Progress toward the Total Synthesis of Saudin: Development of a Tandem Stille-Oxa-Electrocyclization Reaction

A diastereoselective tandem Stille-oxa-electrocyclization reaction provides access to the core of the diterpenoid natural product saudin. Additionally, this new reaction sequence was extended to the convergent preparation of related polycyclic pyran systems

Ph3PCN2: a stable reagent for carbon atom transfer

Precise modification of a chemical site in a molecule at the single-atom level is one of the most elegant yet difficult transformations in chemistry. A reagent specifically designed for chemoselective introduction of monoatomic carbon is a particularly formidable challenge. Here we report a straightforward, azide-free synthesis of a crystalline and isolable diazophosphorus ylide Ph3PCN2, a stable compound with a carbon atom bonded to two chemically labile groups, triphenylphosphine (PPh3) and dinitrogen (N2). Without any additives, the diazophosphorus ylide serves as a highly selective transfer reagent for fragments including Ph3PC to deliver phosphorus ylide-terminated heterocumulenes and CN2 to produce multi-substituted pyrazoles. Ultimately, even exclusive C-atom transfer is possible: In reactions with aldehydes, acyclic and cyclic ketones (R2C=O), the C-atom substitution forms a vinylidene (R2C=C:) en route to alkynes or butatrienes

A Theoretical Light-Curve Model for the 1999 Outburst of U Scorpii

A theoretical light curve for the 1999 outburst of U Scorpii is presented in order to obtain various physical parameters of the recurrent nova. Our U Sco model consists of a very massive white dwarf (WD) with an accretion disk and a lobe-filling, slightly evolved, main-sequence star (MS). The model includes a reflection effect by the companion and the accretion disk together with a shadowing effect on the companion by the accretion disk. The early visual light curve (t ~ 1-15 days after maximum) is well reproduced by a thermonuclear runaway model on a very massive WD close to the Chandrasekhar limit (M_{WD}= 1.37 \pm 0.01 M_\odot), in which optically thick winds blowing from the WD play a key role in determining the nova duration. The duration of the strong wind phase (t~0-17 days) is very consistent with the BeppoSAX supersoft X-ray detection at t~19-20 days because supersoft X-rays are self-absorbed by the massive wind. The envelope mass at the peak is estimated to be ~3x10^{-6} M_\odot, which is indicating an average mass accretion rate ~2.5x10^{-7} M_\odot yr^{-1} during the quiescent phase between 1987 and 1999. These quantities are exactly the same as those predicted in a new progenitor model of Type Ia supernovae.Comment: 7 pages, 3 figures, to appear in ApJL, vol. 52

Phase Diagram of Pressure-Induced Superconductivity in EuFe2As2 Probed by High-Pressure Resistivity up to 3.2 GPa

We have constructed a pressure$-$temperature ($P-T$) phase diagram of $P$-induced superconductivity in EuFe$_2$As$_2$ single crystals, via resistivity ($\rho$) measurements up to 3.2 GPa. As hydrostatic pressure is applied, an antiferromagnetic (AF) transition attributed to the FeAs layers at $T_\mathrm{0}$ shifts to lower temperatures, and the corresponding resistive anomaly becomes undetectable for $P$ $\ge$ 2.5 GPa. This suggests that the critical pressure $P_\mathrm{c}$ where $T_\mathrm{0}$ becomes zero is about 2.5 GPa. We have found that the AF order of the Eu$^{2+}$ moments survives up to 3.2 GPa without significant changes in the AF ordering temperature $T_\mathrm{N}$. The superconducting (SC) ground state with a sharp transition to zero resistivity at $T_\mathrm{c}$ $\sim$ 30 K, indicative of bulk superconductivity, emerges in a pressure range from $P_\mathrm{c}$ $\sim$ 2.5 GPa to $\sim$ 3.0 GPa. At pressures close to but outside the SC phase, the $\rho(T)$ curve shows a partial SC transition (i.e., zero resistivity is not attained) followed by a reentrant-like hump at approximately $T_\mathrm{N}$ with decreasing temperature. When nonhydrostatic pressure with a uniaxial-like strain component is applied using a solid pressure medium, the partial superconductivity is continuously observed in a wide pressure range from 1.1 GPa to 3.2 GPa.Comment: 7 pages, 6 figures, accepted for publication in Physical Review B, selected as "Editors' Suggestion

A mass spectrometric approach to the proteomic profiling of the Canis lupus familiaris acquired enamel pellicle on hydroxyapatite discs

The acquired enamel pellicle (AEP) is a multi-protein film attached to the surface of teeth, which functions to lubricate the dental surface, form an anti-erosive barrier and exhibits antimicrobial properties. The initiation of AEP formation occurs within seconds of exposure to saliva, a biofluid rich in protein species. While there have been many publications on the formation of human AEP there is little research on the composition of canine AEP during its acquisition. The aim of these studies was to explore the composition of canine AEP formation, utilising hydroxyapatite (HA) discs as a tooth substitute matrix, over time. Qualitative and quantitative proteomics techniques using tandem mass tag labelled peptides and LC-MS/MS were used to follow the formation of canine AEP on hydroxyapatite discs over the course of an hour. Proteins adsorbed to the HA surface included highly abundant proteins in canine saliva, antimicrobial proteins, protease inhibitors and the buffering agent carbonic anhydrase. Greater understanding of the canine AEP deepens fundamental knowledge of the early processes driving bacterial colonisation of the tooth surface and subsequent plaque accumulation