Molecular Pumps and Motors

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(15), P. 5569 - 5591

Published: April 8, 2021

Pumps and motors are essential components of the world as we know it. From complex proteins that sustain our cells, to mechanical marvels power industries, much take for granted is only possible because pumps motors. Although molecular have supported life eons, it recently chemists made progress toward designing building artificial forms microscopic machinery present in nature. The advent machines has scientists an unprecedented level control over relative motion molecules through development kinetically controlled, away-from-thermodynamic equilibrium chemistry. We outline history motors, focusing specifically on innovations enable design synthesis central this Perspective. A key insight connecting biomolecular physical motions by which these carry out their function unambiguously at every instant. operation can be described trajectory thermodynamics, a theory based work Onsager, grounded firm foundation principle reversibility. Free energy derived from thermodynamically non-equilibrium reactions favors some reaction pathways others. By with kinetic asymmetry, one engineer potential landscapes harness external drive formation maintenance geometries component parts away-from-equilibrium, would impossible achieve standard synthetic approaches.

Language: Английский

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Designing light-driven rotary molecular motors

Chemical Science, Journal Year: 2021, Volume and Issue: 12(45), P. 14964 - 14986

Published: Jan. 1, 2021

Various families of light-driven rotary molecular motors and the key aspects motor design are discussed. Comparisons made between strengths weaknesses each motor. Challenges, applications, future prospects explored.

Language: Английский

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Photoresponsive Supramolecular Polymers: From Light‐Controlled Small Molecules to Smart Materials

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(10)

Published: Oct. 14, 2022

Photoresponsive supramolecular polymers are well-organized assemblies based on highly oriented and reversible noncovalent interactions containing photosensitive molecules as (co-)monomers. They have attracted increasing interest in smart materials dynamic systems with precisely controllable functions, such light-driven soft actuators, photoresponsive fluorescent anticounterfeiting light-triggered electronic devices. The present review discusses light-activated used their main photo-induced changes, e.g., geometry, dipole moment, chirality. Based these distinct formed by exhibit disassembly reassembly. As a consequence, polymerization, "depolymerization," regulation of the lengths topologies observed. Moreover, light-controlled functions polymers, actuation, emission, chirality transfer along length scales, highlighted. Furthermore, perspective challenges future opportunities is presented. Besides challenge moving from harmful UV light to visible/near IR avoiding fatigue, enabling biomedical applications, include actuators helical motion, light-modulated information transmission, optically recyclable materials, multi-stimuli-responsive systems.

Language: Английский

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Active mechanisorption driven by pumping cassettes

Science, Journal Year: 2021, Volume and Issue: 374(6572), P. 1215 - 1221

Published: Oct. 22, 2021

Over the past century, adsorption has been investigated extensively in equilibrium systems, with a focus on van der Waals interactions associated physisorption and electronic case of chemisorption. In this study, we demonstrate mechanisorption, which results from nonequilibrium pumping to form mechanical bonds between adsorbent adsorbate. This active mode realized surfaces metal-organic frameworks grafted arrays molecular pumps. Adsorbates are transported one well-defined compartment, bulk, another interface, thereby creating large potential gradients chemical capacitors wherein energy is stored metastable states. Mechanisorption extends, fundamental manner, scope phenomena offers transformative approach control chemistry at interfaces.

Language: Английский

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Toward the Design and Construction of Supramolecular Functional Molecular Materials Based on Metal–Metal Interactions

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(50), P. 22805 - 22825

Published: Dec. 9, 2022

Supramolecular functional materials represent an emerging class of that have been governed by the supramolecular chemistry self-assembled molecules. Such high-order molecular hierarchies stabilized various kinds noncovalent intermolecular forces including hydrogen bonding, electrostatic, donor–acceptor, π–π stacking interactions, and dispersion forces. Recently, metal–metal interactions also emerged as unconventional type interaction is unique in metal complex system for construction metal-based materials. These further imparted with rich spectroscopic functionalities. However, systematic control these hierarchical architectures through remains challenging. In this Perspective, we aim to stimulate research direction field utilization such intriguing directional one driving forces, highlighting roles significance ultimately facilitating a controlled rational design synthesis metallosupramolecular properties huge potential applications.

