Disulfide-Mediated Reversible Polymerization toward Intrinsically Dynamic Smart Materials

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2022 - 2033

Published: Jan. 6, 2022

The development of a dynamic chemistry toolbox to endow materials behavior has been key the rational design future smart materials. rise supramolecular and covalent offers many approaches construction polymers that can adapt, respond, repair, recycle. Within this toolbox, building blocks based on 1,2-dithiolanes have become an important scaffold, featuring their reversible polymerization mediated by disulfide bonds, which enables unique class at intersection adaptable networks. This Perspective aims explore as versatile structural unit for summarizing state art well providing overview fundamental challenges involved in research area its potential directions.

Language: Английский

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Photoresponsive Supramolecular Polymers: From Light‐Controlled Small Molecules to Smart Materials

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(10)

Published: Oct. 14, 2022

Photoresponsive supramolecular polymers are well-organized assemblies based on highly oriented and reversible noncovalent interactions containing photosensitive molecules as (co-)monomers. They have attracted increasing interest in smart materials dynamic systems with precisely controllable functions, such light-driven soft actuators, photoresponsive fluorescent anticounterfeiting light-triggered electronic devices. The present review discusses light-activated used their main photo-induced changes, e.g., geometry, dipole moment, chirality. Based these distinct formed by exhibit disassembly reassembly. As a consequence, polymerization, "depolymerization," regulation of the lengths topologies observed. Moreover, light-controlled functions polymers, actuation, emission, chirality transfer along length scales, highlighted. Furthermore, perspective challenges future opportunities is presented. Besides challenge moving from harmful UV light to visible/near IR avoiding fatigue, enabling biomedical applications, include actuators helical motion, light-modulated information transmission, optically recyclable materials, multi-stimuli-responsive systems.

Language: Английский

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Photoinduced Dithiolane Crosslinking for Multiresponsive Dynamic Hydrogels

Advanced Materials, Journal Year: 2023, Volume and Issue: unknown

Published: Jan. 30, 2023

While many hydrogels are elastic networks crosslinked by covalent bonds, viscoelastic with adaptable crosslinks increasingly being developed to better recapitulate time and position-dependent processes found in tissues. In this work, 1,2-dithiolanes presented as dynamic photocrosslinkers of hydrogels, resulting disulfide bonds throughout the hydrogel that respond multiple stimuli. Using lipoic acid a model dithiolane, formed under physiological conditions, enabling cell encapsulation via an initiator-free light-induced dithiolane ring-opening photopolymerization. The allow for photoinduced responses including stress relaxation, stiffening, softening, network functionalization using single chemistry, which can be supplemented permanent reaction alkenes further control properties connectivity irreversible thioether crosslinks. Moreover, complementary photochemical approaches used achieve rapid complete sample degradation radical scission post-gelation stiffening when irradiated presence reactive gel precursor. results herein demonstrate versatility material chemistry study direct 2D 3D cell-material interactions. This work highlights dithiolane-based photocrosslinking robust method generating range biologically relevant mechanical chemical varied on demand.

Language: Английский

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Building Tunable Degradation into High-Performance Poly(acrylate) Pressure-Sensitive Adhesives

ACS Macro Letters, Journal Year: 2023, Volume and Issue: 12(6), P. 787 - 793

Published: May 23, 2023

Pressure-sensitive adhesives (PSAs) based on poly(acrylate) chemistry are common in a wide variety of applications, but the absence backbone degradability causes issues with recycling and sustainability. Here, we report strategy to create degradable PSAs using simple, scalable, functional 1,2-dithiolanes as drop-in replacements for traditional acrylate comonomers. Our key building block is α-lipoic acid, natural, biocompatible, commercially available antioxidant found various consumer supplements. α-Lipoic acid its derivative ethyl lipoate efficiently copolymerize n-butyl under conventional free-radical conditions leading high-molecular-weight copolymers (Mn > 100 kg mol-1) containing tunable concentration disulfide bonds along backbone. The thermal viscoelastic properties these materials practically indistinguishable from nondegradable analogues, significant reduction molecular weight realized upon exposure reducing agents such tris (2-carboxyethyl) phosphine (e.g., Mn = 198 mol-1 → 2.6 mol-1). By virtue thiol chain ends produced after cleavage, degraded oligomers can be further cycled between high low weights through oxidative repolymerization reductive degradation. Transforming otherwise persistent poly(acrylates) into recyclable simple versatile could play pivotal role improving sustainability contemporary adhesives.

