Palmitic acid at high concentration modifies the nanoscale structure of anhydrous milk fat.

We performed a nanoscale study based on X-ray scattering to understand the impact of a promotor of crystallization, palmitic acid (PA), at high concentration, on the networks of triacylglycerols (TAGs) in anhydrous milk fat (AMF). Melted blends containing 10 wt% PA were quenched at 25 °C. X-ray scattering data were compared with those obtained for pure AMF, pure PA, and AMF containing 1 wt% PA. While PA at low concentration did not modify the nanostructure of TAG crystals (direct crystallization in the ß'-2L form), a high concentration of this promotor favored the formation of polymorphic forms suggesting that PA first crystallizes and then directs crystallization of AMF TAGs towards α and ß forms.

Isothermal crystallization of anhydrous milk fat in presence of free fatty acids and their esters: From nanostructure to textural properties.

We performed a multiscale study to understand the impact of pure exogenous compounds at low concentration on the crystallization of triacylglycerols (TAGs) in anhydrous milk fat (AMF). We selected butyric acid, an inhibitor of crystallization, and palmitic acid, a promotor, to investigate the influence of the chain length. Tripalmitin was also used as a promotor to assess the impact of fatty acid esterification. Melted blends containing the additives (1 wt%) were quenched at 25 °C. X-ray scattering data showed that AMF TAGs crystallized directly in the ß'-2L form. The presence of additives did not modify the nanostructure of TAG crystals. However, they significantly altered the microstructure of AMF, as revealed by polarized light microscopy and rheology. This study emphasizes the interest of a multiscale approach to gain knowledge about the behavior of complex fat blends and of the use of modulators at low concentration to monitor their textural properties.

Crystallization of emulsified anhydrous milk fat: The role of confinement and of minor compounds. A DSC study.

We examined the crystallization and melting of anhydrous milk fat (AMF)-in-water emulsions stabilized by sodium caseinate. Various additives at low concentrations (<5 wt%), differing in their hydrocarbon chain length (propionic vs. palmitic acid), unsaturation (palmitic vs. oleic acid), and esterification state (palmitic acid vs. tripalmitin) were used to modulate AMF crystallization kinetics. Three emulsions with different average droplet diameters were cooled down from 60 °C to 4 °C. Fat crystallization was followed by DSC under dynamic (cooling) and static (isothermal) conditions. Propionic acid did not have any noticeable effect. Oleic acid favored supercooling and the formation of unstable polymorphs at short times but its impact faded after 48 h of isothermal storage. The impact of palmitic acid was related to its amphiphilic properties and vanished after 48 h. Tripalmitin influenced crystallization via volume effects that were persistent. It formed mixed crystals which extended the melting range of AMF.

Free fatty acids and their esters modulate isothermal crystallization of anhydrous milk fat.

The effect of free fatty acids with different chain lengths or unsaturation degree on anhydrous milk fat (AMF) crystallization was evaluated. The impact of esterification was also studied using three triglycerides. Melted blends containing the additives at concentrations lower than 12wt.% were quenched at 25°C and isothermal crystallization was monitored by pulsed low-resolution nuclear magnetic resonance. In parallel, polarized light microscopy was used to observe the microstructure. Compounds based on long chain saturated fatty acids, i.e. palmitic, stearic, eicosanoic acids, tripalmitin and tristearin accelerated crystallization. Conversely, propanoic, hexanoic and oleic acids slowed down the process, while triacetin had no impact. Interestingly, above a critical concentration, the addition of palmitic, stearic or eicosanoic acids caused a transition from a one-step to two-step process. Gompertz model was used to fit the experimental data and to assess the influence of the molecular properties of the additives on the kinetic parameters.