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Publication Details
AFRICAN RESEARCH NEXUS
SHINING A SPOTLIGHT ON AFRICAN RESEARCH
chemistry
Entropy driven chain effects on ligation chemistry
Chemical Science, Volume 6, No. 2, Year 2015
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Description
We report the investigation of fundamental entropic chain effects that enable the tuning of modular ligation chemistry - for example dynamic Diels-Alder (DA) reactions in materials applications - not only classically via the chemistry of the applied reaction sites, but also via the physical and steric properties of the molecules that are being joined. Having a substantial impact on the reaction equilibrium of the reversible ligation chemistry, these effects are important when transferring reactions from small molecule studies to larger or other entropically very dissimilar systems. The effects on the DA equilibrium and thus the temperature dependent degree of debonding (%debond) of different cyclopentadienyl (di-)functional poly(meth-)acrylate backbones (poly(methyl methacrylate), poly(iso-butyl methacrylate), poly(tert-butyl methacrylate), poly(iso-butyl acrylate), poly(n-butyl acrylate), poly(tert-butyl acrylate), poly(methyl acrylate) and poly(isobornyl acrylate)), linked via a difunctional cyanodithioester (CDTE) were examined via high temperature (HT) NMR spectroscopy as well as temperature dependent (TD) SEC measurements. A significant impact of not only chain mass and length with a difference in the degree of debonding of up to 30% for different lengths of macromonomers of the same polymer type but - remarkably - as well the chain stiffness with a difference in bonding degrees of nearly 20% for isomeric poly(butyl acrylates) is found. The results were predicted, reproduced and interpreted via quantum chemical calculations, leading to a better understanding of the underlying entropic principles. © The Royal Society of Chemistry 2015.
Authors & Co-Authors
Pahnke, Kai
Germany, Karlsruhe
Karlsruher Institut Für Technologie
Germany, Eggenstein-leopoldshafen
Karlsruher Institut Für Technologie, Campus Nord
Brandt, Josef
Germany, Dresden
Leibniz-institut Für Polymerforschung Dresden E.v.
Germany, Dresden
Technische Universität Dresden
Schweins, Ralf
France, Grenoble
Institut Laue-langevin
Schmidt, Friedrich Georg
Germany, Essen
Evonik Industries ag
Lederer, Albena
Germany, Dresden
Leibniz-institut Für Polymerforschung Dresden E.v.
Germany, Dresden
Technische Universität Dresden
Coote, Michelle L.
Unknown Affiliation
Barner-Kowollik, Christopher
Germany, Karlsruhe
Karlsruher Institut Für Technologie
Germany, Eggenstein-leopoldshafen
Karlsruher Institut Für Technologie, Campus Nord
Statistics
Citations: 32
Authors: 7
Affiliations: 6
Identifiers
Doi:
10.1039/c4sc02908a
ISSN:
20416520