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We report a synthetic route toward a family of functional COS/HS-releasing N-substituted N-thiocarboxyanhydrides (NTAs) with functionalities to accommodate popular conjugation reactions, including olefin cross metathesis, thiol-ene, and copper-catalyzed azide-alkyne cycloaddition. The N-substituted NTAs were attached to small molecules, polymers, and a protein to synthesize novel HS donors convergently. All conjugates showed sustained HS release kinetics.
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http://dx.doi.org/10.1021/acschembio.9b00248 | DOI Listing |
Biomacromolecules
September 2025
Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
To synthesize functional polypeptoids, the most straightforward strategy involves designing tailored amino acids to generate corresponding -substituted glycine -carboxyanhydrides (NNCAs) or -substituted glycine -thiocarboxyanhydrides (NNTAs). An alternative route is offered by postpolymerization modification. However, the potential method of modifying NNCA and NNTA monomers to produce functional polypeptoids has received scant attention.
View Article and Find Full Text PDFBiomacromolecules
April 2021
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China.
Polymerization of -substituted glycine -thiocarboxyanhydrides (NNTAs) is a promising pathway to prepare functional polypeptoids benefiting from their tolerance to nucleophilic impurities. However, controlled NNTA polymerization is hard to achieve in amide polar solvents, including ,-dimethylacetamide (DMAc), ,-dimethylformamide (DMF), and -methyl pyrrolidone (NMP), the only aprotic solvents for many biomacromolecules and polypeptoids. In the present work, we successfully achieve controlled NNTA polymerization in amide polar solvents by adding acetic acid as a promoter.
View Article and Find Full Text PDFACS Chem Biol
June 2019
Department of Chemistry , Virginia Tech , Blacksburg , Virginia 24061 , United States.
We report a synthetic route toward a family of functional COS/HS-releasing N-substituted N-thiocarboxyanhydrides (NTAs) with functionalities to accommodate popular conjugation reactions, including olefin cross metathesis, thiol-ene, and copper-catalyzed azide-alkyne cycloaddition. The N-substituted NTAs were attached to small molecules, polymers, and a protein to synthesize novel HS donors convergently. All conjugates showed sustained HS release kinetics.
View Article and Find Full Text PDFBiomacromolecules
November 2018
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering , Zhejiang University, Hangzhou 310027 , China.
Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization.
View Article and Find Full Text PDF