MOE International Joint Research Laboratory on Synthetic Biology and Medicines, School of Biology and Biological Engineering, South China University of Technology, Guangzhou, 510006, P. R. China.
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore.
Nat Commun. 2023 Aug 26;14(1):5229. doi: 10.1038/s41467-023-40935-1.
Polymerization in living systems has become an effective strategy to regulate cell functions and behavior. However, the requirement of high concentrations of monomers, the existence of complicated intracorporal interferences, and the demand for extra external stimulations hinder their further biological applications. Herein, a nanocompartment-confined strategy that provides a confined and secluded environment for monomer enrichment and isolation is developed to achieve high polymerization efficiency, reduce the interference from external environment, and realize broad-spectrum polymerizations in living systems. For exogenous photopolymerization, the light-mediated free-radical polymerization of sodium 4-styrenesulfonate induces a 2.7-fold increase in the reaction rate with the protection of a confined environment. For endogenous hydrogen peroxide-responsive polymerization, p‑aminodiphenylamine hydrochloride embedded in a nanocompartment not only performs a 6.4-fold higher reaction rate than that of free monomers, but also activates an effective second near-infrared photoacoustic imaging-guided photothermal immunotherapy at tumor sites. This nanocompartment-confined strategy breaks the shackles of conventional polymerization, providing a universal platform for in vivo synthesis of polymers with diverse structures and functions.
在活体系中聚合已成为调控细胞功能和行为的有效策略。然而，单体的高浓度要求、体内复杂的相互干扰以及对外界刺激的额外需求阻碍了它们在进一步的生物应用。在此，开发了一种纳米隔间限制策略，为单体的富集和隔离提供了一个受限和隔离的环境，以实现高聚合效率、减少外部环境的干扰，并在活体系中实现广谱聚合。对于外源性光聚合，受保护的受限环境可使 4-苯乙烯磺酸钠的光介导自由基聚合的反应速率提高 2.7 倍。对于内源性过氧化氢响应聚合，嵌入纳米隔间的盐酸对氨基二苯胺不仅比游离单体的反应速率高 6.4 倍，而且还能在肿瘤部位激活有效的第二次近红外光声成像引导光热免疫治疗。这种纳米隔间限制策略打破了传统聚合的束缚，为体内合成具有多种结构和功能的聚合物提供了一个通用平台。
