Surface-Enhanced Raman and Surface-Enhanced fluorescence of charged dyes based on alginate silver nanoparticles and its calcium alginate hydrogel beads.

This study shows a new SERS (Surface-enhanced Raman Scattering) and SEF (Surface-enhanced Fluorescence) platform approach, in which substrates were constructed from the silver nanoparticles stabilized by alginate polymer (AgALG) and encapsulated in hydrogel calcium alginate beads (AgALGbead). In this regard, the electrostatic repulsion or attraction concerning the charged dyes and the carboxylate groups of the alginate could define the distances between the probe molecules and metallic nanoparticles to determine the SERS or SEF effect. In this sense, the anionic dye named New Indocyanine Green (IR-820) and the cationic dye Rhodamine 6G (Rh6G) were selected to discuss the alginate's ability to quench or enhance the fluorescence and the Raman dyes signals. Furthermore, the SEF effect using the IR-820 dye can be detected for the near-infrared emission (S1 â†’ S0) using the 532 and 633 nm laser lines as well at the visible region (S2 â†’ S0) applying the excitation at 532 nm in the AgALGbead substrates. Nevertheless, the cationic dye provides the Surface-enhanced Resonance Raman Scattering (SERRS) effect and quenching of the fluorescence for the same AgALGbeads substrate at 532 nm laser line.

SERS and resonance Raman of 5-nitroisatin on silver - The distinction between the coordination and surface complexes.

Although Surface Enhanced Raman Spectroscopy (SERS) is a widespread technique with applications in several fields, the SERS effect is still not thoroughly understood due to the challenge in describing how the interaction between the analyte and the metallic surface contributes to the Raman signal enhancement. One approach to distinguish the charge transfer contribution from the metal to the molecule is the comparison of the coordination complex resonance Raman spectral features with the SERS spectra of the surface complex excited at different wavelengths. Herein, we investigated the molecule 5-nitroisatin, Nisa, its complex with a silver cation, Ag(Nisa), its anionic form, Nisa-, and the adsorbed species over Ag colloid, Nisa/AgNP, by resonance Raman and SERS, respectively. The data show that the resonance Raman spectrum of the coordination complex Ag(Nisa) is comparable to the SERS spectrum obtained out of resonance condition. However, when the SERS spectra of Nisa/AgNP at resonance condition is obtained, quite distinct chromophores are observed. The SERS enhancement profile suggests a charge transfer from the metal to molecule in the green region of the visible spectrum and evidences the higher complexity of the electronic transitions that take place within the surface complex. To support the experimental data, DFT and TDDFT calculations were performed for Nisa, Ag(Nisa), Nisa- and Nisa@Ag20 cluster.