Fluorescein and its halogenated derivatives representing a family of homologous dyes with the gradual substitution of halogen atoms for hydrogen ones are widely used in biomedicine as fluorescent probes. This stimulates the intense experimental and theoretical studies of their fluorescent properties in aqueous solutions. However, the theoretical calculations are complicated by the necessity of taking into account the effect of a solvent (water) in the explicit form and the need for effective basic sets. This is especially important for the dyes that contain heavy atoms. In this study, the quantum-chemical investigations of the dianionic form of fluorescein and its Br- and I-substituted derivatives (eosin Y and erythrosin B) have been carried out using the time-dependent density functional theory (B3LYP functional) implemented in the GAMESS software suite. The effect of a solvent has been considered in the framework of the modified Thomas polarizable continuum model. The calculations have been made for vertical (absorption and emission) excitations in the adiabatic approximation and at the nonequilibrium solvation. The results obtained for the nonequilibrium solvation are in excellent agreement with the experimental data for fluorescein and its halogenated derivatives.
We used high adsorption properties of the cationic biopolymer chitosan to synthesize colloidal polymer particles (average size about 0.3 μm) with immobilized CdTe quantum dots (QDs) and organic dye (erythrosin B). A high local concentration of fluorophores bound to the particles (about 10<sup>–3</sup> M), as well as a wide overlap of their optical spectra result in an efficient (up to 80%) Förster resonance energy transfer (FRET) from QDs ensembles to dye molecules. The FRET was registered by both steady-state (quenching of the donor and enhancement of the acceptor fluorescence) and time-resolved methods (decreasing of donor lifetime). The dependence of the transfer efficiency on acceptor concentration was analyzed within the scope of the Förster theory extended for the case of multiple energy transfer configuration. The average distances between the donor and acceptor as well as local concentration of fluorophores within particles were determined. It was demonstrated that the synthesized particles can be used as FRET-based sensitive probes for inter-fluorophore distance calculation within the range of 4 ÷ 9 nm.
Recently synthesized pyrrolanthrone, naphtho[1,2,3-cd]indole-6(2H)-one (PyAn), and its water-soluble derivative, 3(naphtho[1,2,3-cd]indole-6(2H)-one-2-yl) sodium propylsulfonate, are very promising for anticancer therapy due to both the fluorescent and cytotoxic properties. The present study is focused on the spectroscopic analysis of solvent effects in PyAn and its derivative. An increase of the solvent polarity results in the bathochromic shift in emission and absorption spectra that indicates the involvement of ππ*-type transition. The double linear correlation of Stokes shift with bulk solvent polarity functions (in terms of Lippert’s, Bakhshiev’s and Chamma-Viallet’s models) and microscopic solvent polarity parameter ( ) 30 N ET for aprotic and protic solvents is observed. Both general and specific solvent effects are revealed for the solute-solvent systems. Fluorescence quantum yield, fluorescence lifetime and excited-state dipole moment were defined for PyAn and its derivative in different solvents for the first time. The obtained information is of a great importance for the characterization of intermolecular interactions of drugs with biomolecules for the development of new drug delivery systems.
Doping of polymer particles by a fluorophores results in the sensitization within the visible spectral region becoming very promising materials for sensor applications. Colloids of biocompatible chitosan-based polyelectrolyte complexes (PECs) doped with quantum dots (QD) of CdTe and CdSe/ZnS (with sizes of 2.0-2.4 nm) were synthesized and characterized by scanning electron microscopy, dynamic light scattering, ζ-potential measurements, absorption and luminescence (including time-resolved) spectroscopy. The influence of ionic strength (0.02-1.5 M) on absorption and photoluminescence properties of encapsulated into PEC and unencapsulated quantum dots was investigated. The stability of the emission intensity of the encapsulated quantum dots has been shown to be strongly dependent on concentration of quantum dots.