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See detailPhysisorbed poly(ethylene oxide) is a robust tether for AFM-based single-molecule force spectroscopy
Willet, Nicolas ULg; Lussis, Perrine ULg; Giamblanco, Nicoletta et al

Conference (2014, December 01)

Atomic force microscopy (AFM)-based single-molecule force spectroscopy is a prevalent tool for the exploration of individual (bio)molecules, providing exquisite information on many molecular-level ... [more ▼]

Atomic force microscopy (AFM)-based single-molecule force spectroscopy is a prevalent tool for the exploration of individual (bio)molecules, providing exquisite information on many molecular-level processes. For example, proteins, DNA, polysaccharides, supramolecular polymers and polyelectrolytes have been investigated, revealing details about the strength of intramolecular interactions, folding and unfolding pathways, mechanics, conformational changes, reactivity, kinetics, etc. For each particular system under investigation, the experimental design is a decisive phase that often involves a multistep chemical protocol, including grafting, derivatization, coupling, (de-)protection, and other functionalization reactions. Procedures of sample preparation are often complex and time-consuming. Hence, there is a need for new general platforms allowing for straightforward sample preparation adapted to single-molecule studies, i.e. a tight attachment to both the substrate and the tip, and a low density to favor single-molecule detection. We report here on the use of poly(ethylene oxide) (PEO) as a tether to probe various properties of individual molecules. The polymeric linker acts as a handle that stably binds to the AFM tip. The simple adsorption of poly(ethylene oxide) to the tip is versatile and provides an appropriate system configuration for the investigation of many different biological and synthetic molecular systems. To attest for this versatility and adequacy with advanced single-molecule investigation, we present different examples of PEO-mediated studies about the unfolding of a synthetic peptide, the mechanochemical behavior of a molecular machine and finally the stability of a metallo-supramolecular complexed polymer. All the requirements for the study of peptide conformation, tiny molecular machines or metallo-supramolecular interactions in solution are here fulfilled. More generally, this method based on non-covalent sorption of PEO on an AFM tip, can be implemented in a wide range of solvents, for the study of many intra- or intermolecular phenomena at the single-molecule level over orders of magnitude of force loading rates. Connecting PEO tethers to a very broad variety of (bio)molecules is a facile and versatile route. The commercial availability of many different functional PEOs makes this tethering strategy even more accessible. [less ▲]

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See detailProbing the mobility of catenane rings in single molecules
Van Quaethem, Anne; Lussis, Perrine ULg; Leigh, David A. et al

in Chemical Science (2014), 5

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See detailMechanical Processes of a Single Synthetic Molecular Machine Studied by AFM-based Force Spectroscopy
Lussis, Perrine ULg

Doctoral thesis (2012)

Some biomolecules are able to generate directional forces by rectifying random thermal motions. This allows these molecular machines to perform mechanical tasks such as intracellular cargo transport or ... [more ▼]

Some biomolecules are able to generate directional forces by rectifying random thermal motions. This allows these molecular machines to perform mechanical tasks such as intracellular cargo transport or muscle contraction in plants and animals. Although some artificial molecular machines have been synthesized and used collectively to perform mechanical tasks, so far there have been no direct measurements of mechanical processes at the single-molecule level. Here we report measurements of the mechanical work performed by a synthetic molecule less than 5 nm long. We show that biased Brownian motion of the submolecular components in a hydrogen-bonded [2]rotaxane -a molecular ring threaded onto a molecular axle- can be harnessed to generate significant directional forces. We used the cantilever of an atomic force microscope to apply a mechanical load to the ring during single-molecule pulling-relaxing cycles. The ring was pulled along the axle, away from the thermodynamically favoured binding site, and was then found to travel back to this site against an external load of 30 pN. Using fluctuation theorems, we were able to relate the measurements of the work done at the level of individual molecules to the free energy change measured previously by ensemble measurements. Finally, we used dynamic single-molecule force spectroscopy to probe kinetic information of the interaction between the molecular ring and the preferred binding site. The results also demonstrate that AFM-based single-molecule force spectroscopy, which has been widely used to investigate the mechanochemical behaviour of (bio)macromolecules, can be applied to a molecule that is less than 5 nm in its extended form. [less ▲]

