Synthesis of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates using acylative intramolecular cyclization of sulfonium salts

A simple and efficient synthesis of 4,5-dihydro-4-oxo-3-furancarboxylates using an acylative intramolecular cyclization of sulfonium salts is described. The reaction involved the efficient formation of a mixed anhydride between a linear carboxylic acid and trifluoroacetic anhydride in the presence of N-methylimidazole, followed by the sequential conversion into a highly reactive acylammonium species in situ. This procedure is easily handled, uses readily available inexpensive reagents, and provides a variety of 2-substituted 4,5-dihydro-4-oxo-3-furancarboxylates.     

Eu(3+)-mediated polymerization of benzenetetracarboxylic acid studied by spectroscopy, temperature-dependent calorimetry, and density functional theory

Thermodynamic parameters for the complexation of Eu(3+) with pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) as a model system for polymerizable metal-complexing humic acids were determined using temperature-dependent time-resolved laser-induced fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC). At low metal and ligand concentrations (<50 μM Eu(3+), <1 mM BTC), a 1:1 monomeric Eu-BTC complex was identified in the range of 25-60 °C. At elevated concentrations (>500 μM Eu(3+) and BTC) a temperature-dependent polymerization was observed, where BTC monomers are linked via coordinating shared Eu(3+) ions. The two methods lead to comparable thermodynamic data (ΔH = 18.5 ± 1.5/16.5 ± 0.1 kJ mol(-1); ΔS = 152 ± 5/130 ± 5 J mol(-1) K(-1); TRLFS/ITC) in the absence of polymerization. With the onset of polymerization, TRLFS reveals the water coordination number of the lanthanide, whereas calorimetry is superior in determining the thermodynamic data in this regime. Evaluating the heat uptake kinetics, the monomer and polymer formation steps could be separated by "time-resolved" ITC, revealing almost identical binding enthalpies for the sequential reactions. Structural features of the complexes were studied by Fourier-transform infrared (FTIR) spectroscopy in combination with density functional theory (DFT) calculations showing predominantly chelating coordination with two carboxylate groups in the monomeric complex and monodentate binding of a single carboxylate group in the polymeric complex of the polycarboxylate with Eu(3+). The data show that pyromellitic acid is a suitable model for the study of metal-mediated polymerization as a crucial factor in determining the effect of humic acids on the mobility of heavy metals in the environment.     

Ligand field modification around Cu2+ ions in sodium borate glass by codoping

Understanding the effect of codoping on the properties of photonic glasses is important for improving their properties. The effect of codoping on the ligand field around Cu(2+) ions in a sodium borate glass is examined using optical absorption spectroscopy, continuous-wave electron paramagnetic resonance, and three-pulse electron-spin-echo envelope-modulation. Glass with a composition of 0.1CuO·5Na(2)O·95B(2)O(3) was codoped with 2 mol % of Al(3+), Si(4+), P(5+), Zr(4+), or La(3+) oxide. Three codoping effects are found: strengthening the ligand field, as observed for Zr-codoping, which induces a large blue shift of the optical absorption peak of Cu(2+); weakening the ligand field, as observed for P-codoping, which causes a red shift of the Cu(2+) absorption peak; and almost no effect on the ligand field, which is observed for Al-, Si-, and La-codoping. Coordination structure models based on local charge neutrality are proposed for the codoped glasses. The mechanism of the codoping effect is revealed by elucidating the local structure around Cu(2+).     

Two-photon absorption properties of two-dimensional π-conjugated chromophores: combined experimental and theoretical study

The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis.     

Quinone-recognition by Four-point Hydrogen Bonding in Porphyrin System Having Urea Moiety

5,15- cis -bis(Ureidophenyl)porphyrins have significant recognizing ability for p -benzoquinones through four-point hydrogen bonding. Although an unusual temperature-dependence of the complexation is observed with bis( N '-phenylureidophenyl) porphyrin, bis( N '-ethylureidophenyl)porphyrin shows a satisfactorily linear van't Hoff plot and recognizes an electron-rich p -benzoquinone such as tetramethyl- p -benzoquinone more effectively, which is ascribed to the large enthalpy change in the complex.     

Effect of composition of sucrose fatty acid esters on formation of palladium nanoparticles in reverse micelles

Palladium (Pd) nanoparticles were prepared in the reverse micellar system containing sucrose fatty acid esters with various esterification degrees. The TEM showed that Pd nanoparticles were of spherical and relatively uniform. The size of Pd nanoparticles strongly depended upon the composition of sucrose fatty acid esters. The resultant Pd colloid could be preserved for at least 2 months without precipitation.     

Characterization of fibril reinforced membranes for fuel cells

Characteristics of fibril reinforced membranes developed by Asahi Glass Company are reviewed. PTFE-fibrils <1 μm in diameter are dispersed in ion-exchange membranes uniformly. Mechanical properties, such as tensile strength, tear strength, creep property and compressive property were examined and compared with non-reinforced membranes. Fibril reinforced membranes, even by the addition of a small amount of PTFE-fibrils (2.7 wt.%), show excellent mechanical strength, especially in creep and tear strength. Cell performance is nearly equal to the one using a non-reinforced membrane and cell voltage stays about the same during the cell operation at 80 °C for 3000 h.     

Peumusolide A, unprecedented NES non-antagonistic inhibitor for nuclear export of MEK

A new polyketide peumusolide A was disclosed as an unprecedented NES non-antagonistic inhibitor for nuclear export of MEK, a promising scaffold for antitumor agents with novel mechanism of action, from Peumus boldus Molina. The absolute stereostructure as well as optical purity was established by use of the two synthesized enantiomeric model lactones. In addition, the Δε values in their CD spectra were demonstrated to be the conclusive index for determination of not only configuration at C-3 but also optical purity of natural congeneric polyketides. Peumusolide A was revealed to show NES non-antagonistic action by the biotinylated probe and to inhibit proliferation of MEK-activated tumor cells selectively.     

A thermodynamic consistency test for the binary constant-temperature VLE data using numerically optimized binary parameters

A thermodynamic consistency (TC) test for the constant-temperature VLE data was investigated by numerically optimizing the binary parameters of the activity coefficient equations to satisfy the Gibbs–Duhem (GD) equation. It was shown that the one parameter Margules equation can best satisfy the GD equation, even if significant experimental errors are involved. A thermodynamic consistency (TC) criterion was defined using the one parameter Margules equation. The TC criterion showed that, of the 37 alkane–alkane, 18 methanol–water and 44 ethanol–water binaries, 36, 16 and 1 binaries are reliable, respectively. Simple liquid mixtures meet the TC criterion.     

Removal of fine powders from film surface. I. Effect of electrostatic force on the removal efficiency

A novel fine particle removal system composed of a corona-discharge neutralizer, a pulse-jet air unit and an image processing system has been developed. First of all, adhesion force between particle and film was directly measured and effect of electrostatic force on the adhesion force was calculated experimentally and theoretically. The electrostatic force was found to be significant, leading to the suggestion that the countermeasure for the electrostatic force was required to effectively remove fine particles. This system was then applied to the removal of fine particles from surface of a gelatin film used for conventional capsule material. The number of particles removed by the system was calculated by an image processing system and number base removal efficiency was computed with and without the elimination of electrostatic charge by the neutralizer. It was found that the difference between the removal efficiency of particles with elimination of electrostatic charge and that of without the elimination showed linear relationship with the electrostatic adhesion force. The data confirmed the necessity of electrostatic charge elimination for the effective removal of fine particles.