A simplified device for protein identification by microcapillary gradient liquid chromatography-tandem mass spectrometry

A simplified device and procedure have been developed for microcapillary gradient liquid chromatography-tandem mass spectrometry (LC-MS/MS). This procedure has proved useful in identifying low level quantities of proteins from sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) gel bands. Microelectrospray needles are packed with reversed-phase resin and function both as a high performance liquid chromatography (HPLC) column and a nanospray mass spectrometer tip when interfaced between an HPLC and ion trap mass spectrometer. Variable submicroliter flow rates are generated by flow splitting between the microelectrospray capillary and an HPLC system. A manual injector is used to inject a protein digest mixture that binds to the column and is then washed at a high flow rate (2 microL/min post split). Gradient elution of bound peptides was initiated by the injection of a filled loop of 70% v/v methanol (5 microL) concomitant with a reduction of flow rate (0.1 microL/min post split). This forms a diffusion-dependent gradient of variable length (typically 15-30 min in length) depending upon the final flow rate. Chromatographic separations of a standard solution digest demonstrate that this diffusion-dependent gradient provides reasonable separations such that multiple peptide identifications by MS/MS can be obtained. Application of this methodology to the analysis of several in-gel-digested gel-separated proteins is presented to demonstrate its utility.     

Loudness growth observed under partially tripolar stimulation: model and data from cochlear implant listeners

Most cochlear implant strategies utilize monopolar stimulation, likely inducing relatively broad activation of the auditory neurons. The spread of activity may be narrowed with a tripolar stimulation scheme, wherein compensating current of opposite polarity is simultaneously delivered to two adjacent electrodes. In this study, a model and cochlear implant subjects were used to examine loudness growth for varying amounts of tripolar compensation, parameterized by a coefficient sigma, ranging from 0 (monopolar) to 1 (full tripolar). In both the model and the subjects, current required for threshold activation could be approximated by I(sigma)=Ithr(0)(1-sigmaK), with fitted constants Ithr(0) and K. Three of the subjects had a "positioner," intended to place their electrode arrays closer to their neural tissue. The values of K were smaller for the positioner users and for a "close" electrode-to-tissue distance in the model. Above threshold, equal-loudness contours for some subjects deviated significantly from a linear scale-up of the threshold approximations. The patterns of deviation were similar to those observed in the model for conditions in which most of the neurons near the center electrode were excited.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

Wasserfreies Octamolybdat mit Trimethylhexadecylammonium‐Kationen

Anhydrous Octamolybdate with Trimethyl Hexadecyl Ammonium Cations The compound [N(CH₃)₃C₁₆H₃₃]₄Mo₈O₂₆ was synthesized via a template route in form of plate‐like crystals which have been characterized by Xray analysis (P1 (Nr. 2); a = 1003.0(4) pm, b = 1123.6(4) pm, c = 2528(1) pm, α = 97.42(3)°, β = 96.09(3)°, γ = 115.76(3)°; Z = 1). [N(CH₃)₃C₁₆H₃₃]₄Mo₈O₂₆ is a crystalline composite of octamolybdate anions and trimethyl hexadecyl ammonium cations. Cations and anions organize in separate spatial sections forming layers of inorganic and organic species. Another composite of the same constituents has been found which is an amorphous lamellar material consisting of alternating layers of MoO₃ and templates.