Modifying Cassava Starch via Extrusion with Phosphate, Erythorbate and Nitrite: Phosphorylation, Hydrolysis and Plasticization

Abstract

Extrusion processing of plasticized cassava starch, a prominent industrial crop, with chemical additives offers a thermo-mechanical approach to modify starch structures through physical and chemical interactions. This research investigates the interaction and morphology of thermoplastic cassava starch (TPS) blended with tetrasodium pyrophosphate (Na4P2O7), sodium tripolyphosphate (Na5P3O10), sodium hexametaphosphate (Na6(PO3)6), sodium erythorbate (C6H7O6Na), and sodium nitrite (NaNO2) via twin-screw extrusion. The effects of these additives on the chemical structure, thermal profile, water absorption, and solubility of the TPS were examined. The high temperature and shearing forces within the extruder disrupted hydrogen bonding at α-(1-4) and α-(1-6) glycosidic linkages within anhydroglucose units. Na4P2O7, Na5P3O10 and Na6(PO3)6 induced starch phosphorylation, while 1H NMR and ATR-FTIR analyses revealed that C6H7O6Na and NaNO2 caused starch hydrolysis. These additives hindered starch recrystallization, resulting in higher amorphous fractions that subsequently influenced the thermal properties and stability of the extruded TPS. Furthermore, the type and content of the added modifier influenced the water absorption and solubility of the TPS due to varying levels of interaction. These modified starch materials exhibited enhanced antimicrobial properties against Escherichia coli and Staphylococcus aureus in polyester blends fabricated via extrusion, with nitrite demonstrating the most potent antimicrobial efficacy. These findings suggest that starch modification via either phosphorylation or acid hydrolysis impacts the thermal properties, morphology, and hydrophilicity of extruded cassava TPS.