Surface-enhanced Raman scattering (SERS) study of anthocyanidins.

Anthocyanins are an important class of natural compounds responsible for the red, purple and blue colors in a large number of flowers, fruits and cereal grains. They are polyhydroxy- and polymethoxy-derivatives of 2-phenylbenzopyrylium (flavylium) salts, which are present in nature as glycosylated molecules. The aim of the present study is to assess the identification of anthocyanidins, i.e. anthocyanins without the glycosidic moiety, by means of surface-enhanced Raman spectroscopy (SERS), a very chemically-specific technique which is moreover sensitive to subtle changes in molecular structures. These features can lead to elect SERS, among the spectroscopic tools currently at disposal of scientists, as a technique of choice for the identification of anthocyanidins, since: (1) anthocyanidins structurally present the same benzopyrylium moiety and differentiate only for the substitution pattern on their phenyl ring, (2) different species are present in aqueous solution depending on the pH. It will be demonstrated that, while resonance Raman spectra of anthocyanidins are very similar to one another, SER spectra show greater differences, leading to a further step in the identification of such important compounds in diluted solutions by means of vibrational spectroscopy. Moreover, the dependence on the pH of the six most common anthocyanidins, i.e. cyanidin, delphinidin, pelargonidin, peonidin, malvidin and petunidin, is studied. To the best of the authors' knowledge, a complete SERS study of such important molecules is reported in the present work for the first time.