Feedback driven autonomous cycles of assembly and disassembly from minimal building blocks DOI Creative Commons
Antara Reja,

Sangam Jha,

Ashley Sreejan

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 18, 2024

The construction of complex systems by simple chemicals that can display emergent network dynamics might contribute to our understanding behavior from organic reactions. Here we design single amino acid/dipeptide-based exhibit multiple periodic changes (dis)assembly under non-equilibrium conditions in closed system, importantly the absence evolved biocatalysts. two-component based building block exploits pH driven non-covalent assembly and time-delayed accelerated catalysis self-assembled state install orthogonal feedback loops with a batch reactants. Mathematical modelling reaction establishes oscillations are transient for this structure helps predict relative contribution loop ability system such oscillation. Such autonomous purely synthetic molecules starting point enable active materials properties. study formed Here, built on minimal blocks, authors describe utilizing controlled pH-driven assembly.

Язык: Английский

Supramolecular dissipative self‐assembly systems: Approaches and applications DOI Creative Commons

Xiao‐Fang Hou,

Xiaohong Chen,

Jia‐Hao Wei

и другие.

Deleted Journal, Год журнала: 2023, Номер 1(2)

Опубликована: Окт. 18, 2023

Abstract Dissipative self‐assembly (DSA) system requires a continuous supply of fuels to maintain the far‐from‐equilibrium assembled state. Living organisms exist and operate far from thermodynamic equilibrium by consumption energy taken surroundings, so how realize construction artificial DSA has attracted much attention researchers all over world. Owing dynamic controllable noncovalent interactions, supramolecular systems have achieved higher functions fueled various types energy, such as chemical fuels, light, electric acoustic mechanical energy. Upon input external nonactive precursors can be activated form building blocks at levels then self‐assemble into transient structures. As proceeding deactivation reaction, with level dissipate back initial precursors, resulting in disassembly process, complete full cycle. In this review, we summarize recent advances on its strategies energy‐fueled regulation approaches. The applications luminescence modulating, information encryption, self‐regulating gels, drug delivery, catalysis are also discussed. We hope that review article will facilitate further understanding development systems.

Язык: Английский

Процитировано

17
A molecular origin of non-reciprocal interactions between interacting active catalysts DOI
Niladri Sekhar Mandal, Ayusman Sen, R. Dean Astumian

и другие.

Chem, Год журнала: 2023, Номер 10(4), С. 1147 - 1159

Опубликована: Дек. 29, 2023

Язык: Английский

Процитировано

12
Observing the Dynamics of an Electrochemically Driven Active Material with Liquid Electron Microscopy DOI
Wyeth Gibson, Justin T. Mulvey, Swetamber Das

и другие.

ACS Nano, Год журнала: 2024, Номер 18(18), С. 11898 - 11909

Опубликована: Апрель 22, 2024

Electrochemical liquid electron microscopy has revolutionized our understanding of nanomaterial dynamics by allowing for direct observation their electrochemical production. This technique, primarily applied to inorganic materials, is now being used explore the self-assembly active molecular materials. Our study examines these across various scales, from nanoscale behavior individual fibers micrometer-scale hierarchical evolution fiber clusters. To isolate influences beam and electrical potential on material behavior, we conducted thorough beam–sample interaction analyses. findings reveal that materials at are shaped proximity electrode current. By integrating observations with reaction–diffusion simulations, uncover local structures formation history play a crucial role in determining assembly rates. suggests emergence nonequilibrium can locally accelerate further structural development, offering insights into under conditions.

Язык: Английский

Процитировано

5
Beyond Single‐Cycle Autonomous Molecular Machines: Light‐Powered Shuttling in a Multi‐Cycle Reaction Network DOI Creative Commons
Zhiyao Yang, Xirui Wang, Emanuele Penocchio

и другие.

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

Процитировано

4
Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems DOI
R. Dean Astumian

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

Процитировано

3
Kinetic Trapping of an Out‐of‐Equilibrium Dynamic Library of Imines by Changing Solvent DOI Creative Commons
Matteo Valentini, Gianfranco Ercolani, Stefano Di Stefano

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(37)

Опубликована: Апрель 8, 2024

A well-behaved dynamic library composed of two imines and corresponding amines was subjected to the action an activated carboxylic acid (ACA), whose decarboxylation is known be base promoted, in different solvents, namely CD

Язык: Английский

Процитировано

3
Smart self-assembled nanomedicine for ferroptotic tumor therapy DOI
Liang Chen, Tian Zhang, Qingming Zhang

и другие.

Colloids and Interface Science Communications, Год журнала: 2025, Номер 66, С. 100829 - 100829

Опубликована: Март 21, 2025

Язык: Английский

Процитировано

0
Transient Stiffness Patterning in Hydrogels Driven by Dissipative Mechanochemical Coupling DOI Creative Commons
Roberto Baretta, Maria F. Pantano, Marco Frasconi

и другие.

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

Abstract Living systems adapt to mechanical forces through a series of biochemical feedback loops and dissipative signal transduction mechanisms across multiple length scales. By contrast, synthetic materials are static, closed with minimal interaction their surroundings lack the ability deformations. Here, strategy that enables hydrogel temporal modulation its stiffness properties is reported. It demonstrated force‐induced bond rupture at disulfide linkages hydrogel, coupled chemical reoxidation leads dissipative, transient functions. The electrochemical generation oxidant as output loop triggered by an externally applied force provides high spatiotemporal control over process, enabling engineering hydrogels out‐of‐equilibrium patterns. Additionally, dose‐controlled, release model protein payloads from demonstrated. proposed concept has potential enhance autonomous interactive functionalities hydrogels, advancing applications in biomedical field soft robotics.

Язык: Английский

Процитировано

0
Defying chemical equilibrium with light DOI Creative Commons

Brian Sachini,

Stefano Corrà, Massimiliano Curcio

и другие.

Trends in Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

Язык: Английский

Процитировано

0
Artificial Molecular Ratchets: Tools Enabling Endergonic Processes DOI Creative Commons
Thitiporn Sangchai, Shaymaa Al Shehimy, Emanuele Penocchio

и другие.

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

Процитировано

7