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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).

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(a) Chemical structure of the t-butylphenyl andBODIPY-substituted foldamers, and (b) X-ray structure of the t-butylphenyl functionalized foldamer. Carbon atoms of the t-butyl groups and all hydrogen atoms except OH and NH havebeen omitted for clarity. (c) Schematic representation of conformationalswitching. D and A represent energy donor and acceptor modules, respectively.1268−1270 Parts (a) and (c) are adapted with permission from ref (1268). Copyright 2007 Wiley-VCHVerlag GmbH & Co. KGaA, Weinheim. Part (b) is reprinted with permissionfrom ref (1269). Copyright2006 American Chemical Society.
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fig43: (a) Chemical structure of the t-butylphenyl andBODIPY-substituted foldamers, and (b) X-ray structure of the t-butylphenyl functionalized foldamer. Carbon atoms of the t-butyl groups and all hydrogen atoms except OH and NH havebeen omitted for clarity. (c) Schematic representation of conformationalswitching. D and A represent energy donor and acceptor modules, respectively.1268−1270 Parts (a) and (c) are adapted with permission from ref (1268). Copyright 2007 Wiley-VCHVerlag GmbH & Co. KGaA, Weinheim. Part (b) is reprinted with permissionfrom ref (1269). Copyright2006 American Chemical Society.

Mentions: Lee et al. developed a conformational switch based on a cyclichydrogen-bonding network in a tris(N-salicylideneaniline)derivative (Figure 43).1268−1271 Structural distortion induced by folding and unfolding processesresulted in a significant change in the electronic properties of thesystem. BODIPY chromophores were tethered to the molecule as fluorescentenergy acceptors. In the folded form, the molecule adopted a highlyordered hydrogen-bonding array, and energy transfer took place fromthe core tris(N-salicylideneaniline)moiety to theBODIPYs. When a hydrogen-bond acceptor such as fluoride was added,the molecule unfolded, and a substantial decrease in the fluorescenceof the BODIPY dyes was detected. Because each mobile element cooperatedin the folding process via hydrogen bonding, conformational changewas highly cooperative. The initial fluorescence intensity could berecovered when the fluoride anions were captured by trimethylsilylchloride.


Artificial Molecular Machines.

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

(a) Chemical structure of the t-butylphenyl andBODIPY-substituted foldamers, and (b) X-ray structure of the t-butylphenyl functionalized foldamer. Carbon atoms of the t-butyl groups and all hydrogen atoms except OH and NH havebeen omitted for clarity. (c) Schematic representation of conformationalswitching. D and A represent energy donor and acceptor modules, respectively.1268−1270 Parts (a) and (c) are adapted with permission from ref (1268). Copyright 2007 Wiley-VCHVerlag GmbH & Co. KGaA, Weinheim. Part (b) is reprinted with permissionfrom ref (1269). Copyright2006 American Chemical Society.
© Copyright Policy
Related In: Results  -  Collection

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

fig43: (a) Chemical structure of the t-butylphenyl andBODIPY-substituted foldamers, and (b) X-ray structure of the t-butylphenyl functionalized foldamer. Carbon atoms of the t-butyl groups and all hydrogen atoms except OH and NH havebeen omitted for clarity. (c) Schematic representation of conformationalswitching. D and A represent energy donor and acceptor modules, respectively.1268−1270 Parts (a) and (c) are adapted with permission from ref (1268). Copyright 2007 Wiley-VCHVerlag GmbH & Co. KGaA, Weinheim. Part (b) is reprinted with permissionfrom ref (1269). Copyright2006 American Chemical Society.
Mentions: Lee et al. developed a conformational switch based on a cyclichydrogen-bonding network in a tris(N-salicylideneaniline)derivative (Figure 43).1268−1271 Structural distortion induced by folding and unfolding processesresulted in a significant change in the electronic properties of thesystem. BODIPY chromophores were tethered to the molecule as fluorescentenergy acceptors. In the folded form, the molecule adopted a highlyordered hydrogen-bonding array, and energy transfer took place fromthe core tris(N-salicylideneaniline)moiety to theBODIPYs. When a hydrogen-bond acceptor such as fluoride was added,the molecule unfolded, and a substantial decrease in the fluorescenceof the BODIPY dyes was detected. Because each mobile element cooperatedin the folding process via hydrogen bonding, conformational changewas highly cooperative. The initial fluorescence intensity could berecovered when the fluoride anions were captured by trimethylsilylchloride.

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.