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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Beyond Single‐Cycle Autonomous Molecular Machines: Light‐Powered Shuttling in a Multi‐Cycle Reaction Network

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(2)

Опубликована: Авг. 17, 2024

Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular in which kinetic asymmetry has been quantified well described simple single-cycle networks. Here, we report on a unique light-driven [2]rotaxane enables the autonomous operation of machine with multi-cycle network. Unlike prior systems, present one exploits photoactive macrocycle, features different photoreactivity depending binding sites at it resides. Furthermore, E Z isomerization reverses relative affinity macrocycle for two axle, resulting Building most recent theoretical advancements, this work quantifies network first time. Our findings represent simplest rotaxane capable shuttling developed so far and offer general strategy generate quantify beyond systems.

Язык: Английский

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Coacervation in systems chemistry

Communications Chemistry, Год журнала: 2024, Номер 7(1)

Опубликована: Ноя. 22, 2024

Communications Chemistry is delighted to introduce a Collection of articles that combine coacervation with systems chemistry. Here, the Guest Editors importance research at interface between these two topics and highlight current challenges in this area.

Язык: Английский

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Power Strokes in Molecular Motors: Predictive, Irrelevant, or Somewhere in Between?

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 20, 2024

For several decades, molecular motor directionality has been rationalized in terms of the free energy conformations visited before and after takes a step, so-called power stroke mechanism with analogues macroscopic engines. Despite theoretical experimental demonstrations its flaws, language is quite ingrained, some communities still value intuition. By building catalysis-driven into simulated numerical experiments, we here systematically report on how responds when modified accordingly to We confirm that generally does not predict directionality. Nevertheless, simulations illustrate relative stability should be included as potential design element adjust directional bias. Though strokes are formally unimportant for determining directionality, show practical attempts alter have side effects can fact The change bias align what intuition would suggested, offering explanation why flawed retain apparent utility engineering specific systems.

Язык: Английский

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Beyond Single‐Cycle Autonomous Molecular Machines: Light‐Powered Shuttling in a Multi‐Cycle Reaction Network

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Авг. 17, 2024

Abstract Biomolecular machines autonomously convert energy into functions, driving systems away from thermodynamic equilibrium. This conversion is achieved by leveraging complex, kinetically asymmetric chemical reaction networks that are challenging to characterize precisely. In contrast, all known synthetic molecular in which kinetic asymmetry has been quantified well described simple single‐cycle networks. Here, we report on a unique light‐driven [2]rotaxane enables the autonomous operation of machine with multi‐cycle network. Unlike prior systems, present one exploits photoactive macrocycle, features different photoreactivity depending binding sites at it resides. Furthermore, E Z isomerization reverses relative affinity macrocycle for two axle, resulting Building most recent theoretical advancements, this work quantifies network first time. Our findings represent simplest rotaxane capable shuttling developed so far and offer general strategy generate quantify beyond systems.

Язык: Английский

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Requirements of Constrictive Binding and Dynamic Systems on Molecular Cages for Drug Delivery

Targets, Год журнала: 2024, Номер 2(4), С. 372 - 384

Опубликована: Ноя. 19, 2024

Molecular cages have promising host–guest properties for drug delivery applications. Specifically, guest⊂cage complexes can be used the on-command release of encapsulated guest molecules in response to specific stimuli. This research explores both dynamic and constrictive binding systems encapsulation biological environments. In systems, rapidly passes in-and-out through portals cage, enabling vitro but facing limitations vivo due dilution effects that result release. These challenges are addressed by where is trapped a “gate-closed” state within cage. these triggered “gate opening” event, which lowers guest–out energy barrier. A full achieved when gate opening reduces cage–guest affinity, making more effective controlled delivery. As result, this study shows suitable contexts.

Язык: Английский

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Out-of-equilibrium compartments: Thinking inside the box

Chem, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 1, 2024

Язык: Английский

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