Gas-Fueled Non-Equilibrium Co-Assembly via C1 Catalytic Feedback for Gas-Encoded 4D Information Encryption DOI
Qiang Yan, Yulian Zhang,

Cuiqin Yang

et al.

Published: July 17, 2024

Abstract Dissipative self-assembly, which exploits energy inputs of chemical fuels to maintain the functional states far from equilibrium, is essential living systems. Among a variety fuels, carbon dioxide (CO2) gas, as one most ubiquitous but original forms fuel on life depends, has yet been introduced in artificial dissipative materials. Here we describe CO2-fueled non-equilibrium co-assembly system that couples with C1 catalytic feedback path drive dissipation and function output. Using common frustrated Lewis pair (FLP) precursors, CO2 can dynamically bridge between them constitute metastable amphiphiles, not only highly activate also enable their substrates into transient fibrillar gel. In turn, process realized by cooperative insertion owing proximity substrate activated species assembled state. This boost depletion gas facilitate disassembly sol. Moreover, tailoring intrinsic substrate/FLP chemistries, well external cues, shift activity accessible regulate period lifetime sol-gel-sol transition over wide range. Based tunability phase time scale, develop time-dependent information encryption materials using FLP array loaded gas-encoded substrates, correct be read at specified window. study provides inspiration new paradigm for intelligent material applications.

Language: Английский

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

et al.

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: May 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.

Language: Английский

Citations

0
Electrically Powered Dissipative Hydrogel Networks Reveal Transient Stiffness Properties for Out-of-Equilibrium Operations DOI
Roberto Baretta, Marco Frasconi

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7408 - 7418

Published: March 5, 2024

Living systems use dissipative processes to enable precise spatiotemporal control over various functions, including the transient modulation of stiffness tissues, which, however, is challenging achieve in soft materials. Here, we report a new platform program hydrogel films with tunable, time-dependent mechanical properties under out-of-equilibrium conditions, powered by electricity. We show that lifetime network surface-confined film can be effectively controlled programming generation an electrochemically oxidized mediator presence chemical or photoreducing agent solution. It is, therefore, electrically possible direct stiffening softening film, enabling high modularity material functions control. Temporally operations are demonstrated for on-demand, dose-controlled release multiple model protein payloads from electrode arrays using present system. This demonstration driven represents important step toward engineering materials developing future biomedical applications harness temporal, adaptive this class

Language: Английский

Citations

2
Cyclic Macroscopic Assembly and Disassembly Driven by Ionic Strength Fuel: A Waste-Free Approach DOI
Ting Zhao, Zhongrui Wang, Yang Yang

et al.

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(27), P. 33169 - 33179

Published: July 4, 2023

Nonequilibrium assembling systems developed so far have relied on chemical fuels to drive the programmable pH cycles, redox reactions, and metastable bond formations. However, these methods often result in unwanted accumulation of waste. Herein, we present a novel strategy for achieving cyclic waste-free nonequilibrium assembly disassembly macroscopic hydrogels, utilizing an ionic strength-mediated approach. Our involves using ammonium carbonate as fuel temporally regulate attractions between oppositely charged hydrogels via strength-controlled charge screening hydrogel elasticity changes. This effectively mediates assembly/disassembly processes prevents waste accumulation, can completely decompose into volatile The reversible process be achieved without significant damping due self-clearance mechanism, long is repeatedly supplied. concept holds promise creating microscopic self-adaptive materials.

Language: Английский

Citations

5
Bio‐Inspired Far‐From‐Equilibrium Hydrogels: Design Principles and Applications DOI
Jiadong Tang,

Yibo Cheng,

Muhua Ding

et al.

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(12)

Published: Oct. 3, 2023

Abstract Inspired from dynamic living systems that operate under out‐of‐equilibrium conditions in biology, developing supramolecular hydrogels with self‐regulating and autonomously properties to further advance adaptive life‐like behavior is important. This review presents recent progress of bio‐inspired out‐of‐equilibrium. The principle self‐assembly for creating discussed. Various design strategies have been identified, such as chemical‐driven reaction cycles feedback control physically oscillatory systems. These can be coupled achieve temporal spatial over structural mechanical well programmable lifetime. studies open up huge opportunities potential applications, fluidic guidance, information storage, drug delivery, actuators more. Finally, we address the challenges ahead us coming years, future possibilities prospects are identified.

