Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 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.

Язык: Английский

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Skeletal Editing of Mechanically Interlocked Molecules: Nitrogen Atom Deletion from Crown Ether-Dibenzylammonium Rotaxanes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(43), С. 29496 - 29502

Опубликована: Окт. 21, 2024

Removing the nitrogen atom from secondary amines while simultaneously linking remaining fragments is a powerful form of late-stage skeletal editing. Here, we report its use for deletion dibenzylammonium template used to assemble crown ether rotaxanes. The reaction uses an anomeric amide that activates generate carbon-carbon bond replaces amine nitrogen. Despite potential dethreading intermediate diradical pair, was successfully deleted series rotaxane axles as long macrocycle could access coconformations did not inhibit group. skeletally edited interlocked molecules were obtained directly parent ether-dibenzylammonium rotaxanes in modest yields (23-36%) and characterized by NMR spectroscopy, mass spectrometry, X-ray crystallography. One shows network weak CH···O hydrogen bonds between benzylic methylene groups axle solid state, place ether-ammonium binding motif parent, unedited, rotaxane.

Язык: Английский

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Mechanically Interlocked Water-Soluble Pd₆ Host for the Selective Separation of Coal Tar-Based Planar Aromatic Molecules

Inorganic Chemistry, Год журнала: 2024, Номер 63(32), С. 14924 - 14932

Опубликована: Июнь 19, 2024

Research on the synthesis of catenated cages has been a growing field interest in past few years. While multiple types with different structures have synthesized, application such systems much less explored. Specifically, use separation industrially relevant molecules that are present coal tar not explored before. Herein, we demonstrate newly synthesized interlocked cage 1 [C184H240N76O48Pd6] (M6L4), formed through self-assembly ligand L.HNO3 (tris(4-(1H-imidazole-1-yl)benzylidene)hydrazine-1-carbohydrazonhydrazide) acceptor cis-[(tmchda)Pd(NO3)2] [tmchda = ±N,N,N′,N′-tetramethylcyclohexane-1,2-diamine] (M). The was able to separate isomers (anthracene and phenanthrene) using simple solvent extraction technique. Using same technique, more difficult structurally physiochemically similar compounds acenaphthene acenaphthylene performed for first time as host. Other noninterlocked hexanuclear Pd6 having wider cavity proved inefficient separation, demonstrating uniqueness challenging separation.

Язык: Английский

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Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie, Год журнала: 2024, Номер 136(23)

Опубликована: Апрель 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.

Язык: Английский

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基于机械互锁分子的新型发光材料研究进展

Scientia Sinica Chimica, Год журнала: 2024, Номер 54(8), С. 1250 - 1276

Опубликована: Июнь 12, 2024

近些年来,随着机械互锁分子领域的快速发展,化学家们开始尝试将发光基元引入机械互锁分子中,并探究其独特的发光性质。相比于发光小分子,机械键的存在使得所得的功能化机械互锁分子表现出优异的发光性能。进一步地,通过巧妙应用机械互锁分子独特的动态性,成功设计构筑了多样化具有突出刺激响应光学特性的机械互锁分子,并探索了其在光催化、光学传感、智能发光材料等领域的应用。此外,通过将手性元素引入机械互锁发光体系中,其圆偏振发光性能也引起了越来越多的关注。在本篇综述中,我们将从机械键对发光性能的调控、刺激响应型机械互锁发光材料、手性机械互锁分子的圆偏振发光性能三方面出发综述了近年来基于机械互锁分子的新型发光材料的研究进展,并分析了当前面临的挑战以及展望了未来该领域的发展前景。

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