A Unique Temperature‐Induced Reverse Supramolecular Chirality‐Assisted Gel‐to‐Gel Transition

Author:

Duraisamy Dinesh Kumar12,Reddy Samala Murali Mohan1,Saveri Puchalapalli3,Deshpande Abhijit P.3,Shanmugam Ganesh12ORCID

Affiliation:

1. Organic & Bioorganic Chemistry Laboratory Council of Scientific and Industrial Research (CSIR) – Central Leather Research Institute (CLRI) Adyar Chennai 600020 India

2. Academy of Scientific and Innovative Research (AcSIR) Ghaziabad 201002 India

3. Department of Chemical Engineering Indian Institute of Technology Madras Chennai 600036 India

Abstract

AbstractSupramolecular hydrogels typically undergo a gel‐to‐sol transition with heat, as intermolecular interactions within the gel weaken. Although gel‐to‐gel transitions during heating are rare, they may occur due to minor rearrangements caused by thermal forces in the supramolecular self‐assembled structure. Here, an unprecedented temperature‐induced gel‐to‐gel transition assisted by supramolecular chiral inversion in a hydrogel system is presented. The transition results from a left‐handed M‐type helix to a right‐handed P‐type helix, attributed to the π‐system‐conjugated amino acid, l‐Tyrosine (Fm‐ l‐Tyr). Upon solvent dilution, Fm‐l‐Tyr induces translucent hydrogel formed by entangled fibers with a kinetically stable left‐handed M‐type supramolecular helix. At 70 °C, hydrogel transforms into an opaque gel with a reverse supramolecular chirality yielding a thermodynamically stable right‐handed P‐type helix. Supramolecular chiral inversion is substantiated by two chiroptical methods. This unique gel‐to‐gel transition, accompanied by chiral inversion, is anticipated to attract attention, especially for applications sensitive to chirality.

Funder

Central Leather Research Institute

Publisher

Wiley

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