Versatile and Controlled Synthesis of Degradable, Water-Soluble Bottlebrush Polymers with Poly(disulfide) Backbones Derived from α-Lipoic Acid

ACS Macro Letters, Год журнала: 2025, Номер unknown, С. 207 - 213

Опубликована: Фев. 3, 2025

Bottlebrush (BB) polymers, with their densely grafted side chains and unique architecture, are highly advantageous for drug delivery due to high functional group density conjugation, unimolecular nature, enhanced biodistribution properties. These attributes enable extended blood circulation half-life, improved tumor tissue penetration, tumoral accumulation. However, the typically nondegradable, all-carbon backbones of most BB polymers limit suitability applications requiring controlled clearance biodegradability. To address this, we developed degradable poly(disulfide) synthesized via reversible addition–fragmentation chain transfer (RAFT) copolymerization α-lipoic acid (LA), a renewable readily available compound, acrylate-based inimers. copolymers feature initiating sites subsequent synthesis. Using an atom radical polymerization (ATRP) grafting-from methodology, relatively low dispersities (Đ = 1.30–1.53), backbone degrees (DPbb), molar masses (Mn,MALS 650–2700 kg/mol). The easily cleavable disulfide bonds enabled degradation under mild reducing conditions. Beyond hydrophilic tri(ethylene glycol) methyl ether acrylate (TEGA) chains, cationic, anionic, zwitterionic demonstrating broad monomer compatibility. This scalable approach produces water-soluble, tunable architectures predictable molecular weights. By addressing need degradability in this work advances potential delivery, offering functionality, biocompatibility, sustainability.

Язык: Английский

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Mechanochemical Backbone Editing for Controlled Degradation of Vinyl Polymers

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Май 27, 2024

The chemically inert nature of fully saturated hydrocarbon backbones endows vinyl polymers with desirable durability, but it also leads to their significant environmental persistence. Enhancing the sustainability these materials requires a pivotal yet challenging shift: transforming backbone into one that is degradable. Here, we present versatile platform for mechanochemically editing towards degradable polymer chains by integrating cyclobutene-fused succinimide (CBS) units along through photo-iniferter reversible addition-fragmentation chain-transfer (RAFT) copolymerization. Significantly, evenly insertion CBS does not compromise thermal or chemical stability rather offers means adjust properties polymethylacrylate (PMA). Meanwhile, reactive acyclic imide can be selectively introduced mechanochemical activation (pulse ultrasonication ball-milling grinding) when required. Subsequent hydrolysis groups enables efficient degradation, yielding telechelic oligomers. This approach holds promise inspiring design and modification more environmentally friendly editing.

Язык: Английский

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Accurate Determination of Reactivity Ratios for Copolymerization Reactions with Reversible Propagation Mechanisms

Macromolecules, Год журнала: 2024, Номер 57(14), С. 6727 - 6740

Опубликована: Июль 9, 2024

An understanding of monomer sequence is required to predict and engineer the properties copolymers. In stochastic polymerizations involving more than one monomer, typically inferred or determined from reactivity ratios, which are measured through copolymerization experiments. The accurate determination ratios copolymerizations where both monomers undergo reversible propagation, however, has been complicated by difficulty in solving underlying population balance equations, presence myriad copolymer equations literature derived under varying assumptions simplifications, lack an easy-to-fit integrated model. Here, we rectify assert consistency between previously reported disparate forms, introduce a new method explicitly solve perform simulations evaluate ability these three methods produce consistent comonomer consumption predictions fits simulated data. We find that all given same input parameters, implies accuracy precision when modeling copolymerization, fitting experimental data, making sequence. Considering this consistency, make recommendation use numerical integration appropriate equation fit real data due its ease implementation. further identify minimum number parameters for suggest ways measure other information ex situ expedite fitting. Finally, practical utility developed herein demonstrated seven distinct sets, span wide range reactivities.

Язык: Английский

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Scalable Synthesis of Degradable Copolymers Containing α-Lipoic Acid via Miniemulsion Polymerization

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(44), С. 30662 - 30667

Опубликована: Окт. 28, 2024

A robust method is described to synthesize degradable copolymers under aqueous miniemulsion conditions using α-lipoic acid as a cheap and scalable building block. Simple formulations of (up 10 mol %),

Язык: Английский

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New Chemistries for Degradable Pressure‐Sensitive Adhesive Networks

ChemPlusChem, Год журнала: 2024, Номер 89(6)

Опубликована: Фев. 21, 2024

With the increasing use of pressure-sensitive adhesives (PSAs) in various industries, there is a need for greater sustainability, particularly developing polymer materials from renewable resources, as well reuse and recycling to reduce environmental impact, waste, or extend their life. Here, we outlined required properties PSAs which are governed by molecular parameters (molecular weights, dispersities, weight between entanglement, cross-links gel content) subsequently define physical (storage loss moduli, glass transition temperature) that good performance peel, tack shear tests. The sustainable approach discussed here development degradable featuring selectively linkages backbone. This provides viable alternative design could overcome 'stickies' problem make cardboard more efficient.

