Intramolecular hydride addition to pyridinium salts: new routes to enantiopure dihydropyridones

The transformation of a simple disubstituted pyridine into a pyridinium ion bearing an exocyclic hydroxyl group, protected as a silane, enabled an intramolecular hydride transfer reaction to take place when fluoride was used as a nucleophile. The addition was both regio- and stereoselective and enabled the formation of enantiopure dihydropyridones when enantiopure pyridine derivatives were used in this sequence. The heterocyclic products contain ample functionality for further elaboration reactions and subsequent derivatization.     

Use of cation exchange chromatography for human C-peptide isotope dilution - mass spectrometric assay

An application of ion exchange chromatography for C-peptide analysis is described here. At the stage of C-peptide isolation, a strong cation exchanger (SP HP or MonoS) was used to purify the analyte from ballast proteins and peptides. The conditions of ion-exchange chromatographic separations were optimized using theoretical modeling of the net surface electric charge of the peptide as a function of pH. The purified and concentrated sample was further subjected to LC-MS/MS. In order to improve the reliability of analysis, two fragment ions were monitored simultaneously both for native C-peptide and internal standard, isotopically labeled C-peptides analogues (fragments with m/z of 927.7 and 147.2). Using ion-exchange chromatography, it became possible to process larger sample volumes, important for testing patients with very low C peptide levels, compared to currently used solid phase extraction methods.     

Observation of ultrahigh-energy cosmic rays with the ANITA balloon-borne radio interferometer

We report the observation of 16 cosmic ray events with a mean energy of 1.5 × 101? eV via radio pulses originating from the interaction of the cosmic ray air shower with the Antarctic geomagnetic field, a process known as geosynchrotron emission. We present measurements in the 300-900 MHz range, which are the first self-triggered, first ultrawide band, first far-field, and the highest energy sample of cosmic ray events collected with the radio technique. Their properties are inconsistent with current ground-based geosynchrotron models. The emission is 100% polarized in the plane perpendicular to the projected geomagnetic field. Fourteen events are seen to have a phase inversion due to reflection of the radio beam off the ice surface, and two additional events are seen directly from above the horizon. Based on a likelihood analysis, we estimate angular pointing precision of order 2° for the event arrival directions.     

Localized electronic excitations in nickel oxide

Valence-electron ionization and optical excitation energies of NiO have been calculated by the SCF?Xα cluster method and transition-state procedure. Ni 3d-like spin orbitals are localized above the O 2p band, leading to well defined peaks in the photoemission spectra. Ligand-to-metal charge-transfer excitations are responsible for strong optical absorption between 4 and 7eV.