Guiding Transient Peptide Assemblies with Structural Elements Embedded in Abiotic Phosphate Fuels DOI Creative Commons
Mahesh D. Pol, Kun Dai, Ralf Thomann

et al.

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

Kinetic Barrier Diagrams to Visualize and Engineer Molecular Nonequilibrium Systems DOI Creative Commons
Emanuele Penocchio, Giulio Ragazzon

Small, Journal Year: 2023, Volume and Issue: 19(14)

Published: Jan. 26, 2023

Molecular nonequilibrium systems hold great promises for the nanotechnology of future. Yet, their development is slowed by absence an informative representation. Indeed, while potential energy surfaces comprise in principle all information, they hide dynamic interplay multiple reaction pathways underlying systems, i.e., degree kinetic asymmetry. To offer insightful visual representation asymmetry, we extended approach pertaining to catalytic networks, span model, focusing on system dynamics - rather than thermodynamics. Our encompasses both chemically and photochemically driven ranging from unimolecular motors simple self-assembly schemes. The obtained diagrams give immediate access information needed guide experiments, such as states' population, rate machine operation, maximum work output, effects design changes. proposed barrier a unifying graphical tool disparate phenomena.

Language: Английский

Citations

30
Ratcheting synthesis DOI
Stefan Borsley, James Gallagher, David A. Leigh

et al.

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 8(1), P. 8 - 29

Published: Dec. 15, 2023

Language: Английский

Citations

30
Triggered Polymersome Fusion DOI Creative Commons
Stephen D. P. Fielden, Matthew J. Derry, Alisha J. Miller

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(10), P. 5824 - 5833

Published: March 6, 2023

The contents of biological cells are retained within compartments formed phospholipid membranes. movement material and between is often mediated by the fusion membranes, which allows mixing or excretion into surrounding environment. Biological membrane a highly regulated process that catalyzed proteins triggered cellular signaling. In contrast, controlled polymer-based membranes largely unexplored, despite potential application this in nanomedicine, smart materials, reagent trafficking. Here, we demonstrate polymersome fusion. Out-of-equilibrium polymersomes were ring-opening metathesis polymerization-induced self-assembly persist until specific chemical signal (pH change) triggers their Characterization was performed variety techniques, including dynamic light scattering, dry-state/cryogenic-transmission electron microscopy, small-angle X-ray scattering (SAXS). followed time-resolved SAXS analysis. Developing elementary methods communication polymersomes, such as fusion, will prove essential for emulating life-like behaviors synthetic nanotechnology.

Language: Английский

Citations

26
Endergonic synthesis driven by chemical fuelling DOI Creative Commons
Enzo Olivieri, James Gallagher, Alexander Betts

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(6), P. 707 - 714

Published: March 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.

Language: Английский

Citations

13
Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States DOI Creative Commons
Jiarong Wu, Jake L. Greenfield

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20720 - 20727

Published: July 18, 2024

Coupling a photochemical reaction to thermal exchange process can drive the latter nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines fulfill both roles simultaneously, autonomously driving dynamic covalent system into NESS continuous light irradiation. We demonstrate this using transimination reactions, where

Language: Английский

Citations

11
Active droplets through enzyme-free, dynamic phosphorylation DOI Creative Commons
Simone Poprawa, Michele Stasi, Brigitte A. K. Kriebisch

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 17, 2024

Abstract Life continuously transduces energy to perform critical functions using stored in reactive molecules like ATP or NADH. dynamically phosphorylates active sites on proteins and thereby regulates their function. Inspired by such machinery, regulating supramolecular has gained traction. Enzyme-free, synthetic systems that use dynamic phosphorylation regulate processes have not yet been reported, our knowledge. Here, we show an enzyme-free reaction cycle consumes the phosphorylating agent monoamidophosphate transiently histidine histidine-containing peptides. The phosphorylated species are labile deactivate through hydrolysis. exhibits versatility tunability, allowing for of multiple precursors with a tunable half-life. Notably, resulting products can peptide’s phase separation, leading droplets require continuous conversion fuel sustain. will be valuable as model biological but also offer insights into protocell formation.

Language: Английский

Citations

9
Modular Synthesis of Improbable Rotaxanes with All‐Benzene Scaffolds DOI

An Bu,

Jia‐Nan Gao,

Yiming Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 26, 2024

"Improbable" rotaxanes consisting of interlocked conjugated components represent non-trivial synthetic targets, not to mention those with all-benzene scaffolds. Herein, a modular strategy has been established using an isolable azo-linked pre-rotaxane as the core module, in which azo group functions tracelessly removable template direct mechanical bond formations. Through versatile connections and other customizable modules, [2]- [3]rotaxanes derived from scaffolds have accomplished, demonstrating utility potential design for supramolecules.

Language: Английский

Citations

8
Structural Influence of the Chemical Fueling System on a Catalysis-Driven Rotary Molecular Motor DOI Creative Commons

Hua‐Kui Liu,

Toufic W. Mrad, Axel Troncossi

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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%.

Language: Английский

Citations

1
Tuning the Force, Speed, and Efficiency of an Autonomous Chemically Fueled Information Ratchet DOI Creative Commons
Stefan Borsley, David A. Leigh, Benjamin M. W. Roberts

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(37), P. 17241 - 17248

Published: Sept. 8, 2022

Autonomous chemically fueled molecular machines that function through information ratchet mechanisms underpin the nonequilibrium processes sustain life. These biomolecular motors have evolved to be well-suited tasks they perform. Synthetic systems similar recently been developed, and their minimalist structures enable influence of structural changes on machine performance assessed. Here, we probe effect in fuel barrier-forming species operation a carbodiimide-fueled rotaxane-based ratchet. We examine machine's ability catalyze fuel-to-waste reaction harness energy from it drive directional displacement macrocycle. characteristics are intrinsically linked speed, force, power, efficiency output. find that, just as for macroscopic machinery, optimization one feature (such speed) can compromise other features force generated by ratchet). Balancing efficiency, directionality will likely prove important when developing artificial particular applications.

Language: Английский

Citations

34
Conformational selection accelerates catalysis by an organocatalytic molecular motor DOI Creative Commons
James Gallagher, Benjamin M. W. Roberts, Stefan Borsley

et al.

Chem, Journal Year: 2023, Volume and Issue: 10(3), P. 855 - 866

Published: Nov. 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.

Language: Английский

Citations

22