Language: Английский

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Advanced stimuli-responsive membranes for smart separation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(13), P. 4173 - 4207

Published: Jan. 1, 2023

This review summarises the advancements of stimuli-responsive membranes, focusing on chemistry, controllable membrane properties, preparation, and advanced applications.

Language: Английский

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Macrocycle‐Based Covalent Organic Frameworks

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(16)

Published: Jan. 6, 2023

Macrocycles with well-defined cavities and the ability to undergo supramolecular interactions are classical materials that have played an essential role in science. However, one of most substantial barriers limiting utilization macrocycles is their aggregation, which blocks active regions. Among many attempted strategies prevent such installing into covalent organic frameworks (COFs), porous stable reticular networks, has emerged as ideal solution. The resulting macrocycle-based COFs (M-COFs) preserve macrocycles' unique activities, enabling applications various fields single-atom catalysis, adsorption/separation, optoelectronics, phototherapy, structural design forming single-layered or mechanically interlocked COFs. properties unmatchable by any combination other substrates, opening a new chapter advanced materials. This review focuses on latest progress concepts, synthesis, properties, M-COFs, presents in-depth outlook challenges opportunities this emerging field.

Language: Английский

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Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 3, 2024

Abstract Over the last two decades ratchet mechanisms have transformed understanding and design of stochastic molecular systems—biological, chemical physical—in a move away from mechanical macroscopic analogies that dominated thinking regarding dynamics in 1990s early 2000s (e.g. pistons, springs, etc), to more scale‐relevant concepts underpin out‐of‐equilibrium research sciences today. Ratcheting has established nanotechnology as frontier for energy transduction metabolism, enabled reverse engineering biomolecular machinery, delivering insights into how molecules ‘walk’ track‐based synthesisers operate, acceleration reactions enables be transduced by catalysts (both motor proteins synthetic catalysts), dynamic systems can driven equilibrium through catalysis. The recognition biology, their invention systems, is proving significant areas diverse supramolecular chemistry, covalent DNA nanotechnology, polymer materials science, heterogeneous catalysis, endergonic synthesis, origin life, many other branches science. Put simply, give chemistry direction. Kinetic asymmetry, key feature ratcheting, counterpart structural asymmetry (i.e. chirality). Given ubiquity processes significance behaviour function it surely just fundamentally important. This Review charts recognition, development ratchets, focussing particularly on role which they were originally envisaged elements machinery. Different kinetically asymmetric are compared, consequences discussed. These archetypal examples demonstrate inexorably equilibrium, rather than relax towards it.

Language: Английский

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Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 18, 2024

Abstract Scientists have long been fascinated by the biomolecular machines in living systems that process energy and information to sustain life. The first synthetic molecular rotor capable of performing repeated 360° rotations due a combination photo‐ thermally activated processes was reported 1999. progress designing different intervening years has remarkable, with several outstanding examples appearing last few years. Despite accomplishments, there remains confusion regarding fundamental design principles which motions molecules can be controlled, significant intellectual tension between mechanical chemical ways thinking about describing machines. A thermodynamically consistent analysis kinetics rotors pumps shows while light driven operate power‐stroke mechanism, kinetic asymmetry—the relative heights barriers—is sole determinant directionality catalysis Power‐strokes—the depths wells—play no role whatsoever determining sign directionality. These results, elaborated using trajectory thermodynamics nonequilibrium pump equality, show asymmetry governs response many non‐equilibrium phenomena.

Language: Английский

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Radical-pairing-induced molecular assembly and motion

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(7), P. 447 - 465

Published: June 9, 2021

Language: Английский

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