Chiral calcium organophosphate-catalyzed enantioselective electrophilic amination of enamides

Highly enantioselective direct amination of enamides catalyzed by chiral nonracemic calcium bis(phosphate) complex 3g afforded optically active 1,2-hydrazinoimines 4. Following a subsequent in situ hydrolysis or reduction, 2-hydrazinoketones 5 or syn-1,2-disubstituted 1,2-diamines 6 were obtained in high yields and excellent enantiomeric excess.     

Enthalpic relaxation of silica–polyvinyl acetate nanocomposites

Although the effects of filler nanoparticles size and surface treatment on the glass transition temperature of the matrix phase have received well-deserved attention, nanofiller effects on other physical parameters associated with the glass transition have received less interest. To better understand how the incorporation of nanofillers affects the enthalpic relaxations associated with the glass transition, differential scanning calorimeter measurements were carried out on silica–polyvinyl acetate nanocomposites with respect to filler content, annealing temperature, and annealing period. As expected, longer annealing periods below the glass transition temperature resulted in an increase of the subsequent enthalpic relaxations. However, the presence of filler substantially reduces the enthalpic relaxation relative to that of the neat polymer at longer annealing periods only. The underlying enthalpic relaxations and the effects suppressed by the fillers are specific to the annealing temperature. These results suggest a significant alteration in the physical state of the matrix because of the presence of the filler particles. However, this does not imply the existence of a glassy layer or layers with a glass transition gradient near the filler surface. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2733–2740, 2008     

On induced Ramsey numbers for k‐uniform hypergraphs

Let denote the complete k‐uniform k‐partite hypergraph with classes of size t and the complete k‐uniform hypergraph of order s. One can show that the Ramsey number for and satisfies when t = s^o(1) as s →∞. The main part of this paper gives an analogous result for induced Ramsey numbers: Let be an arbitrary k‐partite k‐uniform hypergraph with classes of size t and an arbitrary k‐graph of order s. We use the probabilistic method to show that the induced Ramsey number (i.e. the smallest n for which there exists a hypergraph such that any red/blue coloring of yields either an induced red copy of or an induced blue copy of ) satisfies . © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 48, 5–20, 2016     

Assessment of tandem mass spectrometry and high‐resolution mass spectrometry for the analysis of bupivacaine in plasma

Triple quadrupole mass spectrometers coupled with high performance liquid chromatography are workhorses in quantitative bioanalyses. They provide substantial benefits including reproducibility, sensitivity and selectivity for trace analysis. Selected reaction monitoring allows targeted assay development but datasets generated contain very limited information. Data mining and analysis of nontargeted high‐resolution mass spectrometry profiles of biological samples offer the opportunity to perform more exhaustive assessments, including quantitative and qualitative analysis. The objectives of this study were to test method precision and accuracy, to statistically compare bupivacaine drug concentration in real study samples and to verify if high‐resolution and accurate mass data collected in scan mode can actually permit retrospective data analysis, more specifically, extract metabolite related information. The precision and accuracy data presented using both instruments provided equivalent results. Overall, the accuracy ranged from 106.2 to 113.2% and the precision observed was from 1.0 to 3.7%. Statistical comparisons using a linear regression between both methods revealed a coefficient of determination (R²) of 0.9996 and a slope of 1.02, demonstrating a very strong correlation between the two methods. Individual sample comparison showed differences from ?4.5 to 1.6%, well within the accepted analytical error. Moreover, post‐acquisition extracted ion chromatograms at m/z 233.1648 ± 5 ppm (M ? 56) and m/z 305.2224 ± 5 ppm (M + 16) revealed the presence of desbutyl‐bupivacaine and three distinct hydroxylated bupivacaine metabolites. Post‐acquisition analysis allowed us to produce semi‐quantitative evaluations of the concentration–time profiles for bupicavaine metabolites. Copyright © 2015 John Wiley & Sons, Ltd.     

On the Size‐Ramsey Number of Hypergraphs

The size‐Ramsey number of a graph G is the minimum number of edges in a graph H such that every 2‐edge‐coloring of H yields a monochromatic copy of G. Size‐Ramsey numbers of graphs have been studied for almost 40 years with particular focus on the case of trees and bounded degree graphs. We initiate the study of size‐Ramsey numbers for k‐uniform hypergraphs. Analogous to the graph case, we consider the size‐Ramsey number of cliques, paths, trees, and bounded degree hypergraphs. Our results suggest that size‐Ramsey numbers for hypergraphs are extremely difficult to determine, and many open problems remain.     

