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Radical ring-opening polymerization of sustainably-derived thionoisochromanone

We present the synthesis, characterization and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone to readily homopolymerize under free radical conditions without the presence of a...

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Autores principales: Prebihalo, Emily A., Luke, Anna M., Reddi, Yernaidu, LaSalle, Christopher J., Shah, Vijay M., Cramer, Christopher J., Reineke, Theresa M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10231309/
https://www.ncbi.nlm.nih.gov/pubmed/37265728
http://dx.doi.org/10.1039/d2sc06040j
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author Prebihalo, Emily A.
Luke, Anna M.
Reddi, Yernaidu
LaSalle, Christopher J.
Shah, Vijay M.
Cramer, Christopher J.
Reineke, Theresa M.
author_facet Prebihalo, Emily A.
Luke, Anna M.
Reddi, Yernaidu
LaSalle, Christopher J.
Shah, Vijay M.
Cramer, Christopher J.
Reineke, Theresa M.
author_sort Prebihalo, Emily A.
collection PubMed
description We present the synthesis, characterization and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone to readily homopolymerize under free radical conditions without the presence of a dormant comonomer or repeated initiation. Even more, the resulting polymer is fully degradable under mild, basic conditions. Computations providing molecular-level insights into the mechanistic and energetic details of polymerization identified a unique S,S,O-orthoester intermediate that leads to a sustained chain-end. This sustained chain-end allowed for the synthesis of a block copolymer of TIC and styrene under entirely free radical conditions without explicit radical control methods such as reversible addition–fragmentation chain transfer polymerization (RAFT). We also report the statistical copolymerization of ring-retained TIC and styrene, confirmed by elemental analysis and energy-dispersive X-ray spectroscopy (EDX). Computations into the energetic details of copolymerization indicate kinetic drivers for ring-retaining behavior. This work provides the first example of a sustainable feedstock for rROP and provides the field with the first six-membered monomer susceptible to rROP, expanding the monomer scope to aid our fundamental understanding of thionolactone rROP behavior.
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spelling pubmed-102313092023-06-01 Radical ring-opening polymerization of sustainably-derived thionoisochromanone Prebihalo, Emily A. Luke, Anna M. Reddi, Yernaidu LaSalle, Christopher J. Shah, Vijay M. Cramer, Christopher J. Reineke, Theresa M. Chem Sci Chemistry We present the synthesis, characterization and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone to readily homopolymerize under free radical conditions without the presence of a dormant comonomer or repeated initiation. Even more, the resulting polymer is fully degradable under mild, basic conditions. Computations providing molecular-level insights into the mechanistic and energetic details of polymerization identified a unique S,S,O-orthoester intermediate that leads to a sustained chain-end. This sustained chain-end allowed for the synthesis of a block copolymer of TIC and styrene under entirely free radical conditions without explicit radical control methods such as reversible addition–fragmentation chain transfer polymerization (RAFT). We also report the statistical copolymerization of ring-retained TIC and styrene, confirmed by elemental analysis and energy-dispersive X-ray spectroscopy (EDX). Computations into the energetic details of copolymerization indicate kinetic drivers for ring-retaining behavior. This work provides the first example of a sustainable feedstock for rROP and provides the field with the first six-membered monomer susceptible to rROP, expanding the monomer scope to aid our fundamental understanding of thionolactone rROP behavior. The Royal Society of Chemistry 2023-05-09 /pmc/articles/PMC10231309/ /pubmed/37265728 http://dx.doi.org/10.1039/d2sc06040j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Prebihalo, Emily A.
Luke, Anna M.
Reddi, Yernaidu
LaSalle, Christopher J.
Shah, Vijay M.
Cramer, Christopher J.
Reineke, Theresa M.
Radical ring-opening polymerization of sustainably-derived thionoisochromanone
title Radical ring-opening polymerization of sustainably-derived thionoisochromanone
title_full Radical ring-opening polymerization of sustainably-derived thionoisochromanone
title_fullStr Radical ring-opening polymerization of sustainably-derived thionoisochromanone
title_full_unstemmed Radical ring-opening polymerization of sustainably-derived thionoisochromanone
title_short Radical ring-opening polymerization of sustainably-derived thionoisochromanone
title_sort radical ring-opening polymerization of sustainably-derived thionoisochromanone
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10231309/
https://www.ncbi.nlm.nih.gov/pubmed/37265728
http://dx.doi.org/10.1039/d2sc06040j
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