Analytical rheology as a tool for the structural investigation of citrus pectin

Rheological analysis of citrus pectin at pH 3 and 7 elucidates its structural dynamics, revealing distinct behaviors influenced by pH. At pH 3, pectin exhibits shear‐thinning, with solvent‐independent unified rheological profiles identifying three concentration regimes: 0.5%–1.5%, 2%–3%, and 3.5%–4%. These regimes, alongside Cox–Merz superpositions, outline the semi‐dilute (c*) and concentrated (c**) transitions at 1.5%–2% and 3%–3.5%, respectively. Moreover, a Morris equation exponent of 0.65 indicates flexible, mobility‐restricted macromolecules. Conversely, at pH 7, increased viscosities and Morris plot linearity for p = .1 suggest rigid chain behavior due to electrostatic repulsion among ionized acidic groups. This rigidity leads to concentration‐dependent self‐assembly structures that diverge from expected unified rheological profiles, a deviation amplified by heating–cooling cycles. This study clarifies the impact of pH on citrus pectin's rheology and emphasizes the intricate relationship between polymeric chain rigidity, self‐assembly, and viscosity. By providing a refined understanding of these mechanisms, our findings contribute to the broader field of polysaccharide research, offering insights critical for developing and optimizing pectin‐based applications in various industries.