Fluorescence of tautomeric forms of curcumin in different pH and biosurfactant rhamnolipids systems: Application towards on-off ratiometric fluorescence temperature sensing

Medicinal properties of curcumin are widely getting realized. For its applicability as a hydrophobic drug molecule and food spice interaction of curcumin with rhamnolipids, a biosurfactant, bears importance. Here we have explored interaction of curcumin with rhamnolipids biosurfactant and its aggregation behavior. The impact of pH on critical micelle concentration (cmc) of rhamnolipids has been studied using fluorescence of curcumin and found that cmc of rhamnolipids increases with increase in pH of the medium. In acidic, neutral and slightly alkaline medium (pH 8), at lambda(ex) = 355 nm (for beta-diketone form) curcumin undergoes excited state hydrogen transfer (ESHT) and emits solely from enol form both in the presence and absence of rhamnolipids, but first time we report that in extreme alkaline condition, at pH 13, at lambda(ex) = 355 nm curcumin emits from both beta-diketone as well as enolic ESHT forms in absence of rhamnolipids but in the presence of rhamnolipids beta-diketone is stabilized and the emission solely comes from beta-diketone by completely revoking ESHT process. Fluorescence quenching by hydrophobic cetylpyridinium bromide confirms curcumin penetrates deep inside the hydrophobic pocket of rhamnolipid aggregates/micelle by reducing the distance between N+ -atom of pyridinium ion and curcumin. On the other hand hydrophobic molecule like pyrene stays near to the Stern layer of rhamnolipids facilitating electron transfer from pyrene to N+ -atom of pyridinium ion. Even in neutral condition, in the presence of rhamnolipids the beta-diketone form, though in small proportions, can be stabilized in higher temperature in expense of enolic ESHT form, thus, offering an on off ratiometric fluorescence temperature sensing in solution, which bears significance as ratiometric probe molecules. Interaction of curcumin with rhamnolipids stabilizes curcumin in acidic, neutral and moderate alkaline condition but fails at extreme pH 13.