A single synthetic small molecule that generates force against a load

Lussis, Perrine; Svaldo-Lanero, Tiziana; Bertocco, Andrea; Fustin, Charles-André; Leigh, David A.; Duwez, Anne‐Sophie

doi:10.1038/nnano.2011.132

Cited by 115 publications

(107 citation statements)

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“…The technique has been widely used to determine equilibrium thermodynamic parameters by mechanically driving probed molecules out of equilibrium at various loading rates (16,(20)(21)(22)(23)(24). To date, there have been very few investigations reported on wholly synthetic small molecules (31,(40)(41)(42)(43)(44), mainly because of the difficulty of preparing appropriate molecules that can be interfaced with single-molecule force spectroscopy techniques, but also because the size of the molecules implies that the rupture events occur at very small distances, in the range of 1 nm. Here we have probed donor-acceptor oligorotaxane foldamers, synthetic prototypes of molecular switches, by AFM-based dynamic force spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…The oligorotaxanes were grafted onto gold-coated silicon substrates using our previously established method (31) to obtain a sparse regime of the molecule of interest. The substrates were dipped for 1 h in a solution of the oligorotaxane (2 × 10 −8 mol) containing 90 mol % of dodecyl disulfide in Me 2 CO at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…The stochastic behavior of small molecules in an environment governed by random thermal fluctuations forces us to use theories of nonequilibrium statistic mechanics, known as fluctuation theorems (25)(26)(27)(28)(29), to uncover that part of the work which is reversible and thus deduce energetics information about the probed interactions. For example, the Crooks fluctuation theorem (29) was used to correlate the work measured during the mechanical unfolding and refolding of an RNA hairpin to the free-energy difference (ΔG) between both conformations (30), or to extract the free-energy differences between both conformations of a hydrogen-bonded [2]rotaxane (31).…”

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Dynamic force spectroscopy of synthetic oligorotaxane foldamers

Sluysmans

Devaux

Bruns³

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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Wholly synthetic molecules involving both mechanical bonds and a folded secondary structure are one of the most promising architectures for the design of functional molecular machines with unprecedented properties. Here, we report dynamic single-molecule force spectroscopy experiments that explore the energetic details of donor-acceptor oligorotaxane foldamers, a class of molecular switches. The mechanical breaking of the donor-acceptor interactions responsible for the folded structure shows a high constant rupture force over a broad range of loading rates, covering three orders of magnitude. In comparison with dynamic force spectroscopy performed during the past 20 y on various (bio)molecules, the near-equilibrium regime of oligorotaxanes persists at much higher loading rates, at which biomolecules have reached their kinetic regime, illustrating the very fast dynamics and remarkable rebinding capabilities of the intramolecular donor-acceptor interactions. We focused on one single interaction at a time and probed the stochastic rupture and rebinding paths. Using the Crooks fluctuation theorem, we measured the mechanical work produced during the breaking and rebinding to determine a freeenergy difference, ΔG, of 6 kcal·mol −1 between the two local conformations around a single bond.AFM | single-molecule force spectroscopy | molecular machines | foldamers | equilibrium dynamics B iological molecular machines are known to operate out of their thermodynamic equilibrium to carry out specific tasks such as cargo transport performed by single myosins (1), or cell movements driven by flagella rotary motions (2). The work performed by these natural molecular motors is related to their dynamics in solution, and to the force exerted by the molecule to drive the relevant process in one direction. The invention of synthetic routes to wholly artificial molecular machines with highly precise and controlled architectures has led to the production of amazing molecules able to perform mechanical tasks (3-7). Their integration into materials such as metal-organic frameworks (8) or polymer gels (9, 10) has been described recently. The resulting materials can experience a macroscopic change when each single machine is pulled out of its equilibrium state, as a result of an external stimulus, such as light irradiation or a change in solvent.Collecting information about the behavior of such molecules when driven out of their equilibrium is crucial for the design of more efficient molecular devices. Atomic force microscopy (AFM)-based single-molecule force spectroscopy (SMFS) has emerged as a very elegant technique to probe inter-and intramolecular forces as well as mechanical processes (11-16). By trapping individual molecules between a mechanical probe and a substrate, it is possible to apply an external force to drive them out of the equilibrium and perform very precise and controlled operations in one direction. For 20 y, AFM-based SMFS was used to unravel the behavior of natural biomolecules under mechanical load and has led to a d...

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Dynamic force spectroscopy of synthetic oligorotaxane foldamers

Sluysmans

Devaux

Bruns³

et al. 2017

Proc. Natl. Acad. Sci. U.S.A.

