Biomimetic Chemocatalytic Cascades─A New Strategy for Molecular Design of Degradable Polymer Systems

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-01-13 DOI:10.1021/acs.macromol.4c02241

Bin Tan, John R. Dorgan

{"title":"Biomimetic Chemocatalytic Cascades─A New Strategy for Molecular Design of Degradable Polymer Systems","authors":"Bin Tan, John R. Dorgan","doi":"10.1021/acs.macromol.4c02241","DOIUrl":null,"url":null,"abstract":"Biological systems often involve cascading molecular signals; for example, blood coagulation involves a cascade of serial and parallel reactions catalyzed by enzymes. The present study draws inspiration from such complex biological systems to demonstrate, through a simple example, the purposeful design of a cascade system that enables control over polymer degradation kinetics. Micron size fibers of polylactide (PLA), cellulose acetate (CA), and their mixtures are subjected to hydrolysis at varying temperatures. Cleavage of the PLA produces an organic acid functional group that catalyzes the CA hydrolysis, thus demonstrating the use of synthetic molecular signaling. Furthermore, the presence of CA inhibits the degradation of PLA thereby demonstrating molecular feedback, another hallmark of biological molecular cascades. The parallel reaction cascade causes the hydrolysis rate constant for CA to increase 3.1 times compared to CA alone (from 5.7 × 10–4 to 1.78 × 10–3 L2 mol–2 h–1 at 125 °C); furthermore, due to molecular feedback, the hydrolysis rate constant for PLA decreases by 21% (from 2.40 × 10–3 to 1.90 × 10–3 L2 mol–2 h–1). The results demonstrate that synthetic signaling enables exquisitely tunable degradation kinetics. Technological applications of such purposely designed biomimetic systems are wide ranging and include the design of polymer systems for hydraulic fracturing, for biomedical applications, and for facilitating the recycling of mixed plastic wastes.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"74 6 1","pages":""},"PeriodicalIF":5.2000,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c02241","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}

引用次数: 0

Abstract

Biological systems often involve cascading molecular signals; for example, blood coagulation involves a cascade of serial and parallel reactions catalyzed by enzymes. The present study draws inspiration from such complex biological systems to demonstrate, through a simple example, the purposeful design of a cascade system that enables control over polymer degradation kinetics. Micron size fibers of polylactide (PLA), cellulose acetate (CA), and their mixtures are subjected to hydrolysis at varying temperatures. Cleavage of the PLA produces an organic acid functional group that catalyzes the CA hydrolysis, thus demonstrating the use of synthetic molecular signaling. Furthermore, the presence of CA inhibits the degradation of PLA thereby demonstrating molecular feedback, another hallmark of biological molecular cascades. The parallel reaction cascade causes the hydrolysis rate constant for CA to increase 3.1 times compared to CA alone (from 5.7 × 10^–4 to 1.78 × 10^–3 L² mol^–2 h^–1 at 125 °C); furthermore, due to molecular feedback, the hydrolysis rate constant for PLA decreases by 21% (from 2.40 × 10^–3 to 1.90 × 10^–3 L² mol^–2 h^–1). The results demonstrate that synthetic signaling enables exquisitely tunable degradation kinetics. Technological applications of such purposely designed biomimetic systems are wide ranging and include the design of polymer systems for hydraulic fracturing, for biomedical applications, and for facilitating the recycling of mixed plastic wastes.

Abstract Image

查看原文本刊更多论文

仿生化学催化级联─可降解聚合物体系分子设计的新策略

生物系统通常包含级联分子信号；例如，血液凝固涉及一系列由酶催化的连续平行反应。本研究从这种复杂的生物系统中获得灵感，通过一个简单的例子来证明，一个有目的的级联系统设计能够控制聚合物降解动力学。微米级的聚乳酸纤维（PLA）、醋酸纤维素（CA）及其混合物在不同温度下被水解。PLA的裂解产生一个有机酸官能团，催化CA水解，从而证明了合成分子信号的使用。此外，CA的存在抑制了PLA的降解，从而证明了分子反馈，这是生物分子级联的另一个标志。平行级联反应使CA的水解速率常数比单独使用CA时提高了3.1倍（在125℃时从5.7 × 10-4增加到1.78 × 10-3 L2 mol-2 h-1）；此外，由于分子反馈，PLA的水解速率常数降低了21%（从2.40 × 10-3降低到1.90 × 10-3 L2 mol-2 h-1）。结果表明，合成信号能够精确地调节降解动力学。这种刻意设计的仿生系统的技术应用范围很广，包括用于水力压裂、生物医学应用和促进混合塑料废物回收的聚合物系统的设计。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.