Disulfide-containing monomers in chain-growth polymerization

Pięta, Marlena; Purohit, Vishal B.; Pietrasik, Joanna; Plummer, Christopher M.

doi:10.1039/d2py01291j

Cited by 18 publications

(11 citation statements)

References 166 publications

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“…Inspired by the aforementioned literature and a desire to simplify the synthesis of degradable comonomers for controlled rROP, we were drawn to α-lipoic acid (LA) – a commercially available and naturally occurring small molecule building block that is available on a multikilogram scale due to its wide use as a dietary supplement. − LA features a 1,2-dithiolane ring that undergoes ring-opening polymerization in the presence of acid, base, or radicals, resulting in dynamic and degradable disulfide bonds . Tsarevsky , and Endo , previously demonstrated the rROP of LA derivatives with acrylates via a conventional free-radical process.…”

Section: Introductionmentioning

confidence: 99%

Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

Albanese,

Morris,

Read de Alaniz

et al. 2023

J. Am. Chem. Soc.

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Here, we present the synthesis and characterization of statistical and block copolymers containing α-lipoic acid (LA) using reversible addition–fragmentation chain-transfer (RAFT) polymerization. LA, a readily available nutritional supplement, undergoes efficient radical ring-opening copolymerization with vinyl monomers in a controlled manner with predictable molecular weights and low molar-mass dispersities. Because lipoic acid diads present in the resulting copolymers include disulfide bonds, these materials efficiently and rapidly degrade when exposed to mild reducing agents such as tris(2-carboxyethyl)phosphine (M n = 56 → 3.6 kg mol–1). This scalable and versatile polymerization method affords a facile way to synthesize degradable polymers with controlled architectures, molecular weights, and molar-mass dispersities from α-lipoic acid, a commercially available and renewable monomer.

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Section: Introductionmentioning

confidence: 99%

Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

Albanese,

Morris,

Read de Alaniz

et al. 2023

J. Am. Chem. Soc.

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“…To address these challenges, here we introduce a versatile platform of comonomers for designing degradable poly(acrylate) PSAs based on α-lipoic acid (αLA), an edible natural product found in vegetables, biological redox processes, and a variety of consumer dietary supplements . αLA is commercially available (produced on the ∼250 ton scale per year) and inexpensive, featuring a 1,2-dithiolane ring that undergoes ring-opening polymerization at elevated temperatures or when exposed to ultraviolet light. − The thermal polymerization of pure αLA was recently exploited in constructing dynamic self-healing materials with potential applications as structural adhesives. − αLA and its derivatives are also known to copolymerize with various vinyl monomers, including acrylates. − Pioneering work from the Tsarevsky group reported the radical copolymerization of ethyl lipoate and ethyl acrylate generates disulfide bonds within lipoate–lipoate diads that can be degraded under reductive conditions . However, these past studies were limited to low molecular weights (for acrylates, ≲22000 g mol –1 ) that are too small for PSA (or adhesive) applications where a sufficient number of entanglements are needed to appropriately tune viscoelasticity and adhesion …”

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confidence: 99%

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

et al. 2023

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

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“…[31] Furthermore, by integrating disulfide bonds into the structure of polysaccharides, additional characteristics such as flexural strength, adaptability, degradability, and even the ability to undergo self-repair can be introduced. [142] Thiolated CDs exhibit also in situ gelling properties forming inter-and intramolecular disulfide bonds. [65] Yang et al prepared poly(thiolated chitosan-co alkylated alkynyl-cyclodextrin) hydrogels with excellent cross-linking density using click chemistry.…”

Section: Gelling Propertiesmentioning

confidence: 99%

Section: Properties Of Thiolated Poly‐ and Oligosaccharidesmentioning

confidence: 99%

Thiolated Poly‐ and Oligosaccharide‐Based Hydrogels for Tissue Engineering and Wound Healing

Noreen,

Bernkop‐Schnürch

2023

Adv Funct Materials

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Due to thiolation of poly‐ and oligosaccharides numerous favorable properties for tissue engineering and wound healing can be introduced. Poly‐ and oligosaccharides can be thiolated via hydroxyl‐to‐thiol conversions or the covalent attachment of sulfhydryl ligands to hydroxyl, carbonic acid or amino groups on them. Since thiolated poly‐ and oligosaccharides can cross‐link via disulfide bonds, they form stable 3D networks with defined microarchitecture, stiffness, elasticity, and degradability. Furthermore, thiol groups can enhance cell adhesion since cells exhibit cysteine‐rich subdomains on their surface that form disulfide bonds with them. Sulfhydryl groups can also participate in cell signaling pathways favoring various cellular processes like proliferation, migration, spreading, and differentiation that are beneficial for tissue engineering and wound healing. In addition, a controlled release of active ingredients such as growth factors being bound via disulfide bonds to thiolated poly‐ and oligosaccharides can be achieved via thiol/disulfide exchange reactions. Over the last two decades, the number of thiolated poly‐ and oligosaccharides such as thiolated hyaluronic acid and thiolated chitosan used for tissue engineering and wound healing has increased tremendously. Within this review, an overview is provided about the chemistry of thiolated poly‐ and oligosaccharides, their key properties, applications and performance in clinical trials and as marketed products.

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Disulfide-containing monomers in chain-growth polymerization

Abstract: Due to the significance of disulfide bonds within modern material and medicinal sciences, much attention has been paid to the synthesis of disulfide-containing polymers. Within this review article, we attempt...

Cited by 18 publications

References 166 publications

Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers

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

Thiolated Poly‐ and Oligosaccharide‐Based Hydrogels for Tissue Engineering and Wound Healing

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