On-target deuteration technique in time-of-flight 252Cf plasma desorption mass spectrometry

A new on-target deuteration technique in plasma desorption mass Spectrometry (PDMS) is proposed, involving replacing labile hydrogen atoms in a molecule with deuterium atoms. This technique is very simple and allows direct comparison of spectra before and after deuteration for the same probe. The utility of the deuteration procedure in PDMS has been demonstrated in obtaining additional information on the structure of a molecule and its fragments and on the mechanism of quasi-molecular ion formation.     

Novel natural peptides from Hyla arborea schelkownikowi skin secretion

Hyla arborea schelkownikowi is one of the leaf frog species inhabiting the southern territories of Russia and the former USSR. This frog species is a member of the Hylidae Rafinesque, 1815 batrachians family. The present study deals with the previously uninvestigated peptidome of the Hyla arborea schelkownikowi skin secretion. Nano‐electrospray ionization Fourier transform mass spectrometry (nanoESI‐FTMS) of the skin secretion, in the intact form and after acetylation, was selected as the general method of analysis. Electron‐capture dissociation (ECD) and collision‐induced dissociation (CID) fragmentation were both employed, while de novo sequencing was performed by manual interpretation of the MS data. The suppression of the cyclization of b‐ions in the mass spectrometer by the acetylation reaction proved to be very efficient for the de novo sequencing of short peptides. Ten skin peptides were found and all of them, except for bradykinin, had not previously been reported. Six of the peptides belong to the tryptophyllins and related peptides, while three peptides are similar to the aureins. Copyright © 2010 John Wiley & Sons, Ltd.     

Benefits of 2.94 micron infrared matrix-assisted laser desorption/ionization for analysis of labile molecules by Fourier transform mass spectrometry

A 2.94 microm Er:YAG laser was used together with a commercial Fourier transform mass spectrometer to study labile biomolecules. The combination has shown superior performance over conventional 337 nm ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI) Fourier transform mass spectrometry (FTMS), especially for the analysis of peptides with post-translational modifications. With succinic acid as a matrix, the sensitivity of the single-shot analysis was increased by an order of magnitude to the low femtomole level, with significantly less fragmentation observed. Intact molecular ions of a range of O-glycosylated and sulfated peptides were detected. Urea was found to induce even less fragmentation, although at the expense of the total ion yield. Molecular ions of a noncovalent complex (vancomycin + diacetyl-L-Lys-D-Ala-D-Ala) have been observed for the first time in MALDI-FTMS. 2.94 microm infrared (IR) MALDI also produced abundant molecular ions of a range of nonbiological samples, including C60 and C70 fullerenes as well as dimetal coordination complexes.     

On the theory of oscillating flows in complex liquids

Experiments with highly concentrated suspensions and other complex liquids frequently demonstrate nonmonotonic N- or S-shaped dependences of viscous stress σ on shear rate $ \dot \gamma $ \dot \gamma and strong oscillations of the shear rate at a constant flow-inducing external stress, as well as oscillations of the viscous stress at a constant average shear rate. A phenomenological mathematical model is proposed for oscillating flows according to which oscillations arise when an applied stress (or the average shear rate, depending on the design of an experiment) is in the descending region of the σ-$ \dot \gamma $ \dot \gamma dependence and a complex liquid exhibits pronounced viscoelastic properties.     

From small building blocks to complex molecular architecture

[reaction: see text] We describe a synthesis of a dendrimer-like amphiphile containing a flat rigid core and 12 hydrophobic and hydrophilic arms. We employ a modular approach based on stepwise protection chemistry starting from simple building blocks. The key feature of this approach is the absence of a polymerization step, which makes it applicable for linear monofunctionalized precursors of any kind. This strategy also allows for precise control of the number of arms and ensures their alternating arrangement.