Molecular Machines For The Control Of Transmembrane Transport

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(50), P. 27167 - 27184

Published: Dec. 8, 2023

Nature embeds some of its molecular machinery, including ion pumps, within lipid bilayer membranes. This has inspired chemists to attempt develop synthetic analogues exploit membrane confinement and transmembrane potential gradients, much like their biological cousins. In this perspective, we outline the various strategies by which machines─molecular systems in a nanomechanical motion is exploited for function─have been designed be incorporated membranes utilized mediate transport. We survey machines spanning both switches motors, those that act as mobile carriers or are anchored membrane, mechanically interlocked molecules, examples activated response external stimuli.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4467 - 4472

Published: Feb. 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.

Language: Английский

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Artificial molecular pumps

Nature Reviews Methods Primers, Journal Year: 2024, Volume and Issue: 4(1)

Published: Feb. 22, 2024

Language: Английский

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A Minimalistic Covalent Bond‐Forming Chemical Reaction Cycle that Consumes Adenosine Diphosphate

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 27, 2024

Abstract The development of synthetic active matter requires the ability to design materials capable harnessing energy from a source carry out work. Nature achieves this using chemical reaction cycles in which released an exergonic is used drive biochemical processes. Although many chemically fuelled that control transient responses, such as self‐assembly, have been reported, generally high complexity reported systems hampers full understanding how available actually exploited by these systems. This lack limiting factor matter. Here, we report minimalistic responsive cycle adenosine diphosphate (ADP) triggers formation catalyst for its own hydrolysis. establishes interdependence between concentrations network components resulting catalyst. sufficiently simple all kinetic and thermodynamic parameters governing behaviour can be characterised, allowing models built simulate progress reactions within network. While current does not enable ADP‐hydrolysis populate non‐equilibrium composition, provide insight into way dissipates energy. Furthermore, essential principles are revealed constructing driven systems, composition away equilibrium through consumption

Language: Английский

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Guiding Transient Peptide Assemblies with Structural Elements Embedded in Abiotic Phosphate Fuels

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 27, 2024

Abstract Despite great progress in the construction of non‐equilibrium systems, most approaches do not consider structure fuel as a critical element to control processes. Herein, we show that amino acid side chains (A, F, Nal) abiotic phosphates can direct assembly and reactivity during transient formation. The fuels bind covalently substrates subsequently influence structures process. We focus on ways which phosphate esters guide formation how cross regulate when constructing assemblies. Through chemical functionalization energy‐rich aminoacyl esters, are able yield thioesters upon adding dipeptides containing tyrosine or cysteine residues. structural elements around lifetime formed their supramolecular These properties be further influenced by peptide sequence substrates, incorporating anionic, aliphatic aromatic Furthermore, illustrate oligomerization initiated from single ester residue (Y). findings suggest activated acids with varying energy contents pave way for designing fabricating structured fuels.

Language: Английский

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