Experimental Design in Ion Chromatography: Effect of the Organic Modifier and Complexing Agent on the Retention of Alkaline and Alkaline Earth Ions

A Box–Behnken experimental design combined with response surface methodology was applied to investigate the effect of the eluent composition on the retention of common cations in ion chromatography. In particular, we modelled the retention factors of Na⁺, K⁺, NH₄ ⁺, Ca⁺⁺ and Mg⁺⁺ and the chromatogram resolution. Response surfaces were evaluated to assess interactive effects of nitric acid, pyridine-2,6-dicarboxylic acid and percentage of acetonitrile in the eluent on the above parameters. Nitric acid concentration and acetonitrile content appeared as the most and the least influential components of the eluent in determining the retention factors of individual ions or the global resolution of the chromatogram, while the concentration of the complexing agent exhibits an intermediate role. As expected, acidification of the mobile phase produces a decrease in the retention factors and a progressive worsening of resolution, and this effect can be modulated by the concentration of the complexing agent. The proposed approach seems suitable to investigate the retention phenomena in ion chromatography under application of complex eluent phases.     

On the goethite to hematite phase transformation

This study deals with some microstructural and crystallographic aspects of the thermally induced transformation of goethite (α-FeOOH) into hematite (α-Fe₂O₃), occurring at about 300 °C. Powder specimens of goethite have been annealed in air at different temperatures, ranging from 200 °C up to 1,000 °C. The resulting products have been analyzed for a complete characterization of the changes brought about by the thermal treatments, using a multianalytical approach, based on: thermogravimetry, differential thermal analysis, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction. At lower temperatures, the transition to hematite produces no important changes in size and shape of the original goethite grains. Recrystallization, and partial sintering, occurs only at temperatures in excess of 800 °C. The relevant evolution of pores present in both phases has been also considered, as it may provide important indications on the actual formation mechanism of hematite.     

LC/ESI‐MS/MS characterisation of lipopeptide biosurfactants produced by the Bacillus licheniformis V9T14 strain

Lipopeptide biosurfactants produced by the Bacillus licheniformis V9T14 strain showed an interesting anti‐adhesion activity against biofilm formation of human pathogenic bacterial strains. The chemical characterisation of the crude extract of V9T14 strain was first developed through electrospray ionisation mass spectrometry (ESI‐MS) and ESI‐MS/MS direct infusions: two sets of molecular ion species belonging to the fengycin and surfactin families were revealed and their structures defined, interpreting their product ion spectra. The LC/ESI‐MS analysis of the crude extract allowed to separate in different chromatogram ranges the homologues and the isoforms of the two lipopeptide families. The extract was then fractionated by silica gel chromatography in two main fractions, I and II. The purified biosurfactants were analysed through a new, rapid and suitable LC/ESI‐MS/MS method, which allowed characterising the composition and the structures of the produced lipopeptides. LC/ESI‐MS/MS analysis of fraction I showed the presence of C₁₃, C₁₄ and C₁₅ surfactin homologues, whose structures were confirmed by the product ion spectra of the sodiated molecules [M + Na]⁺ at m/z 1030, 1044 and 1058. LC/ESI‐MS/MS analysis of fraction II confirmed the presence of two main fengycin isoforms, with the protonated molecules [M + H]⁺ at m/z 1478 and 1506 corresponding to C₁₇ fengycin A and C₁₇ fengycin B, respectively. Other homologues (C₁₄ to C₁₆) were revealed and confirmed as belonging to fengycin A or B according to the retention times and the product ions generated, although with the same nominal mass. Finally, a relative percentage content of each homologue for both lipopeptides families in the whole extract was proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

Pyroxene inclusions in paleo-Christian mosaic tesserae: a new tool for constraining the glass manufacturing temperature

The mineral inclusions of two orange glass tesserae from paleo-Christian mosaics were investigated in order to derive the melting temperature reached during their production (sourced from Padua and Vicenza, Veneto region, Italy). In particular, clinopyroxene crystals were studied by single-crystal X-ray diffraction and electron microprobe WDS analysis. The crystals show C2/c symmetry, typical of disordered Ca/Na and Mg/Al distributions indicating high-temperature of formation (>700°C). The cation site populations were obtained by combining results from the two experimental techniques enabled us to derive the following stoichiometric formula:

Characterization of an actively linearized ultrabroadband chirped laser with a fiber-laser optical frequency comb

The optical frequency sweep of an actively linearized, ultrabroadband, chirped laser source is characterized through optical heterodyne detection against a fiber-laser frequency comb. Frequency sweeps were measured over approximately 5 THz bandwidths from 1530 nm to 1570 nm. The dominant deviation from linearity resulted from the nonzero dispersion of the fiber delay used as a reference for the sweep linearization. Removing the low-order dispersion effects, the residual sweep nonlinearity was less than 60 kHz rms, corresponding to a constant chirp with less than 15 ppb deviation across the 5 THz sweep.     

The direct image of the relative dualizing sheaf needs not be semiample

We provide details for the proof of Fujita's second theorem and prove that for a Kähler fibre space f:X→B$f:X\to B$ over a smooth projective curve B  , the direct image of the relative dualizing sheaf V:=f_?ω_X/B$V:=f_{?}{\omega }_{X/B}$ is the direct sum of an ample and a unitary flat bundle. We also show that V needs not be semiample, which is our main result.