Possibility of refining carotenoid geometrical isomer analysis utilizing DFT-based quantum chemical calculations.

We performed quantum chemical calculations based on the density functional theory (DFT) for the all-E- and several Z-isomers of three commercially important carotenoids (lycopene, β-carotene, and astaxanthin) and theoretically obtained the UV-Vis spectrum, response factor (determined from absorption intensities of the all-E- and the Z-isomers), and Q-ratio for each carotenoid isomer. The calculated spectra reproduced the experimental spectral shapes (e.g., the appearance of the Z-peaks and the blue shift of the main peaks for the Z-isomers) very well. The calculated response factors and Q-ratios also showed good agreement with reported values. Notably, response factors, which are difficult to determine experimentally, were well reproduced. These results suggest that quantum chemical calculations can be an effective tool for refining quantitative analysis and obtaining spectral data for carotenoids for which standards are difficult to obtain.