Alexander A. Maskevich

A study was carried out and a comparative analysis of the spectral-kinetic (absorption and fluorescent) characteristics of nanospheres containing luminescent inorganic quantum dots (QDs) CdSe/ZnS, covered with an amphiphilic polymer shell, which ensures the stability of nanospheres in aqueous colloidal solutions and the possibility of introducing into them hydrophobic photochromic diarylethene molecules with different structure. Photoinduced reversible isomerization of diarylethene molecules causes modulation of the photoluminescence signal of quantum dots, including through the control of the efficiency of resonant energy transfer (FRET) from quantum dots to the cyclic isomer of diarylethene. The FRET efficiency turned out to be the highest in nanospheres with DAE2 and DAE4. The value of the quality index (QF) of the FRET photomodulator (which shows the efficiency of modulation of the quantum yield of QD photoluminescence), introduced in this work, varies for samples with different diarylethenes from 0.003 (for DAE1) to 0.09 (for DAE2). Nanospheres containing luminescent nanoparticles of various shapes can be used in the development of luminescent photocontrolled panels, fluorescent markers, etc. Keywords: quantum dots, fluorescence, Forster resonance energy transfer, nanocomposites, photochromism, diarylethenes.

A study was carried out and a comparative analysis of the spectral-kinetic (absorption and fluorescent) characteristics of nanospheres containing luminescent inorganic quantum dots (QDs) CdSe/ZnS, covered with an amphiphilic polymer shell, which ensures the stability of nanospheres in aqueous colloidal solutions and the possibility of introducing into them hydrophobic photochromic diarylethene molecules with different structure. Photoinduced reversible isomerization of diarylethene molecules causes modulation of the photoluminescence signal of quantum dots, including through the control of the efficiency of resonant energy transfer (FRET) from quantum dots to the cyclic isomer of diarylethene. The FRET efficiency turned out to be the highest in nanospheres with DAE2 and DAE4. The value of the quality index (QF) of the FRET photomodulator (which shows the efficiency of modulation of the quantum yield of QD photoluminescence), introduced in this work, varies for samples with different diarylethenes from 0.003 (for DAE1) to 0.09 (for DAE2). Nanospheres containing luminescent nanoparticles of various shapes can be used in the development of luminescent photocontrolled panels, fluorescent markers, etc.

The increase in the solvent polarity induces a significant shift of the long-wavelength absorption band of the thioflavin T (ThT) to the shorter wavelengths. This is due to the fact that the positive charge of the ThT molecule (Z = +1e) is unequally and very differently distributed between the benzthiazole and aminobenzene rings in the ground and excited states. Therefore, ThT ground state is stabilized by the orientational interactions of the polar solvent dipoles with the positively charged ThT fragments, whereas the configuration of the solvation shell of the ThT molecule in the excited Franck−Condon state is likely far from being equilibrium. ThT absorption spectrum has the shortest (412 nm) and the longest (450 nm) wavelengths in water and in water being incorporated to the amyloid fibrils, respectively. Intriguingly, the position of the ThT fluorescence spectrum depends on the polarity of solvent to a significantly lesser degree than its absorption spectrum: being excited at 440 nm, ThT has emission with maxima at 493 and 478 nm in water and fibrils, respectively. This can be due to the fact that, in the excited state, the rotational oscillations of the ThT fragments relative to each other prevent establishing equilibrium with the solvent and fluorescence occurs from the partially equilibrium excited stated to the partially equilibrium ground state. For the fibril-incorporated ThT, the maximum of the fluorescence excitation spectrum coincides with the maximum of the long wavelength absorption band (450 nm), whereas for ThT in aqueous and alcohol solutions, additional short-wavelength bands of fluorescence and fluorescence excitation spectra were described (Naiki et al. Anal. Biochem. 1989, 177, 244−249; Le Vine Methods Enzymol. 1999, 309, 274−284). These bands could result either from some fluorescent admixtures (including free benzthiazole and aminobenzene) or from the specific ThT conformers in which benzthiazole and aminobenzene rings, being oriented at φ angle close to 90 or 270°, serve as independent chromophores. On the basis of the results of the quantum-chemical calculations, it is proposed that at φ = 90° (270°), the relatively low barrier (only 700 cm^-1) of the internal rotation of the benzthiazole and aminobenzene rings relative to each other gives rise to a subpopulation of ThT molecules possessing a violated system of the π-conjugated bonds of the benzthiazole and aminobenzene rings. Keywords: thioflavin T • amyloid fibril • absorption • fluorescence • fluorescence excitation • solvent polarity • solvent orientational polarizability • quantum chemical calculations