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Correlation of Enzymatic Depolymerization Rates with the Structure of Polyethylene-Like Long-Chain Aliphatic Polyesters
ACS Macro Letters ( IF 5.1 ) Pub Date : 2024-09-11 , DOI: 10.1021/acsmacrolett.4c00463 Simon T Schwab 1 , Leonie Y Bühler 1 , David Schleheck 2 , Taylor F Nelson 1 , Stefan Mecking 1
ACS Macro Letters ( IF 5.1 ) Pub Date : 2024-09-11 , DOI: 10.1021/acsmacrolett.4c00463 Simon T Schwab 1 , Leonie Y Bühler 1 , David Schleheck 2 , Taylor F Nelson 1 , Stefan Mecking 1
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Long-chain aliphatic polyesters are emerging sustainable materials that exhibit polyethylene-like properties while being amenable to chemical recycling and biodegradation. However, varying polyester chemical structures results in markedly different degradation rates, which cannot be predicted from commonly correlated bulk polyester properties, such as polymer melting temperature. To elucidate these structure–degradability relationships, long-chain polyesters varying in their monomer composition and crystallinity were subjected to enzymatic hydrolysis, the rates of which were quantified via detection of formed monomers. Copolymers with poorly water-soluble, long-chain diol monomers (e.g., 1,18-octadecanediol) demonstrated strongly reduced depolymerization rates compared to copolymers with shorter chain length diol monomers. This was illustrated by, e.g., the 20× faster hydrolysis of PE-4,18, consisting of 1,4-butanediol and 1,18-octadecanedicarboxylic acid monomers, relative to PE-18,4. The insoluble long-chain diol monomer released upon hydrolysis was proposed to remain attached to the bulk polymer surface, decreasing the accessibility of the remaining ester bonds to enzymes for further hydrolysis. Tuning of polyester crystallinity via the introduction of branched monomers led to variable hydrolysis rates, which increased by an order of magnitude when crystallinity decreased from 72% to 45%. The results reported enables the informed design of polyester structures with balanced material properties and amenability to depolymerization.
中文翻译：
酶解聚速率与类聚乙烯长链脂肪族聚酯结构的相关性
长链脂肪族聚酯是新兴的可持续材料，具有类似聚乙烯的特性，同时易于化学回收和生物降解。然而，不同的聚酯化学结构会导致明显不同的降解速率，这无法从通常相关的块状聚酯特性（如聚合物熔融温度）中预测。为了阐明这些结构-降解性关系，对其单体组成和结晶度不同的长链聚酯进行酶水解，其速率通过检测形成的单体来量化。与具有短链二醇单体的共聚物相比，具有水溶性差的长链二醇单体（例如 1,18-十八烷二醇）的共聚物表现出显著降低的解聚速率。例如，PE-4,18 的水解速度提高了 20×，相对于 PE-18,4，PE-4,18 由 1,4-丁二醇和 1,18-十八烷二羧酸单体组成。水解时释放的不溶性长链二醇单体被认为保持附着在块状聚合物表面，从而降低了剩余酯键对酶进一步水解的可及性。通过引入支链单体来调整聚酯结晶度导致水解速率可变，当结晶度从 72% 降低到 45% 时，水解速率增加了一个数量级。报告的结果有助于设计具有平衡材料特性和解聚适应性的聚酯结构。
更新日期：2024-09-11
中文翻译：
酶解聚速率与类聚乙烯长链脂肪族聚酯结构的相关性
长链脂肪族聚酯是新兴的可持续材料，具有类似聚乙烯的特性，同时易于化学回收和生物降解。然而，不同的聚酯化学结构会导致明显不同的降解速率，这无法从通常相关的块状聚酯特性（如聚合物熔融温度）中预测。为了阐明这些结构-降解性关系，对其单体组成和结晶度不同的长链聚酯进行酶水解，其速率通过检测形成的单体来量化。与具有短链二醇单体的共聚物相比，具有水溶性差的长链二醇单体（例如 1,18-十八烷二醇）的共聚物表现出显著降低的解聚速率。例如，PE-4,18 的水解速度提高了 20×，相对于 PE-18,4，PE-4,18 由 1,4-丁二醇和 1,18-十八烷二羧酸单体组成。水解时释放的不溶性长链二醇单体被认为保持附着在块状聚合物表面，从而降低了剩余酯键对酶进一步水解的可及性。通过引入支链单体来调整聚酯结晶度导致水解速率可变，当结晶度从 72% 降低到 45% 时，水解速率增加了一个数量级。报告的结果有助于设计具有平衡材料特性和解聚适应性的聚酯结构。
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