Ratiometric Singlet Oxygen Sensor Based on BODIPY-DPA Dyad.

Compounds sensitive to reactive oxygen species are widely used in the study of processes in living cells and in the development of therapeutic agents for photodynamic therapy. In the present work, we have synthesized a dyad in which the BODIPY dye is chemically bound to 9,10-diphenylanthracene (DPA). Here, DPA acts as a specific sensor of singlet oxygen and BODIPY as a reference dye.

Synthesis and photophysical properties of halogenated derivatives of (dibenzoylmethanato)boron difluoride.

A series of (dibenzoylmethanato)boron difluoride (BFDBM) derivatives with a halogen atom in one of the phenyl rings at the para-position were synthesized and used to elucidate the effects of changing the attached halogen atom on the photophysical properties of BFDBM. The room-temperature absorption and fluorescence maxima of fluoro-, chloro-, bromo- and iodo-substituted derivatives of BFDBM in THF are red-shifted by about 2-10nm relative to the corresponding peaks of the parent BFDBM. The fluorescence quantum yields of the halogenated BFDBMs (except the iodinated derivative) are larger than that of the unsubstituted BFDBM.

Complexation of Donor-Acceptor Substituted Aza-Crowns with Alkali and Alkaline Earth Metal Cations. Charge Transfer and Recoordination in Excited State.

Complexation between two aza-15-crown-5 ethers bearing electron donor and acceptor fragments and alkali and alkaline earth perchlorates has been studied using absorption, steady-state fluorescence and femtosecond transient absorption spectroscopy. The spectral-luminescent parameters, the stability and dissociation constants of the complexes were calculated. The intramolecular charge transfer reaction takes place both in the excited state of the crowns and their complexes 1:1; the latter is subjected to photorecoordination resulting in a weakening or a complete disruption of coordination bond between nitrogen atom and metal cation, disposed within a cavity of the crown.

Advanced dielectric continuum model of preferential solvation.

A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level.

Preferential solvation of spherical ions in binary DMSO/benzene mixtures.

We consider a new qualitative approach for treating theoretically the solvation of single-atomic ionic solutes in binary mixtures of polar and nonpolar aprotic solvents. It is based on the implicit continuum electrostatic model of the solvent mixture involving distance-dependent dielectric permittivity epsilon(R) (where R is the distance from the ion) and local concentrations C(1)(R) and C(2)(R) of the solvent ingredients. For a given R, the condition for local thermodynamic equilibrium provides the transcendental equation for explicitly establishing the permittivity and concentration profiles.

Molecular simulation of solvent-induced stokes shift in absorption/emission spectra of organic chromophores.

The values of steady-state solvatochromic Stokes shifts (SS) in absorption/emission electronic spectra of organic chromophores are studied theoretically in the framework of the Hush-Marcus model. Charge distributions for chromophore solutes in their S0 and S1 states are found by means of conventional quantum-chemical methods combined with the continuum PCM approach for treating solvation effects. The solvent reorganization energies, which are expected to correlate with the solvent-induced part of 1/2 SS, are found in a molecular dynamics (MD) simulation which invokes a novel method for separation of the inertial piece of the electrostatic response (Vener, et al.

Wavelength-tunable ultrashort-pulse output of a photonic-crystal fiber designed to resolve ultrafast molecular dynamics.

Wavelength-tunable 100 fs pulses generated through the soliton self-frequency shift in a photonic-crystal fiber are employed to visualize femtosecond coherence and population relaxation dynamics in molecular aggregates by means of time-resolved sum-frequency generation. This technique reveals an ultrafast dephasing of coherent molecular excitations with a phase relaxation time of about 120 fs and resolves an ultrafast switching of the nonlinear-optical response of molecular aggregates.

Highly birefringent silicate glass photonic-crystal fiber with polarization-controlled frequency-shifted output: A promising fiber light source for nonlinear Raman microspectroscopy.

A highly birefringent silicate glass photonic-crystal fiber (PCF) is employed for polarization-controlled nonlinear-optical frequency conversion of femtosecond Cr: forsterite laser pulses with a central wavelength of 1.24 mum to the 530--720-nm wavelength range through soliton dispersion-wave emission. The fiber exhibits a modal birefringence of 1.

Ultrafast photonic-crystal fiber light flash for streak-camera fluorescence measurements.

Photonic-crystal fibers (PCFs) provide a high efficiency of frequency upconversion of femtosecond Cr: forsterite laser pulses through the emission of dispersive waves by solitons and third-harmonic generation. Dispersion management allows the central wavelength of the frequency-upconverted signal in PCF output to be tuned within the range of wavelengths from 400 to 900 nm. PCF frequency shifters are employed as excitation sources for time-resolved fluorescence streak-camera measurements on fluorescein solution.