From health supplement to versatile monomer: Radical ring-opening polymerization and depolymerization of α-lipoic acid

Polymer, Journal Year: 2024, Volume and Issue: 304, P. 127167 - 127167

Published: May 11, 2024

Language: Английский

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Biological applications of lipoic acid-based polymers: an old material with new promise

Journal of Materials Chemistry B, Journal Year: 2024, Volume and Issue: 12(19), P. 4574 - 4583

Published: Jan. 1, 2024

Lipoic acid (LA) is a versatile antioxidant that has been used in the treatment of various oxidation-reduction diseases over past 70 years. Owing to its large five-membered ring tension, dynamic disulfide bond LA highly active, enabling formation poly(lipoic acid) (PLA) via ring-opening polymerization (ROP). Herein, we first summarize disulfide-mediated ROP strategies, providing basic routes for designing and preparing PLA-based materials. PLA, as biologically derived, low toxic, easily modified material, possesses bonds universal non-covalent carboxyl groups. We also shed light on biomedical applications materials based their biological structural features further divide recent works into six categories: antibacterial, anti-inflammation, anticancer, adhesive, flexible electronics, 3D-printed tissue scaffolds. Finally, challenges future prospects associated with PLA are discussed.

Language: Английский

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Regioselective Condensation Polymerization of Propargylic Electrophiles Enabled by Catalytic Element-Cupration

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19377 - 19385

Published: July 1, 2024

Here, we report a set of new polymerization reactions enabled by the 1,2-regioselective hydro- and silylcupration enyne-type propargylic electrophiles. Highly regioregular head-to-tail poly(2-butyne-1,4-diyl)s (HT-PBD), bearing either methyl or silylmethyl side chains, are synthesized for first time. A rapid entry into carbon-rich copolymers with adjustable silicon content is developed via in situ monomer bifurcation. Furthermore, one-pot polymerization/semireduction sequence to access cis-poly(butadiene)-derived backbone ligand swap on copper hydride species. Interestingly, borocupration, typically exhibiting identical regioselectivity its silyl analogues, seems proceed 3,4-selective manner. Computational studies suggest possible role leaving group this selectivity switch. This work presents class sp-carbon-rich polymers meanwhile novel approach organosilicon materials.

Language: 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, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

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UV‐Curable High‐Refractive‐Index Resin Based on Polysulfide With Pendant Methacrylate Formed by Selective Cationic Ring‐Opening Polymerization of Thiirane

Journal of Polymer Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 23, 2025

ABSTRACT In this paper, we aimed to synthesize polysulfide with pendant methacryloyl groups in the side chain. They are expected have great potential for various applications as UV‐curable higher‐refractive‐index resins. Thiiran‐2‐ylmethyl methacrylate (TMA) could be synthesized by reaction of glycidyl thiourea using conc. H 2 SO 4 a catalyst. Selective ring‐opening polymerization TMA achieved CuCl an initiator CHCl 3 at 25°C, yielding corresponding polyTMA (MA) chain high yield. The copolymerization and phenoxypropylene sulfide (PPS) was also performed give poly(TMA (MA)m ‐ co ‐PPS n ) M = 1330–1940 ( w / 1.03–2.02) yields. UV‐curing thin films containing photo‐radical proceeded smoothly under UV light, quantitatively affording cured films. refractive indices before after irradiation were determined ellipsometry. Among them, (MA)22 78 showed highest index value 1.763) reaction.

Language: Английский

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Record-High-Molecular-Weight Polyesters from Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides Catalyzed by Hydrogen-Bond-Functionalized Imidazoles

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 26, 2025

Polyesters, with potential for degradability and sustainability, are some of the most versatile polymer materials. However, limitation molecular weight (MW) presents a barrier to their applications. The synthesis polyesters high MW by ring-opening copolymerization (ROCOP) epoxides cyclic anhydrides is promising but rare challenging. Herein, we report series air-stable, hydrogen-bond-functionalized imidazole catalysts copolymerization. These can produce (4 examples) using cyclohexane oxide (CHO), propylene (PO), phenyl glycidyl ether (PGE), 4-vinyl-1-cyclohexene 1,2-epoxide (VCHO), phthalic anhydride (PA) record-high MW: Mn = 171.2 kDa poly(CHO-alt-PA), 518.5 poly(PO-alt-PA), 100.5 poly(PGE-alt-PA), 236.4 poly(VCHO-alt-PA). Furthermore, it achieve an unprecedented efficiency 15.6 kg polyester/g catalyst at molar ratio catalyst/PA/PO 1:40000:60000. achieved be attributed unique anionic-cationic coexisting ROCOP mechanism, which reduce transesterification, chain transfer, annulation side reactions. All showed excellent thermal stability, tensile strength, Young's modulus comparable commodity thermoplastics like polystyrene polylactic acid.

Language: Английский

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Recent advancements in the design and application of Thioctic acid-based self-assembled materials

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 537, P. 216679 - 216679

Published: April 11, 2025

Language: Английский

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Charge-assisted hydrogen bonding in a bicyclic amide cage: an effective approach to anion recognition and catalysis in water

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Hydrogen bonding is prevalent in biological systems, dictating a myriad of life-sustaining functions aqueous environments. Leveraging hydrogen for molecular recognition water encounters significant challenges synthetic receptors on account the hydration their functional groups. Herein, we introduce water-soluble cage, synthesized

Language: Английский

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Data Science Enables Chemical Interpretation of HBC-Catalyzed Polymerization for Poly(disulfide)s

Published: March 11, 2024

H-Bonding catalysts (HBCs) has gained widespread success in improving the selectivity of organic synthesis. The complexity potentially engaging noncovalent interactions have imposed significant challenges deciphering contributing factors these catalytic reactions. Herein, we present use interpretable machine learning on HBCs applied poly(disulfide) synthesis, wherein epiquinine-derived thiourea enable simultaneous regioselectivity control and rate acceleration over otherwise unselective already rapid polymerization. A training set 28 with variation phenyl substituents were synthesized tested to gather experimental observables: apparent (kp) (Pss). Considering limited data size, feature-sensitive XGBoost algorithm for supervised learning. Upon screening 64 relevant descriptors, a reasonable fitting observables was established kp (R2 = 0.76) Pss 0.91), key catalyst features necessary achieving high reaction rates deconvoluted. model suggests that sterically hindered, heavy atom-containing or strongly electro-withdrawing groups HBC adversely affect rate. Substituents enhancing electrostatic potential aromatic N atom are beneficial regioregularity, while presence ortho-substituents ring is unfavorable.

Language: Английский

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Advancing H-Bonding Organocatalysis for Ring-Opening Polymerization: Intramolecular Activation of Initiator/Chain End

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25852 - 25859

Published: Sept. 3, 2024

Organocatalytic ring-opening polymerization (ROP) of lactones is a green method for accessing renewable and biodegradable polyesters. Developing new organocatalysts with high activity controllability major challenging research topic in this field. Here, we report series to achieve fast controlled ROP lactones. These catalysts incorporate (thio)urea alkoxide one molecule act as initiators the ROP. Such enable an effective intramolecular activation initiator/chain end, revealed by computational studies, resulting higher fewer loads than existing (thio)urea/alkoxide binary systems. exhibit ultrahigh comparable metal complexes, i.e., turnover number up 900 frequency 4860 min

Language: Английский

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