Mass displacements in quadrupolar field analysers

The influence of different instrumental parameters on the mass displacements observed in an ion trap and a quadrupole mass filter was investigated. In ion trap measurements it was observed that isolated ions (obtained by both ‘apex’ and ‘two-step’ isolation methods) show the same mass displacements determined in the usual mass spectra; isobaric ions of different structure irradiated with supplementary a.c. fields are ejected at different a.c. voltages, and different cooling times do not affect the mass value. In the quadrupole mass filter, differences in mass were found among isobaric ions of different structure, although to a smaller extent than those observed in the ion trap. All the data obtained are in agreement with the hypothesis of ion–r.f. field interactions originating from the polarizability of the ion.     

Segmented gas–liquid flow characterization in rectangular microchannels

We used optical methods such as Laser Induced Fluorescence (LIF) and confocal Laser Scanning Microscopy (LSM) to characterize gas–liquid phase distribution in rectangular microchannels. Using a 2 m long microchannel with a hydraulic diameter of 200 μm enables the precise measurement of important parameters such as liquid slug length, bubble length, pressure drop and film thickness at the wall as well as in the corner of the microchannel for low Capillary numbers (Ca) ranging from 2 × 10⁻⁴ to 1 × 10⁻². This range of Ca was obtained by using different fluid pairs such as ethanol, water and different concentrated aqueous solutions of glycerol in combination with nitrogen.     

Aggregation of perfluoroctanoate salts studied by 19F NMR and DFT calculations: counterion complexation, poly(ethylene glycol) addition, and conformational effects

The aggregation of perfluoroctanoate salts in H(2)O is studied by (19)F NMR on solutions of LiPFO, NaPFO, and CsPFO, without and with the addition of two poly(ethylene glycol) (PEG) oligomers of molecular weight 1500 and 3400 Da, respectively, and with the addition of suitable crown ethers. The (19)F chemical shift (cs) trends are monitored, at 25 °C, in a concentration range including the critical micellar concentration (cmc) or, in the presence of PEG, the critical aggregation concentration (cac). The cac values in the samples with PEG are lower than the cmc values of the corresponding samples without PEG; moreover, the (19)F cs trends above the cac and above the polymer saturation concentration reveal and help to explain some peculiarities of the aggregation process of PEG on PFO micelles, which, in the first step, seems to occur while the surfactant concentration in water is still increasing. Also in LiPFO/H(2)O or NaPFO/H(2)O solutions containing 12-crown-4 or 15-crown-5 ethers, suitable to complex Li(+) or Na(+) ions, respectively, the cmc decreases. On the other hand, the micellization process in the presence of crown ethers does not show other peculiarities. The prevailing conformations of the PFO chain are discussed on the basis of quantum-mechanical calculations. The theoretical chemical shifts were computed at the DFT level of theory, taking into account the effects of the environment by means of the IEF-PCM method. The helical structure is the most stable one, but anti conformations are easily accessible, in both the aqueous and fluorinated environment. The comparison between computed and experimental chemical shifts indicates that anti conformations are more important in the micelles than in water and in CsPFO micelles than in LiPFO or NaPFO ones.     

Antioxidant and antifungal activity of different extracts obtained from aerial parts of Inula crithmoides L.

The total phenolic content, antioxidant and antifungal activities of three Inula crithmoides extracts (n-hexane, methylene chloride and MeOH) were investigated. The methanolic extract showed the highest total phenolic content. In the DPPH assay, the methanolic and hexane extracts exhibited the highest DPPH-radical scavenging activity; in the 5-lipoxygenase assay, the hexane extract showed greater inhibitory effect with an IC₅₀ similar to that of Trolox and ascorbic acid. The antifungal activity of the methanolic extract revealed a higher activity against Phytophtora cryptogea and Alternaria solani.     

Integrated NMR and computational study of push-pull NLO probes: interplay of solvent and structural effects

In this study we combined QM calculations and NMR measurements to understand at a detailed level the complex interplay of structural/electronic properties with the effects of the solvent in the NLO activity of push-pull systems, quantified in terms of variations of the static hyperpolarizability. Different parameters (bond lengths and bond length alternation, vibrational frequencies, electronic charge distribution) are introduced and tested to rationalize both the solvent sensitivity of three molecular systems (namely, p-nitroaniline, ethyl 4-ammino benzoate, and 5-nitro-1H-indole) and the differences among them. This analysis has finally allowed us to establish a clear correlation between the charge transfer behavior of the systems, their NLO properties, and NMR parameters also validating simplified but effective chemical analyses based on resonance limit forms.     

