Enhanced optical limiting performance of a nonlinear absorber in a solution containing scattering nanoparticles

The optical limiting performance of a water-soluble porphyrin derivative is shown to be improved when small-sized (400-nm-diameter) nonabsorbing polystyrene spheres are added to the solution. The optical limiting enhancement is attributed to absorption of diffusive photons that experience longer light pathways than ballistic photons. The effect is demonstrated for nanosecond laser excitation at 532 nm.     

Principal component analysis of dipole moment derivative signs of chloroform

The use of principal components as a basis for a graphical procedure to analyze polar tensor data is proposed. Molecular orbital and experimental polar tensor data for all possible sign combinations of the ? p /?Q_j of CHCl₃ and CDCl₃ are represented graphically as principal component scores facilitating sign selection for the ? p /?Q_j. The graphs are particularly useful in analyzing an apparent conflict in ? p /?Q_j sign choices based on the isotopic invariance criterion and molecular orbital results for the A₁ symmetry species of these molecules. The numerical impacts of individual sign ambiguities for the ? p /?Q_j on the polar tensor data are measured by the variances associated with the principal components. Assuming the ? p /?Q_j sign sets with indeterminate signs provide replicated results for the polar tensor elements, their errors are estimated and compared with errors obtained previously by propagating intensity uncertainties through the polar tensor equations.     

Electrochemical study of ion transfer of acetylcholine across the interface of water and a lipid-modified 1,2-dichloroethane

The ion transfer of acetylcholine (AcH(+)) ions across the unmodified and phospholipid-modified water|1,2-dichloroethane (DCE) interface has been studied by means of square-wave and cyclic voltammetry, as well as by electrochemical impedance spectroscopy. After being transferred in the organic phase, the AcH(+) ions undergo chemical reactions with the phospholipids. The overall behavior of the experimental system studied in the presence of phospholipids has been compared with the theoretical results of an ECrev reaction. The kinetic parameters of the chemical interactions between AcH(+) and the phospholipids have been determined from the voltammetric and impedance measurements. Additional characterization of those interactions has been made by using the surface tension measurements.     

Elastic, inelastic scattering and fusion of the 14N +59Co system at energies close to the coulomb barrier

Elastic and inelastic scattering differential cross sections were measured in the energy range 30 MeV ≤ E _lab ≤ 55 MeV, for the ¹⁴N +⁵⁹Co system. Ambiguities of the optical potential derived from the analysis of the elastic scattering data were removed by performing calculations at the radius of sensitivity and by comparison with the available fusion cross section data. A simultaneous analysis of the three mechanisms was performed by coupled channel calculations, and a unique energy independent nuclear potential was found to be able to fit the data. Discussions and comparisons concerning the optical model, the threshold anomaly, full and approximated coupled channel calculations are presented. Received: 6 February 1997 / Revised version: 1 August 1997     

13C NMR lineshapes of acetone adsorbed on silica

¹³C NMR data, obtained as a function of temperature with magic-angle spinning (MAS) and either cross polarization or direct polarization, are reported on acetone and a sample of acetone (an approximately equal mixture with ¹³C labels at C-1 or C-2) adsorbed on dry silica gel. Various contributions to the observed linewidths and T^C₂ values are considered in terms of a previously established model of the acetone/SiO₂ system; in that model, acetone species are in equilibrium between a physisorbed-acetone (non-hydrogen-bonded) state and a state consisting of acetone units that are hydrogen bonded to silanol moieties on the silica surface. Spin dynamics simulations are useful in interpreting the effects of variations of experimental parameters. It is concluded that the main linewidth contributions, which increase at lower temperatures, are: (a) a dispersion of chemical shifts in the hydrogen-bonded state, associated with the inhomogeneous character of the silica surface; (b) the interference between MAS averaging of the chemical shift anisotropy (especially for the carbonyl carbon) and molecular motion and/or chemical exchange; and (c) chemical exchange broadening. Prominence of the last of these contributions is most consistent with data obtained as a function of magnetic field strength, MAS speed, and temperature.     