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See detailA single synthetic small molecule that generates force against a load
Lussis, Perrine ULg; Svaldo-Lanero, Tiziana; Bertocco, Andrea et al

Poster (2012, February)

Biological molecular machines are able to rectify random thermal motions to generate directional force and carry out tasks on both the molecular and macroscopic length scales1. Although some artificial ... [more ▼]

Biological molecular machines are able to rectify random thermal motions to generate directional force and carry out tasks on both the molecular and macroscopic length scales1. Although some artificial nanomachines have been synthesized2 and used to collectively carry out mechanical tasks3, so far there have been no direct measurements of mechanical processes at the single-molecule level. Here we report measurements of the mechanical work performed by a synthetic molecule less than 5 nm long. We show that biased Brownian motion of the sub-molecular components in a hydrogen bonded [2]rotaxane4 -a molecular ring threaded onto a molecular axle- can be harnessed to generate significant directional forces. We used the cantilever of an atomic force microscope to apply a mechanical load to the ring during single-molecule pulling–relaxing cycle. The ring was pulled along the axle, away from the thermodynamically favoured binding site, and was then found to travel back to this site against an external load of 30 pN5. Using fluctuation theorems6, we were able to relate the measurements of the work done at the level of individual molecules to the free energy change measured previously by ensemble measurements. The results show that individual rotaxane molecules can generate directional forces of similar magnitude to those generated by natural biological machines, and extend the capabilities of AFM-based single molecule mechanics to the world of small molecules. It opens up the possibility of testing modern theories of non-equilibrium statistical mechanics, such as Jarzynski’s equality7 and the Crooks fluctuation theorem6, in single-molecule AFM measurements. 1. Schilva, M. (ed.) Molecular Motors (Wiley-VCH, Weinheim, 2003). 2. Kay, E. R., Liegh, D. A. & Zerbetto, F., Angew. Chem. Int. Ed. 46, 72-191 (2007). 3. Berna, J., Leigh, D. A., Lubomska, M., Mendoza, S. M., Pérez, E. M., Rudolf, P., Teobaldi, G. & Zerbetto, F., Nature Mater. 4, 704-710 (2005). 4. Kay, E. R. & Liegh, D. A., Top. Curr. Chem. 262, 133-177 (2005). 5. Lussis, P., Svaldo-Lanero T., Bertocco, A., Fustin C-A., Leigh, D. A., Duwez A-S., Nature Nanotech. 6, 553-557 (2011). 6. Crooks, G.E., Phys.Rev.E, 60, 2771-2726 (1999) 7. Jarzynski, C., Phys.Rev.Lett., 78, 2690-2693 (1997) [less ▲]

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See detailA single synthetic small molecule that generates force against a load
Lussis, Perrine ULg; Svaldo-Lanero, Tiziana; Bertocco, Andrea et al

Poster (2011, September 06)

Biological molecular machines are able to rectify random thermal motions to generate directional force and carry out tasks on both the molecular and macroscopic length scales1. Although some artificial ... [more ▼]

