Rheological Study of the Formation of Pullulan Hydrogels and Their Use as Carvacrol-Loaded Nanoemulsion Delivery Systems

Hydrogels have been extensively studied as delivery systems for lipophilic compounds. Pullulan hydrogels were prepared, and their gelation kinetics were studied over time. Pullulan exhibited a relatively slow gelling reaction in basic medium (KOH) using trisodium metaphosphate (STMP) as a cross-linking agent, so capsules cannot be obtained by dripping as easily as in the case of alginate and chitosan. The kinetics of pullulan gelation were studied through rheological analysis over time. An optimal [Pullulan]/[KOH] ratio was found for a fixed [Pullulan]/[STMP] ratio. For this given relationship, gelling time measurements indicated that when the concentration of pullulan increased, the gelation time decreased from 60 min for 6% w/w pullulan to 10 min for 10% w/w. After the gel point, a hardening of the hydrogel was observed over the next 5 h. The formed hydrogels presented high degrees of swelling (up to 1800%). Freeze-dried gels were capable of being rehydrated, obtaining gels with rheological characteristics and visual appearance similar to fresh gels, which makes them ideal to be freeze-dried for storage and rehydrated when needed. The behavior of the hydrogels obtained as active ingredient release systems was studied. In this case, the chosen molecule was carvacrol (the main component of oregano oil). As carvacrol is hydrophobic, it was incorporated into the droplets of an oil-in-water nanoemulsion, and the nanoemulsion was incorporated into the hydrogel. The release of the oil was studied at different pHs. It was observed that as the pH increased (from pH 2 to pH 7), the released amount of carvacrol for the gel with pullulan 10% w/w reached 100%; for the other cases, the cumulative release amount was lower. It was attributed to two opposite phenomena in the porous structure of the hydrogel, where more porosity implied a faster release of carvacrol but also a higher degree of swelling that promoted a higher entry of water flow in the opposite direction. This flow of water prevented the active principle from spreading to the release medium.