Identification of marker proteins for Bacillus anthracis using MALDI-TOF MS and ion trap MS/MS after direct extraction or electrophoretic separation

Direct extraction of bacterial vegetative cells or spores followed by matrix-assisted laser desorption ionization/time of flight mass spectrometry (MALDI TOF MS) has become popular for bacterial identification, since it is simple to perform and mass spectra are readily interpreted. However, only high-abundance proteins that are of low mass and ionize readily are observed. In the case of B. anthracis spores, small acid-soluble spore proteins (SASPs) have been the most widely studied. Additional information can be obtained using tandem mass spectrometry (MS-MS) to confirm the identity of proteins by sequencing. This is most readily accomplished using ion trap (IT) MS-MS. However, enzymatic digestion of these proteins is needed to generate peptides that are within the mass range of the ion trap. The use of sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE), or other forms of electrophoresis, allows one to focus on specific proteins of interest (e.g. the high mass exosporium glycoproteins BcIA and BcIB) that provide additional species- and strain-specific discrimination.     

State-resolved unimolecular dissociation of cis-cis HOONO: Product state distributions and action spectrum in the 2nuOH band region

Nascent OH fragment product state distributions arising from unimolecular dissociation of room temperature HOONO, initiated by excitation in the region of the 2nu(OH) band, are probed using laser-induced fluorescence at sub-Doppler resolution. Phase-space simulations of the measured OH rotational distributions are consistent with the dissociation dynamics being statistical and confirm that all major features in the room temperature action spectrum belong to the cis-cis conformer. The phase-space simulations also allow us to estimate the HO-ONO bond dissociation energy of cis-cis HOONO to be D(0)=19.9+/-0.5 kcal/mol, which when combined with the known heat-of-formation data for the OH and NO(2) fragments gives DeltaH(f) (0)(cis-cis HOONO)=-2.5 kcal/mol. In addition to fragment energy release, spectral features in the cis-cis HOONO action spectrum are examined with respect to their shifts upon (15)N isotope substitution and through ab initio spectral simulation using a two-dimensional dipole surface that takes into account the influence of HOON torsional motion on the OH stretching overtone. The two-dimensional spectral simulations, using CCSD(T)/cc-pVTZ dipole surface, qualitatively reproduces features appearing in the action spectrum and suggest that the strong broad feature occurring approximately 570 cm(-1) to the blue of the cis-cis HOONO 2nu(OH) peak, likely involve excitation of HOON-torsion/OH-stretch combination bands originating from thermally populated excited torsional states. A closer examination of the predictions of the two-dimensional model with experiments also reveals its limitations and suggests that a more elaborate treatment, one which includes several additional modes, will likely be required in order to fully explain the room temperature action spectrum. Ab initio calculations of the HOON torsional potential at the CCSD(T)/cc-pVTZ level of theory are also presented and confirm that cis-perp configuration does not correspond to a bound localized minimum on the HOONO potential energy surface.     

Analysis of ochres from Clearwell Caves: the role of particle size in determining colour

Three ochre samples (A (orange-red in colour), B (red) and C (purple)) from Clearwell Caves, (Gloucestershire, UK) have been examined using an integrated analytical methodology based on the techniques of IR and diffuse reflectance UV-visible-NIR spectroscopy, X-ray diffraction, elemental analysis by ICP-AES and particle size analysis. It is shown that the chromophore in each case is haematite. The differences in colour may be accounted for by (i) different mineralogical and chemical composition in the case of the orange ochre, where higher levels of dolomite and copper are seen and (ii) an unusual particle size distribution in the case of the purple ochre. When the purple ochre was ground to give the same particle size distribution as the red ochre then the colours of the two samples became indistinguishable. An analysis has now been completed of a range of ochre samples with colours from yellow to purple from the important site of Clearwell Caves.     

