Beyond Single‐Cycle Autonomous Molecular Machines: Light‐Powered Shuttling in a Multi‐Cycle Reaction Network DOI Creative Commons
Zhiyao Yang, Xirui Wang, Emanuele Penocchio

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(2)

Published: Aug. 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.

Language: Английский

A catalytically active oscillator made from small organic molecules DOI Creative Commons
Matthijs ter Harmsel, Oliver R. Maguire, Sofiya A. Runikhina

et al.

Nature, Journal Year: 2023, Volume and Issue: 621(7977), P. 87 - 93

Published: Sept. 6, 2023

Oscillatory systems regulate many biological processes, including key cellular functions such as metabolism and cell division, well larger-scale processes circadian rhythm heartbeat1-4. Abiotic chemical oscillations, discovered originally in inorganic systems5,6, inspired the development of various synthetic oscillators for application autonomous time-keeping analytical chemistry, materials chemistry biomedical field7-17. Expanding their role beyond that a pacemaker by having periodically drive secondary function would turn them into significantly more powerful tools. However, this is not trivial because participation components oscillator might jeopardize its ability. We now report small molecule can catalyse an independent reaction situ without impairing oscillating properties. In flow system, concentration catalytically active product shows sustained oscillations catalysed accelerated only during peaks. Augmentation with periodic catalytic action allows construction complex that, future, may benefit applications automated synthesis, polymerization drug delivery.

Language: Английский

Citations

27
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

24
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
Thermodynamic Bounds on Symmetry Breaking in Linear and Catalytic Biochemical Systems DOI Creative Commons
Shiling Liang, Paolo De Los Rios, Daniel Maria Busiello

et al.

Physical Review Letters, Journal Year: 2024, Volume and Issue: 132(22)

Published: May 31, 2024

Living systems are maintained out of equilibrium by external driving forces. At stationarity, they exhibit emergent selection phenomena that break symmetries and originate from the expansion accessible chemical space due to nonequilibrium conditions. Here, we use matrix-tree theorem derive upper lower thermodynamic bounds on these symmetry-breaking features in linear catalytic biochemical systems. Our independent kinetics hold for both closed open reaction networks. We also extend our results master equations space. Using framework, recover constraints kinetic proofreading. Finally, show contrast reaction-diffusion patterns can be bounded only force. provide a general framework understanding role conditions shaping steady-state properties Published American Physical Society 2024

Language: Английский

Citations

9
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
Energy Flows in Static and Programmable Catalysts DOI
Omar Abdelrahman, Paul J. Dauenhauer

ACS Energy Letters, Journal Year: 2023, Volume and Issue: 8(5), P. 2292 - 2299

Published: April 19, 2023

Programmable catalysts that change on the time scale of a catalytic cycle provide new opportunity to control flow energy reactants and products promote faster more selective chemistry. While traditional chemical manufacturing processes consume achieve favorable reaction conditions, programmable aim dynamically add or remove cycles through perturbations surface via strain, charge, light. These flows are quantified by changes in adsorbate binding with time, overall efficiency relating inputs performance is defined characteristics undulating surface. Understanding quantifying provides baseline definitions metrics for comparing dynamic conditions identifying optimal efficient manufacturing.

Language: Английский

Citations

17
A Minimalistic Covalent Bond‐Forming Chemical Reaction Cycle that Consumes Adenosine Diphosphate DOI Creative Commons
Tommaso Marchetti, Benjamin M. W. Roberts, Diego Frezzato

et al.

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

Citations

8
Stepwise Operation of a Molecular Rotary Motor Driven by an Appel Reaction DOI Creative Commons
Patrick Zwick, Axel Troncossi, Stefan Borsley

et al.

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

Citations

7
Analysis of kinetic asymmetry in a multi-cycle reaction network establishes the principles for autonomous compartmentalized molecular ratchets DOI Creative Commons
Emanuele Penocchio,

Ahmad Bachir,

Alberto Credi

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(12), P. 3644 - 3655

Published: Sept. 13, 2024

Language: Английский

Citations

7
Mechanochemical Coupling of Catalysis and Motion in a Cellulose-Degrading Multienzyme Nanomachine DOI Creative Commons
Krisztina Zajki-Zechmeister, Manuel Eibinger, Gaurav Singh Kaira

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2656 - 2663

Published: Feb. 6, 2024

The cellulosome is a megadalton-size protein complex that functions as biological nanomachine of cellulosic fiber degradation. We show the behaves Brownian ratchet rectifies motions on cellulose surface into propulsion mechanism by coupling to hydrolysis chains. Movement fibrils unidirectional and results from "macromolecular crawl" composed dynamic switches between elongated compact spatial arrangements enzyme subunits. Deletion main exocellulase Cel48S eliminates conformational bias for aligning subunits long fibril axis, which we reveal crucial optimum directional movement substrate Implications acting mechanochemical motor suggest distinct enzymatic machinery in deconstruction assemblies.

Language: Английский

Citations

6