3 years ago

Unveiling the Aggregation of Lycopene in Vitro and in Vivo: UV–Vis, Resonance Raman, and Raman Imaging Studies

Unveiling the Aggregation of Lycopene in Vitro and in Vivo: UV–Vis, Resonance Raman, and Raman Imaging Studies
Mika Ishigaki, Yukihiro Ozaki, Hideki Hashimoto, Yasutaka Kitahama, Takuma Genkawa, Leilei Zhang, Phiranuphon Meksiarun
The present study investigates the structure of lycopene aggregates both in vitro and in vivo using ultraviolet–visible (UV–vis) and Raman spectroscopies. The electronic absorption bands of the J- and H-aggregates in vitro shift to lower and higher energies, respectively, compared to that of the lycopene monomer. Along with these results, the frequencies of the ν1 Raman bands were shifted to lower and higher frequencies, respectively. By plotting the frequencies of the ν1 Raman band against the S0 → S2 transition energy, a linear relationship between the data set with different aggregation conformations can be obtained. Therefore, the band positions depending on the different conformations can be explained based on the idea that the effective conjugated C═C chain lengths within lycopene molecules are different due to the environmental effect (site-shift effect) caused by the aggregation conformation. Applying this knowledge to the in vivo measurement of a tomato fruit sample, the relationship between the aggregation conformation of lycopene and the spectral patterns observed in the UV–vis as well as Raman spectra in different parts of tomato fruits was discussed in detail. The results showed that the concentration of lycopene (particularly that of the J-aggregate) specifically increased, whereas that of chlorophyll decreased, with ripening. Furthermore, Raman imaging indicated that lycopene with different aggregate conformations was distributed inhomogeneously, even within one sample. The layer formation in tomato tissues with high concentrations of J- and H-aggregates was successfully visualized. In this manner, the presence of lycopene distributions with different aggregate conformations was unveiled in vivo.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcb.7b04814

DOI: 10.1021/acs.jpcb.7b04814

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