Gas phase ion/molecule reactions in laser desorption mass spectrometry

The desorption of neutrals, alkali ions and quasimolecular ions of sucrose was studied as function of substrate temperature in laser desorption mass spectrometry. These phenomena were also investigated in thermal desorption experiments. It was concluded that in these experiments gas phase cationization is the major ionization process.     

Analytical pyrolysis of carbohydrates: I. Chemical interpretation of matrix influences on pyrolysis-mass spectra of amylose using pyrolysis-gas chromatography-mass spectrometry

Inorganic additives, viz. Na₂CO₃, NaOH, HCl, ZnC₂, NaH₂PO₄, Na₂HPO₄, NaCl. MgSO₄ and sea salt, to the pyrolysis matrix change the pyrolysis-mass spectrum of amylose significantly. Carbonyl compounds, acids and their lactones, furans, pyranones anhydrosugars and aromatic substances are found in different ratios under the various conditions, as determined by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS).Carbonyl compounds, acids and lactones are released from alkaline and neutral matrices. Furans and anhydrohexoses are particularly formed under neutral and acidic conditions. Pyranones are specific for phosphate matrices. Unsaturated hydrocarbons and aromatic substances arise from strongly alkaline or dehydrating matrices. Degradation pathways are proposed for various compound categories.The results of pyrolysis-mass spectrometry and Py-GC-MS are highly compatible.     

Factors affecting gas-phase deuterium scrambling in peptide ions and their implications for protein structure determination

In this report, we evaluate the validity of using hydrogen/deuterium exchange in combination with collision-induced dissociation mass spectrometry (CID MS) for the detailed structural and conformational investigation of peptides and proteins. This methodology, in which partly deuterated peptide ions are subjected to collision-induced dissociation in the vacuum of a mass spectrometer, has emerged as a useful tool in structural biology. It may potentially provide quantitatively the extent of deuterium incorporation per individual amino acid in peptides and proteins, thus providing detailed structural information related to protein structure and folding. We report that this general methodology has limitations caused by the fact that the incorporated deuterium atoms migrate prior or during the CID MS analysis. Our data are focused on a variety of transmembrane peptides, incorporated in a lipid bilayer, in which the near-terminal amino acids that anchor at the lipid-water interface are systematically varied. Our findings suggest that, under the experimental conditions we use, the extent of intramolecular hydrogen scrambling is strongly influenced by experimental factors, such as the exact amino acid sequence of the peptide, the nature of the charge carrier, and therefore most likely by the gas-phase structure of the peptide ion. Moreover, the observed scrambling seems to be independent of the nature of the peptide fragment ions (i.e., protonated B and Y' ' ions, and sodiated A and Y' ions). Our results strongly suggest that scrambling may be reduced by using alkali metal cationization instead of protonation in the ionization process.     

C K‐edge NEXAFS study of fluorocarbon formation on carbon anodes in molten NaF–AlF3–CaF2

Operational instability from processes occurring at the anode during the production of aluminum in the commercial Hall‐Héroult process may lead to an increase in undesirable fluorocarbon emissions, higher energy use, and shorter plant life. One contribution to this instability may be the possible formation of a fluorocarbon film at the electrode interface. Here, the surface composition of graphite anodes after electrolysis in molten NaF–AlF₃–CaF₂ at 990 °C is investigated for evidence of fluorocarbon formation using C K‐edge near edge X‐ray absorption fine structure. Fluorocarbon is identified on an anode surface after prolonged anode effect (very high overpotential with increased cell resistance) and also on an anode surface after normal electrolysis without anode effect. This provides evidence that fluorocarbon formation may occur prior to anode effect lowering the surface tension of the anode and therefore resulting in dewetting to contribute to the onset of the anode effect. Confirmation that such compounds form furthers our understanding of electrochemical reactions of graphite with fluoride and of the fundamental processes that occur in an aluminum smelter cell. Copyright © 2013 John Wiley & Sons, Ltd.     

