Polymorphism Dependent Cytotoxicity, Cellular Uptake, and Live Cell Imaging Studies on Napthalimide-Vinyl-Phenothiazine Conjugate.

Polymorphism-dependent cytotoxicity and cellular uptake of drug molecules have been studied for the past two decades. However, the visualization of polymorph-dependent cellular uptake and cytotoxicity using microscopy imaging techniques has not yet been reported. The luminescent polymorph is an ideal candidate to validate the above hypothesis. Herein, we report the polymorph-dependent cellular uptake, cytotoxicity, and bio-imaging functions of polymorphs 1Y and 1R of a naphthalimide-phenothiazine dyad. These polymorphs show different luminescence colors in the solid state and exhibit aggregation-induced enhanced emission (AIEE) in the DMSO-Water mixture. Bioimaging, cytotoxicity assay, and fluorescence-activated cell sorting (FACS) studies revealed that these polymorphs show different levels of cytotoxicity, cellular uptake, localization, and imaging potential. Detailed photophysical, morphological, and biological studies revealed that the difference in molecular conformation in these polymorphs enables them to form aggregates of different sizes and morphology, which leads to the differential uptake of these into the cells and consequently shows different cytotoxicity and imaging potentials.

Effect of the Molecular Conformation on Excitation Energy Transfer in Conformationally Constrained Boryl-BODIPY Dyads.

We studied the dual emission characteristics of a series of boryl-BODIPYs (1-6) comprised of triarylborane (TAB) as an energy donor and BODIPY as an energy acceptor. The molecular conformations of dyads 1-6 were systematically tuned by judiciously changing the spacer that bridged the boryl and BODIPY moieties. Frontier molecular orbitals (FMOs) are localized in 3, 4, and 6 with a twisted molecular conformation. In contrast, FMOs are significantly delocalized in 1, 2, and 5 with the least-twisted molecular conformation. Dyads 1-6 showed dual emission features when they were excited at the TAB-dominated absorption band. However, the ratio between the two emission bands in 1-6 significantly varied depending on the molecular conformations. Systematic photoluminescence (PL) studies (both steady-state and time-resolved PL) together with computational, crystal structure, and anion binding studies established that the frustrated excited-state energy transfer from borane to BODIPY is the cause of the dual emission features in these molecular dyads. These studies also revealed that the energy transfer from borane to BODIPY can be elegantly tuned by modulating the dihedral angle between these two moieties.

Access to highly substituted oxazoles by the reaction of α-azidochalcone with potassium thiocyanate.

The reactivity of α-azidochalcones has been explored for the preparation of highly substituted oxazoles via a 2H-azirine intermediate. The azidochalcones, when treated with potassium thiocyanate in the presence of potassium persulfate, lead to 2,4,5-trisubstituted oxazoles in good yields. Incidentally, 2-aminothiazoles are the products when ferric nitrate is employed instead of persulfate in the above reaction.

Delayed Fluorescence, Room Temperature Phosphorescence, and Mechanofluorochromic Naphthalimides: Differential Imaging of Normoxia and Hypoxia Live Cancer Cells.

We study the effect of molecular conformation on the electronic coupling between the donor amines and acceptor 1,8-naphthalimide (NPI) in a series of D-A systems 1-4 (A = NPI; D = phenothiazine, phenoxazine, carbazole, diphenylamine, respectively, for 1, 2, 3, and 4). Weakly coupled systems show dual emission in the solution state, while strongly coupled systems show single emission bands. The energy of transitions and photoluminescence (PL) quantum yield are sensitive to the molecular conformation and donor strength. These compounds show delayed emission in the solutions and aggregated state and phosphorescence in the solid state. Compounds 3 and 4 with weak donors exhibit intermolecular slipped π···π interactions in the solid state and consequently exhibit dual (intra- and inter-) phosphorescence at low temperature. Steady state and time-resolved PL studies at variable temperature together with computational and crystal structure analysis were used to rationalize the optical properties of these compounds. The delayed emission of these compounds is sensitive to molecular oxygen; accordingly, these molecules are utilized for differential imaging of normoxia and hypoxia cancer cells.