Controlled Synthesis and Enzyme-Induced Hydrogelation of Poly(l-phosphotyrosine)s via Ring-Opening Polymerization of α-Amino Acid N-Carboxyanhydride

Yunlong Sun; Yingqin Hou; Xuhao Zhou; Jingsong Yuan; Jingyu Wang; Hua Lu

doi:10.1021/acsmacrolett.5b00429

Controlled Synthesis and Enzyme-Induced Hydrogelation of Poly(l-phosphotyrosine)s via Ring-Opening Polymerization of α-Amino Acid N-Carboxyanhydride

ACS Macro Lett. 2015 Sep 15;4(9):1000-1003. doi: 10.1021/acsmacrolett.5b00429. Epub 2015 Aug 27.

Authors

Yunlong Sun¹, Yingqin Hou¹, Xuhao Zhou¹, Jingsong Yuan¹, Jingyu Wang¹, Hua Lu¹

Affiliation

¹ Beijing National Laboratory for Molecular Sciences, Center for Soft Matter Science and Engineering, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, People's Republic of China.

PMID: 35596435
DOI: 10.1021/acsmacrolett.5b00429

Abstract

Tyrosine phosphorylation is an important post-translational modification (PTM) that governs numerous cellular processes. Constructing synthetic phosphotyrosine polypeptides helps expand the horizon of our understanding regarding the fundamental aspects and biological consequences of this PTM. Here, we report the synthesis of a novel monomer, O-diethylphospho l-tyrosine N-carboxyanhydride (pOEt TyrNCA), whose ring-opening polymerization (ROP) mediated by hexamethyldisilazane (HMDS) leads to poly(l-phosphotyrosine) (P(pTyr)) derivatives with controllable molecular weights and narrow molecular-weight distributions. Moreover, P(pTyr)₁₅-b-PEG-b-P(pTyr)₁₅ triblock copolymer (TBP15) undergo sol-gel transition in the presence of alkaline phosphatase. The stiffness of the gel is reinforced by the addition of horseradish peroxidase and hydrogen peroxide. These phosphotyrosine-mimicking polymers are realized for the first time by NCA polymerization and are promising materials for a variety of biological applications.