Cryopolymerization of 1,2-Dithiolanes for the Facile and Reversible Grafting-from Synthesis of Protein–Polydisulfide Conjugates

• DOI: 10.1021/jacs.9b12937
• Publication Date: 2020-01-13T17:42:15Z
• Authors: Jianhua Lu; Hao Wang; Ziyou Tian; Yingqin Hou; Hua Lu
• Keywords: Conjugate

Grafting-from (GF) is an important yet underdeveloped strategy toward protein–polymer conjugates. Here, we report a simple cryopolymerization method that enables highly efficient GF synthesis of cell-penetrating protein–polydisulfide Rapid and controlled ring-opening polymerization 1,2-dithiolanes under cryo-conditions can be initiated by proteins bearing reactive cysteine, owing to both favored thermodynamics augmented kinetics arising from frozen-induced high local concentration substrates. This applicable various wild-type or genetically engineered without the need chemical installation initiation group. The resulting conjugates reversibly degrafted mild conditions regenerate functional "native" in traceless fashion. These unique features make such useful applications as dynamic switch protein functions, cytosolic delivery therapeutics, purification. also potentially for situ growth other types polymers surface.