Fish otolith trace element maps: new approaches with synchrotron microbeam x‐ray fluorescence

Otoliths, the carbonate earstones of fishes, take up minor and trace amounts of elements as they accrete through a fish's life. We apply synchrotron microbeam x‐ray fluorescence methods to establish a breakthrough in high‐resolution, simultaneous area mapping of multiple trace elements in otoliths, with spatial resolution down to 20 µm and trace element detection down into the part per million range for multiple elements. Concentration maps of Ca, Sr, Zn and, for the first time, Ba, Mn, and Se are obtained simultaneously. Combinations of these elemental maps provide new insights into the environmental history of fishes and their lifetime movements, illustrated by several case studies. This method helps pave the way toward improved spatial analysis of otolith microchemistry. Copyright © 2007 John Wiley & Sons, Ltd.     

Isometric Actions of Heisenberg Groups on Compact Lorentz Manifolds

We prove results toward classifying compact Lorentz manifolds on which Heisenberg groups act isometrically. We give a general construction, leading to a new example, of codimension-one actions – those for which the dimension of the Heisenberg group is one less than the dimension of the manifold. The main result is a classification of codimension-one actions, under the assumption they are real-analytic.     

Direct Catalytic Asymmetric Aldol Reaction of an α‐Azido Amide

A direct aldol reaction of an α‐azido 7‐azaindolinylamide, promoted by a Cu‐based cooperative catalyst, is documented. Aromatic aldehydes bearing an ortho substituent exhibited diastereodivergency depending on the nature of the chiral ligands used. Smooth reactions with ynals highlighted the broad substrate scope. A vicinal azido alcohol unit in the product allowed direct access to the corresponding aziridine and facile hydrolysis of the 7‐azaindolinylamide moiety furnished enantioenriched β‐hydroxy‐α‐azido carboxylic acid derivatives.     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

Free-standing biomimetic polymer membrane imaged with atomic force microscopy

Fluid polymeric biomimetic membranes are probed with atomic force microscopy (AFM) using probes with both normal tetrahedrally shaped tips and nanoneedle-shaped Ag(2)Ga rods. When using nanoneedle probes, the collected force volume data show three distinct membrane regions which match the expected membrane structure when spanning an aperture in a hydrophobic scaffold. The method used provides a general method for mapping attractive fluid surfaces. In particular, the nanoneedle probing allows for characterization of free-standing biomimetic membranes with thickness on the nanometer scale suspended over 300-μm-wide apertures, where the membranes are stable toward hundreds of nanoindentations without breakage.     

Thermal phase behavior of DMPG bilayers in aqueous dispersions as revealed by 2H- and 31P-NMR

The synthetic lipid 1,2-dimyristoyl-sn-3-phosphoglycerol (DMPG), when dispersed in water/NaCl exhibits a complex phase behavior caused by its almost unlimited swelling in excess water. Using deuterium ((2)H)- and phosphorus ((31)P)-NMR we have studied the molecular properties of DMPG/water/NaCl dispersions as a function of lipid and NaCl concentration. We have measured the order profile of the hydrophobic part of the lipid bilayer with deuterated DMPG while the orientation of the phosphoglycerol headgroup was deduced from the (31)P NMR chemical shielding anisotropy. At temperatures >30 °C we observe well-resolved (2)H- and (31)P NMR spectra not much different from other liquid crystalline bilayers. From the order profiles it is possible to deduce the average length of the flexible fatty acyl chain. Unusual spectra are obtained in the temperature interval of 20-25 °C, indicating one or several phase transitions. The most dramatic changes are seen at low lipid concentration and low ionic strength. Under these conditions and at 25 °C, the phosphoglycerol headgroup rotates into the hydrocarbon layer and the hydrocarbon chains show larger flexing motions than at higher temperatures. The orientation of the phosphoglycerol headgroup depends on the bilayer surface charge and correlates with the degree of dissociation of DMPG-Na(+). The larger the negative surface charge, the more the headgroup rotates toward the nonpolar region.