Synthesis, characterization, and spectroscopic investigation of benzoxazole conjugated Schiff bases

Two Schiff bases were synthesized by reaction of 2-(4'-aminophenyl)benzoxazole derivatives with 4-N,N-diethylaminobenzaldehyde. UV-visible (UV-vis) and steady-state fluorescence in solution were applied in order to characterize its photophysical behavior. The Schiff bases present absorption in the UV region with fluorescence emission in the blue-green region, with a large Stokes' shift. The UV-vis data indicates that each dye behaves as two different chromophores in solution in the ground state. The fluorescence emission spectra of the dye 5a show that an intramolecular proton transfer (ESIPT) mechanism takes place in the excited state, whereas a twisted internal charge transfer (TICT) state is observed for the dye 5b. Theoretical calculations were performed in order to study the conformation and polarity of the molecules at their ground and excited electronic states. Using density functional theory (DFT) methods at theoretical levels BLYP/Aug-SV(P) for geometry optimizations and B3LYP/6-311++G(2d,p) for single-point energy evaluations, the calculations indicate that the lowest energy conformations are in all cases nonplanar and that the dipole moments of the excited state relaxed structures are much larger than those of the ground state structures, which corroborates the experimental UV-vis absorption results.     

NCO quantitative measurement in premixed low pressure flames by combining LIF and CRDS techniques

NCO is a short-lived species involved in NO(x) formation. It has never been quantitatively measured in flame conditions. In the present study, laser-induced fluorescence (LIF) and cavity ring-down spectroscopy (CRDS) were combined to measure NCO radical concentrations in premixed low-pressure flames (p = 5.3 kPa). NCO LIF excitation spectrum and absorption spectrum (using CRDS) measured in a stoichiometric CH(4)/O(2)/N(2)O/N(2) flame were found in good agreement with a simulated spectrum using PGOPHER program that was used to calculate the high-temperature absorption cross section of NCO in the A(2)Σ(+)-X(2)Π transition around 440.479 nm. The relative NCO-LIF profiles were measured in stoichiometric CH(4)/O(2)/N(2)O/N(2) flames where the ratio N(2)O/O(2) was progressively decreased from 0.50 to 0.01 and in rich CH(4)/O(2)/N(2) premixed flames. Then, the LIF profiles were converted into NCO mole fraction profiles from the absorption measurements using CRDS in a N(2)O-doped flame.     

Low-temperature H2 sensing in self-assembled organotin thin films

Self-assembled nanoporous tin-based hybrid thin films prepared by the sol-gel method from organically-bridged ditin hexaalkynides detect hydrogen gas from 50 to 200 °C at the 200-10,000 ppm level. This finding opens a fully new class of gas-sensing materials as well as a new opportunity to integrate organic functionality in gas sensing metal oxides.     

Selective conversion of {Mo132} Keplerate ion into 4-electron reduced crown-capped Keggin derivative [Te5Mo15O57](8-). A key intermediate to single-phase M1 multielement MoVTeO light-alkanes oxidation catalyst

{Mo(132)} Keplerate anion reacts with tellurites to give a soluble precursor to produce in hydrothermal conditions single-phase M1 MoVTeO light-alkanes oxidation catalyst. Characterization of this Te-containing intermediate by single-crystal X-ray diffraction, (125)Te NMR, UV-visible and redox titration reveals a molybdotellurite anion as a crown-capped Keggin derivative.     

Ionic liquids: structuration agents in a fluorinated matrix

The use of ionic liquids as functional building blocks based on pyridinium, imidazolium and phosphonium cations to achieve materials combining a structuration at nanoscale with the dramatic mechanical properties of the resulting ionomers has been successfully demonstrated for the first time in a fluorinated matrix.     

Multiplexed binding determination of seven glycoconjugates for Pseudomonas aeruginosa lectin I (PA-IL) using a DNA-based carbohydrate microarray

The binding of seven multivalent glycoconjugates displaying linear or antenna-like structures and different electronic environments were evaluated towards PA-IL on a DNA-based carbohydrate microarray. The affinity can be modulated by the charge and the topology of the galactosylated derivatives.     

Self-assembled naphthalenediimide derivative films for light-assisted electrochemical reduction of oxygen

This naphthalene diimide derivative, DC18, forms highly conjugated semiconducting stacked assemblies over electrodes after electrochemical conditioning. These molecular materials are very efficient towards electrochemical photoreduction of oxygen under visible light.     

Gene delivery with polycationic fullerene hexakis-adducts

Polyplexes prepared from DNA and globular compact polycationic derivatives constructed around a fullerene hexakis-adduct core have shown remarkable gene delivery capabilities.     

Quantum chemical computations of 1,3-phenylenediacetic acid

Molecular geometry, vibrational wavenumbers and gauge including atomic orbital (GIAO) 13C NMR and 1H NMR chemical shift values of 1,3-phenylenediacetic acid (C10H10O4), in the ground state have been calculated by using ab initio Hartree-Fock (HF) and density functional theory (DFT/B3LYP) methods with 6-311++G(d,p) basis set for the first time. Comparison of the observed fundamental vibrational modes of 1,3-phenylenediacetic acid and calculated results by density functional B3LYP and Hartree-Fock methods indicate that B3LYP is superior to the scaled Hartree-Fock approach for quantum chemical studies. Geometric parameters (bond lengths and bond angles) and vibrational wavenumbers obtained by the HF and DFT/B3LYP methods are in good agreement with the experimental data. Furthermore, this is the first time the results of the calculated JCH and JCC coupling constants of the C10H10O4 molecule are presented in this study.