Limits...
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.

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.


(a) Ligand-induced variationof the chemical shifts (11B (160 MHz) and 1HNMR (500 MHz)) of the helix in CD3OD at 298 K. (b) Schematicrepresentation of fast exchangebetween two degenerate helical conformers with a single NMR signaland (c) induced bias of helicity upon ligand binding (yellow), andthe anisochronous NMR signal generated. Adapted with permission fromref (1298). Copyright2013 Nature Publishing Group.
© Copyright Policy
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC4585175&req=5

fig44: (a) Ligand-induced variationof the chemical shifts (11B (160 MHz) and 1HNMR (500 MHz)) of the helix in CD3OD at 298 K. (b) Schematicrepresentation of fast exchangebetween two degenerate helical conformers with a single NMR signaland (c) induced bias of helicity upon ligand binding (yellow), andthe anisochronous NMR signal generated. Adapted with permission fromref (1298). Copyright2013 Nature Publishing Group.

Mentions: Techniques other than optical responses have been used tomeasureconformational change. Flood et al. used a change in conductance todirectly measure a folding process because unfolding released a boundchloride anion and changed the conductance (Figure 22 in section 3.1).595 A changein CD response can be a useful indicator of molecular motion and helicityinversion.1298−1308 Many shape changes can be easily analyzed by NMR spectroscopy. Recently,Clayden et al. showed, by 11B, 1H, and 13C NMR, that the equal distribution of left-handed (M) and right-handed (P) conformers of ahelical foldamer could be perturbed by the addition of a chiral ligand(Figure 44).1298 Upon ligand complexation to the boronic ester,chiral information was transferred along the helix, and the isochronousNMR signals of the diastereotopic nuclei were transformed into anisochronoussignals, indicating a bias in the distribution of helical conformers.When the meso diastereoisomer of the diol was usedto complex the boronic ester, no splitting of the 1H NMRsignals was observed due to the symmetry of the ligand.


Artificial Molecular Machines.

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

(a) Ligand-induced variationof the chemical shifts (11B (160 MHz) and 1HNMR (500 MHz)) of the helix in CD3OD at 298 K. (b) Schematicrepresentation of fast exchangebetween two degenerate helical conformers with a single NMR signaland (c) induced bias of helicity upon ligand binding (yellow), andthe anisochronous NMR signal generated. Adapted with permission fromref (1298). Copyright2013 Nature Publishing Group.
© Copyright Policy
Related In: Results  -  Collection

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

fig44: (a) Ligand-induced variationof the chemical shifts (11B (160 MHz) and 1HNMR (500 MHz)) of the helix in CD3OD at 298 K. (b) Schematicrepresentation of fast exchangebetween two degenerate helical conformers with a single NMR signaland (c) induced bias of helicity upon ligand binding (yellow), andthe anisochronous NMR signal generated. Adapted with permission fromref (1298). Copyright2013 Nature Publishing Group.
Mentions: Techniques other than optical responses have been used tomeasureconformational change. Flood et al. used a change in conductance todirectly measure a folding process because unfolding released a boundchloride anion and changed the conductance (Figure 22 in section 3.1).595 A changein CD response can be a useful indicator of molecular motion and helicityinversion.1298−1308 Many shape changes can be easily analyzed by NMR spectroscopy. Recently,Clayden et al. showed, by 11B, 1H, and 13C NMR, that the equal distribution of left-handed (M) and right-handed (P) conformers of ahelical foldamer could be perturbed by the addition of a chiral ligand(Figure 44).1298 Upon ligand complexation to the boronic ester,chiral information was transferred along the helix, and the isochronousNMR signals of the diastereotopic nuclei were transformed into anisochronoussignals, indicating a bias in the distribution of helical conformers.When the meso diastereoisomer of the diol was usedto complex the boronic ester, no splitting of the 1H NMRsignals was observed due to the symmetry of the ligand.

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.