Zhou, Huaxing and Schoen, Eva-Maria and Wang, Muzhou and Glassman, Matthew J. and Liu, Jenny and Zhong, Mingjiang and Diaz, David Diaz and Olsen, Bradley D. and Johnson, Jeremiah A. (2014) Crossover Experiments Applied to Network Formation Reactions: Improved Strategies for Counting Elastically Inactive Molecular Defects in PEG Gels and Hyperbranched Polymers. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136 (26). pp. 9464-9470. ISSN 0002-7863,
Full text not available from this repository. (Request a copy)Abstract
Molecular defects critically impact the properties of materials. Here we introduce a paradigm called "isotopic labeling disassembly spectrometry" (ILDaS) that facilitates unprecedented precise experimental correlations between elastically inactive network defects (dangling chains and primary loops) and network formation kinetics and precursor structure. ILDaS is inspired by classical crossover experiments, which are often used to interrogate whether a reaction mechanism proceeds via an inter- or intramolecular pathway. We show that if networks are designed from labeled bifunctional monomers that transfer their labels to multifunctional junctions upon network formation, then the extent of junction labeling correlates directly with the number of dangling chains and cyclic imperfections within the network. We demonstrate two complementary ILDaS approaches that enable defect measurements with short analysis times, low cost, and synthetic versatility applicable to a broad range of network materials including polydisperse polymer precursors. The results will spur new experimental and theoretical investigations into the interplay between polymer network structure and properties.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MULTIPLE-QUANTUM NMR; MONTE-CARLO SIMULATIONS; MODEL NETWORKS; INTRAMOLECULAR REACTION; POLYURETHANE FORMATION; PROTEIN HYDROGELS; PRIMARY LOOPS; GELATION; CYCLIZATION; CHEMISTRY; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Arbeitskreis Prof. Dr. David Díaz Díaz |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 04 Oct 2019 12:42 |
| Last Modified: | 04 Oct 2019 12:42 |
| URI: | https://pred.uni-regensburg.de/id/eprint/9898 |
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