Enhanced Mechanical and Thermal Strength in Mixed-Enantiomers-Based Supramolecular Gel

• Published in: Langmuir Vol. 34; no. 43; pp. 12957 - 12967
• Main Authors: Tómasson, Daníel Arnar, Ghosh, Dipankar, Kržišnik, Zala, Fasolin, Luiz Henrique, Vicente, António A, Martin, Adam D, Thordarson, Pall, Damodaran, Krishna K
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 30.10.2018
• Subjects: Science & Technology
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/acs.langmuir.8b02729

Mixing supramolecular gels based on enantiomers leads to re-arrangement of gel fibers at the molecular level, which results in more favorable packing and tunable properties. Bis­(urea) compounds tagged with a phenylalanine methyl ester in racemic and enantiopure forms were synthesized. Both enantiopure and racemate compounds formed gels in a wide range of solvents and the racemate (1-rac) formed a stronger gel network compared with the enantiomers. The gel (1R+1S) obtained by mixing equimolar amount of enantiomers (1R and 1S) showed enhanced mechanical and thermal stability compared to enantiomers and racemate gels. The preservation of chirality in these compounds was analyzed by circular dichroism and optical rotation measurements. Analysis of the scanning electron microscopy (SEM) and atomic force microscopy (AFM) images revealed that the network in the mixed gel is a combination of enantiomers and racemate fibers, which was further supported by solid-state NMR. The analysis of the packing in xerogels by solid-state NMR spectra and the existence of twisted-tape morphology in SEM and AFM images confirmed the presence of both self-sorted and co-assembled fibers in mixed gel. The enhanced thermal and mechanical strength may be attributed to the enhanced intermolecular forces between the racemate and the enantiomer and the combination of both self-sorted and co-assembled enantiomers in the mixed gel.