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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. [...]
EN
Tetracationic porphyrin dyes TMPyP and ZnPyP were intercalated into hydrophobized layered silicate films of three smectites. The smectites represented the layered silicate specimens of high (Fluorohectorite, Corning; FHT), medium (Kunipia F montmorillonite; KF) and low layer charge (Laponite, Laporte; LAP). The molecular orientations of the dye cations were studied by means of linearly-polarized ultraviolet-visible (UV-VIS) spectroscopy. The spectral analysis and consequent calculations of tilting angles of the transition moments at the wavelengths of Soret band transitions were in the range of 25°-35°. The determined angles indicated molecular orientation of the dye cations being almost parallel to the surface of the silicates. Slightly higher values (above 35°), determined for a FHT film, indicated either a slightly tilted orientation of the dye cations or the change of molecular comformation after the intercalation of the dye.
EN
This article presents results of near-field scanning optical microscope measurement of local luminescence of rhodamine 3B intercalated in montmorillonite samples. We focus on how local topography affects both the excitation and luminescence signals and resulting optical artifacts. The Finite Difference in Time Domain method (FDTD) is used to model the electromagnetic field distribution of the full tip-sample geometry including far-field radiation. Even complex problems like localized luminescence can be simulated computationally using FDTD and these simulations can be used to separate the luminescence signal from topographic artifacts.
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. [...]
EN
Layer charge is one of the key parameters used for the characterisation of expandable clay minerals, smectites. It determines most significant properties of the material which are important from the industrial application point of view. This work is related to a novel method introduced to characterize the layer charge of smectites, based on using cationic organic dyes as molecular sensors. One xanthene and four phenothiazine cationic dyes were tested using reduced charge montmorillonites (RCMs) and compared with methylene blue, which has been used most frequently. The characterization of the charge was based on the formation of molecular assemblies (H- and J-aggregates) composed by dye cations, which were easily detectable using absorption spectroscopy in the UV/VIS spectrum. More detailed characterization of the spectra required calculations of second-derivative curves. For all of the reaction systems tested in this work, the molecular aggregation increased with the layer charge of RCMs. Slight to moderate differences in the formation of dye assemblies related to the differences in the molecular structures of the individual dye cations. For example, the molecular asymmetry of azure A brought about the formation of coexistent species of similar structures. The structure of the heteroaromatic skeleton affected the extent of the aggregation and spectral changes with time. The presence of reactive, non-substituted amino groups in thionine cations probably partially decomposed in the clay mineral colloids based on high-charge RCMs. Any of the tested dyes could be used as molecular sensors for empirical characterization of the layer charge of clays taking into account the differences mentioned above. [...]
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