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Artificial Molecular Machines.

Erbas-Cakmak S, Leigh DA, McTernan CT, Nussbaumer AL - Chem. Rev. (2015)

View Article: PubMed Central - PubMed

Affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.

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Hydrogen-bonding solvents have been shownto disrupt macrocycle–thread interactions in single stationrotaxanes, and here addition of 5% [D4]methanol increased the rate of shuttling 100-fold, consistentwith lowering the energy barrier to migration by disrupting station–macrocycleinteractions and thus raising ground-state energies... The effect of water on the rate of shuttlinghas been investigated and was found to be greatly superior to thatof other protic solvents... Therate of escape from the station energy well can then be modeled byan Arrhenius equation with a contribution from a distance-dependentdiffusion factor to the overall rate of shuttling... A quantum mechanicaltreatment of this system has found that, as the lengthening of thespacer has no effect on the activation for breaking the hydrogen bonds,the effect on the rate of shuttling is due to the widening of theoverall potential energy well... Molecular motion in mechanically interlocked and thus kineticallystable rotaxanes can be controlled using multiple binding sites withaffinities for the macrocycle that vary under different conditions.The conditions can be modified by electrochemical redox processes,light, pH, and environmental changes... Whenthe stilbene unit adopted the E form, the macrocyclecould move randomly along the full length of the thread by Brownianmotion, while when the Z form is adopted, the macrocyclewas trapped in one or the other of the two compartments... As the stretching of the PEOtether continued, and the force exerted by the PEO linker exceededthe hydrogen-bonding forces between the macrocycle and the fumaramidestation, the ring moved away from the fumaramide station... Tensionin the tether decreased as a result of the shuttling... Extracting useful work at the molecular scalerequires the restriction of the thermal movement of submolecular componentsor the exploitation of thermal motion with additional ratcheting.Shuttling, switching, and rotation processes in solution can be modulatedexternally, and the directionality of each motion can be controlledin single molecules... Third, to drive the walker away fromequilibrium, that is, to generate directional motion, a ratchetingprocess (either an energy or an information ratchet) must take place.In addition to the requirements of a Brownian motor, certain additionalcharacteristics are necessary for a motor to be defined as a walker... For the design of processive small molecule synthetic molecularwalkers, mechanically interlocked architectures are good candidates,because the walker (macrocycle) is mechanically bonded to the track(thread)... To perform tasks that cannot be accomplishedby conventional chemical means, it will be necessary to design systemswith multiple integrated parts, each component performing a dedicatedrole within the machine ensemble... This will not be straightforwardbecause unlike a watch where the second hand, say, does not interferewith the components in the escapement mechanism, the components ofa chemical machine are not easily isolated from each other (or theenvironment) and interference from one reactive part of a machinewith another will be a significant issue as complexity increases beyondthe current rather trivial systems. (iii) The machines we arefamiliar with in the macroscopic worldare generally stable, operating unchanged through many cycles, andby and large they do not make “mistakes”... Or it may bethat evolution just did not discover these solutions to such problemsand that mankind, with the whole of the periodic table and known syntheticchemistry to work with, can... Perhaps the most productive approachwill ultimately be found by following neither of these lines of investigationtoo closely, for example, by using chemical principles for “molecularrobotics” in which ratcheted motions of molecular components(i.e., biologically inspired mechanisms) are used to perform tasksthat have their origins in innovations introduced to advance developmentsin macroscopic technology (e.g., factory assembly lines).

No MeSH data available.


Nonpolar 95 and dipolar 96 altitudinalrotors mounted on an Au(111) surface. Note that rotor and flankingaryl rings are arbitrarily shown perpendicular to the surface forclarity.966
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fig35: Nonpolar 95 and dipolar 96 altitudinalrotors mounted on an Au(111) surface. Note that rotor and flankingaryl rings are arbitrarily shown perpendicular to the surface forclarity.966

Mentions: Several examples of surface-mounted molecular rotors havebeenreported where motion could be driven by alternating electric fieldsor the absorption of pulses of light.952−962 Michl and co-workers synthesized, on the basis of computationalstudies, a series of surface-mounted rotors.963−965Figure 35 showsthe structure of polar and nonpolar versions of their altitudinalrotor. Polar rotor 96 consisted of a 9,10-dihydrophenanthrenesubstituted by four fluorine atoms on the central ring and had a calculateddipole moment of 3.7 D. The nonpolar rotor was a 4,5,9,10-tetrahydropyrenewhose D2 symmetry precluded a dipole moment.X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy(STM), and IR spectroscopy showed that for a fraction of the molecules,the static electric field from an STM tip induced a change in theorientation of the polar rotor, but not in the nonpolar analogue.966 Several molecular dynamics simulations studyingthe influence of an electric field or a fluid flow on the rotationof a molecule fixed on a surface have been published by the same group.967,968 One recent example simulated carborane-based molecular propellersand showed that they could be successfully driven at GHz rates byan oscillating electric field or by a flow of gas.969


Artificial Molecular Machines.

