The effects of sample preparation methods on the variability of the electrospray ionization response for model drug compounds

A post-column infusion system was developed in order to analyze suppression of electrospray ionization (ESI) tandem mass spectrometry response in the presence of endogenous plasma interferences. By enabling direct detection of these interfering components, this experimental system was used to analyze the ability of several common extraction procedures to remove endogenous plasma components that cause changes in the ESI response of model drug substances. Methyl-t-butyl ether (MTBE) liquid-liquid, Oasis and Empore solid-phase, and acetonitrile (ACN) protein precipitation sample preparation methods were tested using the post-column infusion system. In all cases, ACN protein precipitation samples showed the greatest amount of ESI response suppression while liquid-liquid extracts demonstrated the least. In addition, the three test compounds, phenacetin, caffeine, and a representative Merck compound, demonstrated that ESI response suppression is compound dependent. Suppression was greatest with caffeine, the most polar analyte, and the smallest for the Merck compound, the least polar analyte. Copyright 1999 John Wiley & Sons, Ltd.     

Gamma-ray spectroscopy with relativistic exotic heavy-ions

Feasibility of gamma-ray spectroscopy at relativistic energies with exotic heavy-ions and new generation of germanium detectors (segmented Clover) is discussed. An experiment with such detector array and radioactive is discussed.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Complexes of iron and cobalt with new tripodal amido-polyphosphine hybrid ligands

Divalent complexes of iron and cobalt with new, monoanionic tripodal amido-polyphosphine ligands have been thoroughly characterized, and XRD analysis reveals geometries that are distinct for this class of ligand.     

Symmetry-breaking intramolecular charge transfer in the excited state of meso-linked BODIPY dyads

We report the synthesis and characterization of symmetric BODIPY dyads where the chromophores are attached at the meso position, using either a phenylene bridge or direct linkage. Both molecules undergo symmetry-breaking intramolecular charge transfer in the excited state, and the directly linked dyad serves as a visible-light-absorbing analogue of 9,9'-bianthryl.     

Evaluation of blue and green absorbing proteorhodopsins as holographic materials

Transient holographic diffraction is observed for the green (GPR) and blue (BPR) absorbing proteorhodopsins (BAC31A8 and HOT75M1, respectively), as well as the GPR E108Q and BPR E110Q variants. In contrast to bacteriorhodopsin, where the metastable bR-M pair is responsible for generating diffraction, the pR and red-shifted N-like states fulfill that role in both the green and blue wild-type proteorhodopsins. The GPR E108Q and BPR E110Q variants, however, behave more similarly to their bacteriorhodopsin analogue, D96N, with diffraction arising from the PR M-state (strongly enhanced in both GPR E108Q and BPR E110Q). Of the four proteins evaluated, wild type (WT) GPR and GPR E108Q produce the highest diffraction efficiencies, etamax, at approximately 1% for a 1.7 OD sample. GPR E108Q, however, requires 1-2 orders of magnitude less laser intensity to generate eta equivalent to WT GPR and BR D96N under similar conditions (as compared to literature values). WT BPR requires lower actinic powers than GPR but diffracts only about 30% as well. BPR E110Q performs the most poorly of the four, with etamax < 0.05% for a 1.4 OD film. The Kramers-Kronig transformation and Koglenik's coupled wave theory were used to predict the dispersion spectra and diffraction efficiency for the long M-state variants. To a first approximation, the gratings formed by all samples decay upon discontinuing the 520 nm actinic beams with a time constant characteristic of the appropriate intermediate: the N-like state for WT GPR and BPR and the M-state for GPR 108Q and BPR E110Q.