Negative-ion fast atom bombardment mass spectrometry in the characterization of deoxyfluorinated sugars

Negative-ion fast atom bombardment mass spectrometry and metastable ion studies were applied to the characterization of three isomeric fluorine-containing sugars. Peculiar fragmentation processes were evidenced for each isomer, enabling their differentiation. Comparison with the behaviour of a non-fluorinated analogue allowed investigation of the role of fluorine in the decomposition processes of these compounds.     

Gas-liquid chromatographic fractionation of polyoxyethylene non-ionic surfactants : Polyoxyethylene mono-n-alkyl ethers

The gas-liquid chromatographic fractionation of the commercial biodegradable surfactants RO(CH₂CH₂O) _H (where R is an n-alkyl group and is the number-average degree of polymerization) can be approached only for 4, as the truncation of the molecular-weight distribution occurs at higher values. Although conversion into trimethylsily (TMS) derivatives improves the volatility of the oligomers, there is only a slight advantage in using this conversion procedure: TMS derivatives have the same elution temperature as untreated compounds above ca. 330°. The use of an internal standard as a reference compound for comparison of peak areas is a useful procedure, which has been tentatively applied to the reconstruction of the distribution of the surfactant with R = n-dodecyl and = 7.1. The choice of the internal standard is discussed.     

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.     

Monitoring the production yields of vincristine and vinblastine in Catharanthus roseus from somatic embryogenesis. Semiquantitative determination by flow-injection electrospray ionization mass spectrometry

A semiquantitative determination of two bis-indole antitumor alkaloids, vincristine and vinblastine, has been performed by flow-injection electrospray ionization mass spectrometric analysis of the extracts of Catharanthus roseus. Leaves and flowers of two different phenotypes (pink flower and white flower) obtained from somatic embryogenesis were thus examined and compared with the field-grown mother plant. Different amounts of vincristine and vinblastine were detected depending on the examined samples.     

Study on volatile components in salami by reverse carrier gas headspace gas chromatography-mass spectrometry

Salami are a typical seasoned sausage of Italy; a number of types are produced, according to local traditional recipes. As industrial production has taken place, a number of problems rise in obtaining products similar to the traditional ones. The use of selected microbial starters is permitted by Italian law for some years and at present, microbiological research is engaged in selecting starters similar to the ones isolated from traditional products, with the aim of obtaining organoleptic characteristics close to the ones of traditional recipes. A study was carried out concerning the characterisation of volatile components of salami by headspace capillary gas chromatography-mass spectrometry. As during the sampling step, analytes could reach the analytical column, the carrier gas rate was back flushed in the latter, while a pre column was used as cold trap. Then GC-MS analysis follows. By these techniques, we were able to highlight typical profiles of different salami, as well as monitoring the ripening of a traditional and a starter added salami. Main peaks are of fermentative origin, while also peaks from spices were detected. Ethyl propionate was used as internal standard to be able to normalise the peaks amounts.     

Electrospray ionisation tandem mass spectrometry in the characterisation of isomeric benzofurocoumarins

A set of aminoalkoxy-substituted, differently annullated furocoumarins, differing in the position of the aminoalkoxy chain and in the unsaturation level of the fused ring, has been subjected to electron impact and electrospray ionisation (ESI) experiments. In order to achieve a distinct characterisation of isomeric compounds, which partially failed under electron impact conditions, collision-induced dissociation experiments were performed on protonated molecules. The breakdown curves obtained by varying the tickle voltage on an ion trap ESI instrument led to the desired characterisation.     

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.