Analysis of non-enzymatically glycated peptides: neutral-loss-triggered MS(3) versus multi-stage activation tandem mass spectrometry

Non-enzymatic glycation of tissue proteins has important implications in the development of complications of diabetes mellitus. While electron transfer dissociation (ETD) has been shown to outperform collision-induced dissociation (CID) in sequencing glycated peptides by tandem mass spectrometry, ETD instrumentation is not yet widely available and often suffers from significantly lower sensitivity than CID. In this study, we evaluated different advanced CID techniques (i.e., neutral-loss-triggered MS(3) and multi-stage activation) during liquid chromatography/multi-stage mass spectrometric (LC/MS(n)) analyses of Amadori-modified peptides enriched from human serum glycated in vitro. During neutral-loss-triggered MS(3) experiments, MS(3) scans triggered by neutral losses of 3 H(2)O or 3 H(2)O + HCHO produced similar results in terms of glycated peptide identifications. However, neutral losses of 3 H(2)O resulted in significantly more glycated peptide identifications during multi-stage activation experiments. Overall, the multi-stage activation approach produced more glycated peptide identifications, while the neutral-loss-triggered MS(3) approach resulted in much higher specificity. Both techniques are viable alternatives to ETD for identifying glycated peptides. Copyright (c) 2008 John Wiley & Sons, Ltd.     

Zur Analyse der Essigs?ure und des Essigs?ureanhydrids

Ohne Zusammenfassung     

Donor-Acceptor Dyads and Triads Employing Core-Substituted Naphthalene Diimides: A Synthetic and Spectro (Electrochemical) Study

Donor-acceptor dyads and triads comprising core-substituted naphthalene diimide (NDI) chromophores and either phenothiazine or phenoxazine donors are described. Synthesis combined with electrochemical and spectroelectrochemical investigations facilitates characterisation of the various redox states of these molecules, confirming the ability to combine arrays of electron donating and accepting moieties into single species that retain the redox properties of these individual moieties.     

Butane and propane oxidation by engineered cytochrome P450cam

The haem monooxygenase cytochrome P450cam has been engineered to oxidise the gaseous alkanes butane and propane to butan-2-ol and propan-2-ol, respectively, by the use of bulky amino acid substitutions to reduce the volume of the substrate pocket and thus improve the enzyme-substrate fit: the F87W/Y96F/T101L/V247L mutant oxidizes butane with a turnover rate of 750 min-1 and 95% yield based on NADH consumed while the wild-type enzyme has an activity of 0.4 min-1 with 4% yield.     

X-ray photoelectron spectroscopy of bulk glassy Se under Ar ion bombardment

It has been found that Ar ion bombardment produces reversible changes in the XPS structure of the valence band of glassy Se. The result of ion bombardment is that the 4 p bonding and non-bonding peaks merge to give a single broad peak at a binding energy similar to that of the non-bonding peak. This merger of the bonding and non-bonding peaks occurs in density of state calculations when the dihedral angle between adjacent bonds is allowe to take any angle. It is concluded, therefore, that ion bombardment introduces a random dihedral angle into the glassy structure, which subsequently relaxes to give the fixed dihedral angle, but with a random direction which density of states calculations and diffraction work indicate as the structure of the glass.     

The single-mode rate equations for semiconductor lasers with thermal effects

A mathematical model describing the coupling of electrical,optical and thermal effects in semiconductor lasers is introduced.Numerical and asymptotic solutions are derived, including expressionsfor key physical quantities such as the initial time delay,the frequency of spike oscillation and the temperature rise,together with its influence on the photon density, the electronconcentration and the threshold current. The consequences ofthermal effects in reducing efficiency are thus quantified.     

Metal transition complexes of tridentate Schiff base ligands derived from 2-hydrazinopyridine: synthesis,spectroscopic characterization and X-ray structures

Transition Metal Chemistry - Mononuclear complexes of 1-(pyridin-2-ylmethylidene)-2-(pyridin-2-yl)hydrazine (HL1) and 1-(pyridin-2-yl)-2-(1-(pyridin-2-yl)ethylidene)hydrazine (HL2),...     

Protein NMR Resonance Assignment without Spectral Analysis: 5D SOlid‐State Automated Projection SpectroscopY (SO‐APSY)

Narrow proton signals, high sensitivity, and efficient coherence transfers provided by fast magic‐angle spinning at high magnetic fields make automated projection spectroscopy feasible for the solid‐state NMR analysis of proteins. We present the first ultrahigh dimensional implementation of this approach, where 5D peak lists are reconstructed from a number of 2D projections for protein samples of different molecular sizes and aggregation states, which show limited dispersion of chemical shifts or inhomogeneous broadenings. The resulting datasets are particularly suitable to automated analysis and yield rapid and unbiased assignments of backbone resonances.