Adriana Czímerová

Molecular arrangement of rhodamine 6G cations in the films of layered silicates: the effect of the layer charge

Montmorillonite nanocor saturated with Li+ cations was used for the synthesis of reduced charge montmorillonites (RCMs). The films of RCMs with intercalated rhodamine 6G (R6G) were prepared by adsorption of the dye on montmorillonite film deposited on a quartz slide. Penetration of the dye into the interlayer spaces of silicates was monitored by elemental analysis and X-ray diffraction measurements of the prepared R6G/silicate films. Polarized UV-Vis spectroscopy was used for the characterization of the molecular orientation of dye cations on silicate surface. There were several species of R6G cations in the interlayer spaces of the inorganic host, which was easily resolvable by the polarized spectra. The cations forming H-aggregates and absorbing light at low wavelengths were oriented in nearly perpendicular fashion, which was observed as a strongly positive dichroism, i.e., the increase of the dichroic ratio with film tilting. Adsorbed isolated dye cations were inclined at low angles with respect to the plane of the silicate surface. The layer charge of the inorganic host affected only partially the orientation of dye cations in the H-aggregates, but rather it controlled the extent of aggregation and in this way the number of nearly perpendicularly oriented cations.

Fluorescence resonance energy transfer between two cationic laser dyes in presence of the series of reduced-charge montmorillonites: Effect of the layer charge

Series of montmorillonites with systematically reduced layer charges represent a suitable model for studying various properties and interactions of layered inorganic compounds. The reduced-charge montmorillonites (RCMs) used in this study were prepared by a standard method of Li+-fixation in Nanocor montmorillonite at 100-300 degrees C. The layer charge gradually decreased with increasing temperature of RCM preparation. Li+-fixation led in some cases to the loss of expandability due to the formation of mixed swelling/nonswelling and homogeneous nonswelling phases. The interaction of two cationic dyes-rhodamine 3B (R3B) and oxazine 4 (Ox4)-with reduced-charge montmorillonites in dispersions was studied by means of UV/vis absorption and fluorescence spectroscopy. Montmorillonite with the highest charge density induced the formation of H-aggregates of the dye cations characterized by a sandwich-type structure. As the layer charge decreased, the amount of the H-aggregates was reduced in favor of H-dimers and monomers. RCMs with low charge density suppressed dye cation aggregation and mainly monomeric forms were detected. The process of energy transfer from R3B to Ox4 was detected as decreasing the emission from the energy donor and increasing the emission from the energy acceptor. The energy transfer was clearly influenced by the properties of RCM templates. The dye cations adsorbed at the surface of the highest-charge specimen formed H-aggregates, which were efficient luminescence quenchers. Fluorescence resonance energy transfer (FRET) gradually increased with the charge reduction to be optimal at the templates with medium layer charge. Substantial decrease of the layer charge and reduction of clay mineral swelling led to the decrease of both the luminescence and the efficiency of FRET. The relations of energy transfer processes to the layer charges and swelling properties of montmorillonite are analyzed in detail.

Spectral properties of TMPyP intercalated in thin films of layered silicates

The objective of this study was to investigate the spectral characteristics of tetracationic porphyrin dye (TMPyP), intercalated into films of three smectites. The smectites represented the specimens of high (Fluorohectorite; FHT), medium (Kunipia F montmorillonite; KF), and low layer charge (Laponite; LAP). Intercalation of TMPyP molecules was proven by XRD measurements. The molecular orientations of the dye cations were studied by means of linearly polarized ultraviolet-visible (UV-vis) and infrared (IR) spectroscopies. Both the UV-vis and the IR spectroscopy proved the anisotropic character of the films. The spectral analysis of the polarized UV-vis spectra and consequent calculations of tilting angles of the transition moments in the region of Soret band transitions were in the range of 25-35 degrees . The determined angles indicated that the molecular orientation of the dye cations was almost parallel to the surface of the silicates. Slightly higher values, determined for a FHT film, indicated either a slightly more tilted orientation of the dye cations or the change of molecular conformation after the intercalation of the dye. Quenching of TMPyP fluorescence was observed, resulting from the formation of bimolecular layer arrangements with sandwich-type assemblies of the dye molecules.

Two-step resonance energy transfer between dyes in layered silicate films.

