THE mod-p LOWER CENTRAL SERIES AND THE ADAMS SPECTRAL SEQUENCE?

USING A mod-p version of the lower central series one of us recently [lo] constructed a mod-p version of the spectral sequence of one of the others [3] and showed that for every topological space X there exists a spectral sequence {E’X, d’X) with the following properties: (i) E’X depends only on H,(X; Z,)

Characterization of micro-plasmas for Ambient Mass Spectrometry Imaging

Results are presented on the characterisation and optimisation of a non-thermal atmospheric pressure micro-plasma ion source used for ambient mass spectrometry imaging. The geometry of the experiment is optimised to produce the most intense and stable ion signals. Signal stabilities (relative standard deviation) of 2.3–6.5% are achieved for total ion current measurements from chromatograms. Parameters are utilised to achieve MS imaging by raster scanning of PTFE/glass samples with a spatial resolution of 147 ± 31 μm. A systematic study of resolution as a function of acquisition parameters was also undertaken to underpin future technique development. Mass spectra are obtained from PTFE/glass sample edges in negative ion mode and used to construct images to calculate the spatial resolution. Images are constructed using the intensity variation of the dominant ion observed in the PTFE spectrum. Mass spectra originating from the polymer are dominated by three series of ions in a m/z spectral window from 200–500 Da. These ions are each separated by 50 Da and have the chemical formula [C2F + [CF2]n]−, [CF + [CF2]n + O]− and [CF + [CF2]n + O3]−. The mechanism for the generation of these ions appears to be a polymer chain scission followed by ionisation by atmospheric ion adduction. Positive and negative ion mode mass spectra of personal care products, amino acids and pharmaceuticals, dominated by the proton abstracted/protonated molecular ion, highlight the potential areas of application for such a device. Further to this end a mass spectral image of cardamom seeds, constructed using the variation in intensity of possible fragments of the 1,8-cineole molecule, is included to reveal the potential application to the imaging of foods and other biological materials

Ambient Surface Mass Spectrometry Using Plasma-Assisted Desorption Ionization: Effects and Optimization of Analytical Parameters for Signal Intensities of Molecules and Polymers

Results are presented on the optimization and characterization of a plasma-assisted desorption ionization (PADI) source for ambient mass spectrometry. It is found that by optimizing the geometry we can increase ion intensities for valine and by tuning the plasma power we can also select a more fragmented or less fragmented spectrum. The temperature of the surface rises linearly with plasma power: at 19 W it is 71 °C and at 28 W it is 126 °C. To understand if the changes in signal intensity are related to thermal desorption, experiments using a temperature-controlled sample stage and low plasma power settings were conducted. These show markedly different signal intensities to experiments of equivalent surface temperature but higher plasma power, proving that the mechanisms of ionization and desorption are more complicated than just thermal processes. Four different polymers, poly­(methyl methacrylate) (PMMA), poly­(ethylene terephthalate) (PET), poly­(lactic acid) (PLA), and poly­(tetrafluoroethylene) (PTFE), are analyzed using PADI. Mass spectra are obtained from all the polymers in the negative ion mode and from PMMA and PLA in the positive ion mode. For each polymer, characteristic ions are identified showing the ability to identify materials. The ions are formed from bond cleavage with O and CH₂ as common adducts. Ions were detected up to <i>m</i>/<i>z</i> 1200 for PTFE

Fundamental differences in model cell-surface polysaccharides revealed by complementary optical and spectroscopic techniques

The propensity of two classes of polysaccharides, charged heparins and uncharged dextrans serving as models of those found in the extracellular matrix, to form ordered arrangements in solids and in solution, were explored employing polarising optical microscopy and reflection anisotropy spectroscopy. The fundamental modes of molecular vibration in the solid state, which relate to the occupancy of conformational states at ambient temperatures, were also investigated using terahertz (1–15 THz) spectroscopy on purpose built beam lines at SRS, Daresbury and ANKA, Karlsruhe. In the solid state, evidence for the anisotropic arrangement of ion centres was observed for the Na, Ca and Mg ion forms of heparin by RAS but, this was absent in aqueous solution at 100 mg ml−1 and the absence of molecular ordering in solution was confirmed by polarised optical microscopy. The ion charged heparin specimens showed very strong absorption of THz radiation indicating the accessibility of unoccupied higher energy conformational states in these materials whereas the uncharged dextrans showed only weak THz absorption, implying that the majority of conformational states are occupied and there are few unoccupied higher energy states in these materials. This suggests the two classes of material will have very different conformational properties, particularly in response to temperature changes in the extracellular matrix

Detection of DNA hybridisation on a functionalised diamond surface using reflection anisotropy spectroscopy

The analysis of single-stranded DNA attached to a polycrystalline diamond surface by reflection anisotropy spectroscopy (RAS) demonstrates that the DNA is oriented essentially vertically to the surface. RAS is able to detect the hybridisation between the attached strand and the homologous sequence