Corrigendum to “A tandem enol silane Formation-Mukaiyama aldol reaction mediated by TMSOTf” [Tetrahedron Lett. 48 (2007) 3559–3562]

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Compositional dependence of the thermal,structural, and electrical properties of AsTeI glasses

Thermal, structural, and electrical properties of semiconducting AsTeI (and AsTe) glasses have been examined as a function of concentration. Analytical techniques have been developed for quantitative chemical analysis of all three components. Differential scanning calorimetry data indicate a broad endothermic reaction, T_min ∼ 145 °C, above the glass transition (T_g = 120 ± 8 °C) for iodine compositions of 0 to ∼ 20 at%. Above this reaction temperature the thermal data are composition dependent. For glasses with I ? 35 at %, T_g is much lower (65–70 °C) and the endothermic reaction is much sharper with a minimum at ∼ 133 °C. The wide variation in thermal properties with composition suggests that electrical effects associated with high temperatures (e.g. switching and memory phenomena) may also be composition dependent, as well as being dependent upon kinetics. Structural studies show that phase segregation above T_g is dependent upon kinetics as well as upon temperature. Thermal, structural, and electrical data give evidence that As₂Te₃ exists as a unit in the non-crystalline state. This structural unit, stable at high temperatures, is present in the molten material and is thought to be present as the supercooled liquid is quenched. The short-range order extends to long-range order upon devitrification and the first crystalline phase detected is monoclinic As₂Te₃. Apparently metastable under the conditions of formation, this phase converts to a previously unreported fcc phase upon further heat treatment. Similar crystalline structures are known to be associated with thermally- and electrically-induced memory phenomena in AsTeGe and AsTeI glasses. Density measurements at room temperature show that (1) there are no phase miscibility gaps in the glass substructure or different crystalline phases segregating as the I content is varied, and (2) there is a large change in molar volume with increasing I concentration, whereas the molar weight does not change significantly. Electrical conductivity, σ, data in the region around room temperature, show that the σ₀ values, determined from σ = σ₀e^−E/kt, range from 10² to 10³ (Ω-cm)⁻¹. A possible dependence of σ₀ on I content may be due to changes in molar volume. The more homogeneous glasses appear to show breakpoints in the σ versus 1/T data; the corresponding changes in E are only 0.02–0.06 eV, with E = 0.04 eV being most frequently observed. For As₅₀Te_50−xI_x glasses, σ at a given temperature increases as the iodine concentration is increased to about 5 at % and then decreases with further increase in I content. Correspondingly there is a minimum in the E versus I concentration data at I ∼ 5 at %. Results suggest that dependence of the σ breakpoints on glass homogeneity and the variation of E with I concentration may be due to trapping effects.     

Convergent chemo-enzymatic synthesis of mannosylated glycopeptides; targeting of putative vaccine candidates to antigen presenting cells

The combination of solid phase peptide synthesis and endo-β-N-acetylglucosaminidase (ENGase) catalysed glycosylation is a powerful convergent synthetic method allowing access to glycopeptides bearing full-length N-glycan structures. Mannose-terminated N-glycan oligosaccharides, produced by either total or semi-synthesis, were converted into oxazoline donor substrates. A peptide from the human cytomegalovirus (CMV) tegument protein pp65 that incorporates a well-characterised T cell epitope, containing N-acetylglucosamine at specific Asn residues, was accessed by solid phase peptide synthesis, and used as an acceptor substrate. High-yielding enzymatic glycosylation afforded glycopeptides bearing defined homogeneous high-mannose N-glycan structures. These high-mannose containing glycopeptides were tested for enhanced targeting to human antigen presenting cells (APCs), putatively mediated via the mannose receptor, and for processing by the APCs for presentation to human CD8+ T cells specific for a 9-mer epitope within the peptide. Binding assays showed increased binding of glycopeptides to APCs compared to the non-glycosylated control. Glycopeptides bearing high-mannose N-glycan structures at a single site outside the T cell epitope were processed and presented by the APCs to allow activation of a T cell clone. However, the addition of a second glycan within the T cell epitope resulted in ablation of T cell activation. We conclude that chemo-enzymatic synthesis of mannosylated glycopeptides enhances uptake by human APCs while preserving the immunogenicity of peptide epitopes within the glycopeptides, provided those epitopes are not themselves glycosylated.     

Use of Pyridine as Cocatalyst for the Synthesis of N-Phenylanthranilic Acids

It is reported the use of pyridine as cocatalyst for the synthesis of N-phenylantranilic acids by the Ullmann-Goldberg condensation in water or amyl alcohol as solvents, with good yield.     

The conformal Killing equation on forms—prolongations and applications

We construct a conformally invariant vector bundle connection such that its equation of parallel transport is a first order system that gives a prolongation of the conformal Killing equation on differential forms. Parallel sections of this connection are related bijectively to solutions of the conformal Killing equation. We construct other conformally invariant connections, also giving prolongations of the conformal Killing equation, that bijectively relate solutions of the conformal Killing equation on k-forms to a twisting of the conformal Killing equation on (k−?)-forms for various integers ?. These tools are used to develop a helicity raising and lowering construction in the general setting and on conformally Einstein manifolds.     

Semi‐supervised linear discriminant analysis

Fisher's linear discriminant analysis is one of the most commonly used and studied classification methods in chemometrics. The method finds a projection of multivariate data into a lower dimensional space so that the groups in the data are well separated. The resulting projected values are subsequently used to classify unlabeled observations into the groups. A semi‐supervised version of Fisher's linear discriminant analysis is developed so that the unlabeled observations are also used in the model‐fitting procedure. This approach is advantageous when few labeled and many unlabeled observations are available. The semi‐supervised linear discriminant analysis method is demonstrated on a number of data sets where it is shown to yield better separation of the groups and improved classification over Fisher's linear discriminant analysis. Copyright © 2011 John Wiley & Sons, Ltd.