Biological molecular machines are able to rectify random thermal motions to generate directional force and carry out tasks on both the molecular and macroscopic length scales1. Although some artificial nanomachines have been synthesized2-4 and used to collectively carry out mechanical tasks5-8, the direct measurement of the mechanical processes at the single molecule level has yet to be realized. We show that biased Brownian motion of the sub-molecular components in a hydrogen bonded [2]rotaxane9-a molecular ring threaded onto a molecular axle-can be harnessed to generate significant directional forces. We applied a mechanical load to the ring by atomic force microscopy (AFM) cantilever during single molecule pulling-relaxing cycle. Using fluctuation theorems, we were able to relate the measurements of the work done at the level of individual molecules to the free energy change measured previously by ensemble measurements. The results show that individual rotaxane molecules can generate directional forces of similar magnitude to biological machines, and extend the capabilities of AFM-based single molecule mechanics to the world of small molecules. 1. Schilva, M. (ed.) Molecular Motors (Wiley-VCH, Weinheim, 2003). 2. Kinbara, K. & Aida, T. Toward intelligent molecular machines : Directed motions of biological and artificial molecules and assemblies. Chem. Rev. 105, 1377-1400 (2005). 3. Kay, E. R., Liegh, D. A. & Zerbetto, F. Synthetic molecular motors and mechanical machines. Angew. Chem. Int. Ed. 46, 72-191 (2007). 4. Browne, W., Feringa, B. L. Making molecular machines work. Nature Nanotech. 1, 25-35 (2006). 5. Berna, J., Leigh, D. A., Lubomska, M., Mendoza, S. M., Pérez, E. M., Rudolf, P., Teobaldi, G. & Zerbetto, F. Macroscopic transport by synthetic molecular machines. Nature Mater. 4, 704-710 (2005). 6. Liu, Y., Flood, A. H., Bonvallet, P. A., Vignon, S. A., Northrop, B. H., Tseng, H.-R., Jeppesen, J. O., Huang, T. J., Brough, B., Baller, M., Magonov, S., Solares, S. D., Goddard, W. A., Ho, C.-M. & Stoddart, J. F. Linear artificial molecular muscles. J. Am. Chem. Soc. 127, 9745-9759 (2005) 7. Eelkema, R., Pollard, M. M., Vicario, J., Katsonis, N., Ramon, B. S., Bastiaansen, C. W. M., Broer, D. J. & Feringa, B. L. Molecular machines: Nanomotor rotates microscale objects. Nature 440, 163 (2006). 8. Muraoka, T., Kinbara, K., Aida, T. Mechanical twisting of a guest by a photoresponsive host. Nature 440, 512-515 (2006). 9. Kay, E. R. & Liegh, D. A. Hydrogen bond-assembled synthetic molecular motors and machines. Top. Curr. Chem. 262, 133-177 (2005). [less ▲]

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See detailA single synthetic molecular machine that generates force against a load
Lussis, Perrine ULg; Svaldo-lanero, Tiziana; Bertocco, Andrea et al

Conference (2011, April 29)

Biological molecular machines are able to rectify random thermal motions to generate directional force and carry out tasks on both the molecular and macroscopic length scales1. Although some artificial ... [more ▼]

Biological molecular machines are able to rectify random thermal motions to generate directional force and carry out tasks on both the molecular and macroscopic length scales1. Although some artificial nanomachines have been synthesized2-4 and used to collectively carry out mechanical tasks5-8, the direct measurement of the mechanical processes at the single molecule level has yet to be realized. We show that biased Brownian motion of the sub-molecular components in a hydrogen bonded [2]rotaxane9-a molecular ring threaded onto a molecular axle-can be harnessed to generate significant directional forces. We applied a mechanical load to the ring by atomic force microscopy (AFM) cantilever during single molecule pulling-relaxing cycle. Using fluctuation theorems, we were able to relate the measurements of the work done at the level of individual molecules to the free energy change measured previously by ensemble measurements. The results show that individual rotaxane molecules can generate directional forces of similar magnitude to biological machines, and extend the capabilities of AFM-based single molecule mechanics to the world of small molecules. 1. Schilva, M. (ed.) Molecular Motors (Wiley-VCH, Weinheim, 2003). 2. Kinbara, K. & Aida, T. Toward intelligent molecular machines : Directed motions of biological and artificial molecules and assemblies. Chem. Rev. 105, 1377-1400 (2005). 3. Kay, E. R., Liegh, D. A. & Zerbetto, F. Synthetic molecular motors and mechanical machines. Angew. Chem. Int. Ed. 46, 72-191 (2007). 4. Browne, W., Feringa, B. L. Making molecular machines work. Nature Nanotech. 1, 25-35 (2006). 5. Berna, J., Leigh, D. A., Lubomska, M., Mendoza, S. M., Pérez, E. M., Rudolf, P., Teobaldi, G. & Zerbetto, F. Macroscopic transport by synthetic molecular machines. Nature Mater. 4, 704-710 (2005). 6. Liu, Y., Flood, A. H., Bonvallet, P. A., Vignon, S. A., Northrop, B. H., Tseng, H.-R., Jeppesen, J. O., Huang, T. J., Brough, B., Baller, M., Magonov, S., Solares, S. D., Goddard, W. A., Ho, C.-M. & Stoddart, J. F. Linear artificial molecular muscles. J. Am. Chem. Soc. 127, 9745-9759 (2005) 7. Eelkema, R., Pollard, M. M., Vicario, J., Katsonis, N., Ramon, B. S., Bastiaansen, C. W. M., Broer, D. J. & Feringa, B. L. Molecular machines: Nanomotor rotates microscale objects. Nature 440, 163 (2006). 8. Muraoka, T., Kinbara, K., Aida, T. Mechanical twisting of a guest by a photoresponsive host. Nature 440, 512-515 (2006). 9. Kay, E. R. & Liegh, D. A. Hydrogen bond-assembled synthetic molecular motors and machines. Top. Curr. Chem. 262, 133-177 (2005). [less ▲]

