Using EPR spectroscopy as a unique probe of molecular-scale reorganization and solvation in self-assembled gel-phase materials

Caragheorgheopol, Agneta and Edwards, William and Hardy, John G. and Smith, David K. and Chechik, Victor (2014) Using EPR spectroscopy as a unique probe of molecular-scale reorganization and solvation in self-assembled gel-phase materials. Langmuir, 30 (30). pp. 9210-9218. ISSN 0743-7463

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Abstract

We describe the synthesis of spin-labeled bis-ureas which coassemble with bis-urea gelators and report on self-assembly as detected using electron paramagnetic resonance spectroscopy (EPR). Specifically, EPR detects the gel-sol transition and allows us to quantify how much spin-label is immobilized within the gel fibers and how much is present in mobile solvent pools-as controlled by temperature, gelator structure, and thermal history. EPR is also able to report on the initial self-assembly processes below the gelation threshold which are not macroscopically visible and appears to be more sensitive than NMR to intermediate-sized nongelating oligomeric species. By studying dilute solutions of gelator molecules and using either single or double spin-labels, EPR allows quantification of the initial steps of the hierarchical self-assembly process in terms of cooperativity and association constant. Finally, EPR enables us to estimate the degree of gel-fiber solvation by probing the distances between spin-labels. Comparison of experimental data against the predicted distances assuming the nanofibers are only composed of gelator molecules indicates a significant difference, which can be assigned to the presence of a quantifiable number of explicit solvent molecules. In summary, EPR provides unique data and yields powerful insight into how molecular-scale mobility and solvation impact on assembly of supramolecular gels.

Item Type:
Journal Article
Journal or Publication Title:
Langmuir
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/3100/3104
Subjects:
ID Code:
75373
Deposited By:
Deposited On:
09 Sep 2015 06:32
Refereed?:
Yes
Published?:
Published
Last Modified:
16 Nov 2020 03:56