Functional Polyesters: Tailoring Structure and Biomedical Functions

Polymer science & technology., Journal Year: 2025, Volume and Issue: unknown

Published: March 21, 2025

Language: Английский

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An Expedient Route to Bio‐based Polyacrylate Alternatives with Inherent Degradation Capabilities by Organic Catalysis for Polymerization of Muconate Esters

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

Published: Sept. 24, 2024

Abstract The quest for polymers that would be at the same time bio‐based and degradable after usage, in addition to offering chemical post‐modification options, remains a daunting challenge contemporary polymer science. Despite advances chemistry, attempts controlling chain‐growth polymerization of muconate esters remain unexplored. Here we show dialkyl muconates can rapidly polymerized by organocatalyzed group transfer (O‐GTP). O‐GTP is conducted completion room temperature toluene within few minutes, using 1‐ethoxy‐1‐(trimethylsiloxy)‐1,3‐butadiene (ETSB) as initiator 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)‐phosphoranylidenamino]‐2 5,4 5 catenadi(phosphazene) (P 4 ‐ t ‐Bu) catalyst. Chain extension experiments synthesis all muconate‐type block copolymers also achieved. Furthermore, polymuconates are amenable facile post‐polymerization modification reactions. This showcased through hydrolysis ester side chains leading well‐defined poly(muconic acid), epoxidation C=C double bonds main chain. Last but not least, these internal alkene groups selectively cleaved ozonolysis, demonstrating upcyclability under oxidative conditions. work demonstrates constitute unique platform polymers, easily modifiable being chemically user friendly experimental

Language: Английский

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Design, Exploitation, and Rational Improvements of Diazirine-Based Universal Polymer Crosslinkers

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(22), P. 3327 - 3342

Published: Oct. 31, 2024

ConspectusAddition of new covalent bonds between the chains thermoplastic polymers (i.e., crosslinking) provides improved mechanical strength and enhanced high-temperature performance while also providing an effective strategy for photopatterning. Traditionally, however, crosslinking each polymer substrate has required use a specific technology (hydrosilylation PDMS, vulcanization rubber, etc.). The lack general solution to challenge means that there are many thermoplastics (e.g., polypropylene or polyhydroxyalkanoates) have desirable properties, but which cannot be upgraded by traditional technologies.Our lab developed first universal crosslinkers aliphatic leveraging trifluoromethyl aryl diazirine motifs, functional groups been widely used in chemical biology >30 years, seldom exploited materials science. These novel reagents work (via C–H insertion) on essentially any commodity contains bonds, including industrial plastics like (the outstanding field >50 years), as well commercially important elastomers polydimethylsiloxane), biodegradable polycaprolactone), green derived from biomass polyhydroxyalkanoates).Subsequent structure–function our group led were >10-fold more undergoing insertion with substrates. We then synthesis electronically optimized diazirines incorporated them into family cleavable crosslinker reagents, permit on-demand generation reprocessable thermosets. At same time, other replaced perfluoropropyl linker first-generation series dynamic linkages; these ready vitrimeric can reactive compatibilization immiscible plastic waste.Since publication initial Science paper 2019, this burgeoning diazirine-based experienced explosion interest. Publications others described adhesion, photopatterning low dielectric microelectronics, direct optical printing quantum dots. Our shown heighten robustness ice-phobic coatings improve woven ballistic fabric, while─perhaps most unexpectedly─substantially improving stability high-performance perovskite solar cells. Electronically covalently link proteins surfaces, suggesting broad range applications biocompatibilization medical devices. This Account will summarize development science over past 5 years. A brief comparison made, Summary Outlook section at end Account, competing (and often complementary) based upon azide diazoalkyl motifs. Finally, we compiled Frequently Asked Questions list covers practical aspects design application; is appended Supporting Information.

Language: Английский

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An Expedient Route to Bio‐based Polyacrylate Alternatives with Inherent Degradation Capabilities by Organic Catalysis for Polymerization of Muconate Esters

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 24, 2024

Abstract The quest for polymers that would be at the same time bio‐based and degradable after usage, in addition to offering chemical post‐modification options, remains a daunting challenge contemporary polymer science. Despite advances chemistry, attempts controlling chain‐growth polymerization of muconate esters remain unexplored. Here we show dialkyl muconates can rapidly polymerized by organocatalyzed group transfer (O‐GTP). O‐GTP is conducted completion room temperature toluene within few minutes, using 1‐ethoxy‐1‐(trimethylsiloxy)‐1,3‐butadiene (ETSB) as initiator 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)‐phosphoranylidenamino]‐2 5,4 5 catenadi(phosphazene) (P 4 ‐ t ‐Bu) catalyst. Chain extension experiments synthesis all muconate‐type block copolymers also achieved. Furthermore, polymuconates are amenable facile post‐polymerization modification reactions. This showcased through hydrolysis ester side chains leading well‐defined poly(muconic acid), epoxidation C=C double bonds main chain. Last but not least, these internal alkene groups selectively cleaved ozonolysis, demonstrating upcyclability under oxidative conditions. work demonstrates constitute unique platform polymers, easily modifiable being chemically user friendly experimental

Language: Английский

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