Light Induced Proton Coupled Charge Transfer Triggers Counterion Directional Translocation.

We demonstrate directed translocation of ClO anions from cationic to neutral binding site along the synthetized BPym-OH dye molecule that exhibits coupled excited-state intramolecular proton-transfer (ESIPT) and charge-transfer (CT) reaction (PCCT). The results of steady-state and time-resolved spectroscopy together with computer simulation and modeling show that in low polar toluene the excited-state redistribution of electronic charge enhanced by ESIPT generates the driving force, which is much stronger than by CT reaction itself and provides more informative gigantic shifts of fluorescence spectra signaling on ultrafast ion motion. The associated with ion translocation red-shifted fluorescence band (at 750 nm, extending to near-IR region) appears at the time ~83 ps as a result of electrochromic modulation of PCCT reaction.

Excitonic Properties of Organic Dye Aggregates: Contribution of Ukrainian Science.

Unexpected discovery that molecules of organic dyes when they form regular structures can change dramatically their light absorption and fluorescence properties were attracting the minds of researchers for more than eight decades. The progress in investigation of this unique phenomenon described in terms of H- and J-aggregation has led to many practical applications. Here the author expresses his personal view on the dramatic story of switching this research area from empirical knowledge to that standing on strong background of molecular exciton theory.

Proton transfer reactions: From photochemistry to biochemistry and bioenergetics.

The present Review is an attempt by projecting the basic knowledge on photochemical proton transfer to achieve consistent understanding of proton motions in biocatalysis, photobiocatalysis, operation of selective proton channels and systems of photosynthesis and cellular respiration. The basic mechanisms of proton transfer are in active research in the electronic excited states of organic molecules. This allows observing the reactions directly in real time, providing their dynamic and thermodynamic description and coupling with structural and energetic variables.

Dual emission and its-ratiometric detection in analytical fluorimetry. Pt. I. Basic mechanisms of generating the reporter signal.

The wavelength-ratiometric techniques gain increasing popularity in fluorescence probing and sensing for providing inner reference to output signal and removing instrumental artefacts, in this way increasing the sensitivity and reliability of assays. Recent developments demonstrate that such approach can allow achieving much more, with the application of broad range of novel molecular and nanoscale fluorophores (luminophores), exploring the whole power of photophysical and photochemical effects and using extended range of assay formats. Simplicity of detection and potentially rich content of output data allows realizing these techniques in different simplified, miniaturized and multiplexing devices.

Dual emission and its-ratiometric detection in analytical fluorimetry Pt. II. Exploration in sensing and imaging.

The wavelength-ratiometric techniques demonstrate strong advantages in fluorescence sensing and imaging over techniques employing variations of intensity at single wavelength. We present different possibilities for realization of these advantages in different simplified, miniaturized and multiplexing devices. They include the smartphone-based detection systems and strips, in which the color changes are observed with naked eye.

Fluorescence Probes Exhibit Photoinduced Structural Planarization: Sensing and Microscopic Dynamics of Viscosity Free from Polarity Interference.

We demonstrate the construction of wavelength λ-ratiometric images that allow visualizing the distribution of microscopic dynamics within living cells and tissues by using the newly developed principle of fluorescence response. The bent-to-planar motion in the excited state of incorporated fluorescence probes leads to elongation of the π-delocalization, resulting in microviscosity-dependent but polarity-insensitive interplay between well-separated blue and red bands in emission spectra. This allows constructing the exceptionally contrasted images of cellular dynamics.

Probing of Nucleic Acid Structures, Dynamics, and Interactions With Environment-Sensitive Fluorescent Labels.

Fluorescence labeling and probing are fundamental techniques for nucleic acid analysis and quantification. However, new fluorescent probes and approaches are urgently needed in order to accurately determine structural and conformational dynamics of DNA and RNA at the level of single nucleobases/base pairs, and to probe the interactions between nucleic acids with proteins. This review describes the means by which to achieve these goals using nucleobase replacement or modification with advanced fluorescent dyes that respond by the changing of their fluorescence parameters to their local environment (altered polarity, hydration, flipping dynamics, and formation/breaking of hydrogen bonds).

Photobleaching of organic fluorophores: quantitative characterization, mechanisms, protection.

Photochemical stability is one of the most important parameters that determine the usefulness of organic dyes in different applications. This Review addresses key factors that determine the dye photostability. It is shown that photodegradation can follow different oxygen-dependent and oxygen-independent mechanisms and may involve both S-T and higher-energy S-T excited states.

Electrophoretic Mobility of Some Tattoo Dyes as an Approach to Remove Their Subcutaneous Traces.

The electrokinetic (ζ, zeta) potential was determined for a series of commercial tattoo pigments. A standard experimental method involving the measuring of the level difference formed in a U-shaped tube filled with a solution containing the dye after application of some potential difference was used to find ζ-potential values. All of them were negative and sufficiently large to ensure electrophoretic mobility of the pigment particles in a special gelatin-based electrophoretic bed.