Spectral-fluorescent and photochemical study of 6,6′-di(benzoylamino)trimethine cyanine dyes in solutions as possible probes for DNA

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 292; p. 122416
• Main Authors: Pronkin, P.G., Tatikolov, A.S.
• Format: Journal Article
• Language: English
• Published: England Elsevier B.V 05-05-2023
• Subjects: Carbocyanines - chemistry; DNA - chemistry; Ethanol; Fluorescent Dyes - chemistry; Humans; Molecular Docking Simulation; Spectrometry, Fluorescence; Surface-Active Agents; Water
• ISSN: 1386-1425; 1873-3557
• DOI: 10.1016/j.saa.2023.122416

[Display omitted]
•6,6′-substituents dramatically increase hydrophobicity/aggregation of trimethine cyanine dyes in aqueous media.•Moderate doses of surfactants or ethanol affect dye aggregation but do not eliminate it completely.•With DNA trimethine cyanine dyes increase fluorescence and triplet state yield.•Molecular docking suggests the possibility of dye intercalation with DNA.•The studied dyes (especially T-304) can be used as sufficiently sensitive fluorescent probes for DNA detection.
Spectral-fluorescent and photochemical properties of trimethine cyanine dyes T-304, T-306, and T-307, having substituents in 6,6′-positions, in various organic solvents, in aqueous buffer solutions, in the presence of surfactants and ethanol additives, and the effect on these properties of addition of DNA have been studied. Strong aggregation of the dyes in aqueous and aqueous buffer solutions has been shown. This is due to increased hydrophobicity of the dyes, which makes it difficult to use them as spectral-fluorescent probes for DNA. In the presence of DNA, trimethine cyanines partially form highly fluorescent complexes of dye monomers with the biomolecule, with slight decomposition of the initial aggregates and the formation of aggregates on DNA molecules. The formation of different types of dye–DNA complexes, i.e., intercalation and binding in the DNA grooves, was modeled by molecular docking. Dye–DNA complexes were also studied by circular dichroism spectroscopy and by thermal dissociation of DNA. To reveal selectivity of the dyes, their interaction with human serum albumin was briefly studied. The presence of moderate concentrations of nonionic surfactants does not lead to a significant decomposition of aggregates, but leads to a biphasic dependence of the fluorescence intensity on the DNA concentration. At the same time, ethanol additives (15%) lead to a more or less linear concentration dependence of the fluorescence intensity, which makes it possible to use these dyes as fluorescent probes for DNA. The effective binding constants of the dyes to DNA and the limits of DNA detection using the dyes in the presence of 15% ethanol were estimated. Photoisomerization and generation of the triplet states of T-304, T-306, and T-307 have been also studied. Along with the fluorescence growth, complexation with DNA leads to an increase in the yield of the triplet states of the dyes. This creates a prerequisite for using the dyes in targeted PDT. In the presence of DNA, the decay kinetics of the triplet states are biexponential, which indicates different types of dye complexes with DNA. The rate constants of oxygen quenching of the triplet states of the dyes bound to DNA are significantly lower than the diffusion-controlled values (taking into account the spin-statistical factor), which is explained by the shielding effect on the triplet molecules in complexes with DNA. The data obtained show that dyes T-304, T-306 and T-307, with addition of 15% ethanol, can be used as possible fluorescent probes for DNA.