Palladium-catalyzed reaction of acylzirconocene chloride and stereoselective formation of bicyclo[3.3.0] compounds

The acylzirconocene chloride complex as an acyl group donor reacts with omega-unsaturated alpha,beta-enones and -ynones under Pd-Me(2)Zn(Me(2)AlCl)-catalyzed conditions to give stereoselectively bicyclo[3.3.0] compounds through (i) formation of a Pd(II) intermediate by an oxidative addition of the Pd(0) catalyst to an enone function, (ii) cyclization of the Pd intermediate to an omega-unsaturated group, (iii) an acyl group transfer from zirconium to Pd metal, (iv) reductive elimination of the Pd metal, and (v) intramolecular cis-selective aldol reaction. [reaction: see text]     

Ultrafast fluorescence detection in tris(2,2'-bipyridine)ruthenium(II) complex in solution: relaxation dynamics involving higher excited states

The excited-state dynamics of a transition metal complex, tris(2,2'-bipyridine)ruthenium(II), [Ru(bpy)(3)](2+), has been investigated using femtosecond fluorescence upconversion spectroscopy. The relaxation dynamics in these molecules is of great importance in understanding the various ultrafast processes related to interfacial electron transfer, especially in semiconductor nanoparticles. Despite several experimental and theoretical efforts, direct observation of a Franck-Condon singlet excited state in this molecule was missing. In this study, emission from the Franck-Condon excited singlet state of [Ru(bpy)(3)](2+) has been observed for the first time, and its lifetime has been estimated to be 40 +/- 15 fs. Biexponential decays with a fast rise component observed at longer wavelengths indicated the existence of more than one emitting state in the system. From a detailed data analysis, it has been proposed that, on excitation at 410 nm, crossover from higher excited (1)(MLCT) states to the vibrationally hot triplet manifold occurs with an intersystem crossing time constant of 40 +/- 15 fs. Mixing of the higher levels in the triplet state with the singlet state due to strong spin-orbit coupling is proposed. This enhances the radiative rate constant, k(r), of the vibrationally hot states within the triplet manifold, facilitating the upconversion of the emitted photons. The vibrationally excited triplet, which is emissive, undergoes vibrational cooling with a decay time in the range of 0.56-1.3 ps and relaxes to the long-lived triplet state. The results on the relaxation dynamics of the higher excited states in [Ru(bpy)(3)](2+) are valuable in explaining the role of nonequilibrated higher excited sensitizer states of transition metal complexes in the electron injection and other ultrafast processes.     

Surface and morphological characterization of polysiloxane-block-polyimides

Two series of polysiloxane-block-polyimides were synthesized by the method of solution imidization of the polyamic acids prepared from the dianhydride/diamine combinations of 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA)/2,2-bis[4-(4-aminophenoxy) phenyl] propane (BAPP) (Series A) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA)/bis[4-(3-aminophenoxy) phenyl] sulfone (BAPSM) (Series B) with three kinds of w-diamino-poly(dimethylsiloxane) with different number-average molecular weight added as a part of diamine. These polysiloxane-block-polyimides, having various compositions and chain lengths of the polysiloxane segments, were subjected to solution casting to prepare their films, and their surface and interface properties were analyzed by contact angle, XPS, AFM, and SEM. It was found that the surface tension and surface topography were greatly influenced by the composition and molecular weight of the polysiloxane segments because of their surface enrichment, which was affected by the environment and substrate with which the copolyimides had contacted. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2239–2251, 1997     

Density dependence of the Stokes shift and solvent reorganization energy in supercritical fluids

The Stokes shifts of coumarin 153 (C153) in CF₃H, CO₂ and C₂H₆ have been measured at several reduced densities (0.3–1.8). For C153 in CF₃H, the shifts increase with a decrease in reduced density and show a maximum value at a reduced density of 0.5. In non-polar solvents, the shifts are not dramatically altered as a function of reduced density but slightly increase with a decrease in the reduced density.     

Fixation of Atmospheric Nitrogen: Synthesis of Heterocycles with Atmospheric Nitrogen as the Nitrogen Source

Dry air is the source of molecular nitrogen for reactions with TiL₄, Li, and TMSCl (L = Cl, OiPr; TMS = trimethylsilyl). The nitrogen–titanium complexes thus prepared can be used to synthesize indoles, pyrroles, and lactams from carbonyl compounds. Applying this method to 1 provides access to 2 , the key compound in the synthesis of (±)-lycopodine.     

A facile method for oxytelluration of olefins

Treatment of olefins with phenyltellurium(I) or (IV) species [(PhTe)₂, PhTeCN, PhTeBr₃] in alcohol at room to reflux temperature for 1–24 h produces the corresponding (2-alkoxyalkyl)phenyltellurium dihalides in good yields, the reaction being trans-stereoselective and highly regioselective.     

On Heuristics for Solving Winner Determination Problem in Combinatorial Auctions

The winner determination problem (WDP) in combinatorial auctions is the problem of, given a finite set of combinatorial bids B, finding a feasible subset B of B with a maximum revenue. WDP is known to be equivalent to the maximum weight set packing problem, and hard to approximate by polynomial time algorithms. This paper proposes three heuristic bid ordering schemes for solving WDP; the first two schemes take into account the number of goods shared by conflicting bids, and the third one is based on a recursive application of such local heuristic functions. We conducted several experiments to evaluate the goodness of the proposed schemes. The result of experiments implies that the first two schemes are particularly effective to improve the performance of the resulting heuristic search procedures. More concretely, they are scalable compared with the conventional linear programming (LP) relaxation based schemes, and could quickly provide an optimum solution under optimization schemes such as the branch-and-bound method. In addition, they exhibit a good anytime performance competitive to the LP-based schemes, although it is sensitive to configurable parameters controlling the strength of contributions of bid conflicts to the resultant bid ordering schemes.