Abstract A new class of degradable polymers—AABB-type polydepsipeptides (PDPs) composed of four building blocks—naturally occurring α-amino and α-hydroxy acids, fatty diol and dicarboxylic acid were synthesized for the first time. For the synthesis of novel PDPs, new diester diacids—O,O′-diacyl-bis-glycolic acids (DAGAs) were prepared by interaction of diacid chlorides with glycolic acid and then they were transformed into activated di-p-nitrophenyl esters (DAGN), which were further used in solution active polycondensation (SAP) as bis-electrophilic monomers. High-molecular-weight (Mw up to 66.5 kDa) AABB PDPs having film-forming properties were obtained by reacting activated diesters with two different bis-nucleophilic diester-diamine monomers—di-p-toluenesulfonic acid salts of bis-(l-phenylalanine)-1,6-hexylene diester, F6, and bis-(l-leucine)-1,6-hexylene diester, L6. The developed synthetic strategy was also found to be suitable for the synthesis of so called 3M poly(ester amide)s (3M PEAs) by SAP of the activated diesters with 1,6-hexanediamine (HDA). The suggested approach allows the synthesis of the functional AABB PDPs and 3M-type PEAs containing pendant functional groups (OH or COOH) suitable for subsequent modifications. Nonspecific in vitro degradation (hydrolysis) study of selected samples of AABB PDPs showed enhanced degradation rates compared to regular amino acid based PEAs. The new polymers are promising for various biomedical applications. Graphical Abstract

中文翻译：

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基于O,O'-二酰基-双-乙醇酸的AABB-聚缩肽、聚（酯酰胺）和功能聚合物的合成

摘要 首次合成了一类新的可降解聚合物——AABB 型聚缩肽（PDPs），由四个结构单元组成——天然存在的α-氨基和α-羟基酸、脂肪二醇和二羧酸。为了合成新型 PDP，通过二酰氯与乙醇酸的相互作用制备了新型二酯二酸——O,O'-二酰基-双乙醇酸 (DAGA)，然后将它们转化为活化的二对硝基苯酯 (DAGN)。 )，它们作为双亲电单体进一步用于溶液活性缩聚 (SAP)。具有成膜特性的高分子量（Mw 高达 66.5 kDa）AABB PDP 是通过将活化的二酯与两种不同的双亲核二酯二胺单体——双（l-苯丙氨酸的二对甲苯磺酸盐）反应获得的)-1,6-己烯二酯、F6和双-(l-亮氨酸)-1，6-己烯二酯，L6。还发现所开发的合成策略适用于通过活化二酯与 1,6-己二胺 (HDA) 的 SAP 合成所谓的 3M 聚（酯酰胺）（3M PEA）。建议的方法允许合成功能性 AABB PDP 和 3M 型 PEA，其中包含适用于后续修改的侧基官能团（OH 或 COOH）。对选定的 AABB PDP 样品进行的非特异性体外降解（水解）研究表明，与基于常规氨基酸的 PEA 相比，降解率更高。新聚合物有望用于各种生物医学应用。图形概要 建议的方法允许合成功能性 AABB PDP 和 3M 型 PEA，其中包含适用于后续修改的侧基官能团（OH 或 COOH）。对选定的 AABB PDP 样品进行的非特异性体外降解（水解）研究表明，与基于常规氨基酸的 PEA 相比，降解率更高。新聚合物有望用于各种生物医学应用。图形概要 建议的方法允许合成功能性 AABB PDP 和 3M 型 PEA，其中包含适用于后续修改的侧基官能团（OH 或 COOH）。对选定的 AABB PDP 样品进行的非特异性体外降解（水解）研究表明，与基于常规氨基酸的 PEA 相比，降解率更高。新聚合物有望用于各种生物医学应用。图形概要