O'Neill, Robert T and Boulatov, Roman 
ORCID: 0000-0002-7601-4279
(2023)
Experimental quantitation of molecular conditions responsible for flow-induced polymer mechanochemistry.
NATURE CHEMISTRY, 15 (9).
1214-+.
|
Text
nchem22102131Final.pdf - Author Accepted Manuscript Download (408kB) | Preview |
Abstract
Fragmentation of macromolecular solutes in rapid flows is of considerable fundamental and practical importance. The sequence of molecular events preceding chain fracture is poorly understood, because such events cannot be visualized directly but must be inferred from changes in the bulk composition of the flowing solution. Here we describe how analysis of same-chain competition between fracture of a polystyrene chain and isomerization of a chromophore embedded in its backbone yields detailed characterization of the distribution of molecular geometries of mechanochemically reacting chains in sonicated solutions. In our experiments the overstretched (mechanically loaded) chain segment grew and drifted along the backbone on the same timescale as, and in competition with, the mechanochemical reactions. Consequently, only <30% of the backbone of a fragmenting chain is overstretched, with both the maximum force and the maximum reaction probabilities located away from the chain centre. We argue that quantifying intrachain competition is likely to be mechanistically informative for any flow fast enough to fracture polymer chains.
| Item Type: | Article |
|---|---|
| Divisions: | Faculty of Science and Engineering > School of Physical Sciences |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 04 Sep 2023 08:24 |
| Last Modified: | 10 Jan 2024 02:30 |
| DOI: | 10.1038/s41557-023-01266-2 |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3172492 |
Dimensions
Dimensions