Language: Английский

Citations

4
Transient Covalent Polymers through Carbodiimide‐driven Assembly DOI Creative Commons
Nirob K. Saha, William S. Salvia, Dominik Konkolewicz

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 21, 2024

Abstract Biochemical systems make use of out‐of‐equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular driven chemical fuel reactions have been reported. Conversely, based on transient covalent bonds received little attention, even though they the potential to complement generating structures stronger and offering a straightforward tuning reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with carbodiimide EDC. Transient molecular weights exceeding 15,000 are which then decompose over course hours weeks. Disassembly kinetics can be controlled using substituent effects in monomer design. The impact solvent polarity, concentration, temperature, pyridine concentration polymer properties lifetimes has investigated. results reveal substantial control assembly disassembly kinetics, highlighting for fine‐tuned nonequilibrium polymerization systems.

Language: Английский

Citations

1
Transient Covalent Polymers through Carbodiimide‐driven Assembly DOI Creative Commons
Nirob K. Saha, William S. Salvia, Dominik Konkolewicz

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 21, 2024

Abstract Biochemical systems make use of out‐of‐equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular driven chemical fuel reactions have been reported. Conversely, based on transient covalent bonds received little attention, even though they the potential to complement generating structures stronger and offering a straightforward tuning reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with carbodiimide EDC. Transient molecular weights exceeding 15,000 are which then decompose over course hours weeks. Disassembly kinetics can be controlled using substituent effects in monomer design. The impact solvent polarity, concentration, temperature, pyridine concentration polymer properties lifetimes has investigated. results reveal substantial control assembly disassembly kinetics, highlighting for fine‐tuned nonequilibrium polymerization systems.

Language: Английский

Citations

1
Positioning dynamic polymeric materials within the modern polymer economy: From application to recycling and circularity DOI Creative Commons
Meng Jiang,

Nadim Mahmud,

Christopher Koelbl

et al.

Journal of Polymer Science, Journal Year: 2024, Volume and Issue: 62(15), P. 3562 - 3583

Published: May 22, 2024

Abstract Innovations in dynamic polymeric materials offer prospects to improve the circularity and lower environmental impact of modern polymer economy. These are also beginning blur distinction between re‐use recycling methods since bulk material properties may be rationally changed after applying a stimulus or performing controlled chemical reaction. In this Perspective, we propose that polymers denote unique class versatile post‐consumer waste, which shares similarities emergent upcycling approaches while offering additional opportunities within more classical schemes. A brief overview stimuli‐responsive is presented where illustrative examples discussed context developing practical materials. Dynamic covalent then highlighted, along with emerging techniques such as editing, focus on recent reports demonstrating rational manipulation properties. Finally, discuss these alongside explore how could perform sphere.

Language: Английский

Citations

1
Dynamic surface chemistry and interparticle interactions mediating chemically fueled dissipative assembly of colloids DOI

Thilini Umesha Dissanayake,

Justin Hughes,

Taylor J. Woehl

et al.

Journal of Colloid and Interface Science, Journal Year: 2023, Volume and Issue: 650, P. 972 - 982

Published: July 1, 2023

Language: Английский

Citations

3
Carbodiimide‐Driven Toughening of Interpenetrated Polymer Networks DOI Creative Commons

Chamoni W. H. Rajawasam,

Corvo Tran, Jessica L. Sparks

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(20)

Published: March 22, 2024

Abstract Recent work has demonstrated that temporary crosslinks in polymer networks generated by chemical “fuels” afford materials with large, transient changes their mechanical properties. This can be accomplished carboxylic‐acid‐functionalized hydrogels using carbodiimides, which generate anhydride lifetimes on the order of minutes to hours. Here, impact network architecture properties transiently crosslinked was explored. Single (SNs) were compared interpenetrated (IPNs). Notably, semi‐IPN precursors give IPNs treatment carbodiimide much higher fracture energies (i.e., resistance fracture) and superior compressive strain other architectures. A precursor material featuring acrylic acid only free chains yields, carbodiimide, an IPN a energy 2400 J/m 2 , fourfold increase analogous yields SN. enables formation macroscopic complex cut patterns, even at high strain, underscoring pivotal role performance.

Language: Английский

Citations

0
Controlling Carbodiimide-Driven Reaction Networks Through the Reversible Formation of Pyridine Adducts DOI
William S. Salvia, Georgia Mantel, Nirob K. Saha

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(88), P. 12876 - 12879

Published: Jan. 1, 2024

The reversible formation of adducts between a carbodiimide and pyridine allows the slow release fuels for transient anhydride bond formation.

Language: Английский

Citations

0