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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The role of kinetic asymmetry and power strokes in an information ratchet

Chem, Год журнала: 2023, Номер 9(10), С. 2902 - 2917

Опубликована: Июнь 19, 2023

Biomolecular machines are driven by information ratchet mechanisms, where kinetic asymmetry in the machine's chemomechanical cycle of fuel-to-waste catalysis induces net directional dynamics. A large-scale energetically downhill conformational change, termed a "power stroke," has often been erroneously implicated as mechanistic driving feature such machines. We investigated roles and power strokes series rotaxane-based ratchets found that alone determines directionality all use same amount fuel to reach normalized steady state. However, can nonetheless influence performance, how fast state is reached. Moreover, nonequilibrium thermodynamic analysis revealed alter form (information [Shannon entropy] versus intercomponent binding energy) free energy stored ratchets. These findings have implications for both understanding biological design principles artificial (supra)molecular

Язык: Английский

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Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(47)

Опубликована: Авг. 7, 2023

Abstract Non‐equilibrium chemical systems underpin multiple domains of contemporary interest, including supramolecular chemistry, molecular machines, prebiotic and energy transduction. Experimental chemists are now pioneering the realization artificial that can harvest away from equilibrium. In this tutorial Review, we provide an overview ratchets: mechanisms enabling absorption environment. By focusing on mechanism type—rather than application domain or source—we offer a unifying picture seemingly disparate phenomena, which hope will foster progress in fascinating science.

Язык: Английский

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Ratcheting synthesis

Nature Reviews Chemistry, Год журнала: 2023, Номер 8(1), С. 8 - 29

Опубликована: Дек. 15, 2023

Язык: Английский

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Endergonic synthesis driven by chemical fuelling

Nature Synthesis, Год журнала: 2024, Номер 3(6), С. 707 - 714

Опубликована: Март 11, 2024

Abstract Spontaneous chemical reactions proceed energetically downhill to either a local or global minimum, limiting possible transformations those that are exergonic. Endergonic do not spontaneously and require an input of energy. Light has been used drive number deracemizations thermodynamically unfavourable bond-forming reactions, but is restricted substrates can absorb, directly indirectly, energy provided by photons. In contrast, anabolism involves uphill powered fuels. Here we report on the transduction from artificial fuel Diels–Alder reaction. Carboxylic acid catalysed carbodiimide-to-urea formation chemically orthogonal reaction diene dienophile, transiently brings functional groups into close proximity, causing otherwise prohibited cycloaddition in modest yield (15% after two fuelling cycles) with high levels regio- (>99%) stereoselectivity (92:8 exo : endo ). Kinetic asymmetry cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism (an information ratchet, depending synthetic protocol), reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand chemistry toolbox terms reactivity, complexity control.

Язык: Английский

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Reversible Switching Based on Truly Intramolecular Long-Range Proton Transfer─Turning the Theoretical Concept into Experimental Reality

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(3), С. 2043 - 2053

Опубликована: Янв. 12, 2024

Herein, we demonstrate a working prototype of conjugated proton crane, reversible tautomeric switching molecule in which truly intramolecular long-range transfer occurs solution at room temperature. The system consists benzothiazole rotor attached to 7-hydroxy quinoline stator. According the experimental and theoretical results, OH is delivered under irradiation quinolyl nitrogen atom through series consecutive twisting steps. use rigid prevents undesired side processes that decrease performance previously described cranes provides an unprecedented efficiency fatigue resistance. newly designed confirms concept for application transfer-initiated as mechanism, developed more than 10 years ago, unique insights further development molecular switches motors, logic gates, new molecular-level energy storage systems.

Язык: Английский

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Structural Influence of the Chemical Fueling System on a Catalysis-Driven Rotary Molecular Motor

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

Continuous directionally biased 360° rotation about a covalent single bond was recently realized in the form of chemically fueled 1-phenylpyrrole 2,2′-dicarboxylic acid rotary molecular motor. However, original fueling system and reaction conditions resulted motor directionality only ∼3:1 (i.e., on average backward for every three forward rotations), along with catalytic efficiency operation 97% fuel 14%. Here, we report efficacy series chiral carbodiimide fuels hydrolysis promoters (pyridine pyridine N-oxide derivatives) driving improved directional this motor-molecule. We outline complete network operation, composed directional, futile, slip cycles. Using derivatives where final conformational step is either very slow or completely blocked, phenylpyrrole diacid becomes enantiomerically enriched, allowing kinetic gating individual steps cycle to be measured. The that produces highest gives 13% enantiomeric excess (e.e.) anhydride-forming kinetically gated step, while most effective promoter generates 90% e.e. step. Combining best-performing into results 92% e.e.. Under dilute chemostated regime (to avoid N-acyl urea formation at high concentrations promoters), continuously rotates ∼24:1 24 rotations) >99% 51%.

Язык: Английский

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Conformational selection accelerates catalysis by an organocatalytic molecular motor

Chem, Год журнала: 2023, Номер 10(3), С. 855 - 866

Опубликована: Ноя. 22, 2023

Conformational dynamics are increasingly recognized as an important contributor to enzyme catalysis but often overlooked in synthetic catalyst design. Here, we experimentally demonstrate faster by conformational selection caused stochastic interconversion of two conformations a catenane-based organocatalyst. The dependencies the reaction rates on relative positioning components during different stages catalytic cycle enable dynamic organocatalyst achieve order-of-magnitude rate accelerations over static or predominantly single-conformer analogs. acceleration results emergent property acting directionally rotating motor. In demonstrating that can overcome linear scaling relationships, these findings have implications for theories and artificial link between biased may suggest "motor molecules" could first arisen primitive form due prebiotic evolutionary pressure catalysis.

Язык: Английский

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The current science of sequence-defined macromolecules

Progress in Polymer Science, Год журнала: 2023, Номер 147, С. 101754 - 101754

Опубликована: Окт. 20, 2023

A fundamental endeavour in macromolecular science is the control of molecular-level complexity, including molecular weight distribution, end groups and architecture. Since discovery that native biomacromolecules can have a specific sequence translating biological function, controlling individual monomer has become ultimate expression complexity. Replicating this remarkable structural precision abiological macromolecules emerged as defining goal challenge within polymer science. In Review, we survey developments synthetic methods, characterisation techniques, simulation workflows applications relevant to goal. We also address broader question what extent such complexity significant macromolecules. Specifically, will focus on Review because its importance connecting synthesis with applications.

Язык: Английский

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Stepwise Operation of a Molecular Rotary Motor Driven by an Appel Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4467 - 4472

Опубликована: Фев. 6, 2024

To date, only a small number of chemistries and chemical fueling strategies have been successfully used to operate artificial molecular motors. Here, we report the 360° directionally biased rotation phenyl groups about C–C bond, driven by stepwise Appel reaction sequence. The motor molecule consists biaryl-embedded phosphine oxide phenol, in which full around biaryl bond is blocked P–O oxygen atom on rotor being too bulky pass stator. Treatment with SOCl2 forms cyclic oxyphosphonium salt (removing oxide), temporarily linking Conformational exchange via ring flipping then allows stator twist back forth past previous limit rotation. Subsequently, opening tethered intermediate chiral alcohol occurs preferentially through nucleophilic attack one face. Thus, original reformed net directional over course two-step Each repetition SOCl2–chiral additions generates another Using same sequence derivative that atropisomers rather than fully rotating results enantioenrichment, suggesting that, average, rotates "wrong" direction once every three cycles. interconversion oxides form temporary tethers enable rotational barrier be overcome adds available for generating chemically fueled kinetic asymmetry systems.

Язык: Английский

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