Fluorescence Studies on New Potential Antitumoral Benzothienopyran-1-ones in Solution and in Liposomes

Fluorescence properties of four new potential antitumoral compounds, 3-arylbenzothieno[2,3-c]pyran-1-ones, were studied in solution and in lipid membranes of dipalmitoyl phosphatidylcholine (DPPC), egg yolk phosphatidylcholine (Egg-PC) and dioctadecyldimethylammonium bromide (DODAB). The 3-(4-methoxyphenyl)benzothieno[2,3-c]pyran-1-one (1c) exhibits the higher fluorescence quantum yields in all solvents studied. All compounds present a solvent sensitive emission, with significant red shifts in polar solvents for the methoxylated compounds. The results point to an ICT character of the excited state, more pronounced for compound 1c. Fluorescence (steady-state) anisotropy measurements of the compounds incorporated in liposomes of DPPC, DODAB and Egg-PC indicate that all compounds have two different locations, one due to a deep penetration in the lipid membrane and another corresponding to a more hydrated environment. In general, the methoxylated compounds prefer hydrated environments inside the liposomes. The 3-(4-fluorophenyl)benzothieno[2,3-c]pyran-1-one (1a) clearly prefers a hydrated environment, with some molecules located at the outer part of the liposome interface. On the contrary, the preferential location of 3-(2-fluorophenyl)benzothieno[2,3-c]pyran-1-one (1b) is in the region of lipid hydrophobic tails. Compounds with a planar geometry (1a and 1c) have higher mobility in the lipid membranes when phase transition occurs.     

Hypotensive effects of the Crotalus durissus cascavella venom: involvement of NO

Crotalus durissus cascavella is a snake native of northeastern Brazil. The aim of the study was to investigate the effects of C. d. cascavella venom on rat mean arterial pressure and vascular reactivity in the mesenteric vascular bed. The venom evoked a dose-dependent decrease in mean arterial pressure, cardiac and respiratory frequency with increased plasma nitrite levels. L-NAME (10 mg/kg) blunted both the hypotension and increased nitrite production observed after the venom administration. To investigate the effects of C. d. cascavella in resistance vessels, the vascular mesenteric bed was studied, and the results suggested that the hypotensive effect of the venom is not dependent on a direct vasodilatory activity. In conclusion, C. d. cascavella venom presented indirect hypotensive effects with the involvement of nitric oxide.     

Transitive orientations in bull-reducible Berge graphs

A bull is a graph with five vertices r,y,x,z,s and five edges ry, yx, yz, xz, zs. A graph G is bull-reducible if every vertex of G lies in at most one bull of G. We prove that every bull-reducible Berge graph G that contains no antihole is weakly chordal, or has a homogeneous set, or is transitively orientable. This yields a fast polynomial time algorithm to color the vertices of such a graph exactly.     

Electrochemical reduction of dehydroamino acids: synthesis and photophysical properties of β,β-diarylalanines

Several β,β-disubstituted dehydroalanines were prepared from β,β-dibromo or β-bromo, β-substituted dehydroalanines and aryl boronic acids using a Suzuki-Miyaura cross-coupling reaction. The electrochemical behaviour of these compounds was studied by cyclic voltammetry. All compounds studied showed similar reduction potentials and these were similar to the peak potential of the methyl ester of N-tert-butoxycarbonyl dehydrophenylalanine. Thus, the presence of a second aryl moiety in the dehydroalanine scaffold does not significantly change the reduction potential.Controlled potential electrolyses were performed at the cathodic peak potential in the presence of triethylammonium chloride as proton donor. The only products isolated in good to high yields were the corresponding β,β-diarylalanines. This reaction was also carried out using a dipeptide containing a β,β-diaryldehydroalanine to give a 1:1 diastereomeric mixture of the reduction product.The photophysical properties of two of the β,β-diaryldehydroalanines and of the corresponding β,β-diarylalanines were studied in three solvents of different polarity. The β,β-diaryldehydroalanines show low fluorescent quantum yields (Φ_F<9%) due to the conjugation of the aromatic moieties with the α,β-double bond and with the carbonyl group, which favours the non-radiative deactivation pathways. The absence of conjugation in the reduction products leads to a significant increase in the fluorescence quantum yields. These results show that the β,β-disubstituted alanines could be used as fluorescent markers.