Bodipy Based Fluorescent Materials in Cellulose Matrices: Synthesis, Spectral Properties and Vapochromic Fluorescent Recognition of Alcohols and Acetone.

This paper highlights advances made using the 4-bora-3a,4a-diaza-s-indacene (BODIPY) as a fluorophore in design and application of fluorescent sensors for microenvironment polarity. Sections of the paper cover broad analysis of a range of fluorescent indicators immobilized in ethyl- and methyl cellulose matrices. The present study demonstrates that BODIPY-based fluorescent materials could be successfully utilized for ratiometric detection of ethanol and acetone in gas phase. The achieved limit of detection value equals 0.02 mg/ml for acetone and 0.08 mg/ml for ethanol, whereas obtained sensoric materials are reusable without regeneration required.

Spectral Properties and Possibilities of meso-Substituted BODIPY Usage in Sol-Gel Process and Materials.

Hybrid materials based on organically modified silica with immobilized boron-dipyrrins (BODIPY) dyes were obtained. Spectral characteristics of the dyes were measured during the matrix formation and in obtained materials. It was stated, that immobilization does not affect the character of the absorption and fluorescence spectra of the dye, but due to the effect of fluorescent molecular rotor observed for meso-substituted BODIPY, the fluorescent quantum yields were found to increase during the matrix sealing. Quantum yield increase is linear for all of the investigated matrices except phenyl-substituted one, where the π-π interactions of the dye molecule with matrix could be observed. This effect could be used for fine control of the matrix formation process and leads to increase of the dye emission in the final material for further practical applications. All obtained hybrid materials were found to be stable upon UV light irradiation, hence immobilization enhance the stability of the dye in comparison with the BODIPY in organic solvents.

Interaction of BODIPY Dyes with the Blood Plasma Proteins.

Photophysical properties of several BODIPY-based fluorescent dyes were investigated in systems containing blood plasma biomolecules and in model system containing bovine serum albumin in terms of electronic absorption and fluorescence spectroscopy. The interaction between the investigated dyes and protein plasma components changes spectral characteristics of the dyes and leads to bathochromic and hypochromic absorption spectra shifts accompanied by changing of fluorescence intensity. The mechanism of fluorescence changing was defined in the terms of Stern-Volmer theory. It was shown that the static factor of molecular dye-biopolymers complex formation prevails at plasma protein concentration up to 1 g/l, while the higher viscosity range is characterized mainly by nonspecific fluorophore interactions. The increase of fluorescent characteristics of phenyl-substituted BODIPY in the presence of proteins caused by resonance energy transfer and change of physicochemical properties of the molecular environment of the fluorophore was shown for the first time.

Fluorescent Properties of BODIPY Sensors Based on Photoinduced Electron Transfer.

Two boron-dipyrrin (BODIPY) based dyes with dimethylaminophenyl and carboxyphenyl substituents in 8-position of dipyrrin ligand have been synthesized and characterized. Photophysical and spectral properties of the obtained compounds have been investigated in water-ethanol mixture and water-cyclohexane system with variation of pH values. The equilibria constants of the compounds were identified by classical methods of acid-base titration. BODIPY bearing dimethylaminophenyl and carboxyphenyl subunits show deprotonation/protonation dependent fluorescence off/on-switching. The change of the emission could be mechanistically explained by a PET (photoinduced electron transfer) from the 8-substituent to the fluorophore. The present study demonstrates that BODIPY-based fluorescent sensors can be used to measure the pH in the range of 2-13 extending the scope of BODIPY dyes available as pH-indicators. Investigated compounds demonstrate weak dye-dye interaction allowing their cooperative usage as indicators.

Analysis of solvation and structural contributions in spectral characteristics of dipyrrin Zn(II) complexes.

Photophysical characteristics of several alkylated dipyrrin Zn(II) complexes in organic solvents were analyzed. Relations between spectral properties of complexes and physical-chemical parameters of solvents were determined with the use of linear regression analysis method. Each solvent parameter contribution in investigated spectral characteristics was estimated. Spectral properties of complexes under study depend on the specific interactions of zinc with the solvent molecules by specific axial coordination. Increasing of alkyl substitution lead to the bathochromic shifts in spectra due to the positive induction effect of alkyl groups.