Resonance‐Enhanced CARS Spectroscopy of Biliproteins: a Comparison Between Phycoerythrocyanin and Phycocyanin of Mastigocladus laminosus

Abstract— Resonance‐enhanced coherent anti‐Stokes Raman (CARS) spectra are reported for trimers of phycoerthrocyanin (PEC) dissolved in H2O and D2O. The CARS spectra are significantly different when recorded with pump wavelength either at 585 nm or 630 nm. By comparison of the 630 nm spectra with those of phycocyanin one can conclude that there is a change in the relative location of the lowest excited states of the β84 and β155 chromophores. Upon additional illumination with 514.5 nm laser light, only the spectra recorded with 585 nm pump wavelength change. This is in accordance with earlier observations that the phycoviolobilin chromophore of the a‐subunit exhibits photochromic behavior. The changes in the CARS spectra provide evidence that it is the methine bridge between rings C and D that undergoes the geometrical changes. Furthermore, it is suggested that there are different types of photoinduced rearrangements operative and that the isomeric distribution is different in H2O and D2O.

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