Absorption spectrum analysis based on singular value decomposition for photoisomerization and photodegradation in organic dyes

Abstract

© 2015 SPIE.In order to analyze the spectra of inseparable chemical mixtures, many mathematical methods have been developed to decompose them into the components relevant to species from series of spectral data obtained under different conditions. We formulated a method based on singular value decomposition (SVD) of linear algebra, and applied it to two example systems of organic dyes, being successful in reproducing absorption spectra assignable to cis/trans azocarbazole dyes from the spectral data after photoisomerization and to monomer/dimer of cyanine dyes from those during photodegaradation process. For the example of photoisomerization, polymer films containing the azocarbazole dyes were prepared, which have showed updatable holographic stereogram for real images with high performance. We made continuous monitoring of absorption spectrum after optical excitation and found that their spectral shapes varied slightly after the excitation and during recovery process, of which fact suggested the contribution from a generated photoisomer. Application of the method was successful to identify two spectral components due to trans and cis forms of azocarbazoles. Temporal evolution of their weight factors suggested important roles of long lifetimed cis states in azocarbazole derivatives. We also applied the method to the photodegradation of cyanine dyes doped in DNA-lipid complexes which have shown efficient and durable optical amplification and/or lasing under optical pumping. The same SVD method was successful in the extraction of two spectral components presumably due to monomer and H-type dimer. During the photodegradation process, absorption magnitude gradually decreased due to decomposition of molecules and their decaying rates strongly depended on the spectral components, suggesting that the long persistency of the dyes in DNA-complex related to weak tendency of aggregate formation.