Physico-chemical changes in casein micelles of buffalo and cow milks as a function of alkalinisation

By modifying the forces (hydrophobic and electrostatic interactions, hydrogen bonding and presence of micellar calcium phosphate) responsible for the structure and the stability of casein micelles, alkalinisation induces a disruption of casein micelles in milk. The objective of this work was to compare the alkalinisation-induced physico-chemical changes of casein micelles of buffalo and cow milks with a special attention to the mineral fraction. The whiteness and viscosity were determined as global characteristics of milk. The aqueous and micellar phases of milks were ascertained for the distributions of the concentrations of nitrogen, casein molecules, calcium, inorganic phosphate and water as their supramolecular and molecular characteristics. These parameters were measured at six pH values between pH 6.7 and 10.8. Between pH 6.7 and 10.8, the whiteness decreased from 73.5 to 50.9 and from 71.3 to 50.9 units and the viscosity increased from 1.8 to 10.2 and from 1.5 to 4.8 mPa·s for buffalo and cow milks, respectively. Simultaneously, > 90% of nitrogen contents were in the supernatants of ultracentrifugation at pH 9.7 and 8.6 for buffalo and cow milks, respectively. Chromatographic analyses showed that caseins were totally solubilised at these pH values. Calcium and inorganic phosphate concentrations progressively increased in the supernatants of ultracentrifugation and decreased in the ultrafiltrates. At alkaline pH, the negative charge of caseins increased and the inorganic phosphate ion changed its ionisation state from HPO4 2− to PO4 3− form. This form has a greater affinity for calcium and can demineralise casein micelles. The consequences were modifications of protein-protein and protein-minerals interactions resulting in micellar disruption. The dissociations took place at pH 9.7 and 8.6 for buffalo and cow milks, respectively. These differences were due to higher concentrations of casein and minerals in buffalo than in cow milk,which were also our criteria of selection of the former as a model