The first synthesis of an epidiselenodiketopiperazine

Epidithiodiketopiperazines (ETPs) are natural products (e.g., gliotoxin) with varied and important biological activity, which often is attributed to the redox properties of the disulfide moiety. As such, analogs with altered redox properties and similar structural characteristics would be of value to biological investigations. The use of an ETP as the point of departure in the first synthesis of an epidiselenodiketopiperazine (ESeP) and its activity against Mycobacterium tuberculosis (MTB) is reported.     

Pathway-Selective Sensitization of Mycobacterium tuberculosis for Target-Based Whole-Cell Screening

Whole-cell screening of Mycobacterium tuberculosis (Mtb) remains a mainstay of drug discovery, but subsequent target elucidation often proves difficult. Conditional mutants that underexpress essential genes have been used to identify compounds with known mechanism of action by target-based whole-cell screening (TB-WCS). Here, the feasibility of TB-WCS in Mtb was assessed by generating mutants that conditionally express pantothenate synthetase (panC), diaminopimelate decarboxylase (lysA), and isocitrate lyase (icl1). The essentiality of panC and lysA, and conditional essentiality of icl1 for growth on fatty acids, was confirmed. Depletion of PanC and Icl1 rendered mutants hypersensitive to target-specific inhibitors. Stable reporter strains were generated for use in high-throughput screening, and their utility was demonstrated by identifying compounds that display greater potency against a PanC-depleted strain. These findings illustrate the power of TB-WCS as a tool for tuberculosis drug discovery.     

Avoidance of Majorana resonances in periodic topological superconductor-nanowire structures

Semiconducting nanowires in proximity to superconductors are promising experimental systems for Majorana fermions which may ultimately be used as building blocks for topological quantum computers. A serious challenge in the experimental realization of the Majorana fermion in these semiconductor-superconductor-nanowire structures is tuning the semiconductor chemical potential in close proximity to the metallic superconductor. We show that presently realizable structures in experiments with tunable chemical potential lead to Majorana resonances, which are interesting in their own right, but do not manifest non-Abelian statistics. To resolve this crucial barrier to the solid state realization of Majorana fermions, we propose a new topological superconducting array structure where introducing the superconducting proximity effect from adjacent nanowires generates Majorana fermions with non-Abelian statistics.     

Ab initio study of shear strain effects on ferroelectricity at PbTiO3 thin films

Ferroelectric thin film with the perovskite ABO₃ structure have been widely used in technology applications, e.g., actuators in MEMS/NEMS and nonvolatile random access memories (FeRAM). In order to clarify the effect of the shear strain on the ferroelectricity, the PbTiO₃ thin film as a typical one is chosen. The focus of this study is to put on the PbO-terminated (1? × ?1) and c(2? × ?2) surfaces and the TiO₂-terminated (1? × ?1) surface. Based on ab initio density functional theory calculations with the local density approximation, we have found out that in both the PbO and TiO₂-terminated (1? × ?1) models, the ferroelectricity in the PbO layers was enhanced under the positive shear strain while it was suppressed under the negative one. For the TiO₂ layers, the ferroelectricity was slightly enhanced and sharply suppressed under the positive and negative shear strains, respectively. In the PbO-terminated (2? × ?2) model, the AFE phase was suppressed by the FE phase under the positive shear strain while the opposite trend was found under the negative shear strain. For the PbO layers, the ferroelectricity was enhanced under the positive and negative shear strains. For the TiO₂ layers, the influence of the negative shear strain on the ferroelectricity was larger than that of the positive one. In addition, the ideal strength of the PbTiO₃ thin film with the different terminations was investigated as well.     

