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Strategies for the Mechanically Triggered Release of Small Molecules


Husic, Corey Christopher (2023) Strategies for the Mechanically Triggered Release of Small Molecules. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/0add-6n09.


The development of force-responsive molecules called mechanophores is a central component of the field of polymer mechanochemistry. Mechanophores enable the design and fabrication of polymers for a variety of applications ranging from sensing to self-healing materials. Nevertheless, an insufficient understanding of structure–activity relationships limits experimental development, and thus computation is necessary to guide structural design. Herein, we use the constrained geometries simulate external force (CoGEF) method to evaluate a library of covalent mechanophores using density functional theory (DFT). We use these results to identify key parameters that accurately predict experimentally determined mechanochemical reactivity.

Polymers that release small molecules upon external stimulation are promising for a wide range of applications, including sensing, catalysis, and drug delivery. Mechanophores are uniquely suited to enable molecular release with excellent selectivity and control. We have designed a general platform for mechanically gated small molecule release that leverages a latent 2-furylcarbinol species masked as a mechanically labile Diels–Alder adduct. Here, we describe the computationally guided design of metastable 2-furylcarbinol derivatives through the prediction of activation energy values and construction of structure–activity relationships. These results enable a molecular release platform suitable for a wide scope of cargo molecules across a broad range of chemical environments.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:polymer mechanochemistry, mechanochemistry, organic chemistry, physical organic chemistry, small molecule release, constrained geometries simulate external force
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Robb, Maxwell J.
Thesis Committee:
  • Reisman, Sarah E. (chair)
  • Robb, Maxwell J.
  • Nelson, Hosea M.
  • Ismagilov, Rustem F.
Defense Date:21 April 2023
Record Number:CaltechTHESIS:04242023-215416950
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for chapter 1 of article adapted for chapter 2 of article adapted for chapter 2 adapted for chapter 3
Husic, Corey Christopher0000-0003-0248-7484
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15142
Deposited By: Corey Husic
Deposited On:26 May 2023 22:16
Last Modified:27 Nov 2023 19:54

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