Fine-Tuning Crystallization-Induced Gelation in Amphiphilic Double-Brush Polymers

Bej, S and Dhayani, A and Vemula, P and Ramakrishnan, S (2021) Fine-Tuning Crystallization-Induced Gelation in Amphiphilic Double-Brush Polymers. In: Langmuir, 37 (5). pp. 1788-1798.

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Abstract

A series of amphiphilic double-brush polymers based on itaconate diesters were synthesized with the objective of tailoring the thermal and mechanical properties of hydrogels formed by them; the amphiphilic itaconate diesters carried an MPEG350 segment and an alkyl chain, whose length was varied from C12 to C18. As was reported by us earlier (Macromolecules 2017, 50, 5004), the formation of the hydrogel was due to the crystallization of alkyl segments, as confirmed by the match of the rheological gel-to-sol transition with that of differential scanning calorimetry melting transition of the gel. In an effort to fine-tune the hydrogel-melting temperature and its strength, we varied the length of the alkyl chain length while keeping the hydrophilic segment length constant at MPEG350; apart from varying the alkyl chain length, an oxyethylene spacer was incorporated to examine the effect of decoupling the alkyl side-chain crystallization from the backbone. With these modifications, the melting temperature of the hydrogel was varied from 30 to 56 °C. Likewise, the strength of the hydrogel, as reflected by its storage modulus, varied from around 220 to 970 Pa; the softer gels typically exhibited a slightly larger critical shear strain beyond which the gel transformed into a sol. The thermal and shear-induced gel-to-sol transitions were reversible; however, the modulus after the shear-induced transition did not fully recover instantly (a 80), suggesting that the formation of the extended gel network is slow. Further fine-tuning could be achieved by copolymerization of two different amphiphilic itaconate monomers, namely, those with C16 and C18, which provided an intermediate gel-melting temperature; however, co-gelation of the two preformed homopolymer gels yielded two distinct gel-melting transitions. Thus, this class of tuneable stimuli-responsive polymeric hydrogels prepared from biobenign components, namely, itaconic acid, 1-alkanols, and MPEGs, could serve as potential candidates for biomedical applications. ©

Item Type:	Journal Article
Publication:	Langmuir
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Keywords:	Chain length; Dendrimers; Differential scanning calorimetry; Gelation; Gels; Hydrogels; Medical applications; Melting point; Shear strain; Sols, Alkyl chain lengths; Biomedical applications; Gel-melting temperatures; Hydrophilic segments; Melting transitions; Polymeric hydrogels; Shear induced transitions; Thermal and mechanical properties, Functional polymers
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	16 Feb 2023 10:22
Last Modified:	16 Feb 2023 10:22
URI:	https://eprints.iisc.ac.in/id/eprint/80525

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