Donor acceptor fluorophores: synthesis, optical properties, TD-DFT and cytotoxicity studies.

Donor-π-acceptor (D-π-A) fluorophores consisting of a donor unit, a π linker, and an acceptor moiety have attracted attention in the last decade. In this study, we report the synthesis, characterization, optical properties, TD-DFT, and cytotoxicity studies of 17 near infrared (NIR) D-π-A analogs which have not been reported so far to the best of our knowledge. These fluorophores have chloroacrylic acid as the acceptor unit and various donor units such as indole, benzothiazole, benzo[e]indole, and quinoline. The fluorophores showed strong absorption in the NIR (700-970 nm) region due to their enhanced intramolecular charge transfer (ICT) between chloroacrylic acid and the donor moieties connected with the Vilsmeier-Haack linker. The emission wavelength maxima of the fluorophores were in between 798 and 870 nm. Compound 20 with a 4-quinoline donor moiety showed an emission wavelength above 1000 nm in the NIR II window. The synthesized fluorophores were characterized by 1H NMR and 13C NMR, and their optical properties were studied. Time dependent density functional theory (TD-DFT) calculations showed that the charge transfer occurs from the donor groups (indole, benzothiazole, benzo[e]indole, and quinoline) to the acceptor chloroacrylic acid moiety. Fluorophores with [HOMO] to [LUMO+1] transitions were shown to possess a charge separation character. The cytotoxicity of selected fluorophores, 4, 7, 10 and 12 was investigated against breast cancer cell lines and they showed better activity than the anti-cancer agent docetaxel.

Dual ionic liquid-based crosslinked chitosan for fine-tuning of antifouling, water throughput, and denitrification performance of polysulfone membrane.

This study aimed to design a facile and efficient protocol for upgrading the performance indices of polysulfone (PS) membrane (porosity, hydrophilicity, pure water flux (PWF), surface charge, and fouling-resistance) by blending with newly synthesized poly(ionic) crosslinked chitosan Schiff bases (PICCSBs). The PS-PICCSBs mixed-matrix membranes (MMMs) have successfully fabricated and characterized based on spectral and microscopic analyses, porosity, zeta potential, water contact angle, and water uptake (wettability) measurements. The PWF, fouling-resistance against bovine serum albumin (BSA), as well as ion exchange capacity (IEC) against nitrate anion were studied. The wettability, hydrophilicity and overall porosity of new MMMs have greatly increased, in comparison to a pristine PS membrane (M0). In addition, blending of PS with PICCSBs resulted in switching its surface from negatively- to positively-charged. The PWF of MMMs has increased to reach a maximum value of 238.6 L/m2 h for MMM1 (9.3-fold higher than M0). Meanwhile, BSA rejection has declined from 96.62% for M0 to 41.9% for MMM1. The fouling parameters results of MMMs indicated their low fouling propensity. The IEC of nitrate anions revealed that the nitrate uptake by MMM1 is higher than that for M0 and MMM2 by 34% and 14%, respectively.

Photoexcitation Processes in Oligomethine Cyanine Dyes for Dye-Sensitized Solar Cells-Synthesis and Computational Study.

We report density functional theory (DFT) calculations of three newly synthesized oligomethine cyanine-based dyes as potential TiO2-sensitizers in dye-sensitized solar cells. The three dyes have π-symmetry and the same acceptor side, terminating in the carboxylic anchor, but they differ through the π-bridge and the donor groups. We perform DFT and time-dependent DFT studies and present the electronic structure and optical properties of the dyes alone as well as adsorbed to the TiO2 nanocluster, to provide some predictions on the photovoltaic performance of the system. We analyze theoretically the factors that can influence the short circuit current and the open circuit voltage of the dye-sensitized solar cells. We examine the matching of the absorption spectra of the dye and dye-nanocluster system with the solar irradiation spectrum. We display the energy level diagrams and discuss the alignment between the excited state of the dyes and the conduction band edge of the oxide as well as between the redox level of the electrolyte and the ground state of the dyes. We determine the electron density of the key molecular orbitals and analyze comparatively the electron transfer from the dye to the semiconducting substrate. To put our findings in the right perspective we compare the results of our calculations with those obtained for a coumarin-based dye used in fabricating and testing actual devices, for which experimental data regarding the photovoltaic performance are available.