Synthesis of enantiopure substituted piperidines via an aziridinium ring expansion

Herein we report a novel methodology for the asymmetric synthesis of 3-substituted piperidines from readily available chiral building blocks. This method, which features a novel irreversible dihydropyrole-tetrahydropyridine ring expansion, allows the introduction of a large variety of substituents at the 3-position and permits substitution at the 2- and 6-position giving mono-, di-, or trisubstituted piperidines with high diastereocontrol.     

SModelS: a tool for interpreting simplified-model results from the LHC and its application to supersymmetry

We present a general procedure to decompose Beyond the Standard Model (BSM) collider signatures presenting a $\mathbb {Z}_2$ symmetry into Simplified Model Spectrum (SMS) topologies. Our method provides a way to cast BSM predictions for the LHC in a model independent framework, which can be directly confronted with the relevant experimental constraints. Our concrete implementation currently focusses on supersymmetry searches with missing energy, for which a large variety of SMS results from ATLAS and CMS are available. As show-case examples we apply our procedure to two scans of the minimal supersymmetric standard model. We discuss how the SMS limits constrain various particle masses and which regions of parameter space remain unchallenged by the current SMS interpretations of the LHC results.     

Interference of Different Types of Mastication on Static Balance in Individuals without Temporomandibular Disorder

Purpose: This study was to determine whether non-habitual (isotonic) bilateral and unilateral mastication with eyes open and eyes closed exerts an influence on static balance in individuals without temporomandibular disorder (TMD). Method: An observational, cross-sectional study was conducted involving 20 volunteers aged 20 to 40 years without temporomandibular disorder. Static balance was assessed with the individuals in a quiet standing position on a force plate performing different types of mastication under six separate conditions. Results: Significant differences (p < .05) were found in the area of oscillation during bilateral mastication (eyes open) and the right unilateral mastication, significant differences were only found for oscillation area with eyes open and mediolateral center of pressure with eyes closed (p < .05). Conclusions: The findings of the present study reveal that the stomatognathic system (bilateral and unilateral mastication) promote changes in some variables of static balance.     

The effects of indefinite nonlinear boundary conditions on the structure of the positive solutions set of a logistic equation

We investigate a semilinear elliptic equation with a logistic nonlinearity and an indefinite nonlinear boundary condition, both depending on a parameter λ. Overall, we analyze the effect of the indefinite nonlinear boundary condition on the structure of the positive solutions set. Based on variational and bifurcation techniques, our main results establish the existence of three nontrivial non-negative solutions for some values of λ, as well as their asymptotic behavior. These results suggest that the positive solutions set contains an S-shaped component in some case, as well as a combination of a C-shaped and an S-shaped components in another case.     

Laser Beam Filtration for High Spatial Resolution MALDI Imaging Mass Spectrometry

We describe an easy and inexpensive way to provide a highly defined Gaussian shaped laser spot on target of 5 μm diameter for imaging mass spectrometry using a commercial MALDI TOF instrument that is designed to produce a 20 μm diameter laser beam on target at its lowest setting. A 25 μm pinhole filter on a swivel arm was installed in the laser beam optics outside the vacuum ion source chamber so it is easily flipped into or out of the beam as desired by the operator. The resulting ion images at 5 μm spatial resolution are sharp since the satellite secondary laser beam maxima have been removed by the filter. Ion images are shown to demonstrate the performance and are compared with the method of oversampling to achieve higher spatial resolution when only a larger laser beam spot on target is available.

Calix[4]arenes as molecules for second order nonlinear optics

Abstract

The synthesis of a novel class of molecules for second order nonlinear optics, i.e. calix[4]arenes with extended π-systems, is described. These compounds are obtained via Wittig-Horner reactions of the formylated calix[4]arenes 5 and 6 to give the stilbene derivatives 7–9, or by diazotization of calix[4]arene, 1, followed by alkylation to give the phenylazocalix[4]arenes 11 and 12. The molecular second order nonlinear optical properties (β_z) of these calix[4]arenes have been measured by electric field-induced second harmonic generation. The influence of different acceptors as well as the influence of the different conformations of the calix[4]arenes on β_z values were determined. Surprisingly, the wavelength of the charge-transfer band λ_max is lower when β_z increases upon increasing the number of acceptors.     

Ultrasonic approach for formation of erbium oxide nanoparticles with variable geometries

Ultrasound (20 kHz, 29 W·cm(-2)) is employed to form three types of erbium oxide nanoparticles in the presence of multiwalled carbon nanotubes as a template material in water. The nanoparticles are (i) erbium carboxioxide nanoparticles deposited on the external walls of multiwalled carbon nanotubes and Er(2)O(3) in the bulk with (ii) hexagonal and (iii) spherical geometries. Each type of ultrasonically formed nanoparticle reveals Er(3+) photoluminescence from crystal lattice. The main advantage of the erbium carboxioxide nanoparticles on the carbon nanotubes is the electromagnetic emission in the visible region, which is new and not examined up to the present date. On the other hand, the photoluminescence of hexagonal erbium oxide nanoparticles is long-lived (μs) and enables the higher energy transition ((4)S(3/2)-(4)I(15/2)), which is not observed for spherical nanoparticles. Our work is unique because it combines for the first time spectroscopy of Er(3+) electronic transitions in the host crystal lattices of nanoparticles with the geometry established by ultrasound in aqueous solution of carbon nanotubes employed as a template material. The work can be of great interest for "green" chemistry synthesis of photoluminescent nanoparticles in water.     

Cembradienes from the Caribbean sea whip Eunicea sp.

A new cembradiene diterpenoid 1, together with the known antiplasmodial cembradiene 2, was isolated from the sea whip Eunicea sp. collected from Santa Marta Bay on the Colombian Caribbean sea. The structures and absolute stereochemistry of 1-2 were determined by extensive spectroscopic analysis, chemical transformation of 2 to the new diterpenoid 3, and by using modified Mosher’s method. This is the first known report regarding the determination of the absolute configuration of 2.