Raman and surface-enhanced Raman scattering (SERS) investigation of the quercetin interaction with metals: Evidence of structural changing processes in aqueous solution and on metal nanoparticles

Abstract

The structural modifications of quercetin (QUC), one of the most common dietary flavonols also used as dye, were investigated in this work at alkaline pH and in the presence of metal ions. The parallel analysis of the Raman and surface-enhanced Raman scattering (SERS) and the UV–vis spectra allowed to demonstrate that the interaction of QUC with Zn(II), Cu(II), or Ag(I) ions can result in the formation of complexes and/or the oxidation of the molecule. The catechol group in the B-ring resulted to be important both for metal chelation and in oxidation processes. In fact, the conversion of this reactive group to o-quinone is the first step of the QUC oxidizing processes which are strongly affected by pH both in the absence and in the presence of metal ions. In alkaline solutions (pH > 9.5) the autoxidation processes of QUC initially lead to the formation of a benzofuranone derivative and, successively, to oligomeric/polymeric species. The QUC oxidation takes place also at lower pH in the presence of metal ions such as silver. In this case, QUC acts only as a reductant and not as a metal-chelating agent. The existence of several condensation pathways was clearly evidenced by the SERS spectra. In fact, depending on pH the interaction of QUC with metal nanoparticles favors one or more polymerization reactions. In particular, the “head to tail” condensations (A-ring of one unit and the B-ring of another) seem to be favored under alkaline conditions.