Entropy-driven selectivity for chain scission: Where macromolecules cleave
Pahnke, Kai, Brandt, Josef, Gryn'ova, Ganna, Lin, Ching Y., Altintas, Ozcan, Schmidt, Friedrich G., Lederer, Albena, Coote, Michelle L., & Barner-Kowollik, Christopher (2016) Entropy-driven selectivity for chain scission: Where macromolecules cleave. Angewandte Chemie International Edition, 55(4), pp. 1514-1518.
We show that, all other conditions being equal, bond cleavage in the middle of molecules is entropically much more favored than bond cleavage at the end. Multiple experimental and theoretical approaches have been used to study the selectivity for bond cleavage or dissociation in the middle versus the end of both covalent and supramolecular adducts and the extensive implications for other fields of chemistry including, e.g., chain transfer, polymer degradation, and control agent addition are discussed. The observed effects, which are a consequence of the underlying entropic factors, were predicted on the basis of simple theoretical models and demonstrated via high-temperature (HT) NMR spectroscopy of self-assembled supramolecular diblock systems as well as temperature-dependent size-exclusion chromatography (TD SEC) of covalently bonded Diels–Alder step-growth polymers.
Impact and interest:
Citation counts are sourced monthly from and citation databases.
These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.
Citations counts from theindexing service can be viewed at the linked Google Scholar™ search.
|Item Type:||Journal Article|
|Keywords:||cycloadditions; entropic effects; polymers; supramolecular chemistry; thermodynamics|
|Divisions:||Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
|Copyright Owner:||Copyright 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim|
|Deposited On:||11 Aug 2016 23:19|
|Last Modified:||15 Aug 2016 00:08|
Repository Staff Only: item control page