Язык: Английский

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Biomass‐Derived Optically Clear Adhesives for Foldable Displays

ChemSusChem, Год журнала: 2024, Номер unknown

Опубликована: Март 29, 2024

Acrylic pressure sensitive adhesives (PSAs) are the most widely used and play a crucial role in ensuring stable operation of foldable displays. With focus on product sustainability, numerous studies have aimed to enhance eco-friendliness acrylic PSAs. However, few specifically address development environmentally friendly PSAs for devices. In this work, we synthesized new monomers by modifying citronellol, terpenoid, use as functional low glass transition temperature (Tg) optical clear (OCAs). We prepared OCAs using these via an visible-light-driven polymerization process due its greater energy efficiency reduced harm humans, opposed ultraviolet light that is normally conventional photopolymerization processes. Their properties were confirmed through rheological analysis. The resultant exhibit Tg, appropriate storage modulus across wide range, reliable adhesion force various substrates, decent creep recovery properties. These characteristics indicate their potential

Язык: Английский

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Responsive Degradable Bottlebrush Polymers Enable Drugs With Superior Efficacy and Minimal Systemic Toxicity

Advanced Healthcare Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 5, 2025

Bottlebrush polymers (BBPs) have garnered significant attention as advanced drug delivery systems, capable of transporting a diverse range therapeutic agents, including both chemical drugs and biologics. Despite their effectiveness, the empty BBP vectors post-drug release may pose long-term safety risks due to difficult systemic clearance. Here, responsive degradable platform for cancer therapy is developed, featuring poly(disulfide) backbone grafted with fluorine-terminated zwitterionic side chains. Anti-cancer are tethered via clinically approved valine-citrulline (VC) linker. This design leverages tumor's reductive environment Cathepsin B overexpression rapid degradation precise restricted within tumor cells, thereby addressing concerns over synthetic expanding window anti-cancer simultaneously. Surface fluorination further enhances accumulation deep penetration. In vivo studies monomethyl auristatin E (MMAE)-loaded in tumor-bearing mice demonstrate substantial suppression minimal effects. Together, these findings highlight potential versatile unimolecular delivery, existing challenges associated nanomedicines.

Язык: Английский

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Enhanced Degradation of Vinyl Copolymers Based on Lipoic Acid

Journal of Polymer Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 17, 2025

ABSTRACT The introduction of degradable units into the backbone commodity vinyl polymers represents a major opportunity to address societal challenge plastic waste and polymer recycling. Previously, we reported facile copolymerization α ‐lipoic acid derivatives containing 1,2‐dithiolane rings with monomers leading incorporation S–S disulfide bonds along at relatively high dithiolane monomer feed ratios. To further enhance recyclability these systems, here describe user‐friendly strategy for degradation significantly lower loading levels through cleavage both SS SC units. Copolymers n ‐butyl acrylate ( BA) or styrene (St) small amounts either (LA) ethyl lipoate (ELp) dissolved in DMF were observed undergo efficient when heated 100°C under air. For example, only 5 mol% ELp, molecular weight poly(ELp‐ co ‐ M = 62 kg mol −1 ) degraded low oligomers 3.2 by simple heating DMF. In contrast, extended poly( poly(St) homopolymers same conditions did not lead any change C–C backbone. This novel approach allows effective vinyl‐based negligible impact on properties performance due incorporation.

Язык: Английский

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In Situ Synthesis of Chemically Stable Hybrid Co‐Networks of Poly(thioctic Acid) with Fe³⁺ via Controlled/Living Cationic Ring‐Opening Polymerization

Macromolecular Rapid Communications, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

Abstract The novel chemically stable hybrid co‐networks (PTA‐Fe) of poly(thioctic acid) coordinated with molar content ( C Fe ) 1%∼12% 3+ generated from [FeCl 4 ·POH] − can be in situ synthesized via controlled/living cationic ring‐opening polymerization α ‐thioctic acid (TA) tert ‐butyl chloride(BCl)/FeCl 3 /isopropanol(POH) initiating system at 0 °C. polymerizations are all first order respect to monomer, initiator and co‐initiator. resulting PTAs desired molecular weights relatively narrow unimodal weight distribution obtained quantitative initiation by changing [BCl] . livingness without chain transfer termination is confirmed the linear relationship between polymer yields unchanged average chains during process Incremental Monomer Addition All In techniques. possible mechanism above proposed. Interestingly, it found that PTA‐Fe hybrids behave storage room temperature for 24 months when ≥ 6.9%. To best knowledge, example green synthesis excellent chemical stability. would have potential application field elastomer, adhesive self‐healing materials.

Язык: Английский

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Backbone Degradable Polymers via Chain-growth Radical Polymerization

Chinese Journal of Polymer Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 24, 2025

Язык: Английский

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