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See detailClicking single molecules on surfaces
Svaldo Lanero, Tiziana ULg; Lussis, Perrine ULg; Detrembleur, Christophe ULg et al

Conference (2011, February 04)

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See detailA single synthetic small molecule that generates force against a load
Lussis, Perrine ULg; Svaldo Lanero, Tiziana ULg; Bertocco, Andrea et al

in Nature Nanotechnology (2011), 6

Some biomolecules are able to generate directional forces by rectifying random thermal motions. This allows these molecular machines to perform mechanical tasks such as intracellular cargo transport or ... [more ▼]

Some biomolecules are able to generate directional forces by rectifying random thermal motions. This allows these molecular machines to perform mechanical tasks such as intracellular cargo transport or muscle contraction in plants and animals. Although some artificial molecular machines have been synthesized and used collectively to perform mechanical tasks, so far there have been no direct measurements of mechanical processes at the single-molecule level. Here we report measurements of the mechanical work performed by a synthetic molecule less than 5 nm long. We show that biased Brownian motion of the sub-molecular components in a hydro- gen-bonded [2]rotaxane—a molecular ring threaded onto a molecular axle—can be harnessed to generate significant directional forces. We used the cantilever of an atomic force microscope to apply a mechanical load to the ring during single-molecule pulling–relaxing cycles. The ring was pulled along the axle, away from the thermodynamically favoured binding site, and was then found to travel back to this site against an external load of 30 pN. Using fluctuation theorems, we were able to relate measurements of the work done at the level of individual rotaxane molecules to the free-energy change as previously determined from ensemble measurements. The results show that individual rotaxanes can generate directional forces of similar magnitude to those generated by natural molecular machines. [less ▲]

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See detailProbing recognition processes, forces, and motions in single bio-inspired molecules
Willet, N; Lussis, Perrine ULg; Svaldo Lanero, Tiziana ULg et al

Conference (2010, October 24)

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See detailThe pulling force of a synthetic molecular machine
Lussis, Perrine ULg; Svaldo-Lanero, Tiziana; Willet, Nicolas ULg et al

Conference (2010, September 07)

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists who synthesize molecular machines able to imitate the machinery of biological world. It has been proved ... [more ▼]

