Laser spectroscopy of CaF2:Eu:Sm thin films grown by pulsed laser deposition

Thin films of CaF₂ co-doped with low concentrations of Eu and Sm ions were grown by pulsed laser deposition (PLD) using a KrF (λ=248 nm) as the ablation source. To the best of our knowledge, the work presented here is the first report of rare-earth-doped CaF₂ films grown by PLD with this source. Combined laser excitation-emission spectroscopy was used to map out electronic transitions of Eu³⁺ with ⁷F₀→⁵D₁ excitation and the ⁵D₀→⁷F₁ emission. At the low concentrations used here the crystal field center of cubic symmetry is dominant in the films that are same for laser targets. However, charge compensated centers are present in the bulk crystal precursor. The removal of the charge compensated centers in the films and the target is likely caused by the target preparation where high pressure and temperature were applied.     

One-step construction of 2-substituted-4,6-diazaindoles from carboxylic acid derivatives

Treatment of unprotected 5-amino-4-methylpyrimidine (2) with n-BuLi gave dianion 3. Direct condensation of the dianion with various carboxylic acid derivatives furnished a range of 2-substituted-4,6-diazaindoles in good yields in one step without the need for protecting groups or oxidation-state adjustment.     

Activation of TMSCN by N-heterocyclic carbenes for facile cyanosilylation of carbonyl compounds

N-Heterocyclic carbenes were found to be highly effective organocatalysts in activating TMSCN for facile cyanosilylation of carbonyl compounds. Cyano transfer from TMSCN to aldehydes and ketones proceeds at room temperature in the presence of only 0.01-0.5 mol % of N-heterocyclic carbene (1), leading to a range of trimethylsilylated cyanohydrins in very good to excellent yields. These conditions are extremely mild and simple and tolerate various functional groups.     

Selecting tolerances in chance-constrained programming: A multiple objective linear programming approach

An importance issue concerning the practical application of chance-constrained programming is the lack of a rational method for choosing risk levels or tolerances on the chance constraints. While there has also been much recent debate on the relationship, equivalence, usefulness, and other characteristics of chance-constrained programming relative to stochastic programming with recourse, this paper focuses on the problem of improving the selection of tolerances within the chance-constrained framework. An approach is presented, based on multiple objective linear programming, which allows the decision maker to be more involved in the tolerance selection process, but does not demand a priori decisions on appropriate tolerances. An example is presented which illustrates the approach.     

Carbolithiation for the generation of cyclooctadienyl anions and tandem electrocyclization/alkylation to functionalized cis-bicyclo[3.3.0]octenes

A powerful cascade reaction process for the construction of functionalized cis-bicyclo[3.3.0]octenes has been developed. Carbolithiation of 3-methylene-1,4-cyclooctadiene with 1 degrees , 2 degrees , or 3 degrees alkyllithium reagents leads to cyclooctadienyl anions, which undergo disrotatory electrocyclization and subsequent trapping with carbon, oxygen, sulfur, or silicon electrophiles to provide functionalized cis-bicyclo[3.3.0]octenes. Transmetalation of the allyllithium intermediates allowed access to the cuprate manifold of reactivity. The rapid construction of a linear triquinane using this methodology demonstrates the potential for synthetic applications.     

Cavity resonators of metal-coated dielectric nanorods

Metallic nanoparticles bridge the length scale between atoms and crystals, exhibiting mesoscopic properties unique to their size. Thus, they have generated much interest for their potential applications as chemical or biological sensors and particularly as waveguides for light in nanoscale structures. [Y. W. C. Cao, R. C. Jin, and C. A. Mirkin, Science 297, 1536 (2002); H. J. Lezec et al., Science 297, 820 (2002); S. A. Maier, P. G. Kik, and H. A. Atwater, Appl. Phys. Lett. 81, 1714 (2002); J. M. Oliva and S. K. Gray, Chem. Phys. Lett. 379, 325 (2003)]. One important direction of research into the properties of individual metal nanoparticles involves the controlled variation of their geometry, which can yield new and tunable optical properties that simple spherical configurations do not possess. [T. S. Ahmadi, Z. L. Wang, T. C. Green, A. Henglein, and M. A. Ei-Sayed, Science 272, 1924 (1996)]. A prime example of this is the core-shell nanostructure that has a central material surrounded by differing cladding layer.     

Titration of phytic acid

Titrimetric assays for phytic acid by titration with iron(III) or thorium are described. Stannous chloride interferes in both systems, causing negative errors directly proportional to the amount of stannous chloride. The thorium:phytate ratio in the complex formed is 2:1, which is interpreted as resulting from the possession of two chelating centres by phytic acid.