Multiscale structural and rheological features of colloidal low-methoxyl pectin solutions and calcium-induced sol–gel transition

Abstract

The multiscale structural and rheological features of a series of dilute and semidilute low-methoxyl (LM) pectin solutions and a representative pectin/calcium sol–gel sample were systematically explored using a comprehensive combination of dynamic (DLS) and static light/X-ray scattering (SALS/SLS/SAXS), rheology, and microscopy (OM/SEM) characterizations. The study focused on the rarely explored colloidal aspect of LM pectin solutions and sol–gel transition, in contrast to the polymeric features extensively explored in previous studies. A highly uniform colloid-like, micron-sized agglomerate species was revealed in dilute solutions, with a progressively increased degree of flocculation in the semidilute regime (≥1.5 wt%). The agglomerate species in these solutions was resolved to be formed by random associations of individual pectin chains (L = 30 nm, r = 0.4 nm). Adding a critical amount of Ca²⁺ (10 wt%) to a semidilute solution (2 wt%) has an instant and pronounced effect of enhancing the agglomerate flocculation and resulting in a locally jammed state. Meanwhile, the agglomerate interior underwent microstructural transformation, leading to hierarchical structures defined by intermediate (spherical) aggregate species (R_g,aggregate ≈ 150 nm) and its packing cylindrical bundle (d ≈ 4 nm) composed of five pectin chains. Novel rheological features observed during the LM pectin/Ca²⁺ sol–gel transition include the following: the dynamic modulus data exhibited excellent TTS (gelling time/relaxation time superposition) as previously observed for weakly attractive colloidal gels. Three yield points were noticed for the final gel sample, suggested to mark the bond breaking of the cluster network, cage breaking of the resulting jammed flocculates, and, eventually, breakup of a flocculate into smaller agglomerates with increasing stress amplitude.