Effects of Surfactants on the Aggregation of 6,6'-Disubstituted Thiacarbocyanine Dyes in Aqueous Solutions

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Abstract

The aggregation properties of a number of 6,6'-substituted thiacarbocyanine dyes were studied by spectral-fluorescent methods: T-304, T-306, T-307, T-336 and, for comparison, thiacarbocyanine Cyan 2, which has no substituents in the 6,6'-positions, in aqueous buffer solutions and in the presence of various types of surfactants. The method of moments was used to characterize the absorption spectra (band positions, width, shape). Substituents in the 6,6'-positions significantly increase the ability of dyes T-304, T-306, T-307, T-336 to aggregation (dimerization, as well as to the formation of disordered aggregates with broad low-intensity absorption spectra). The introduction of surfactants leads to rearrangement of the spectra associated with the complex nature of the equilibria between monomers and aggregates of various structures (including surfactant molecules, if present), in particular, with a decrease in the contribution of disordered aggregates. However, the decomposition of dimeric aggregates of 6,6'-substituted cyanines is observed only at very high surfactant concentrations (~20 CMC and higher, where CMC is the critical micelle concentration). At the same time, the passing of surfactant concentrations through CMC does not significantly affect the spectral-fluorescent properties of the dyes, which is probably due to rather strong interactions of the dyes with individual surfactant molecules and premicellar associates of surfactants.

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P. G. Pronkin

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences

Author for correspondence.
Email: pronkinp@gmail.com
Russian Federation, Moscow

L. A. Shvedova

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences

Email: pronkinp@gmail.com
Russian Federation, Moscow

A. S. Tatikolov

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences

Email: pronkinp@gmail.com
Russian Federation, Moscow

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Supplementary files

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2. Fig. 1. Structures of the investigated cyanine dyes.

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3. Fig. 2. a - Absorption spectra of dyes T-304 (curve 1; cT-304 = 1 ‧ 10-6 mol ‧ l-1) and T-336 obtained at different dye concentrations: cT-336 = = = 1.92 ‧ 10-6 (curve 2), 1.2 ‧ 10-6 (3), 9.72 ‧ 10-7 (4), 6.47 ‧ 10-7 (5) and 4. 18 ‧ 10-7 mol ‧ l-1 (6) in HEPES buffer solution; b - dependences of M-1 (1) and abs on the concentration of T-336 in buffer solution; c - spectra of fluorescence (1 - T-304, λex = 490 nm and 4 - T-336, λex = 550 nm) and fluorescence excitation (2 - T-304, λreg = 550 nm; 3 - T-304, λreg = 700 nm; 5 - T-336, λreg = 640 nm).

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4. Fig. 3. a - Absorption spectra of Cyan 2 dye (cCyan 2 = 1 ‧ 10-5 mol ‧l-1) at different concentrations of CTAB: cCTAB = 0 (curve 1), 0.10 KCM (2), 0. 20 KCM (3), 1.01 KCM (4), 2.01 KCM (5), 4.0 KCM (6), 6.0 KCM (7), 8.01 KCM (8), and 10.0 KCM (9) in HEPES buffer solution; in the inset, absorption spectra of T-307 (cT-307 ~ 1. 5 ‧ 10-6 mol ‧ l-1) in the absence of surfactant (curve 1), in the presence of ≥ 20 KCM CTAB (2), Triton X-100 (3), Brij 35 (4), Tween-20 (5), and SDS (6); b - dependences of М-1 (1) and abs, obtained from the absorption spectra of Cyan 2, on the concentration of CTAB; c - fluorescence (1, 3, 5) and fluorescence excitation (2, 4, 6) spectra of Cyan 2 at ≥ 20 KCM CTAB (1, λex = 520 nm; 2, λreg = 600 nm) and T-307 at ≥20 KCM CTAB (3, λex = 550 nm; 4, λreg = 630 nm) and at ≥20 KCM SDS (5, λex = 550 nm; 6, λreg = 620 nm). The inset shows the dependence of the fluorescence intensity of the T-307 dye (cT-307 ~ 1.5 ‧ 10-6 mol ‧ l-1) on the SDS concentration ((2.2÷20) KCM; λex = 550 nm, λreg = 596 nm).

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5. Fig. 3. End.

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6. Fig. 4. Absorption (1-5), fluorescence (6, λex = 570 nm), and fluorescence excitation (7, λreg = 620 nm) spectra of T-306 dye in HEPES buffer solution in the presence of high concentration of Tween-20 (≥ 20 KCM). Absorption spectra of 1-5 were recorded at 0 (curve 1), 2 (2), 4 (3), 6 (4), 16 min (5) after sample preparation.

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