Cycloaddition protocol for the assembly of the hexacyclic framework associated with the kopsifoline alkaloids

An approach to the hexacyclic framework of the kopsifoline alkaloids has been developed and is based on a Rh(II)-catalyzed cyclization-cycloaddition cascade. The resulting [3+2]-cycloadduct was readily converted into the TBS enol ether 23. Oxidation of the primary alcohol present in 23 followed by reaction with CsF afforded compound 24 that contains the complete hexacyclic skeleton of the kopsifolines. [reaction: see text]     

Relation between asymmetrical orbital angular momentum and irradiance-profile rotation for partially coherent beams

On the basis of the irradiance-moment formalism for describing general partially coherent beams, we investigate the relation between the spatial orientation of the transverse beam profile upon propagation and the asymmetrical part of its orbital angular momentum (OAM). More specifically, a necessary and sufficient condition (one-to-one correspondence) is shown between freely propagating non-rotating beams and vanishing asymmetrical OAM. As a corollary, it is obtained that any beam emerging from optical systems that transform a rotating field into a non-rotating beam exhibits vortex OAM only.     

Explanation of Variability and Removal of Confounding Factors from Data through Optimal Transport

A methodology based on the theory of optimal transport is developed to attribute variability in data sets to known and unknown factors and to remove such attributable components of the variability from the data. Denoting by x the quantities of interest and by z the explanatory factors, the procedure transforms x into filtered variables y through a z‐dependent map, so that the conditional probability distributions ρ(x|z) are pushed forward into a target distribution μ(y), independent of z. Among all maps and target distributions that achieve this goal, the procedure selects the one that minimally distorts the original data: the barycenter of the ρ(x|z). Connections are found to unsupervised learning and to fundamental problems in statistics such as conditional density estimation and sampling. Particularly simple instances of the methodology are shown to be equivalent to k‐means and principal component analysis. An application is shown to a time series of ground temperature hourly data across the United States.© 2017 Wiley Periodicals, Inc.     

High‐power HgGa2S4 optical parametric oscillator pumped at 1064 nm and operating at 100 Hz

The defect chalcopyrite crystal HgGa₂S₄ has been employed in a 1064‐nm pumped optical parametric oscillator operating at 100 Hz, to generate ∼5 ns long idler pulses near 4 µm with energies as high as 6.1 mJ and average power of 610 mW. At crystal dimensions comparable to those available for the commercial AgGaS₂ crystal, operation of the 1064‐nm pumped HgGa₂S₄ OPO is characterized by much lower pump threshold and higher conversion efficiency, with the most important consequence that such a device might become practical at pump levels sufficiently lower than the optical damage threshold.     

The Cauchy Problem for the Kadomtsev-Petviashvili (KPII) Equation in Three Space Dimensions

We prove the existence and uniqueness of local solutions in time for the Kadomtsev-Petviashvili equation (KPII) in ?³ for initial data in a suitable anisotropic Sobolev space of functions which have essentially 1⁺ derivative in the variable x and 0⁺ derivatives in the variables y and z.     

Consumer price sensitivity in the retail industry: Latitude of acceptance with heterogeneous demand

Estimating the effect of price changes on demand is an essential task for retailers. This study proposes a methodology based on consumer utility for modeling the price thresholds phenomenon that allows for threshold asymmetry, incorporates consumer heterogeneity and uses weekly aggregated brand-level data. Unlike other studies based on consumer utility models, which generate results only for the price elasticity of market share, a methodology for estimating price elasticity of demand is also included. Data on fast-moving goods (detergents, toilet paper, soft drinks, meats, liquid juices and yogurts) supplied by a major retail chain are used to demonstrate the existence of price thresholds and their effects on price elasticity. In every case it was found that within the thresholds or latitude of acceptance, consumers are relatively less sensitive to price variations while beyond them a higher sensitivity was observed. In some cases a product brand was classified as inelastic within the latitude of acceptance and elastic outside of it.     

Effect of sulphur doping on manganese clusters: an ab initio study

We report a structural, electronic and magnetic analysis of minimal Mn_nS clusters, n = 1–13, from ab initio calculations. Total geometry optimizations were performed by considering compact manganese clusters, doped with a single sulphur atom. The doping was added to the cluster by considering substitution, interstitial and adsorbed positions. To further investigate the influence of the sulphur doping on the magnetic properties of manganese clusters, we performed non collinear magnetic calculations within the local spin density approximation (LSDA) for the exchange-correlation. We find that the electronic properties can be better controlled when the cluster is doped with a sulphur atom, and less size dependent. There are no differences in the magnetic properties of doped and non-doped clusters, except for n=7 and 8, in which the total magnetic moment per atom are smaller in doped clusters.     

Phenazine Radical Cations as Efficient Homogeneous and Heterogeneous Catalysts for the Cross-Dehydrogenative Aza-Henry Reaction

The redox activity of molecular phenazine catalysts has been previously exploited for aerobic oxidative amine homo- and cross-coupling reactions. In this contribution, we have extended the reaction scope of this novel type of organocatalyst and used them in the cross-dehydrogenative aza-Henry coupling of isoquinolines with nitromethane under aerobic conditions. Additionally, we have designed and prepared a novel porous organic polymer by cross-linking of tetrakis(4-bromophenyl)silane and dihydrophenazine through Pd-catalyzed Buchwald-Hartwig cross-coupling. This new type of heterogeneous catalyst, apart from being robust and easily reusable, also showed outstanding catalytic activities and improved selectivity compared to its molecular counterpart. A plausible reaction mechanism was proposed based on spectroscopic and kinetic measurements.     

Nucleobases,Nucleosides and Nucleotides Determination in Yeasts Isolated from Extreme Environments

Chromatographia - Nucleobases, nucleosides and nucleotides can act as chemical markers and immunnostimulants. Ultra-high-performance liquid chromatography with electrospray ionization and...