Iron(III)-siderophore coordination chemistry: Reactivity of marine siderophores

Two remarkable features of many siderophores produced by oceanic bacteria are the prevalence of an α-hydroxy-carboxylic acid functionality either in the form of the amino acid β-hydroxy aspartic acid or in the form of citric acid, as well as the predominance of amphiphilic siderophores. This review will provide an overview of the photoreactivity that takes place when siderophores containing β-hydroxy aspartic acid and citric acid are coordinated to iron(III). This photoreactivity raises questions about the role of this photochemistry in microbial iron acquisition as well as upper-ocean iron cycling. The self-assembly of amphiphilic siderophores and the coordination-induced phase-change of the micelle-to-vesicle transformation will also be reviewed. The distinctive photosensitive and self-assembly properties of marine siderophores hint at possibly new microbial iron acquisition mechanisms.     

Conformation‐Controlled Diplatinum(II)–Ferrocene Dyads to Achieve Long‐Lived Charge‐Separated States

Square‐planar polypyridyl platinum(II) complexes possess a rich range of structural and spectroscopic properties that are ideal for designing artificial photosynthetic centers. Taking advantage of the directionality in the charge‐transfer excitation from the metal to the polypyridyl ligand, we describe here diplatinum(II)–ferrocene dyads, open‐butterfly‐like dyad 1 and closed‐butterfly‐like dyad 2 , which were designed to understand the conformation and orientation effects to prolong the lifetime of charge‐separated state. In contrast to the open‐butterfly‐like dyad 1 , the closed‐butterfly‐like dyad 2 shows three‐times long lifetime of charge separated state upon photoexcitation, demonstrating that the orientation in the rigid structure of dyad 2 is a very important issue to achieve long‐lived charge separated state.     

Determining the topology of virus assembly intermediates using ion mobility spectrometry–mass spectrometry

We have combined ion mobility spectrometry–mass spectrometry with tandem mass spectrometry to characterise large, non‐covalently bound macromolecular complexes in terms of mass, shape (cross‐sectional area) and stability (dissociation) in a single experiment. The results indicate that the quaternary architecture of a complex influences its residual shape following removal of a single subunit by collision‐induced dissociation tandem mass spectrometry. Complexes whose subunits are bound to several neighbouring subunits to create a ring‐like three‐dimensional (3D) architecture undergo significant collapse upon dissociation. In contrast, subunits which have only a single neighbouring subunit within a complex retain much of their original shape upon complex dissociation. Specifically, we have determined the architecture of two transient, on‐pathway intermediates observed during in vitro viral capsid assembly. Knowledge of the mass, stoichiometry and cross‐sectional area of each viral assembly intermediate allowed us to model a range of potential structures based on the known X‐ray structure of the coat protein building blocks. Comparing the cross‐sectional areas of these potential architectures before and after dissociation provided tangible evidence for the assignment of the topologies of the complexes, which have been found to encompass both the 3‐fold and the 5‐fold symmetry axes of the final icosahedral viral shell. Such insights provide unique information about virus assembly pathways that could allow the design of anti‐viral therapeutics directed at the assembly step. This methodology can be readily applied to the structural characterisation of many other non‐covalently bound macromolecular complexes and their assembly pathways. Copyright © 2010 John Wiley & Sons, Ltd.     

The quantification of total lead in lipstick specimens by total reflection X‐ray fluorescence spectrometry

Lipstick is known to contain lead, and this has been a general area of concern. Methods of quantifying lead in lipstick currently require the use of rather harsh digestion procedures given that lipstick specimens are high in their lipid content and contain many refractory materials. A simple method of performing lead analysis in lipstick specimens based on total reflection X‐ray fluorescence spectrometry (TXRF) is presented here. Samples were prepared by melting lipstick specimens along with a non‐ionic surfactant and an yttrium internal standard followed by homogenization. Solid prepared samples were then finely streaked directly onto a quartz reflector, and TXRF measurements made for 900‐s live time. The method was found to produce a mean limit of detection for lead of 0.04μg/g. Precisions were found to be on the order of 11–38% relative standard deviation (RSD) and apparent recoveries for lead between 92% and 106% (n = 8). Although the spreading technique may result in thickness variations that may contribute to the higher than expected variances about the determined lead concentrations, the method presented in this work does show promise as a means of performing routine lead analysis in lipstick specimens without the need for harsh digestion procedures. Copyright © 2015 John Wiley & Sons, Ltd.