Gold nanoparticles produced in a microalga

An efficient biological route to production of gold nanoparticles which allows the nanoparticles to be easily recovered remains elusive. Live cells of the green microalga Chlorella vulgaris were incubated with a solution of gold chloride and harvested by centrifugation. Nanoparticles inside intact cells were identified by transmission electron microscopy and confirmed to be metallic gold by synchrotron based X-ray powder diffraction and X-ray absorption spectroscopy. These intracellular gold nanoparticles were 40–60 nm in diameter. At a concentration of 1.4% Au in the alga, a better than 97% recovery of the gold from solution was achieved. A maximum of 4.2% Au in the alga was obtained. Exposure of C. vulgaris to solutions containing dissolved salts of palladium, ruthenium, and rhodium also resulted in the production of the corresponding nanoparticles within the cells. These were surmised to be also metallic, but were produced at a much lower intracellular concentration than achieved with gold. Iridium was apparently toxic to the alga. No nanoparticles were observed using platinum solutions. C. vulgaris provides a possible route to large scale production of gold nanoparticles.     

Calculating parameters for infiltration equations from soil hydraulic functions

Simple equations for predicting infiltration of water into soil are valuable both for hydrological application and for investigating soil hydraulic properties. Their value is greatly enhanced if they involve parameters that can be related to more basic soil hydraulic properties. In this paper we extend infiltration equations developed previously for positive surface heads to negative heads. The equations are then used to calculate infiltration into a sand and a clay for a range of initial and surface conditions. Results show errors of less than three percent compared with accurate numerical solutions. Analytical approximations to parameters in the equations are developed for a Brooks and Corey power law hydraulic conductivity-water content relation combined with either a Brooks and Corey or a van Genuchten water retention function. These are compared with accurate numerical values for a range of hydraulic parameters encompassing the majority of soil types and a range of initial and boundary conditions. The approximations are excellent for a wide range of soil parameters.An important attribute of the infiltration equations is their use of dimensionless parameters that can be calculated from normalised water retention and hydraulic conductivity functions. These normalised functions involve only parameters that it may be possible to estimate from surrogate data such as soil particle size distribution. Application of the equations for predicting infiltration, or their use in inferring hydraulic properties, then involves only simple scaling parameters.     

PMR and CMR spectroscopy of methyl 2,3,4,6-tetra-O-methyl-α- and -β-d-glucopyranoside : An application to the identification of partially methylated glucoses

The proton and ¹³C magnetic resonance spectra of methyl 2,3,4,6-tetra-O-methyl-α- and -β-d-glucopyranoside are completely assigned. For this purpose specific deuterium and ¹³C labelling, spin decoupling and spectrum simulation are employed. The NMR data are discussed and compared with those of the free monomers and the methylglucosides. A partially methylated glucose obtained as a degradation product in the permethylation analysis of a carbohydrate can be identified after permethylation of the compound with labelled Me groups and comparison of the PMR or CMR spectra with those of reference permethylglucoses. From these spectra information is obtained about type and ring form of the monomers and position(s) of the glycosidic bond(s) in the original oligo- or polysaccharide. The number of reference compounds necessary for identification is strongly reduced. The method can be extended to other monomers because there are significant differences between the NMR data of the various permethylmonosaccharides.     

Interaction of wetting fronts with an impervious surface — Longer time behaviour

The interaction of a wetting front with an impervious surface can be described very easily in the early stages of interaction by using a superposition principle. After the time when the superposition principle fails to describe the interaction properly, two flow regimes are analysed. For most of the interaction the profile is only affected by the impervious surface near that surface and in particular the inflow into the soil layer is unchanged. Then, only at the very end of the process is the inflow decreasing because of the impervious surface.     

Chemical characterization of yeasts and yeast-like fungi by factor analysis of their pyrolysis—mass spectra

A factor analysis technique is described for determining differences in the pyrolysis—mass spectra of complex biological material in terms of chemical components. The technique is based on factor analysis with subsequent graphical rotation in order to find axes, describing changes in chemical components. Three yeast species could be clearly distinguished on the basis of four classes of chemical building blocks, viz. N-acetylamino-sugar, protein, hexose and pentose.