Inverse Thermoreversible Mechanical Stiffening and Birefringence in a Methylcellulose/Cellulose Nanocrystal Hydrogel

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Hynninen , V , Hietala , S , McKee , J R , Murtomäki , L , Rojas , O J , Ikkala , O & Nonappa , N V 2018 , ' Inverse Thermoreversible Mechanical Stiffening and Birefringence in a Methylcellulose/Cellulose Nanocrystal Hydrogel ' , Biomacromolecules , vol. 19 , no. 7 , pp. 2795-2804 . https://doi.org/10.1021/acs.biomac.8b00392

Title: Inverse Thermoreversible Mechanical Stiffening and Birefringence in a Methylcellulose/Cellulose Nanocrystal Hydrogel
Author: Hynninen, Ville; Hietala, Sami; McKee, Jason R.; Murtomäki, Lasse; Rojas, Orlando J.; Ikkala, Olli; Nonappa, [No Value]
Contributor: University of Helsinki, Department of Chemistry
Date: 2018-07
Language: eng
Number of pages: 10
Belongs to series: Biomacromolecules
ISSN: 1525-7797
URI: http://hdl.handle.net/10138/301161
Abstract: We show that composite hydrogels comprising methyl cellulose (MC) and cellulose nanocrystal (CNC) colloidal rods display a reversible and enhanced rheological storage modulus and optical birefringence upon heating, i.e., inverse thermoreversibility. Dynamic rheology, quantitative polarized optical microscopy, isothermal titration calorimetry (ITC), circular dichroism (CD), and scanning and transmission electron microscopy (SEM and TEM) were used for characterization. The concentration of CNCs in aqueous media was varied up to 3.5 wt % (i.e, keeping the concentration below the critical aq concentration) while maintaining the MC aq concentration at 1.0 wt %. At 20 degrees C, MC/CNC underwent gelation upon passing the CNC concentration of 1.5 wt %. At this point, the storage modulus (G') reached a plateau, and the birefringence underwent a stepwise increase, thus suggesting a percolative phenomenon. The storage modulus (G') of the composite gels was an order of magnitude higher at 60 degrees C compared to that at 20 degrees C. ITC results suggested that, at 60 degrees C, the CNC rods were entropically driven to interact with MC chains, which according to recent studies collapse at this temperature into ring-like, colloidal-scale persistent fibrils with hollow cross-sections. Consequently, the tendency of the MC to form more persistent aggregates promotes the interactions between the CNC chiral aggregates towards enhanced storage modulus and birefringence. At room temperature, ITC shows enthalpic binding between CNCs and MC with the latter comprising aqueous, molecularly dispersed polymer chains that lead to looser and less birefringent material. TEM, SEM, and CD indicate CNC chiral fragments within a MC/CNC composite gel. Thus, MC/CNC hybrid networks offer materials with tunable rheological properties and access to liquid crystalline properties at low CNC concentrations.
Subject: ALGINATE NANOCOMPOSITE FIBERS
CELLULOSE NANOCRYSTALS
FIBRILLAR STRUCTURE
METHYL CELLULOSE
PHASE-SEPARATION
IONIC-STRENGTH
IMAGE-ANALYSIS
SUSPENSIONS
FILMS
GELATION
116 Chemical sciences
221 Nano-technology
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