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Open Chemistry
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2008
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vol. 6
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issue 4
569-574
EN
Formamide colloidal suspensions of layered double hydroxides (LDHs) with anionic dye, meso-tetrakis(4-sulfonatophenyl)porphine (TPPS) were prepared. Optical properties of these suspensions were investigated by means of absorption and fluorescence spectroscopies in the visible region. For more detailed characterization, second derivative curves of the spectra were calculated. The adsorption of the dye on LDH nanosheets led to partial molecular aggregation, reflected in significant changes of the dye optical properties. The Soret band in the absorption spectra was split into two peaks and decreased in intensity. Changes were observed also for the Q-bands. The molecular aggregation significantly quenched the emission of the dye. The low intensity emission from dye H-aggregates was identified at slightly longer wavelengths. The molecular aggregation increased with the dye/LDH ratio. At low dye loadings, the optical properties were very similar to the dye solution. The yields of the dye molecular aggregation increased with LDH surface charge. [...]
Open Chemistry
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2013
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vol. 11
|
issue 10
1606-1619
EN
Stopped-flow mixing device and visible absorption spectroscopy were used for the analysis of dye rhodamine 6G (R6G) molecular aggregation in the colloids based on Na-saturated montmorillonite. Two stages of the reaction were identified: The first stage was very short and taking only several seconds, involving the adsorption of R6G cations and their initial aggregation on the surface of colloid particles. The initially formed J-aggregates exhibited similar spectral properties as monomeric form of R6G. In the second stage, initially formed aggregates converted to sandwich-type H-aggregates absorbing light at significantly lower wavelengths and adsorbed monomers. The aggregate rearrangement took several hours. Monomers, with the spectral properties identical to R6G solution, were also identified as a component in complex spectra using principal component analysis (PCA) and multivariate curve resolution (MCR). Partial bleaching of the dye was also proven. Reaction kinetics of the rearrangement of the aggregates followed the model considering a complex mechanism of the molecular aggregation. Data fits using stretched-exponential function led to the determination of rate constants, which had been in the range 10−3−4×10−3s−1. [...]
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