Restricted Normal Cones and the Method of Alternating Projections: Applications

The method of alternating projections (MAP) is a common method for solving feasibility problems. While employed traditionally to subspaces or to convex sets, little was known about the behavior of the MAP in the nonconvex case until 2009, when Lewis, Luke, and Malick derived local linear convergence results provided that a condition involving normal cones holds and at least one of the sets is superregular (a property less restrictive than convexity). However, their results failed to capture very simple classical convex instances such as two lines in a three-dimensional space. In this paper, we extend and develop the Lewis-Luke-Malick framework so that not only any two linear subspaces but also any two closed convex sets whose relative interiors meet are covered. We also allow for sets that are more structured such as unions of convex sets. The key tool required is the restricted normal cone, which is a generalization of the classical Mordukhovich normal cone. Numerous examples are provided to illustrate the theory.     

On groups with large character degree sums

Let G be a finite group, and let T(G) be the sum of all complex irreducible character degrees of G. Define ${f(G) = \frac{T(G)}{|G|}}$ . In this paper, we show that if G is a finite group and ${f(G) > \frac{4}{15}}$ , then G is solvable.     

MALDI-TOF MS analysis of native and permethylated or benzimidazole-derivatized polysaccharides

MALDI-TOF MS provides rapid and sensitive analyses of larger biomolecules. However, MS analyses of polysaccharide have been reported to have lower sensitivity compared to peptides and proteins. Here, we investigated some polysaccharides chemically derivatized by permethylation and ortho-phenylene diamine (OPD) tagging. Methylated glycan is obviously able to improve the sensitivity for mass spectrometry detection. Oxidative condensation by UV-activation tagging to saccharides by OPD and peptide-OPD also improve the sensitivity of MALDI-TOF MS analyses. Polysaccharides including dextran, glucomannan, arabinoxylan, arabinogalactan and beta-1,3-glucan, isolated from nutritional supplements of Ganoderma lucidum and Saccharomyces pastorianus were measured using MALDI-TOF MS with 2,5-dihydroxybenzoic acid (2,5-DHB) as the matrix. These glycans were also derivatized to methylated and benzimidazole-tagged glycans by chemical transformation for molecular weight analysis. The derivatized polysaccharides showed excellent MALDI-TOF MS signal enhancement in the molecular weight range from 1 to 5 kDa. Here, we demonstrate an efficient method to give glycan-benzimidazole (glycan-BIM) derivatives for polysaccharide determination in MALDI-TOF MS. Therefore, permethylated or benzimidazole-derivatized polysaccharides provide a new option for polysaccharide analysis using MALDI-TOF MS.     

A wide-range Parallel Radial Mirror Analyzer for scanning electron/ion microscopes

This paper presents the design of a wide-range Parallel Radial Mirror Analyzer (RMA) for use as an attachment inside the specimen chambers of scanning electron/ion microscopes. The range of energies for the PRMA typically varies by a factor of 50, and it is predicted to have second-order focusing properties for all electrons/ions that are detected. For a polar angular spread of ±3°, the simulated energy resolution at an energy of 100 eV is around 0.65%, and it drops to less than 0.2% for energies between 300 eV and 5000 eV. The PRMA is predicted to have a transmittance of over an order magnitude better than previous wide-range parallel energy analyzer designs.     

Resonance raman excitation profile of a ruthenium(II) complex of dipyrido[2,3-a:3',2'-c]phenazine

The lowest energy transition of [Ru(CN)(4)(ppb)](2-) (ppb = dipyrido[2,3-a:3',2'-c]phenazine), a metal-to-ligand charge transfer, has been probed using resonance Raman spectroscopy with excitation wavelengths (488, 514, 530, and 568 nm) spanning the lowest energy absorption band centered at 522 nm. Wave packet modeling was used to simultaneously model this lowest energy absorption band and the cross sections of the resonance Raman bands at the series of excitation wavelengths across this absorption band. A fit to within +/-20% was obtained for the Raman cross sections, close to the experimental uncertainty which is typically 10-20%. Delta values of 0.1-0.4 were obtained for modes which were either localized on the ppb ligand (345-1599 cm(-1)) or the CN modes (2063 and 2097 cm(-1)). DFT calculations reveal that the resonance Raman bands observed are due to modes delocalized over the entire ppb ligand.