Temporal (Dis)Assembly of Peptide Nanostructures Dictated by Native Multistep Catalytic Transformations

Nano Letters, Год журнала: 2024, Номер 24(7), С. 2250 - 2256

Опубликована: Фев. 8, 2024

Emergence of complex catalytic machinery via simple building blocks under non-equilibrium conditions can contribute toward the system level understanding extant biocatalytic reaction network that fuels metabolism. Herein, we report temporal (dis)assembly peptide nanostructures in presence a cofactor dictated by native multistep cascade transformations. The short form dynamic covalent bond with thermodynamically activated substrate and recruit hemin to access (positive feedback). neighboring imidazole moieties assembled state rapidly converted product(s) two-step (hydrolase-peroxidase like) subsequently triggered disassembly (negative feedback coupled cycle involving intrinsic prowess peptides realize advanced trait two-stage degradation foreshadows protometabolic networks might have preceded chemical emergence life.

Язык: Английский

---

Analysis of kinetic asymmetry in a multi-cycle chemical reaction network establishes the principles for autonomous compartmentalized molecular ratchets

Опубликована: Фев. 21, 2024

Kinetic asymmetry is a key parameter describing non-equilibrium chemical systems: it indicates the directionality of reaction network under steady-state, conditions. So far, kinetic has been evaluated only in networks featuring single cycle. Here, we have investigated multi-cycle system using combined theoretical and numerical approach. Inspired by latest experimental developments, selected com-partmentalized redox-controlled as model system. We report general analytical expression for networks, specify present system, which allows anticipating how parameters influence directionality. establish that compartmentalization can enable autonomous energy ratchet mechanisms, with dictated system's thermodynamics. simulations confirm findings illustrate interplay between diffusion, chemical, electrochemical processes. The presented treatment general, same procedure be used to assess other facilitating realization en-dergonic processes across domains.

Язык: Английский

---

A Catalysis-Driven Dual Molecular Motor

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

Опубликована: Март 17, 2025

We report on a head-to-tail dual molecular motor consisting of two (identical) units whose pyrrole-2-carboxylic rings are turned in contra-rotary (i.e., disrotatory) fashion about common phenyl-2,5-dicarboxylic acid stator. The motors directionally rotate via information ratchet mechanisms, which the hydration carbodiimide (fuel) to form urea (waste) is catalyzed through chemomechanical cycle unit, resulting directional rotation biaryl C–N bond. arrangement produces coaxial contra-rotation end groups while central phenyl ring axis remains dynamically unbiased. electron-rich nature stator contributes rotary catalysis by dual-motor (and therefore itself) being ∼7× faster than parent 1-phenylpyrrole-2,2-dicarboxylic single-motor when operated under identical conditions, and 90× using originally reported reaction conditions. Under batch-fueled operation all fuel present at start operation), rotates an initial rate 0.43 rotations per minute (rpm). Chemostating concentration syringe pump addition produced sustained repetitive 0.24 rpm for period 100 min. demonstration chemically fueled continuous time scale 2–4 min significantly advances chemistry mechanics artificial catalysis-driven machinery.

Язык: Английский

---

Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems

Angewandte Chemie, Год журнала: 2024, Номер 136(9)

Опубликована: Янв. 18, 2024

Abstract Scientists have long been fascinated by the biomolecular machines in living systems that process energy and information to sustain life. The first synthetic molecular rotor capable of performing repeated 360° rotations due a combination photo‐ thermally activated processes was reported 1999. progress designing different intervening years has remarkable, with several outstanding examples appearing last few years. Despite accomplishments, there remains confusion regarding fundamental design principles which motions molecules can be controlled, significant intellectual tension between mechanical chemical ways thinking about describing machines. A thermodynamically consistent analysis kinetics rotors pumps shows while light driven operate power‐stroke mechanism, kinetic asymmetry—the relative heights barriers—is sole determinant directionality catalysis Power‐strokes—the depths wells—play no role whatsoever determining sign directionality. These results, elaborated using trajectory thermodynamics nonequilibrium pump equality, show asymmetry governs response many non‐equilibrium phenomena.

Язык: Английский

---

Membrane Transport, Molecular Machines, and Maxwell's Demon

ChemSystemsChem, Год журнала: 2024, Номер 6(3)

Опубликована: Фев. 9, 2024

Abstract The spontaneous generation of transmembrane gradients is an important fundamental research goal for artificial nanotechnology. active transport processes that give rise to such directly mirror the famous Maxwell's Demon thought experiment, where a partitions particles between two chambers generate nonequilibrium state. Despite these similarities, discussion absent in literature on membrane transport. By contrast, emergence rational design principles molecular motors can trace its intellectual roots this experiment. This perspective highlights links and machines, argues understanding implications 19 th century experiment crucial future development processes.

Язык: Английский

---

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

---

A role for conformational changes in enzyme catalysis

Biophysical Journal, Год журнала: 2024, Номер 123(12), С. 1563 - 1578

Опубликована: Май 3, 2024

Язык: Английский

---

Allosteric Control of the Catalytic Properties of Dipeptide-Based Supramolecular Assemblies

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22522 - 22529

Опубликована: Авг. 1, 2024

Allostery, as seen in extant biology, governs the activity regulation of enzymes through redistribution conformational equilibria upon binding an effector. Herein, a minimal design is demonstrated where dipeptide can exploit dynamic imine linkage to condense with simple aldehydes access spherical aggregates catalytically active states, which facilitates orthogonal reaction due closer proximity catalytic residues (imidazoles). The allosteric site (amine) catalyst concomitantly bind inhibitor via exchange, leads alternation energy landscape self-assembled state, resulting downregulation activity. Further, temporal control over realized feedback-controlled autonomous network that utilizes hydrolytic (in)active state function time.

Язык: Английский

---

Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie, Год журнала: 2023, Номер 135(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

---

ATP Drives the Formation of a Catalytic Hydrazone through an Energy Ratchet Mechanism

Angewandte Chemie, Год журнала: 2023, Номер 135(33)

Опубликована: Июнь 27, 2023

Abstract An energy ratchet mechanism is exploited for the synthesis of a molecule. In presence adenosine triphosphate (ATP), hydrazone‐bond formation between an aldehyde and hydrazide accelerated composition at thermodynamic equilibrium shifted towards hydrazone. Enzymatic hydrolysis ATP installs kinetically stable state, which hydrazone present higher concentration compared to in degradation products ATP. It shown that kinetic state has enhanced catalytic activity RNA‐model compound.

Язык: Английский

---