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists who synthesize molecular machines able to imitate the machinery of biological world. It has been proved possible to design synthetic molecular systems in which positional displacements of sub-molecular components occur upon the application of external stimuli.1-3 The architecture of synthetic systems is crucial to translate molecular level effects into a useful response exploitable in the macroscopic world. Pioneering works1-2 have shown that rotaxanes (molecules consisting of a ring threaded onto an axle capped with bulky end-stoppers) are a particularly promising kind of synthetic 'molecular shuttles'. Although nanodevices based on molecular machines have been conceived, there is a huge gap between those exploratory studies and truly functional systems, able to use an external source of energy to induce a directional motion and perform useful tasks.4 One of the major challenges is the interfacing between the molecular machines and the outside world. Here we to demonstrate the feasibility of transducing sub-molecular movements into mechanical work by combining the controlled translational motion of the ring in a rotaxane coupled to a polymer chain, and the ability of AFM-based single molecule force spectroscopy to be used as a mechanical device.5 For that purpose, a rotaxane with a long thread and two stations onto which the ring can bind through H-bonds was synthesized. We have attached a polymer chain to the ring and the resulting system was grafted onto substrates. We then fished the polymer chain with an AFM tip and realized single molecule pulling-relaxing cycles. The ring was moved away from the most stable station along the thread and was found to shuttle back to this station against the external force, thus delivering mechanical work against the AFM cantilever. We have estimated the work done by the ring and show that the value is in good agreement with predicted theoretical values.2 1 J.F. Stoddart et al., Special Issue on Molecular Machines, Acc. Chem. Res. 2001, 34, 409-522. 2 E R Kay, D A Leigh and F Zerbetto, Angew. Chem. Int. Ed. 2007, 46, 72. 3 D. A. Leigh et al., Nature 2000, 406, 608; Science 2001, 291, 2124; Nature 2003, 424, 174; Science 2004, 306, 153; Nature 2006, 440, 286; Nature 2007, 445, 523; Nature 2009, 458, 314. 4 W. R. Browne, B. L. Feringa, Nature Nanotech. 2006, 1, 25. 5 H. E. Gaub et al., Science 2002, 296, 1103. [less ▲]

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See detailInterfacing a Synthetic Molecular Shuttle with the AFM
Lussis, Perrine ULg; Svalto-Lanero, T; Fustin, C.-A et al

Conference (2010, August 30)

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See detailContribution of "click chemistry" to the macromolecular engineering of aliphatic polyesters
Riva, Raphaël ULg; Schmeits, Stephanie ULg; Croisier, Florence ULg et al

Poster (2010, July 13)

In this work, click chemistry was sucessfully applied to the chemical modification of aliphatic polyesters with the purpose to tailor their physical properties. The developped strategy was then applied to ... [more ▼]

In this work, click chemistry was sucessfully applied to the chemical modification of aliphatic polyesters with the purpose to tailor their physical properties. The developped strategy was then applied to the synthesis of materials, such as smart partially degradable hydrogels or antibacterial polyesters. Last, the synthesis of amphiphilic star-shaped copolyester was investigated. [less ▲]

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See detailMolecular Elasticity of a Mechanically-Linked Polymer
Lussis, Perrine ULg; Fustin, C.-A; Van Quaethem, A et al

Conference (2010, July 11)

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See detailSynthesis and Characterization of Mechanically linked copolymers
Van Quaethem, A.; Lussis, Perrine ULg; Duwez, Anne-Sophie ULg et al

Conference (2010, May 25)

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See detailFeeling the Force of a Bistable Molecular Shuttle
Lussis, Perrine ULg; Fustin, C.-A; Bertocco, A. et al

Conference (2009, May 14)

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See detailFeeling the force of a synthetic molecular shuttle
Lussis, Perrine ULg; Willet, Nicolas ULg; Bertocco, Andrea et al

Conference (2009, May 14)

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists that have been trying to synthesize molecular machines able to imitate the machinery of biological ... [more ▼]