Language: Английский

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Acid‐catalyzed Disulfide‐mediated Reversible Polymerization for Recyclable Dynamic Covalent Materials

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 5, 2023

Poly(1,2-dithiolane)s are a family of intrinsically recyclable polymers due to their dynamic covalent disulfide linkages. Despite the common use thiolate-initiated anionic ring-opening polymerization (ROP) under basic condition, cationic ROP is still not exploited. Here we report that bond can act as proton acceptor, being protonated by acids form sulfonium cations, which efficiently initiate 1,2-dithiolanes and result in high-molecular-weight (over 1000 kDa) poly(disulfide)s. The reaction be triggered adding catalytic amounts non-coordinating anion salts, completed few minutes at room temperature. acidic conditions allow applicability for monomers. Importantly, condition open air without inert protection, enabling nearly quantitative chemical recycling from bulk materials original

Language: Английский

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A renewably sourced, circular photopolymer resin for additive manufacturing

Nature, Journal Year: 2024, Volume and Issue: 629(8014), P. 1069 - 1074

Published: May 15, 2024

The additive manufacturing of photopolymer resins by means vat photopolymerization enables the rapid fabrication bespoke 3D-printed parts. Advances in methodology have continually improved resolution and speed, yet both process design resin technology remained largely consistent since its inception 1980s

Language: Английский

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Robust and dynamic underwater adhesives enabled by catechol-functionalized poly(disulfides) network

National Science Review, Journal Year: 2022, Volume and Issue: 10(2)

Published: July 25, 2022

Developing molecular approaches to the creation of robust and water-resistant adhesive materials promotes a fundamental understanding interfacial adhesion mechanisms as well future applications biomedical materials. Here, we present simple strategy that combines natural thioctic acid mussel-inspired iron-catechol complexes enable ultra-strong can be used underwater simultaneously exhibit unprecedentedly high strength on diverse surfaces. Our experimental results show crosslinking interaction complexes, high-density hydrogen bonding, are responsible for ultra-high strength. The embedding effect hydrophobic solvent-free network poly(disulfides) further enhances water-resistance. dynamic covalent also makes resulting reconfigurable, thus enabling reusability via repeated heating cooling. This molecule-engineering offers general versatile solution design construction supramolecular

Language: Английский

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Mucus-Inspired Dynamic Hydrogels: Synthesis and Future Perspectives

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(44), P. 20137 - 20152

Published: Sept. 8, 2022

Mucus hydrogels at biointerfaces are crucial for protecting against foreign pathogens and the biological functions of underlying cells. Since mucus can bind to host both viruses bacteria, establishing a synthetic model system that emulate properties native be synthesized large scale would revolutionize mucus-related research is essential understanding pathways many infectious diseases. The synthesis such biofunctional in laboratory highly challenging, owing their complex chemical compositions specific interactions occur throughout gel network. In this perspective, we discuss basic structures diverse physicochemical responsible unique hydrogels. We scrutinize different approaches preparing mucus-inspired hydrogels, with examples. also recent what it reveals about challenges must addressed opportunities considered achieve desirable de novo

Language: Английский

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Robust and healable poly(disulfides) supramolecular adhesives enabled by dynamic covalent adaptable networks and noncovalent hydrogen-bonding interactions

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 461, P. 142066 - 142066

Published: Feb. 23, 2023

Language: Английский

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Mussel‐Inspired, Underwater Self‐Healing Ionoelastomers Based on α‐Lipoic Acid for Iontronics

Small, Journal Year: 2023, Volume and Issue: 19(21)

Published: March 3, 2023

Weak adhesion and lack of underwater self-healability hinder advancing soft iontronics particularly in wet environments like sweaty skin biological fluids. Mussel-inspired, liquid-free ionoelastomers are reported based on seminal thermal ring-opening polymerization a biomass molecule α-lipoic acid (LA), followed by sequentially incorporating dopamine methacrylamide as chain extender, N,N'-bis(acryloyl) cystamine, lithium bis(trifluoromethanesulphonyl) imide (LiTFSI). The exhibit universal to 12 substrates both dry states, superfast self-healing underwater, sensing capability for monitoring human motion, flame retardancy. self-repairabilitiy prolongs over three months without deterioration, sustains even when mechanical properties greatly increase. unprecedented self-mendability benefits synergistically from the maximized availability dynamic disulfide bonds diverse reversible noncovalent interactions endowed carboxylic groups, catechols, LiTFSI, along with prevented depolymerization LiTFSI tunability strength. ionic conductivity reaches 1.4 × 10-6 -2.7 10-5 S m-1 because partial dissociation LiTFSI. design rationale offers new route creating wide range LA- sulfur-derived supramolecular (bio)polymers superior adhesion, healability, other functionalities, thus has technological implications coatings, adhesives, binders sealants, biomedical engineering drug delivery, wearable flexible electronics, human-machine interfaces.

Language: Английский

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