Model Development in Thermal Styrene Polymerization

Summary: The thermal polymerization of styrene is usually modeled by relying on a reaction scheme and a set of equations that were developed more than three decades ago by Hui and Hamielec. Many detailed models of styrene polymerization are available in the open literature and they are mostly based on the work of Hui and Hamielec, which nearly makes this the standard to follow in explaining the behavior of polystyrene reactors. The model of Hui and Hamielec does a very nice job of describing monomer conversion data but discrepancies are seen between observed and predicted values of number and weight average molecular weights, M_n and M_w. Discrepancies in number average molecular weight seem to be the result of random noise. Discrepancies in weight average molecular weight grow as the polymerization temperature decreases and some of the trends observed in the residuals over the entire temperature range cannot be attributed to random noise. Hui and Hamielec attributed the observed deficiencies to a standard deviation of ±10% in their GPC measurements. A new data set with an experimental error of 2% for average molecular weights is presented. The set contains measured values of M_n, M_w and M_z, so the polymerization scheme has been extended to include third order moments. The data set also includes the effect of ethylbenzene as a chain transfer agent. We present the results of comparing model predictions to our measurements and the adjustments made in the original set of kinetic parameters published by Hui and Hamielec.     

The Incorporation of Titania into Modified Silicates for Solar Photodegradation of Aqueous Species

A new class of sol-gel-derived photocatalytic materials has been synthesized and used in solar-assisted photodegradation studies. The materials are comprised of a homogeneous dispersion of commercial TiO₂ powder into silica and organically modified silicate (Ormosil) hosts. The efficiency of the photocatalytic properties of these TiO₂-containing materials was determined by their relative performance in the solar photodecomposition of aqueous rhodamine B. The improved adsorption properties of the modified materials compared to commercial TiO₂ increase the photodecomposition rate and the buoyancy properties, although excess hydrophobicity decreases the wetted section of the catalyst and its photocatalytic performance. These materials can be used as floatable catalysts for solar-assisted water purification.     

L 1 factorizations and invariant subspaces for weighted composition operators

For a contraction operator T with spectral radius less than one on a Banach space , it is shown that the factorization of certain L¹ functions by vectors x in and x*. in , in the sense that for n ≧ 0, implies the existence of invariant subspaces for T. Explicit formulae for such factorizations are given in the case of weighted composition operators on reproducing kernel Hilbert spaces. An interpolation result of McPhail is applied to show how this can be used to construct invariant subspaces of hyperbolic weighted composition operators on H². Received: 1 November 2005     

Completions of partial metrics into value lattices

In this paper we investigate some notions of completion of partial metric spaces, including the bicompletion, the Smyth completion, and a new “spherical completion”. Given an auxiliary relation, we show that it arises from a totally bounded partial metric space, and the spherical completion of such a space is its round ideal completion. We also give an example of a totally bounded partial metric space whose bicompletion and Smyth completion are not continuous posets. Finally, we present an example of a totally bounded partial metric giving rise to the Scott and lower topologies of a continuous poset, but whose spherical completion is not a continuous poset.     

Perfect state transfer in Laplacian quantum walk

For a graph G and a related symmetric matrix M, the continuous-time quantum walk on G relative to M is defined as the unitary matrix \(U(t) = \exp (-itM)\), where t varies over the reals. Perfect state transfer occurs between vertices u and v at time \(\tau \) if the (u, v)-entry of \(U(\tau )\) has unit magnitude. This paper studies quantum walks relative to graph Laplacians. Some main observations include the following closure properties for perfect state transfer. If an n-vertex graph has perfect state transfer at time \(\tau \) relative to the Laplacian, then so does its complement if \(n\tau \in 2\pi {\mathbb {Z}}\). As a corollary, the join of \(\overline{K}_{2}\) with any m-vertex graph has perfect state transfer relative to the Laplacian if and only if \(m \equiv 2\pmod {4}\). This was previously known for the join of \(\overline{K}_{2}\) with a clique (Bose et al. in Int J Quant Inf 7:713–723, 2009). If a graph G has perfect state transfer at time \(\tau \) relative to the normalized Laplacian, then so does the weak product \(G \times H\) if for any normalized Laplacian eigenvalues \(\lambda \) of G and \(\mu \) of H, we have \(\mu (\lambda -1)\tau \in 2\pi {\mathbb {Z}}\). As a corollary, a weak product of \(P_{3}\) with an even clique or an odd cube has perfect state transfer relative to the normalized Laplacian. It was known earlier that a weak product of a circulant with odd integer eigenvalues and an even cube or a Cartesian power of \(P_{3}\) has perfect state transfer relative to the adjacency matrix. As for negative results, no path with four vertices or more has antipodal perfect state transfer relative to the normalized Laplacian. This almost matches the state of affairs under the adjacency matrix (Godsil in Discret Math 312(1):129–147, 2011).