Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039, India.
Chemistry. 2023 Apr 25;29(24):e202203820. doi: 10.1002/chem.202203820. Epub 2023 Mar 20.
An intricate synergism between multiple biochemical processes and physical conditions determines the formation and function of various biological self-assemblies. Thus, a complex set of variables dictate the far-from-equilibrium nature of these biological assemblies. Mimicking such systems synthetically is a challenging task. We report multi-stimuli responsive transient coacervation of an aldehyde-appended polymer and a short peptide. The coacervates are formed by the disulphide linkages between the peptide molecules and the imine bond between the polymer and the peptide. Imines are susceptible to pH changes and the disulphide bonds can be tuned by oxidation/reduction processes. Thus, the coacervation is operational only under the combined effect of appropriate pH and oxidative conditions. Taking advantage of these facts, the coacervates are transiently formed under a pH cycle (urea-urease/gluconolactone) and a non-equilibrium redox cycle (TCEP/H O ). Importantly, the system showed high adaptability toward environmental changes. The transient existence of the coacervates can be generated without any apparent change in size and shape within the same system through the sequential application of the above-mentioned nonequilibrium reaction cycles. Additionally, the coacervation allows for efficient encapsulation/stabilisation of proteins. Thus, the system has the potential to be used for protein/drug delivery purposes in the future.
多种生化过程和物理条件之间的复杂协同作用决定了各种生物自组装体的形成和功能。因此，一系列复杂的变量决定了这些生物组装体的远离平衡态性质。在合成上模拟这样的系统是一项具有挑战性的任务。我们报告了醛基化聚合物和短肽的多刺激响应瞬态凝聚。凝聚物是通过肽分子之间的二硫键和聚合物与肽之间的亚胺键形成的。亚胺易受 pH 值变化的影响，而二硫键可以通过氧化/还原过程进行调节。因此，凝聚作用仅在适当的 pH 值和氧化条件的共同作用下才能发挥作用。利用这些事实，凝聚物在 pH 循环（脲酶/葡萄糖酸内酯）和非平衡氧化还原循环（TCEP/H O ）下短暂形成。重要的是，该系统对环境变化表现出高度的适应性。通过顺序应用上述非平衡反应循环，可以在同一系统内不改变大小和形状的情况下产生凝聚物的短暂存在。此外，凝聚作用允许有效地封装/稳定蛋白质。因此，该系统有可能在未来用于蛋白质/药物递送目的。