Micro‐Raman spectroscopy and VP‐SEM/EDS applied to the identification of mineral particles and fibres in histological sections

Histological sections of a patient affected by an important respiratory disease were analysed firstly by optical microscope(OM)—crossed polarisers—to identify the presence of incorporated inorganic particles, with particular attention to the fibrous ones. Then, the particles/fibres that were found were studied both with micro‐Raman spectroscopy and variable‐pressure scanning electron microscopy with energy‐dispersive spectroscopy (VP‐SEM/EDS). The two techniques allowed the in situ characterisation of the inorganic phases without disintegration of the organic matter. Micro‐Raman spectroscopy was able to identify the vibrating chemical groups of the mineral phase associated with the inorganic grain while the crystalline structure was preserved by the biological system. The VP‐SEM/EDS characterisation, defining the elemental chemical composition of the analysed particle/fibre, allowed confirmation of the mineral phase deducible from spectroscopic data or its identification with certainty when the spectroscopic data were not exhaustive. Copyright © 2009 John Wiley & Sons, Ltd.     

Simultaneous determination of atracurium and its metabolite laudanosine in post-mortem fluids by liquid chromatography/multiple-stage mass spectrometry on an ion trap

A method was developed to accurately quantify atracurium (a non-depolarizing skeletal muscle relaxant) and its metabolite laudanosine in post-mortem specimens. Analytes were isolated from blood and tissues by liquid/liquid extraction after adding vecuronium as an internal standard. Chromatographic separation was accomplished by gradient elution in a Synergy Max RP 150 x 2.1 mm column. Positive ion electrospray ionization and mass spectrometric analyses were carried out in an ion trap mass spectrometer under collision-induced dissociation conditions. The method proved selective and sensitive, and was validated in post-mortem blood, heart, lung and liver in the range of 1-2000 ng/mL (blood) and 5-5000 ng/g (tissues); the limits of quantification obtained were 1 ng/mL in blood and 5 ng/g in tissues.     

Phases in the Al–Yb–Zn system between 25 and 50 at% ytterbium

Phases YbZn_1−xAl_x, YbZn_2−xAl_x and YbZn_3−xAl_x were studied by electron microprobe analysis and X-ray single crystal and powder methods. The compound YbZn_0.8Al_0.2 crystallizes with the CsCl-type, a=3.635(2) Å. Four phases were investigated by single crystal X-ray diffraction: YbZn_0.996(6)Al_1.004(6), MgNi₂-type, P6₃/mmc, a=5.573(1), c=18.051(3) Å, Z=8, wR2=0.040 and YbZn_0.88(3)Al_1.12(3), MgCu₂-type, , a=7.860(2) Å, Z=8, wR2=0.060, both showing mixed Zn/Al occupancy; YbZn_2.50(1)Al_0.50(1), CeNi₃-type, P6₃/mmc, a=5.496(1), c=17.336(2) Å, Z=6, wR2=0.036 and YbZn_1.92(2)Al_1.08(2), PuNi₃- or NbBe₃-type, , a=5.499(1), c=26.134(5) Å, Z=9, wR2=0.053, where the zinc atoms are ordered in the CaCu₅ segment, while share the sites with aluminium in the Laves phase segment. In the pseudobinary section YbZn_2−xAl_x four structures occur in sequence with increasing the electron concentration: CeCu₂ or KHg₂ (x=0–0.3), MgZn₂ (x=0.33–0.54), MgNi₂ (x=0.68–1.01) and MgCu₂ (x=1.12–2). This sequence agrees with the results of first-principles calculations, already reported in the literature for other similar series. In the YbZn_3−xAl_x section CeNi₃-type compounds occur with x=0.40–0.88 followed by PuNi₃-type compounds with x=0.92–1.10. The stability ranges of these phases are related to the valence electron concentration.