Propagation of a reaction front accompanied by island formation: CO/Au/Ni(1 1 1)

Recent high-pressure scanning tunneling microscopy studies, performed at room temperature, have explicitly demonstrated the specifics of the CO-mediated removal of Ni atoms from the topmost layer of an Au/Ni(1 1 1) surface alloy. After an incubation period, the reaction is found to start at step edges. On each edge, a large fraction of Ni atoms is removed from the terrace in certain areas, whereas other areas are nearly intact after a given time. With increasing time, the former areas begin to overlap and the reaction front becomes somewhat more homogeneous. The Au atoms remaining behind the front form nm-sized islands. Here, we present Monte Carlo simulations reproducing all these observations.     

Determination of trace amounts of bisphenol A in urine by negative-ion chemical-ionization-gas chromatography/mass spectrometry.

We improved an analytical method for determining trace amounts of bisphenol A (BPA) in urine. BPA was subjected to enzymolysis and then to solid phase extraction with a C18 cartridge. The extract was eluted with methanol, and the eluate was concentrated under a nitrogen stream, and then pentafluorobenzylized in an alkali solution. The obtained pentafluorobenzylized compound was purifed using a florisil cartridge, followed by a determination using NCI-GC/MS. This method exhibited an excellent selectivity and reproducibility with a determination limit of 0.1 ng/ml.     

Poly(vinylidene fluoride)/polyaniline/carbon nanotubes nanocomposites: Influence of preparation method and oscillatory shear on morphology and electrical conductivity

Nanocomposites of poly(vinylidene fluoride) (PVDF)/polyaniline (PAni)/carbon nanotubes (CNT) were prepared through melt blending using three different methods. The PVDF, CNT and PAni were added into the internal mixer at the same time in method I. In method II, PAni was polymerized in the presence of different amounts of CNT, and then added to PVDF. In method III, PAni was obtained with half the CNT content, and then added to PVDF with the other half of CNT. The morphology, rheological behavior and electrical conductivity of these systems were investigated through transmission electron microscopy (TEM) and combined electro-rheological measurements. As expected, the preparation method strongly influenced the final morphology of the nanocomposites, as shown by TEM analysis. The deformation and destruction of PAni-PAni and CNT-CNT bonds during the oscillatory shear experiments strongly affected the electrical conductivity, probably in two different ways: it breaks the PAni into smaller domains and also disrupts the CNT percolated network. Concluding, a good correlation between the electrical, flow behavior and preparation method could be achieved for PVDF/PAni/CNT nanocomposites, mainly by means of the combined electro-rheological measurements.     

Thermomorphic polyethylene-supported olefin metathesis catalysts

The preparation of polyethylene-oligomer (PE(olig))-supported N-heterocyclic carbene ligands (NHCs) and their Ru complexes is described. These complexes are structurally analogous to their low molecular weight counterparts and can serve as thermomorphic, recoverable/recyclable ring-closing metathesis (RCM) catalysts. Because of the insolubility of PE(olig)-supported species at 25 °C, such complexes can perform homogeneous RCM reactions at 65 °C and, upon cooling, precipitate as solids. This allows for their quantitative separation from solutions of products.     

Gay-Berne and electrostatic multipole based coarse-grain potential in implicit solvent

A general, transferable coarse-grain (CG) framework based on the Gay-Berne potential and electrostatic point multipole expansion is presented for polypeptide simulations. The solvent effect is described by the Generalized Kirkwood theory. The CG model is calibrated using the results of all-atom simulations of model compounds in solution. Instead of matching the overall effective forces produced by atomic models, the fundamental intermolecular forces such as electrostatic, repulsion-dispersion, and solvation are represented explicitly at a CG level. We demonstrate that the CG alanine dipeptide model is able to reproduce quantitatively the conformational energy of all-atom force fields in both gas and solution phases, including the electrostatic and solvation components. Replica exchange molecular dynamics and microsecond dynamic simulations of polyalanine of 5 and 12 residues reveal that the CG polyalanines fold into "alpha helix" and "beta sheet" structures. The 5-residue polyalanine displays a substantial increase in the "beta strand" fraction relative to the 12-residue polyalanine. The detailed conformational distribution is compared with those reported from recent all-atom simulations and experiments. The results suggest that the new coarse-graining approach presented in this study has the potential to offer both accuracy and efficiency for biomolecular modeling.     

The Stability of Cα Peptide Radicals: Why Glycyl Radical Enzymes?

The conformational space of dipeptide models derived from glycine, alanine, phenylalanine, proline, tyrosine, and cysteine has been searched extensively and compared with the corresponding C(α) dipeptide radicals at the G3(MP2)-RAD level of theory. The results indicate that the (least-substituted) glycine dipeptide radical is the thermochemically most stable of these species. Analysis of the structural parameters indicates that this is due to repulsive interactions between the C(α) substituents and peptide units in the radical. A comparison of the conformational preferences of dipeptide radicals and their closed-shell parents also indicates that radical stability is a strongly conformation-dependent property.     

Anti‐periodic solutions for a gradient system with resonance via a variational approach

In this paper, we investigate a second‐order resonance anti‐periodic boundary value problem where is the m‐th eigenvalue of the corresponding eigenvalue problem. By using the dual least action principle, we obtain an existence result. In addition, we obtain the existence of 2T‐periodic solutions for .     

Refurbishment of a used in‐vacuum undulator from the National Synchrotron Light Source for the National Synchrotron Light Source‐II ring

The National Synchrotron Light Source (NSLS) ceased operation in September 2014 and was succeeded by NSLS‐II. There were four in‐vacuum undulators (IVUs) in operation at NSLS. The most recently constructed IVU for NSLS was the mini‐gap undulator (MGU‐X25, to be renamed IVU18 for NSLS‐II), which was constructed in 2006. This device was selected to be reused for the New York Structural Biology Consortium Microdiffraction beamline at NSLS‐II. At the time of construction, IVU18 was a state‐of‐the‐art undulator designed to be operated as a cryogenic permanent‐magnet undulator. Due to the more stringent field quality and impedance requirements of the NSLS‐II ring, the transition region was redesigned. The control system was also updated to NSLS‐II specifications. This paper reports the details of the IVU18 refurbishment activities including additional magnetic measurement and tuning.     

Borane–Lewis Base Complexes as Homolytic Hydrogen Atom Donors

Radical stabilization energies (RSE)s have been calculated for a variety of boryl radicals complexed to Lewis bases at the G3(MP2)‐RAD level of theory. These are referenced to the B? H bond dissociation energy (BDE) in BH₃ determined at W4.3 level. High RSE values (and thus low BDE(B? H) values) have been found for borane complexes of a variety of five‐ and six‐membered ring heterocycles. Variations of RSE values have been correlated with the strength of Lewis acid–Lewis base complex formation at the boryl radical stage. The analysis of charge‐ and spin‐density distributions shows that spin delocalization in the boryl radical complexes constitutes one of the mechanisms of radical stabilization.     

Efficient synthesis of fluorobenzyloxoimidazolidinone derivatives: precursors for the radiosynthesis of [F]fluorophenylamino acids

This paper describes an efficient synthesis of fluorobenzyloxoimidazolidinone derivatives. The title compounds 1a, 1b and 1c could be prepared with high diasteromeric purity (>99%) and overall yields of 19%, 48% and 41% in a ten or six-step synthetic procedure, respectively. These compounds are used as precursors for isotopic ¹⁸F-labelling.