of device applications, switching has been shown to operate in condensed phases such as in a polymer electrolyte gel (12), on a self-assembled monolayer (SAM) (13), on the solid supports of engineered systems (14), and in molecular switch tunnel junctions (15). Bistable rotaxanes benefit from their synthesis being highly modular, a virtue that allows for a considerable degree of flexibility in their des...
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