4.7 Article

Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride through Regioselective Initiation of Cysteamine: A Direct Way toward Thiol-Capped Polypeptoids

Journal

MACROMOLECULES
Volume 51, Issue 12, Pages 4494-4501

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.8b00259

Keywords

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Funding

  1. National Natural Science Foundation of China [21674091, 21528402]
  2. Fundamental Research Funds for the Central Universities [2018QNA4057]

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Because of the high reactivity, N-carboxyanhydride (NCA) can be initiated by the thiol group. On the contrary, N-thiocarboxyanhydride (NTA) is more stable and is able to tolerate it. Herein, we apply cysteamine as a regioselective initiator for ring-opening polymerization (ROP) of N-substituted glycine N-thiocarboxyanhydride (NNTA) to synthesize well-defined thiol-capped polypeptoids. ROPs of sarcosine NTA (Sar-NTA) and N-ethylglycine NTA (NEG-NTA) are well controlled when [M]/[I] <= 100 with high yields (>87.5%) producing polypeptoids with designable molecular weights and low polydispersity indices (<1.2). All the polypeptoid chains contain a thiol end group, which is confirmed by NMR analyses, MALDI-ToF MS spectra, and Ellman's assay. Through radical-mediated thiol-ene reaction with styrene, all the thiol chain ends are transferred to oligostyrene, revealing the convenience of further modification. Benefiting from the thiol-ene click chemistry, thiol-capped polysarcosine (PSar) and poly(N-ethylglycine) (PNEG) are promising candidates to replace PEG for their nontoxicity and biocompatibility.

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