pH-Responsive Aminobenzocoumarins as Fluorescent Probes for Biological Acidity.

Regulation of pH plays an essential role in orchestrating the delicate cellular machinery responsible for life as we know it. Its abnormal values are indicative of aberrant cellular behavior and associated with pathologies including cancer progression or solid tumors. Here, we report a series of bent and linear aminobenzocoumarins decorated with different substituents. We investigate their photophysical properties and demonstrate that the probes display strong pH-responsive fluorescence "turn on" behavior in highly acidic environments, with enhancement up to 300-fold. In combination with their low cytotoxicity, this behavior enabled their application in bioimaging of acidic lysosomes in live human cells. We believe that these molecules serve as attractive lead structures for future rational design of novel biocompatible fluorescent pH probes.

Deracemization of Binaphthyl by Suzuki Diarylation: The Role of Electronic and Steric Effects.

We report a Suzuki 2,2'-diarylation of the racemic 2,2'-diiodo-1,1'-binaphthyl which proceeds with deracemization via a pallada(IV)cyclic intermediate, induced by a simple chiral ligand─BINAP [2,2'-bis(diphenylphosphino)-1,1',-binaphthyl]. A systematic study of the reaction scope, using 45 arylboronic acids, reveals that the diarylated product is formed when meta- and/or para-substituted phenylboronic acids are functionalized with a substituent with the Hammett constant from -0.5 to +0.4. Multiparametric analysis accounting for the effect of geometry on the reactivity using Boltzmann-weighted Sterimol parameters and electronic effects described by Hammett descriptors shows that the enantioselectivity depends on steric effects only, with enhanced enantioselectivity observed for substituents with a larger length, wL, and reduced for substituents with a larger maximum width, wB5. We show that careful tuning of these parameters, with the aid of the presented mathematical model, can lead to excellent enantioselectivity. Additional factors that are investigated and found to affect the stereoselective course of the reaction include the reaction temperature, palladium source, palladium to ligand ratio, and the type of boronic acid derivative. During the chromatographic separation of diarylated products on an achiral silica gel, we observed a rare phenomenon: the diarylated products undergo self-disproportionation of enantiomers, with the major enantiomer being eluted first.

Elucidation of Photoisomerization-Related Structural Changes in an Acrylamide-Bridged Binaphthalene-Diazene Macrocyclic Chiroptical Switch by Experimental Electronic Circular Dichroism Spectra Simulation: Role of Dispersion Corrections.

Nondestructive readout of light-driven molecular memory devices can be achieved by monitoring the alterations in the chiroptical properties of 1,1'-binaphthalene as a conformationally responsive chiral group. In our system, this signaling unit is connected via acrylamide linkers to the receiving diphenyldiazene fragment, which undergoes significant geometrical changes upon (E)/(Z)-photoisomerization. The compound functions as a stable photochromic switch by alternating irradiation at 365/465 nm, with fully reversible modulation of circular dichroism (CD) signal intensity (up to 1:3) and extended thermal stability of the (Z)-isomer. According to molecular modeling, the acrylamide spacers are due to the imposed cyclic strain upon photoisomerization forced to switch amide conformations, which is markedly reflected in the CD spectra, whereas binaphthalene conformational changes are mostly neglected both by theory and by experiment. In CD simulation by TD-DFT, CAM-B3LYP outperforms B3LYP and M06 by means of similarity analysis, whereas the last mentioned functional also delivers satisfactory performance qualitatively. The inclusion of dispersion corrections during geometry optimization was crucial to retain consistency with the measured spectra. By carefully considering all relevant conformations of this 20-membered macrocycle, reasonable agreement with the experiment is reached not only for the CD simulation of the individual conformers but also of the photoisomerization process of their admixture.

Synthesis and Effect of the Structure of Bithienyl-Terminated Surfactants for Dielectric Layer Modification in Organic Transistor.

A series of bithienyl-terminated surfactants with various alkyl chain lengths (from C8 to C13) and phosphono or chlorodimethylsilyl anchoring groups were synthesized by palladium-catalyzed hydrophosphonation, or platinum-catalyzed hydrosilylation as a key step. Surfactants were tested in pentacene or α-sexithiophene-based organic field-effect transistors (OFETs) for the modification of the dielectric surface. The studied surfactants increased the effective mobility of the α-sexithiophene-based device by up to one order of magnitude. The length of alkyl chain showed to be significant for the pentacene-based device, as the effective mobility only increased in the case of dielectric modification with bithienylundecylphosphonic acid. AFM allowed a better understanding of the morphology of semiconductors on bare SiO2 and surfaces treated with bithienylundecylphosphonic acid.

Determination of molecular structure of bisphenylene homologues of BINOL-based phosphoramidites by chiroptical methods.

Vibrational (VCD), electronic circular dichroism (ECD), and IR absorption spectra together with transparent spectral region optical rotation (OR) of two derivatives of bisphenylene 1,1'-binaphthyl-based phosphoramidites containing three stereogenic axes were measured and the results were compared with simulated data obtained by ab initio calculations with density functional theory. An excellent agreement between experimental and predicted B3LYP/6-31G** and BPW91/6-31G** VCD spectra enabled the assignment of all VCD bands in the experimental spectra, while the Gibbs free energy of all the conformers allowed the determination of their relative populations. The calculation of ECD spectra showed that CAM-B3LYP/6-311G** provided results superior to those of B3LYP/6-311G**. The theoretical results for the OR at the B3LYP/6-311G** and CAM-B3LYP/6-311G** levels were in good agreement with experimental optical rotations, but exhibited lower sensitivity in determining particular conformers than VCD and ECD. By a careful comparison of experimental VCD, IR, and ECD spectra and OR with calculated data, it was possible to assign the absolute configuration of all three stereogenic axes and to determine the molecular structure of the studied bisphenylene 1,1'-binaphthyl-based phosphoramidites in solution with a high degree of confidence.

Stereoconservative Negishi arylation and alkynylation as an efficient approach to enantiopure 2,2'-diarylated 1,1'-binaphthyls.

Negishi arylation and alkynylation of easily synthesized chiral 2,2'-diodo-1,1'-binaphthyl rapidly proceeds in refluxing THF utilizing controlled microwave irradiation, affording enantiopure 2,2'-diarylated 1,1'-binaphthyls in good to excellent yields.

Spectral properties of binaphthalene-coumarins interconnected through hydrazone linkage.

Photophysical properties of new coumarin-3-carbaldehyde (dihydrodinaphtho[2,1-c:1',2'-e]azepin-N-yl)imines bearing dimethylamino and methoxy groups at position 7 of coumarin were investigated. Dimethylamino derivative exhibits different solvent polarity dependence of fluorescent characteristics for nonpolar, medium polar and highly polar solvents. This effect can be rationalized by diverse charge distribution in the singlet excited state due to its different stabilization by solvation in the solvents of particular group. While 2-fold higher values of Stokes shift were observed for methoxy derivative, its quantum yield of fluorescence is much lower due to high nonradiative decay rate constant of the excited state.