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

Using Chemistry To Recreate the Complexity of the Extracellular Matrix: Guidelines for Supramolecular Hydrogel–Cell Interactions DOI Creative Commons
Laura Rijns, Matthew B. Baker, Patricia Y. W. Dankers

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17539 - 17558

Published: June 18, 2024

Hydrogels have emerged as a promising class of extracellular matrix (ECM)-mimicking materials in regenerative medicine. Here, we briefly describe current state-of-the-art ECM-mimicking hydrogels, ranging from natural to hybrid completely synthetic versions, giving the prelude importance supramolecular interactions make true ECM mimics. The potential create mimics for cell culture is illustrated through focus on two different hydrogel systems, both developed our laboratories. We use some recent, significant findings present important design principles underlying cell–material interaction. To achieve spreading, propose that slow molecular dynamics (monomer exchange within fibers) crucial ensure robust incorporation adhesion ligands fibers. Slow bulk (stress–relaxation─fiber rearrangements, τ1/2 ≈ 1000 s) required spreading soft gels (<1 kPa), while gel stiffness overrules stiffer gels. Importantly, this resonates with others which specialize material types: impaired case substrate relaxation occurs faster than clutch binding and focal lifetime. conclude discussing considerations limitations approach well provide forward thinking perspective further understand hydrogel–cell interactions. Future work may utilize presented guidelines not only arrive at next generation hydrogels but also advance other fields, such bioelectronics, opening up new opportunities innovative applications.

Language: Английский

Citations

19
Polymer gels for aqueous metal batteries DOI
Tianfu Zhang, Keliang Wang,

Hengwei Wang

et al.

Progress in Materials Science, Journal Year: 2025, Volume and Issue: unknown, P. 101426 - 101426

Published: Jan. 1, 2025

Citations

2
Suppressing catalyst poisoning in the carbodiimide-fueled reaction cycle DOI Creative Commons
Xiaoyao Chen, Héctor Soria‐Carrera, Oleksii Zozulia

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(44), P. 12653 - 12660

Published: Jan. 1, 2023

In biology, cells regulate the function of molecules using catalytic reaction cycles that convert reagents with high chemical potential (fuel) to waste molecules. Inspired by synthetic analogs such have been devised, and a widely used cycle uses carboxylates as catalysts accelerate hydration carbodiimides. The is versatile easy use, so it applied motors, pumps, self-assembly, phase separation. However, suffers from side reactions, especially formation N-acylurea. cycles, reactions are disastrous they decrease fuel's efficiency and, more importantly, destroy molecular machinery or assembling Therefore, this work tested how suppress N-acylurea screening precursor concentration, its structure, carbodiimide additives, temperature, pH. It turned out combination low pH, 10% pyridine fraction fuel could significantly product keep highly effective successful assembly. We anticipate our will provide guidelines for carbodiimide-fueled choose optimal conditions.

Language: Английский

Citations

23
Kinetically Controlled and Nonequilibrium Assembly of Block Copolymers in Solution DOI Creative Commons
Stephen D. P. Fielden

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18781 - 18796

Published: July 5, 2024

Covalent polymers are versatile macromolecules that have found widespread use in society. Contemporary methods of polymerization made it possible to construct sequence polymers, including block copolymers, with high precision. Such copolymers assemble solution when the blocks differing solubilities. This produces nano- and microparticles various shapes sizes. While is straightforward draw an analogy between such amphiphilic phospholipids, these two classes molecules show quite different assembly characteristics. In particular, often under kinetic control, thus producing nonequilibrium structures. leads a rich variety behaviors being observed copolymer assembly, as pathway dependence (e.g., thermal history), nonergodicity responsiveness. The dynamics polymer assemblies can be readily controlled using changes environmental conditions and/or integrating functional groups situated on external chemical reactions. perspective highlights control both pervasive useful attribute mechanics assembly. Recent examples highlighted order toggling static dynamic behavior used generate, manipulate dismantle states. New kinetics will provide endless unanticipated applications materials science, biomimicry medicine.

Language: Английский

Citations

10
Carbodiimide‐Driven Toughening of Interpenetrated Polymer Networks DOI Creative Commons

Chamoni W. H. Rajawasam,

Corvo Tran, Jessica L. Sparks

et al.

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

5
Chemical and Photochemical-Driven Dissipative Fe3+/Fe2+-Ion Cross-Linked Carboxymethyl Cellulose Gels Operating Under Aerobic Conditions: Applications for Transient Controlled Release and Mechanical Actuation DOI Creative Commons
Roberto Baretta, Gilad Davidson‐Rozenfeld,

Vitaly Gutkin

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9957 - 9966

Published: March 28, 2024

A Fe3+-ion cross-linked carboxymethyl cellulose, Fe3+-CMC, redox-active gel exhibiting dissipative, transient stiffness properties is introduced. Chemical or photosensitized reduction of the higher-stiffness Fe3+-CMC to lower-stiffness Fe2+-CMC gel, accompanied by aerobic reoxidation matrix, leads stiffness, functional matrix. The light-induced, temporal, release a load (Texas red dextran) and light-triggered, mechanical bending poly-N-isopropylacrylamide (p-NIPAM)/Fe3+-CMC bilayer construct are introduced, thus demonstrating potential use dissipative for controlled drug soft robotic applications.

Language: Английский

Citations

5
Fluorescence-readout as a powerful macromolecular characterisation tool DOI Creative Commons
Xingyu Wu, Christopher Barner‐Kowollik

Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 12815 - 12849

Published: Jan. 1, 2023

We discuss the current state-of-the-art in exploiting fluorescence-based techniques for analysing polymer systems and soft matter materials, as well provide an outlook on future opportunities challenges.

Language: Английский

Citations

12
Pumping Small Molecules Selectively through an Energy-Assisted Assembling Process at Nonequilibrium States DOI

Huimin Fu,

Nengjie Cao,

Zeng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3323 - 3330

Published: Jan. 26, 2024

In living organisms, precise control over the spatial and temporal distribution of molecules, including pheromones, is crucial. This level equally important for development artificial active materials. this study, we successfully controlled small molecules in system at nonequilibrium states by actively transporting them, even against apparent concentration gradient, with high selectivity. As a demonstration, aqueous solution acid orange (AO7) TMC

Language: Английский

Citations

4
Transient regulation of gel properties by chemical reaction networks DOI
Zhongrui Wang, Jing Xiao, Ting Zhao

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(65), P. 9818 - 9831

Published: Jan. 1, 2023

The significance, achievements, and expectations in transiently regulating the gel properties by chemical reaction networks are discussed.

Language: Английский

Citations

10
Photoresponsive Polymers for Carbodiimide-Fueled Transient Hydrogels DOI Creative Commons
Ibrahim O. Raji,

Torin C. Wilcox,

C. Scott Hartley

et al.

Polymer Chemistry, Journal Year: 2025, Volume and Issue: 16(8), P. 947 - 953

Published: Jan. 1, 2025

Light and fuel responsive polymers were developed. Transient hydrogels could be formed only after exposure to both photochemical stimuli.

Language: Английский

Citations

0