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists that have been trying to synthesize molecular machines able to imitate the machinery of biological world. In recent years, it has been proved possible to design synthetic molecular systems in which positional displacements of sub-molecular components occur upon the application of external stimuli.[1-4] The architecture of synthetic systems is crucial to translate molecular level effect into a useful response exploitable in the macroscopic world. The pioneering work of Stoddart, Sauvage and others[1-3] has shown that molecular machines with mechanically interlocked architecture are particularly suited for these sorts of applications, because they permit the controlled, large amplitude, movement and positioning of one mechanically interlocked component with respect to another. Among these architectures, rotaxanes -i.e. molecules consisting of a ring threaded on a linear molecule capped with bulky end stoppers- are a particularly promising kind of synthetic 'molecular shuttles'. Truly functional systems based on synthetic molecular machines have not yet been proposed because some key questions remain unanswered: What are the structural features necessary for molecules to convert this controlled motion into useful function? At what level (single molecule, nanoscopic, microscopic, macroscopic) can this be done? Can we address and utilize the induced-motion in a single molecular machine? To answer those questions we are advocating the use of molecular shuttles coupled to a polymeric scaffold and interfaced with AFM. We are convinced that this is an efficient route to translate the sub-molecular motion into a useful response that can be exploited to perform physical tasks Our objective is to demonstrate the feasibility of transducing sub-molecular movements into mechanical work by combining the controlled translational motion of the ring in a rotaxane coupled to a polymer chain, and the ability of AFM-based single molecule force spectroscopy to be used as a mechanical device.[5] For that purpose, a bistable hydrogen-bonded rotaxane with one fumaramide and one succinic amide ester station was synthesized. The equilibrium distribution of the ring between the two stations is in favour of the fumaramide station (>95%).[6] If an external force forces the ring to leave the preferred binding site, it will move back to this preferred binding site through biased Brownian motion. We have attached a poly-ethylene oxide (PEO) chain to the ring and the resulting rotaxane-polymer compound was grafted onto gold substrates. We then fished the PEO chain with an AFM tip. The applied force exerted on the ring when pulling on the polymer chain causes the H bonds linking the ring to the fumaramide station to break. When trying to move away the ring, it shuttles back to its station in the opposite direction of the pulling force, doing work against the AFM cantilever. We have estimated the work done by the ring and show that the value is in good agreement with the theoretical value predicted by Altieri et. al.[6] [1] Special Issue on Molecular Machines, Acc. Chem. Res. 2001, 34, p. 409-522. [2] V. Balzani, A. Credi, M. Venturi, Molecular Devices and Machines – A Journey into the Nano World, Wiley-VCH, Weinheim, Germany, 2003. [3] E R Kay, D A Leigh and F Zerbetto, Angew. Chem. Int. Ed. 2007, 46, 72. [4] a) V Bermudez, N Capron, T Gase, F G Gatti, F Kajzar, D A Leigh, F Zerbetto and S Zhang, Nature, 2000, 406, 608. b) A M Brouwer, C Frochot, F G Gatti, D A Leigh, L Mottier, F Paolucci, S Roffia, G W H Wurpel, Science , 2001, 291, 2124. c) D A Leigh, J K Y Wong, F Dehez and F Zerbetto, Nature, 2003, 424, 174. d) J V Hernandez, E R Kay and D A Leigh, Science, 2004, 306, 153. e) E R Kay and D A Leigh, Nature, 2006, 440, 286. f) V Serreli, C-F Lee, E R Kay and D A Leigh, Nature, 2007, 445, 523. [5] T. Hugel, N. B. Holland, A. Cattani, L. Moroder, M. Seitz, H. E. Gaub, Science 2002, 296, 1103. [6] A. Altieri, G. Bottari, F. Dehez, D A Leigh, J.K.Y Wong, F Zerbetto, Angew. Chem. Int. Ed. 2003, 42, 2296. [less ▲]

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See detailFeeling the force of a synthetic molecular shuttle
Lussis, Perrine ULg; Fustin, Charles-André; Bertocco, Andrea et al

Poster (2009, May 08)

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists that have been trying to synthesize molecular machines able to imitate the machinery of biological ... [more ▼]

