Investigations by various analytical techniques to the correct classification of archaeological finds and delineation of technological features: Late Roman lamps from Egnatia: From imports to local production

Late Roman oil lamps from the archaeological site of Egnatia (Fasano, Brindisi, Italy) were characterized from physical–chemical, mineralogical and morphological points of view. Atomic Spectroscopy, Scanning Electron Microscopy and X-Ray Diffraction analyses were carried out on ceramic body and coatings with the aim of identifying the provenance of lamps, in order to arrive at a correct archaeological classification of finds and to outline their technological features.The analytical results show that the finds differ in raw materials and in production technology. The statistical multivariate treatment of compositional data of ceramic bodies groups the objects into two macro clusters and, according to a study of their different petrographic features and by a comparison with coeval pottery whose provenance is already known, suggests one group to have been imported from North Africa and the other to have been locally produced. Moreover, chemical results and in-depth archaeological analyses allow us to split the imported lamps into two subgroups, hypothesizing the first group to originate from central Tunisia and the second from the north of the same country.The analytical characterisation of finds, by different complementary techniques, has allowed us to identify the raw materials and the technological solutions used by the ancient potters from Egnatia to produce lamps. The potters made lamps which had an external appearance very similar to that of African prototypes, but which were nevertheless different as they employed the locally available materials.     

Efficient removal of DNA from proteomic samples prior to two-dimensional map analysis

Several methods have been described in the literature for removal of DNA from protein samples prior to proteome analysis. They in general involve protein precipitation techniques. In other protocols, DNAse treatment is suggested prior to precipitation of proteins in excess acetone. All these methods have been evaluated and found to perform poorly in DNA removal, as illustrated by two-dimensional (2D) maps where horizontal and vertical sample streaking are still substantial. Such removal is in general necessary in tissue lysates and especially when analysing sub-cellular organelles, such as nuclei, where the high DNA levels strongly interfere with proteome analysis. Another method is proposed here for efficient DNA removal: two-phase extraction of DNA in chloroform/phenol/isoamyl alcohol, a procedure commonly used to rid DNA samples of protein contaminants, but rarely applied to protein preparation. This extraction is not very efficient if performed at slightly acidic to neutral pH values, but it performs extremely well at pH values of 9.5 or higher. The 2D maps thus obtained of Escherichia coli lysates as well as extracts from purified nuclei of eukaryotic cells are not only devoid of any vertical or horizontal streaking, but exhibit many more spots, especially in the alkaline region of the 2D gels, suggesting that these basic proteins were in general lost to proteome analysis due to co-precipitation in tenacious protein–DNA complexes. It is hypothesized that the alkaline pH values adopted in the two-phase extraction help to fully disrupt any residual DNA–protein complexes, due to strong Coulombic repulsion.     

The role of the scalar curvature in a nonlinear elliptic problem on Riemannian manifolds

Given (M, g) a smooth compact Riemannian N-manifold, N ≥ 2, we show that positive solutions to the problem

Heterodimers based on CoPt3-Au nanocrystals with tunable domain size

We describe an approach to synthesize colloidal nanocrystal heterodimers composed of CoPt(3) and Au. The growth is based on the nucleation of gold domains on preformed CoPt(3) nanocrystals. It is a highly versatile methodology which allows us to tune independently the size of the two domains in each dimer by varying several reaction parameters. The statistical analysis of the distribution of the domain sizes in the dimers and the compositional mapping achieved by dark field imaging and energy dispersive spectroscopy confirm that the two domains in each dimer are indeed made of CoPt(3) and Au, respectively. Structural characterization by high-resolution transmission electron microscopy shows that the two domains, both having cubic fcc Bravais lattice, can share a common {111}, {100}, or {110} facet, depending on the size of the initial CoPt(3) seeds. The magnetization measurements evidence a ferromagnetic CoPt(3) phase with a relatively low anisotropy as a consequence of their disordered crystalline structure, regardless of the presence of a Au tip. We believe that this prototype of nanocrystal dimer, which can be manipulated under air, can find several applications in nanoscience, as the Au section can be exploited as the preferential anchor point for various molecules, while the CoPt(3) domain can be used for magnetic detection.     

Investigation of intramolecular proton migration in a series of model, metal-cationized tripeptides using in situ generation of an isotope label

In this study we used an isotope label, generated in situ, to investigate intramolecular proton migration or scrambling during formation of [b(2)+17+Li](+) products by collision-induced dissociation (CID) of Li(+)-cationized tripeptides. To generate the isotope label, we used a McLafferty-type rearrangement of N-terminally acetylated, C-terminal peptide tert-butyl esters in which all amide positions were exchanged with deuterium. Using a set of small, model peptides, we show that intramolecular proton scrambling occurs during CID, particularly amongst adjacent sites along a peptide backbone, on the time scales employed for low-energy collisional activation in an ion-trap mass spectrometer.     

Photoconvertible fluorescent protein EosFP: biophysical properties and cell biology applications

EosFP is a fluorescent protein from the coral Lobophyllia hemprichii that changes its fluorescence emission from green to red upon irradiation with near-UV light. Here we present the spectroscopic properties of wild-type EosFP and a variety of monomeric and dimeric mutants and provide a structural interpretation of its oligomerization and photoconversion, which is based on X-ray structure analysis of the green and red species that we reported recently. Because functional expression of the monomeric EosFP variant is limited to temperatures of 30 degrees C, we have developed a tandem dimer. This construct, in which two EosFP subunits are connected by a flexible 12 amino acid linker, expresses well after fusion with the androgen and endothelin A receptors at 37 degrees C. A variety of applications in cellular imaging, developmental biology and automated high-content screening applications are presented, which demonstrate that EosFP is a powerful tool for in vivo monitoring of cellular processes.     

Characterisation by liquid chromatography-electrospray tandem mass spectrometry of anthocyanins in extracts of Myrtus communis L. berries used for the preparation of myrtle liqueur

Anthocyanins in extracts of berries of Myrtus communis, prepared following a typical Sardinia myrtle liqueur recipe, were identified and quantified by HPLC coupled with electrospray/tandem mass spectrometry using, respectively, an ion trap and a triple quadrupole mass analyser. The fragmentation patterns of the anthocyanidins were dependent on the MS technique employed, and differed considerably from those previously reported. The anthocyanin profile of five anthocyanin glucosides and four anthocyanin arabinosides, the latter not previously identified in this specie, was specific for myrtle berry extracts. The quantitative compositions of extracts of myrtle berries derived from different geographical areas in Italy were compared.     

Synthesis of 2,4-disubstituted piperidines via radical cyclization: unexpected enhancement in diastereoselectivity with tris(trimethylsilyl)silane

A novel approach to 2,4-disubstituted piperidines is reported, involving the radical cyclization of 7-substituted-6-aza-8-bromooct-2-enoates. Cyclization with tributyltin hydride affords the trans piperidines with trans/cis diastereomeric ratios ranging typically from 3:1 to 6:1. Cyclization with tris(trimethylsilyl)silane affords the same products with diastereomeric ratios of up to 99:1 in certain cases. The enhancement in diastereoselectivity results from the selective rearrangement of the minor stereoisomer through a cascade process involving radical cyclization to the piperidine radical, 1,5-radical translocation, and attack of the translocated radical onto the sulfonamide with extrusion of SO2 in a Smiles-type rearrangement. Slower trapping of the piperidine radical by tris(trimethylsilyl)silane compared to tributyltin hydride accounts for the occurrence of the rearrangement cascade in the former case.