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.
In the present study, it is shown that the spreading rate of a mixing layer can be greatly manipulated at very low forcing level if the mixing layer is perturbed near a subharmonic of the most-amplified frequency. The subharmonic forcing technique is able to make several vortices merge simultaneously and hence increases the spreading rate dramatically. A new mechanism, ‘collective interaction’, was found which can bypass the sequential stages of vortex merging and make a large number of vortices (ten or more) coalesce.A deeper physical insight into the evolution of the coherent structures is revealed through the investigation of a forced mixing layer. The stability and the forcing function play important roles in determining the initial formation of the vortices. The subharmonic starts to amplify at the location where the phase speed of the subharmonic matches that of the fundamental. The position where vortices are seen to align vertically coincides with the position where the measured subharmonic reaches its peak. This location is defined as the merging location, and it can be determined from the feedback equation (Ho & Nosseir 1981).The spreading rate and the velocity profiles of the forced mixing layer are distinctly different from the unforced case. The data show that the initial condition has a longlasting effect on the development of the mixing layer.
A macroscopic evaporating water droplet with suspended particles on a solid surface will form a ring-like structure at the pinned contact line due to induced capillary flow. As the droplet size shrinks, the competition between the time scales of the liquid evaporation and the particle movement may influence the resulting ring formation. When the liquid evaporates much faster than the particle movement, coffee ring formation may cease. Here, we experimentally show that there exists a lower limit of droplet size, D c , for the successful formation of a coffee ring structure. When the particle concentration is above a threshold value, D c can be estimated by considering the collective effects of the liquid evaporation and the particle diffusive motion within the droplet. For suspended particles of size ~100 nm, the minimum diameter of the coffee ring structure is found to be ~10 µm.
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