1 Department of Chemistry, Technical University of Denmark
Abstract: Raman spectroscopy investigations of l(+)-ascorbic acid and its mono- and di-deprotonated anions (AH(-) and A(2-)) are reviewed and new measurements reported with several wavelengths, 229, 244, 266, 488, and 532nm. Results are interpreted, assisted by new DFT/B3LYP quantum chemical calculations with 6-311++G(d,p) basis sets for several conformations of ascorbic acid and the anions. Raman spectra were measured during titration with NaOH base in an oxygen-poor environment to avoid fluorescence when solutions were alkaline. The ultraviolet (UV) absorption band for ascorbic acid in aqueous solution at similar to 247nm was found to cause strong resonance enhancement for the ring C-C stretching mode (called B) at similar to 1692cm(-1). The ascorbate mono-anion absorbs at similar to 264.8nm giving Raman resonance enhancement for the same ring C-C bond stretching, downshifted to similar to 1591cm(-1). Finally, for the ascorbate di-anion, absorption was found at similar to 298.4nm with molar absorptivity of similar to 7,000 L mol(-1) cm(-1) and below similar to 220nm. With UV light (244 and 266nm), strongly basic solutions gave pronounced Raman resonance enhancement at similar to 1556cm(-1). Relatively weak preresonance enhancement was seen for A(2-) when excitation was done with 229nm UV light, allowing water bands to become observable as for normal visible light Raman spectra.
Applied Spectroscopy Reviews, 2015, Vol 50, Issue 3, p. 193-239