Lewis acid-catalyzed Mannich type reactions with potassium organotrifluoroborates

Three-component Lewis acid-catalyzed Mannich type reactions using potassium organotrifluoroborates (aryl, vinyl, and allyl reagents) has been developed as an extension of the standard Petasis reaction.     

Travelling wave solutions of multisymplectic discretizations of semi-linear wave equations

How well do multisymplectic discretisations preserve travelling wave solutions? To answer this question, the 5-point central difference scheme is applied to the semi-linear wave equation. A travelling wave ansatz leads to an ordinary difference equation whose solutions can be compared to travelling wave solutions of the PDE. For a discontinuous nonlinearity the difference equation is solved exactly. For continuous nonlinearities the difference equation is solved using a Fourier series, and resonances that depend on the grid-size are revealed for a smooth nonlinearity. In general, the infinite dimensional functional equation, which must be solved to get the travelling wave solutions, is intractable, but backward error analysis proves to be a powerful tool, as it provides a way to study the solutions of equation through a simple ODE that describes the behavior to arbitrarily high order. A general framework for using backward error analysis to analyze preservation of travelling waves for other equations and discretisations is presented. Then, the advantages that multisymplectic methods have over other methods are briefly highlighted.     

Three-dimensional images generated by quadrature interferometry

Quadrature detection techniques have been applied to images obtained from a Mach-Zehnder interferometer with differently polarized beams to yield the real and the imaginary parts of the diffracted fields simultaneously. This approach eliminates the need for phase retrieval by providing complete information on the complex amplitude of the diffracted signal. We present results in which we demonstrate our ability to reconstruct two- and three-dimensional microscopic objects from their complex diffraction patterns.     

Workplace exposure to nanoparticles and the application of provisional nanoreference values in times of uncertain risks

Nano reference values (NRVs) for occupational use of nanomaterials were tested as provisional substitute for Occupational Exposure Limits (OELs). NRVs can be used as provisional limit values until Health-Based OELs or derived no-effect levels (DNEL) become available. NRVs were defined for 8?h periods (time weighted average) and for short-term exposure periods (15?min-time weighted average). To assess the usefulness of these NRVs, airborne number concentrations of nanoparticles (NPs) in the workplace environment were measured during paint manufacturing, electroplating, light equipment manufacturing, non-reflective glass production, production of pigment concentrates and car refinishing. Activities monitored were handling of solid engineered NPs (ENP), abrasion, spraying and heating during occupational use of nanomaterials (containing ENPs) and machining nanosurfaces. The measured concentrations are often presumed to contain ENPs as well as process-generated NPs (PGNP). The PGNP are found to be a significant source for potential exposure and cannot be ignored in risk assessment. Levels of NPs identified in workplace air were up to several millions of nanoparticles/cm³. Conventional components in paint manufacturing like CaCO₃ and talc may contain a substantial amount of nanosized particulates giving rise to airborne nanoparticle concentrations. It is argued that risk assessments carried out for e.g. paint manufacturing processes using conventional non-nano components should take into account potential nanoparticle emissions as well. The concentrations measured were compared with particle-based NRVs and with mass-based values that have also been proposed for workers protection. It is concluded that NRVs can be used for risk management for handling or processing of nanomaterials at workplaces provided that the scope of NRVs is not limited to ENPs only, but extended to the exposure to process-generated NPs as well.     

Chiral Calcium–BINOL Phosphate Catalyzed Diastereo‐ and Enantioselective Synthesis of syn‐1,2‐Disubstituted 1,2‐Diamines: Scope and Mechanistic Studies

A highly enantioselective, chiral, Lewis acid calcium–bis(phosphate) complex, Ca[ 3 a ]_n, which catalyzes the electrophilic amination of enamides with azodicarboxylate derivatives 2 to provide versatile chiral 1,2‐hydrazinoimines 4 is disclosed. The reaction gives an easy entry to optically active syn‐1,2‐disubstituted 1,2‐diamines 6 in high yields with excellent enantioselectivities, after a one‐pot reduction of the intermediate 1,2‐hydrazinoimines 4 . The geometry and nature of the N‐substituent of the enamide affect dramatically both the reactivity and the enantioselectivity. Although the calcium–bis(phosphate) complex was a uniquely effective catalyst, the exact nature of the active catalytic species remains unclear. NMR spectroscopy and MS analysis of the various calcium complexes Ca[ 3 ]_n reveals that the catalysts exist in various oligomer forms. The present mechanistic study, which includes nonlinear effects and kinetic measurements, constitutes a first step in understanding these calcium–bis(phosphate) complex catalysts. DFT calculations were carried out to explore the mechanism and the origin of the enantioselectivity with the Ca[ 3 ]_n catalysts.