Single- and two-step fluorescence resonance energy transfer (FRET) was investigated between laser dyes rhodamine 123 (R123), rhodamine 610 (R610), and oxazine 4 (Ox4). The dye molecules played the role of molecular antennas and energy donors (ED, R123), energy acceptors (EA, Ox4), or both (R610). The dye cations were embedded in the films based on layered silicate laponite (Lap) with the thickness of several μm. Optically homogeneous films were prepared directly from dye/Lap colloids. Dye concentration in the films was high enough for FRET to occur but sufficiently low to prevent the formation of large amounts of molecular aggregates. The films were characterized by absorption and fluorescence spectroscopies, and their optical properties were compared with colloid precursors and dye aqueous solutions. The phenomenon of FRET was confirmed by means of steady-state and time-resolved fluorescence spectroscopies. Significant quenching of ED emission in favor of the luminescence from EA molecules was observed. FRET led to the decrease in the lifetimes of excited states of ED molecules. Molecular orientation of dye molecules was determined by polarized absorption and fluorescence spectroscopies. Almost parallel orientation with respect to silicate surface (∼30°) was determined for all fluorescent species of the dyes. Theoretical model on relationship between anisotropy and molecular orientation of the fluorophores fits well with measured data. The analysis of anisotropy measurements confirmed the significant role of FRET in the phenomenon of light depolarization.

Spectral properties of rhodamine 6G in smectite dispersions: Effect of the monovalent cations

Montmorillonite monoionic forms with alkali metal and NH(4)(+)-cations were prepared by ion exchange. The hydration properties and binding of the ions to montmorillonite surface and the swelling properties of the mineral specimens were analyzed. Whereas Na(+)- and Li(+)-ions were fully hydrated over a large range of conditions, large size K(+), NH(4)(+), and mainly Rb(+) and Cs(+) ions were apt to bind directly to the oxygen atoms on the mineral surface. The forms with large ions exhibited reduced hydration and swelling and the absence of macroscopic swelling of the respective aqueous colloids. The interaction of laser dye rhodamine 6G (R6G) in montmorillonite colloids was investigated by absorption and steady-state fluorescence spectroscopies. Significant effects of the properties of both the inorganic ions and swelling properties of colloidal dispersions on R6G molecular aggregation were observed. Large amounts of the molecular aggregates were formed in the colloids of Na(+)- and Li(+)-montmorillonites. The aggregates absorbed light at significantly lower wavelengths (~460 nm) with respect to the light absorption by monomers (535 nm). Fluorescence spectroscopy provided a key evidence for the assignment of the type of the aggregates: The emission of the aggregates at relatively low energies proved these assemblies are rather a mixed H-/J-type than ideal H-aggregates. The presence of parent inorganic cations of larger size led to a significant lowering of the amount of the R6G aggregates in favor of the monomers. Investigations of the evolution of the dye aggregation with time indicated basic features of dye aggregation reaction: The size of parent inorganic ions did not affect the reaction mechanism, but rather limited the extent of the reaction. Probably the forms with large inorganic ions, such as Rb(+) and Cs(+), did not provide sufficient surface for the formation of the large size assemblies of the dye. This property can be explained in terms of strong association of the large alkali metal ions to clay mineral surface, as well as to reduced swelling in the colloidal systems of respective forms.

Layered silicate films with photochemically active porphyrin cations

The objective of this study was to prepare and characterize hybrid films based on layered silicates with a tetracationic porphyrin dye 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) intercalated in the inorganic matrix. The properties of the TMPyP cations in the materials were compared with those of other systems (solutions, colloids) characterized mainly by absorption and fluorescence spectroscopies. Linearly polarized absorption spectroscopy, X-ray diffraction (XRD), and fluorescence microscopy were used as well. Using appropriate layered silicate templates, applying the premodification of the inorganic component with hydrophobic alkylammonium surfactants and selecting an appropriate method, one can prepare the materials of broadly variable spectral properties of the dye. The spectral variation takes place while preserving the photochemical activity of TMPyP. The interpretations of spectral changes are based on the structural changes of the TMPyP molecules adsorbed on layered silicate surface related to the flattening of cationic pyridinium substituents.

Interaction of montmorillonite with phenothiazine dyes and pyronin in aqueous dispersions: A visible spectroscopy study

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.

Fused-ring derivatives of quinoxalines: spectroscopic characterization and photoinduced processes investigated by EPR spin trapping technique.

10-Ethyl-7-oxo-7,10-dihydropyrido[2,3-f]quinoxaline derivatives, synthesized as promising biologically/photobiologically active compounds were characterized by UV/vis, FT-IR and fluorescent spectroscopy. Photoinduced processes of these derivatives were studied by EPR spectroscopy, monitoring in situ the generation of reactive intermediates upon UVA (λmax = 365 nm) irradiation. The formation of reactive oxygen species and further oxygen- and carbon-centered radical intermediates was detected and possible reaction routes were suggested. To quantify the investigated processes, the quantum yields of the superoxide radical anion spin-adduct and 4-oxo-2,2,6,6-tetramethylpiperidine N-oxyl generation were determined, reflecting the activation of molecular oxygen by the excited state of the quinoxaline derivative.

Spectral study on the molecular orientation of a tetracationic porphyrin dye on the surface of layered silicates

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.