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A Thermally Stable SO2-Releasing Mechanophore: Facile Activation, Single-Event Spectroscopy, and Molecular Dynamic Simulations

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    A Thermally Stable SO2-Releasing Mechanophore: Facile Activation, Single-Event Spectroscopy, and Molecular Dynamic Simulations
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    • Yunyan Sun
      Yunyan Sun
      Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
      Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
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      Orcidhttps://orcid.org/0000-0002-6846-531X
    • William J. Neary
      William J. Neary
      Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
      Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
      More by William J. Neary
      Orcidhttps://orcid.org/0000-0003-3933-1571
    • Xiao Huang
      Xiao Huang
      Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
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    • Tatiana B. Kouznetsova
      Tatiana B. Kouznetsova
      Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
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    • Tetsu Ouchi
      Tetsu Ouchi
      Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
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      Orcidhttps://orcid.org/0000-0002-4054-9028
    • Ilia Kevlishvili
      Ilia Kevlishvili
      Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
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      Orcidhttps://orcid.org/0000-0001-8133-4165
    • Kecheng Wang
      Kecheng Wang
      Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
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    • Yingying Chen
      Yingying Chen
      Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
      Department of Material Science and Engineering, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
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    • Heather J. Kulik*
      Heather J. Kulik
      Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
      Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-9342-0191
    • Stephen L. Craig*
      Stephen L. Craig
      Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0002-8810-0369
    • Jeffrey S. Moore*
      Jeffrey S. Moore
      Department of Chemistry, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
      Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana−Champaign, Urbana, Illinois 61801, United States
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-5841-6269
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 15, 10943–10952
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    https://doi.org/10.1021/jacs.4c02139
    Published April 6, 2024
    Copyright © 2024 American Chemical Society
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    Abstract

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    Polymers that release small molecules in response to mechanical force are promising candidates as next-generation on-demand delivery systems. Despite advancements in the development of mechanophores for releasing diverse payloads through careful molecular design, the availability of scaffolds capable of discharging biomedically significant cargos in substantial quantities remains scarce. In this report, we detail a nonscissile mechanophore built from an 8-thiabicyclo[3.2.1]octane 8,8-dioxide (TBO) motif that releases one equivalent of sulfur dioxide (SO2) from each repeat unit. The TBO mechanophore exhibits high thermal stability but is activated mechanochemically using solution ultrasonication in either organic solvent or aqueous media with up to 63% efficiency, equating to 206 molecules of SO2 released per 143.3 kDa chain. We quantified the mechanochemical reactivity of TBO by single-molecule force spectroscopy and resolved its single-event activation. The force-coupled rate constant for TBO opening reaches ∼9.0 s–1 at ∼1520 pN, and each reaction of a single TBO domain releases a stored length of ∼0.68 nm. We investigated the mechanism of TBO activation using ab initio steered molecular dynamic simulations and rationalized the observed stereoselectivity. These comprehensive studies of the TBO mechanophore provide a mechanically coupled mechanism of multi-SO2 release from one polymer chain, facilitating the translation of polymer mechanochemistry to potential biomedical applications.

    Copyright © 2024 American Chemical Society

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    • Detailed descriptions of synthetic procedures, experimental methods, ultrasonication characterizations, SMFS results, and computational details (PDF)

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    CCDC 2322909 and 2322911 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    This article is cited by 13 publications.

