The Rise and Promise of Artificial Molecular Machines
PublicIn this Thesis, I describe some recent developments in the field of artificial molecular machines to which I have made contributions. In Chapter 1, I survey the rise and promise of molecular nanotopology, a relatively new discipline focusing on molecular knots and links that offers unprecedented opportunities to access high-energy conformations and create nanoconfined environments in molecules with profound consequences for all aspects of chemical reactivity. In Chapter 2, I describe a molecular dual pump that is capable of unidirectional transport wherein a ring is pumped both chemically and electrochemically by an energy ratchet mechanism in two successive redox cycles along a dumbbell from solution and back into solution. A similar mechanism and overall outcome, which relies on a photocleavable stopper attached at the end of the collecting chain, constitutes a molecular pump that operates in response to electricity followed by light, is introduced in Chapter 3. Chapter 4 describes a polyrotaxane synthesizer that is a textbook example of how an artificial molecular machine can produce precisely exotic compounds with far-from-equilibrium properties that cannot be obtained by traditional synthetic approaches. In Chapter 5, I chronicle the field of molecular machines, starting from the introduction of biomolecular pumps and motors. I highlight the importance of kinetic asymmetry and apply this principle to the design and synthesis of artificial molecular machines. Finally, in Chapter 6, I reflect on what I expect will be the next big development in the field of artificial molecular machines — most likely integrating them with soft and hard materials, leading to major breakthroughs in chemistry and molecular nanotechnology in the fullness of time.
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