Validation of a SPE HPLC-UV method for the quantification of a new ER-specific photosensitizer OR-141 in blood serum using total error concept.

The aim of this work is to develop the first validated HPLC-UV method quantification in blood serum for a new endoplasmic reticulum (ER)-specific benzophenazine photosensitizer (OR-141). A fast solid phase extraction (SPE) cleaning sample procedure was achieved on C18 encapped (ec) SPE cartridges and the separation was performed on a RP-18e column (5µM) using an isocratic elution with methanol. The method has been fully validated according to accuracy profiles based on total error and tolerance intervals. Calibration was performed in the matrix and trueness (<4.25% relative bias), repeatability (<4.75% relative standard deviation (RSD)), intermediate precision (<5.37% RSD), selectivity, response function, linearity, and dilution effect were evaluated for both OR-141 regio-isomers. Afterwards the developed method was successfully applied to perform the quantitative determination of OR-141 in mouse blood serum samples in a preliminary pharmacokinetic study.

New N,N,N',N'-tetradentate Pyrazoly Agents: Synthesis and Evaluation of their Antifungal and Antibacterial Activities.

A new library of N,N,N',N' -tetradentate pyrazoly compounds containing a pyrazole moiety was synthesized by the condensation of (3,5-dimethyl-1H-pyrazol-1-yl)methanol 2a or (1H-pyrazol-1-yl)methanol 2b with a series of primary diamines in refluxed acetonitrile for 6h. The antifungal activity against the budding yeast Saccharomyces cerevisiae, as well as the antibacterial activity against Escherichia coli of these new tetradentate ligands were studied. We found that these tetradentate ligands act specifically as antifungal agents and lack antibacterial activity. Their biological activities depend on the nature of the structure of the compounds.

Versatile Cu(I)/Pd(0) dual catalysis for the synthesis of quaternary α-allylated carbonyl compounds: development, mechanistic investigations and scope.

We report herein a versatile cooperative dual catalysis reaction based on a Cu(I)/Pd(0) system. Mechanistic investigation shows that every component plays a crucial role in determining the reaction outcome. The reaction is successfully extended to various substrates; such as α,ß-unsaturated ketones, malonates and coumarins. The strategy tolerates different substitution patterns and affords good yields for each family of substrates.

Octupolar derivatives functionalized with superacceptor peripheral groups: synthesis and evaluation of the electron-withdrawing ability of potent unusual groups.

Novel tripodal derivatives with a triphenylamine core and that bear "superacidifiers" (i.e., fluorinated sulfoximinyl blocks) or novel sulfiliminyl moieties as peripheral groups were synthesized. These new chromophores show strong absorption in the near-UV region and emission in the visible region. The fluorinated sulfoximinyl moieties were found to behave as potent auxochromic and electron-withdrawing (EW) groups, thus leading to redshifted absorption and emission. These moieties promote a core-to-periphery intramolecular charge transfer (ctp-ICT) transition, the energy of which was found to be correlated to their EW strength. In this study, we provide evidence of a linear correlation between the Hammett constant (σ(p)) values and the electronic gap between the ground and first excited state of the three-branched derivatives. This in turn was used to derive σ(p) values of fluorinated sulfoximinyl moieties. These EWGs show unprecedentedly high σ(p) values, up to 1.45 relative to 0.8 for NO(2). Also, by using this method, the sulfiliminyl moiety was shown to exhibit similar EW strength as NO(2) , while promoting improved transparency and solubility. Finally, the superior EW strength of the fluorinated sulfoximine peripheral moieties was shown to induce significant enhancement of the two-photon absorption responses in the red near-IR region of the three-branched derivatives relative to similar octupoles that bear more usual strong EW groups. These characteristics (improved nonlinear responses or transparency) open new routes for the design of nonlinear optical (NLO) chromophores for optical limiting or electro-optical modulation. Such building blocks could also be of interest for optoelectronic applications, including the development of solar cells.