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists that have been trying to synthesize molecular machines able to imitate the machinery of biological world. In recent years, it has been proved possible to design synthetic molecular systems in which positional displacements of sub-molecular components occur upon the application of external stimuli.[1-4] The architecture of synthetic systems is crucial to translate molecular level effect into a useful response exploitable in the macroscopic world. The pioneering work of Stoddart, Sauvage and others[1-3] has shown that molecular machines with mechanically interlocked architecture are particularly suited for these sorts of applications, because they permit the controlled, large amplitude, movement and positioning of one mechanically interlocked component with respect to another. Among these architectures, rotaxanes -i.e. molecules consisting of a ring threaded on a linear molecule capped with bulky end stoppers- are a particularly promising kind of synthetic 'molecular shuttles'. Truly functional systems based on synthetic molecular machines have not yet been proposed because some key questions remain unanswered: What are the structural features necessary for molecules to convert this controlled motion into useful function? At what level (single molecule, nanoscopic, microscopic, macroscopic) can this be done? Can we address and utilize the induced-motion in a single molecular machine? To answer those questions we are advocating the use of molecular shuttles coupled to a polymeric scaffold and interfaced with AFM. We are convinced that this is an efficient route to translate the sub-molecular motion into a useful response that can be exploited to perform physical tasks Our objective is to demonstrate the feasibility of transducing sub-molecular movements into mechanical work by combining the controlled translational motion of the ring in a rotaxane coupled to a polymer chain, and the ability of AFM-based single molecule force spectroscopy to be used as a mechanical device.[5] For that purpose, a bistable hydrogen-bonded rotaxane with one fumaramide and one succinic amide ester station was synthesized. The equilibrium distribution of the ring between the two stations is in favour of the fumaramide station (>95%).[6] If an external force forces the ring to leave the preferred binding site, it will move back to this preferred binding site through biased Brownian motion. We have attached a poly-ethylene oxide (PEO) chain to the ring and the resulting rotaxane-polymer compound was grafted onto gold substrates. We then fished the PEO chain with an AFM tip. The applied force exerted on the ring when pulling on the polymer chain causes the H bonds linking the ring to the fumaramide station to break. When trying to move away the ring, it shuttles back to its station in the opposite direction of the pulling force, doing work against the AFM cantilever. We have estimated the work done by the ring and show that the value is in good agreement with the theoretical value predicted by Altieri et. al.[6] [1] Special Issue on Molecular Machines, Acc. Chem. Res. 2001, 34, p. 409-522. [2] V. Balzani, A. Credi, M. Venturi, Molecular Devices and Machines – A Journey into the Nano World, Wiley-VCH, Weinheim, Germany, 2003. [3] E R Kay, D A Leigh and F Zerbetto, Angew. Chem. Int. Ed. 2007, 46, 72. [4] a) V Bermudez, N Capron, T Gase, F G Gatti, F Kajzar, D A Leigh, F Zerbetto and S Zhang, Nature, 2000, 406, 608. b) A M Brouwer, C Frochot, F G Gatti, D A Leigh, L Mottier, F Paolucci, S Roffia, G W H Wurpel, Science , 2001, 291, 2124. c) D A Leigh, J K Y Wong, F Dehez and F Zerbetto, Nature, 2003, 424, 174. d) J V Hernandez, E R Kay and D A Leigh, Science, 2004, 306, 153. e) E R Kay and D A Leigh, Nature, 2006, 440, 286. f) V Serreli, C-F Lee, E R Kay and D A Leigh, Nature, 2007, 445, 523. [5] T. Hugel, N. B. Holland, A. Cattani, L. Moroder, M. Seitz, H. E. Gaub, Science 2002, 296, 1103. [6] A. Altieri, G. Bottari, F. Dehez, D A Leigh, J.K.Y Wong, F Zerbetto, Angew. Chem. Int. Ed. 2003, 42, 2296. [less ▲]

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See detailFeeling the force of a bistable molecular shuttle
Lussis, Perrine ULg; Fustin, Charles-André; Bertocco, Andrea et al

Conference (2009, March 19)

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists that have been trying to synthesize molecular machines able to imitate the machinery of biological ... [more ▼]