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“…For instance, the nonequilibrium work is a fluctuating quantity of interest in small systems such as single molecules subjected to the time-dependent forces of optical tweezers or atomic force microscopy [19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Time‐Reversal Symmetry Relations for Currents in Quantum and Stochastic Nonequilibrium Systems

Gaspard

2013

Nonequilibrium Statistical Physics of Small Systems

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An overview is given of recent advances in the nonequilibrium statistical mechanics of quantum systems and, especially, of time-reversal symmetry relations that have been discovered in this context. The systems considered are driven out of equilibrium by time-dependent forces or by coupling to large reservoirs of particles and energy. The symmetry relations are established for the exchange of energy and particles between the subsystem and its environment. These results have important consequences. In particular, generalizations of the Kubo formula and the Casimir-Onsager reciprocity relations can be deduced beyond linear response properties. Applications to electron quantum transport in mesoscopic semiconducting circuits are discussed.

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“…4,5 Stoddart et al demonstrated the first solid-state rotaxane switch system directed toward molecular electronic devices and opened the door for the rotaxane-based molecular machine creating macroscopic work. 6 The actual observation of the switching behavior of rotaxane in solid state has been recently achieved.…”

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confidence: 99%

Solid-state Rotaxane Switch: Synthesis of Thermoresponsive Rotaxane Shuttle Utilizing a Thermally Decomposable Acid

2016

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A thermoresponsive crown ether/amine-type rotaxane switch worked under solvent-free condition was developed. The wheel component moved to switch the local position on the axle by the solid-state acidbase reaction between tert-amine moiety of the rotaxane and trichloroacetic acid. The wheel shuttling on the axle proceeded via neutralization by heating and protonation with trichloroacetic acid, being confirmed by 1 H NMR and TGA.Keywords: Rotaxane | Solid-state switch | Thermoresponsive Rotaxane switches available in solid state have versatile potential applicability, which attracts much attention from the viewpoint of not only scientific interest but also practical use. 13Rotaxane shows a unique and reliable switching mode attributable to its mechanical linkage, and can induce macroscopic events in bulk systems. 4,5 Stoddart et al. demonstrated the first solid-state rotaxane switch system directed toward molecular electronic devices and opened the door for the rotaxane-based molecular machine creating macroscopic work. 6 The actual observation of the switching behavior of rotaxane in solid state has been recently achieved. Loeb et al. reported 7 the rate of the shuttling of a crown ether-based rotaxane moiety in a crystalline metal organic framework. Meanwhile, rotaxane consisting of crown ether and an ammonium salt-containing axle seems interesting due to its useful and convenient architecture based on the synthetic easiness. 810Local position of the crown ether wheel on the rotaxane axle is regulated by controlling the interaction between these components. In 2008, we reported a crown ether and tert-ammonium/aminebased rotaxane as a convenient molecular switch with high performance 11 even in polymer systems, 12 which could be driven with one stimulus. The crown ether wheel is fixed on the tertammonium moiety by hydrogen bonding, while it moves to a metastable position by neutralization due to the electrostatic repulsion to the amine moiety formed.We have recently developed a novel rotaxane switch having a trichloroacetate counter anion that showed its switching ability even in solid state. 13 Trichloroacetic acid (TCA) thermally decomposes at 167°C to chloroform and carbon dioxide, 13 whereas the decomposition is accelerated in the presence of a suitable amine base. One of the most important points of this system is that it accumulates no salt by the repeated switching, although the stimuli involve simple acidbase reactions, because of the TCA's decomposition to volatile materials. Therefore, this type of rotaxane switch responsive to thermal stimuli in solid state should have potential utility in a wide variety of applications. Herein, we describe the synthesis and characterization of thermoresponsive rotaxanes working in solid state (Figure 1), with emphasis on the structure effect of the rotaxanes on the switching behavior.In addition to the previously reported ester end-cap method for rotaxane synthesis, 14 we have recently developed two useful endcap methods. One is the urethane end-cap with bulky isocy...

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A single synthetic small molecule that generates force against a load

Cited by 115 publications

References 31 publications

Dynamic force spectroscopy of synthetic oligorotaxane foldamers

Dynamic force spectroscopy of synthetic oligorotaxane foldamers

Time‐Reversal Symmetry Relations for Currents in Quantum and Stochastic Nonequilibrium Systems

Solid-state Rotaxane Switch: Synthesis of Thermoresponsive Rotaxane Shuttle Utilizing a Thermally Decomposable Acid

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