Erbas-Cakmak S, Leigh DA, McTernan CT, Nussbaumer AL - Chem. Rev. (2015)

Nonpolar 95 and dipolar 96 altitudinalrotors mounted on an Au(111) surface. Note that rotor and flankingaryl rings are arbitrarily shown perpendicular to the surface forclarity.966
© Copyright Policy
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4585175&req=5

fig35: Nonpolar 95 and dipolar 96 altitudinalrotors mounted on an Au(111) surface. Note that rotor and flankingaryl rings are arbitrarily shown perpendicular to the surface forclarity.966
Mentions: Several examples of surface-mounted molecular rotors havebeenreported where motion could be driven by alternating electric fieldsor the absorption of pulses of light.952−962 Michl and co-workers synthesized, on the basis of computationalstudies, a series of surface-mounted rotors.963−965Figure 35 showsthe structure of polar and nonpolar versions of their altitudinalrotor. Polar rotor 96 consisted of a 9,10-dihydrophenanthrenesubstituted by four fluorine atoms on the central ring and had a calculateddipole moment of 3.7 D. The nonpolar rotor was a 4,5,9,10-tetrahydropyrenewhose D2 symmetry precluded a dipole moment.X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy(STM), and IR spectroscopy showed that for a fraction of the molecules,the static electric field from an STM tip induced a change in theorientation of the polar rotor, but not in the nonpolar analogue.966 Several molecular dynamics simulations studyingthe influence of an electric field or a fluid flow on the rotationof a molecule fixed on a surface have been published by the same group.967,968 One recent example simulated carborane-based molecular propellersand showed that they could be successfully driven at GHz rates byan oscillating electric field or by a flow of gas.969

View Article: PubMed Central - PubMed

Affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.

AUTOMATICALLY GENERATED EXCERPT
Please rate it.

Hydrogen-bonding solvents have been shownto disrupt macrocycle–thread interactions in single stationrotaxanes, and here addition of 5% [D4]methanol increased the rate of shuttling 100-fold, consistentwith lowering the energy barrier to migration by disrupting station–macrocycleinteractions and thus raising ground-state energies... The effect of water on the rate of shuttlinghas been investigated and was found to be greatly superior to thatof other protic solvents... Therate of escape from the station energy well can then be modeled byan Arrhenius equation with a contribution from a distance-dependentdiffusion factor to the overall rate of shuttling... A quantum mechanicaltreatment of this system has found that, as the lengthening of thespacer has no effect on the activation for breaking the hydrogen bonds,the effect on the rate of shuttling is due to the widening of theoverall potential energy well... Molecular motion in mechanically interlocked and thus kineticallystable rotaxanes can be controlled using multiple binding sites withaffinities for the macrocycle that vary under different conditions.The conditions can be modified by electrochemical redox processes,light, pH, and environmental changes... Whenthe stilbene unit adopted the E form, the macrocyclecould move randomly along the full length of the thread by Brownianmotion, while when the Z form is adopted, the macrocyclewas trapped in one or the other of the two compartments... As the stretching of the PEOtether continued, and the force exerted by the PEO linker exceededthe hydrogen-bonding forces between the macrocycle and the fumaramidestation, the ring moved away from the fumaramide station... Tensionin the tether decreased as a result of the shuttling... Extracting useful work at the molecular scalerequires the restriction of the thermal movement of submolecular componentsor the exploitation of thermal motion with additional ratcheting.Shuttling, switching, and rotation processes in solution can be modulatedexternally, and the directionality of each motion can be controlledin single molecules... Third, to drive the walker away fromequilibrium, that is, to generate directional motion, a ratchetingprocess (either an energy or an information ratchet) must take place.In addition to the requirements of a Brownian motor, certain additionalcharacteristics are necessary for a motor to be defined as a walker... For the design of processive small molecule synthetic molecularwalkers, mechanically interlocked architectures are good candidates,because the walker (macrocycle) is mechanically bonded to the track(thread)... To perform tasks that cannot be accomplishedby conventional chemical means, it will be necessary to design systemswith multiple integrated parts, each component performing a dedicatedrole within the machine ensemble... This will not be straightforwardbecause unlike a watch where the second hand, say, does not interferewith the components in the escapement mechanism, the components ofa chemical machine are not easily isolated from each other (or theenvironment) and interference from one reactive part of a machinewith another will be a significant issue as complexity increases beyondthe current rather trivial systems. (iii) The machines we arefamiliar with in the macroscopic worldare generally stable, operating unchanged through many cycles, andby and large they do not make “mistakes”... Or it may bethat evolution just did not discover these solutions to such problemsand that mankind, with the whole of the periodic table and known syntheticchemistry to work with, can... Perhaps the most productive approachwill ultimately be found by following neither of these lines of investigationtoo closely, for example, by using chemical principles for “molecularrobotics” in which ratcheted motions of molecular components(i.e., biologically inspired mechanisms) are used to perform tasksthat have their origins in innovations introduced to advance developmentsin macroscopic technology (e.g., factory assembly lines).

No MeSH data available.