The widespread utilization of sub-molecular motion in key biological processes is inspiring chemists that have been trying to synthesize molecular machines able to imitate the machinery of biological world. In recent years, it has been proved possible to design synthetic molecular systems in which positional displacements of sub-molecular components occur upon the application of external stimuli.[1-4] The architecture of synthetic systems is crucial to translate molecular level effect into a useful response exploitable in the macroscopic world. The pioneering work of Stoddart, Sauvage and others[1-3] has shown that molecular machines with mechanically interlocked architecture are particularly suited for these sorts of applications, because they permit the controlled, large amplitude, movement and positioning of one mechanically interlocked component with respect to another. Among these architectures, rotaxanes -i.e. molecules consisting of a ring threaded on a linear molecule capped with bulky end stoppers- are a particularly promising kind of synthetic 'molecular shuttles'. Truly functional systems based on synthetic molecular machines have not yet been proposed because some key questions remain unanswered: What are the structural features necessary for molecules to convert this controlled motion into useful function? At what level (single molecule, nanoscopic, microscopic, macroscopic) can this be done? Can we address and utilize the induced-motion in a single molecular machine? To answer those questions we are advocating the use of molecular shuttles coupled to a polymeric scaffold and interfaced with AFM. We are convinced that this is an efficient route to translate the sub-molecular motion into a useful response that can be exploited to perform physical tasks Our objective is to demonstrate the feasibility of transducing sub-molecular movements into mechanical work by combining the controlled translational motion of the ring in a rotaxane coupled to a polymer chain, and the ability of AFM-based single molecule force spectroscopy to be used as a mechanical device.[5] For that purpose, a bistable hydrogen-bonded rotaxane with one fumaramide and one succinic amide ester station was synthesized. The equilibrium distribution of the ring between the two stations is in favour of the fumaramide station (>95%).[6] If an external force forces the ring to leave the preferred binding site, it will move back to this preferred binding site through biased Brownian motion. We have attached a poly-ethylene oxide (PEO) chain to the ring and the resulting rotaxane-polymer compound was grafted onto gold substrates. We then fished the PEO chain with an AFM tip. The applied force exerted on the ring when pulling on the polymer chain causes the H bonds linking the ring to the fumaramide station to break. When trying to move away the ring, it shuttles back to its station in the opposite direction of the pulling force, doing work against the AFM cantilever. We have estimated the work done by the ring and show that the value is in good agreement with the theoretical value predicted by Altieri et. al.[6] [1] Special Issue on Molecular Machines, Acc. Chem. Res. 2001, 34, p. 409-522. [2] V. Balzani, A. Credi, M. Venturi, Molecular Devices and Machines – A Journey into the Nano World, Wiley-VCH, Weinheim, Germany, 2003. [3] E R Kay, D A Leigh and F Zerbetto, Angew. Chem. Int. Ed. 2007, 46, 72. [4] a) V Bermudez, N Capron, T Gase, F G Gatti, F Kajzar, D A Leigh, F Zerbetto and S Zhang, Nature, 2000, 406, 608. b) A M Brouwer, C Frochot, F G Gatti, D A Leigh, L Mottier, F Paolucci, S Roffia, G W H Wurpel, Science , 2001, 291, 2124. c) D A Leigh, J K Y Wong, F Dehez and F Zerbetto, Nature, 2003, 424, 174. d) J V Hernandez, E R Kay and D A Leigh, Science, 2004, 306, 153. e) E R Kay and D A Leigh, Nature, 2006, 440, 286. f) V Serreli, C-F Lee, E R Kay and D A Leigh, Nature, 2007, 445, 523. [5] T. Hugel, N. B. Holland, A. Cattani, L. Moroder, M. Seitz, H. E. Gaub, Science 2002, 296, 1103. [6] A. Altieri, G. Bottari, F. Dehez, D A Leigh, J.K.Y Wong, F Zerbetto, Angew. Chem. Int. Ed. 2003, 42, 2296. [less ▲]

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