The pyridyl-tag strategy applied to the hydrocarbon/perfluorocarbon phase-switching of a porphyrin and a fullerene

A new hydrocarbon/perfluorocarbon phase-switching strategy based on coordination of pyridyl-tagged molecules to a highly fluorinated dicopper-carboxylate complex possessing two accessible axial coordination sites is described. When a chloroform solution of the tetrapyridyl-substituted porphyrin 3 (0.1 mM, 2 mL) is layered on a perfluorodecalin solution of 2 (3.25 mM, 1.5 mL), complete extraction of the porphyrin into the fluorous phase is observed after 30 min of stirring. Quantitative release of both the porphyrin and 2 is achieved simply by adding excess THF to the biphasic system, the THF acting as a pyridine competing ligand. The recovered perfluorocarbon solution containing 2 can be reused for another complexation with the same efficiency. The scope of this approach is emphasized by the phase-switching of a dipyridyl-substituted fullerene, another example of a molecule for which solubilization in perfluorocarbons is very challenging.     

A biosynthetic proposal for ring formation in the antitumor agent halichomycin. Asymmetric synthesis of the AB-carbon backbone of halichomycin

[reaction: see text] A biosynthetic proposal for ring formation in the antitumor agent halichomycin is presented in which macrocyclization of the putative prehalichomycin intermediate 1 is the first step. Compound 2 then undergoes dehydration to the alpha-keto N-acylimine 3 followed by tandem nucleophilic addition of the C(16)-hydroxyl to form the hemimacrolactam. A stereospecific Michael ring closure and enol protonation complete C-ring assembly. So far, synthetic efforts toward 1 have resulted in 8.     

Milliwatt-peak-power pulse characterization at 1.55 microm by wavelength-conversion frequency-resolved optical gating

A novel wavelength-conversion configuration based on four-wave mixing in an optical fiber has been used to generate a frequency-resolved optical gating (FROG) trace identical to that obtained from second-harmonic generation (SHG). The use of an optical fiber waveguide permits enhanced measurement sensitivity compared with that of conventional SHG-FROG and has been used for complete characterization of 1-mW peak-power picosecond pulses at 1.55 microm from an unamplified semiconductor laser diode gain switched at 10 GHz.     

Clustering for routing in densely populated areas

This paper introduces a new approach for generating school bus routes in a dense urban area. First, a districting algorithm is used to determine clusters including appropriate numbers of students. Then, for each cluster, a route and the stops along this route are determined. Numerical results are reported and compared with those obtained previously. Although the algorithm has been developped and tested in a specific context, it could easily be extended to more general vehicle routing problems.     

Spectral distributions for long range perturbations

We study distributions which generalize the concept of spectral shift function, for pseudo-differential operators on . We call such distributions spectral distributions. Relations between relative scattering determinants and spectral distributions are established; they lead to the definition of regularized scattering phase. These relations are analogous to the usual one for the standard spectral shift function. We give several asymptotic properties in the high energy and semiclassical limits where both nontrapping and trapping cases are considered. In particular, we prove Breit-Wigner formulae for the regularized scattering phases, for semiclassical Schrödinger operators with long-range potentials.     

Roughness analysis of the cracked surfaces of a face centered cubic alloy

Intergranular and transgranular fracture surfaces obtained in a face centered cubic alloy are studied using 3D maps reconstructed by scanning electron microscopy stereo imaging. The roughness exponents measured in the intergranular and transgranular surfaces, respectively, zeta = 0.83 +/- 0.05 and zeta = 0.75 +/- 0.05, are in agreement with the universal roughness value of 3D fractures. However, the slightly smaller value related to the transgranular surface could be a consequence of crystallographic transgranular zones disseminated on the surface whose roughness exponent zeta = 0.65 +/- 0.07 is close to the one usually measured on 2D fractures.