    1. Hang Zhang, Charles E. Diesendruck. Mechanochemical Retro-Diels–Alder–Heteroatom Radical Stabilization of a Two-Step Mechanism?. Macromolecules 2025, 58 (9) , 4819-4825. https://doi.org/10.1021/acs.macromol.5c00084
    2. Chengyuan Lv, Zipeng Li, Wenkai Liu, Mingwang Yang, Hua Zhang, Jiangli Fan, Xiaojun Peng. An Activatable Chemiluminescent Self-Reporting Sulfur Dioxide Donor for Inflammatory Response and Regulation of Gaseous Vasodilation. ACS Sensors 2025, 10 (2) , 1147-1154. https://doi.org/10.1021/acssensors.4c02986
    3. Cijun Zhang, Tatiana B. Kouznetsova, Boyu Zhu, Liam Sweeney, Max Lancer, Ivan Gitsov, Stephen L. Craig, Xiaoran Hu. Advancing the Mechanosensitivity of Atropisomeric Diarylethene Mechanophores through a Lever-Arm Effect. Journal of the American Chemical Society 2025, 147 (3) , 2502-2509. https://doi.org/10.1021/jacs.4c13480
    4. Hui Hu, Lvjiang Meng, Yang Zhou, Yujing Chen, Yecheng Zhou, Bin Xi, Yuanchao Li. Mechanochemical Release of 9,10-Diphenylanthracene via Flex-Activation of Its 1,4-Diels–Alder Adduct. ACS Macro Letters 2025, 14 (1) , 14-19. https://doi.org/10.1021/acsmacrolett.4c00766
    5. Xiao Huang, Ilia Kevlishvili, Stephen L. Craig, Heather J. Kulik. Force-Activated Spin-Crossover in Fe2+ and Co2+ Transition Metal Mechanophores. Inorganic Chemistry 2025, 64 (1) , 380-392. https://doi.org/10.1021/acs.inorgchem.4c04732
    6. Maggie Horst, Søren Holm, Leoš Valenta, Tatiana B. Kouznetsova, Jinghui Yang, Noah Z. Burns, Stephen L. Craig, Todd J. Martínez, Yan Xia. Fluorination Affects the Force Sensitivity and Nonequilibrium Dynamics of the Mechanochemical Unzipping of Ladderanes. Journal of the American Chemical Society 2024, 146 (47) , 32651-32659. https://doi.org/10.1021/jacs.4c11912
    7. Yunyan Sun, Fangbai Xie, Jeffrey S. Moore. The Restoring Force Triangle: A Mnemonic Device for Polymer Mechanochemistry. Journal of the American Chemical Society 2024, 146 (46) , 31702-31714. https://doi.org/10.1021/jacs.4c10346
    8. Yunyan Sun, Kecheng Wang, Xiao Huang, Shixuan Wei, Enrique Contreras, Prashant K. Jain, Luis M. Campos, Heather J. Kulik, Jeffrey S. Moore. Caged AIEgens: Multicolor and White Emission Triggered by Mechanical Activation. Journal of the American Chemical Society 2024, 146 (39) , 27117-27126. https://doi.org/10.1021/jacs.4c09926
    9. Anushree Mondal, Swastika Dey, Soumya Paul, Arnab Gupta, Priyadarsi De. Visible Light‐Triggered Precision SO 2 Release from Polymeric Nanomedicine for Cancer Therapy. Small 2025, 18 https://doi.org/10.1002/smll.202502727
    10. Deqiang Wang, Yifan Ge, Fengbiao Chen, Hairui Deng, Yang Liu, Yinjun Chen. The Design, Synthesis, and Characterization of Photochromic and Mechanochromic Functional Fibers. Macromolecular Rapid Communications 2025, 16 https://doi.org/10.1002/marc.202400979
    11. Justus P. Wesseler, James R. Hemmer, Christoph Weder, José Augusto Berrocal. Solid-state mechanochemical activation of anthracene–maleimide adducts: the influence of the polymer matrix. RSC Mechanochemistry 2025, 48 https://doi.org/10.1039/D5MR00026B
    12. Niamh Willis-Fox. In-situ monitoring of polymer mechanochemistry: what can be learned from small molecule systems. Frontiers in Chemistry 2024, 12 https://doi.org/10.3389/fchem.2024.1490847
    13. . Thermally Stable, Mechano-sensitive SO2-Releasing Polymer. Synfacts 2024, 0813. https://doi.org/10.1055/s-0043-1775231
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 15, 10943–10952
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.4c02139
    Published April 6, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

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