Effects of Controlled Relative Humidity Storage on Moisture Sorption and Amylopectin Retrogradation in Gelatinized Starch Lyophiles

Water plays a significant role in the gelatinization and retrogradation (crystallization) of starch. Amylopectin crystalline regions can adopt several hydrated polymorphic forms; however, reports differ on the migration of water during retrogradation. The objectives of this study were to determine the moisture sorption patterns of gelatinized starch lyophiles during retrogradation in controlled relative humidity (RH) environments and document the amylopectin polymorph(s) formed. Starches from different botanical sources containing A‐type and B‐type amylopectin polymorphs were studied. Suspensions of starch were heated and then frozen and freeze‐dried to make primarily amorphous matrices. Moisture sorption profiles of the dried samples were collected from 5% RH to 95% RH at 25 °C. To capture the retrogradation event, sample masses were also monitored at constant RHs over time (95%, 92.5%, and 90% RH). Powder X‐ray diffraction was used to document the physical state of the samples, including the amylopectin polymorph formed upon retrogradation, and differential scanning calorimetry was used to determine glass transition temperatures (Tgs). In all lyophiles, water was first absorbed (mass gain), and if a critical water content was reached (at ≥92.5%RH), sample Tgs dropped below room temperature and concurrent retrogradation and water expulsion (mass loss) occurred, regardless of starch botanical source and whether A‐ or B‐type polymorphs were formed. Overall, retrogradation and water expulsion increased as storage RH increased. These results offer further knowledge into the role of water in amylopectin retrogradation and the relationship among starch type, environmental RH, moisture sorption prior to retrogradation, and water redistribution during retrogradation. PRACTICAL APPLICATION: Starch gelatinization and retrogradation require molecular mobility, which is facilitated by water. Limited retrogradation occurred in lyophiles in the glassy state (90% RH, 25 °C), but increasing the storage RH (to ≥92.5% RH) resulted in increasing amylopectin retrogradation (note: many baked products have water activities in this range). Regardless of starch type (botanical source and amylose content), when the storage RH was high enough, the starch lyophiles first absorbed water, which depressed the Tg below the storage temperature, and then exhibited concomitant retrogradation and water expulsion. The water expelled during amylopectin retrogradation was not (fully) retained in the amorphous starch fraction, which is why samples lost weight. Water leaving the starch matrix during retrogradation could pose challenges for quality, texture, and shelf‐life of starch‐based products.