Synthesis and crystal structure of unexpected (1S,4R,5R,6S)-4-cyano-2,2,6-trimethyl-3-azabicyclo[3.3.1]nonan-6-yl acetate

The reaction of (-)-β-pinene with KCN under a mild bridged Ritter reaction gave (1S,5R,6S)-2,2,6-trimethyl-3-aza-bicyclo[3.3.1]non-3-en-6-yl acetate that subsequently reacted to provide an unexpected (1S,4R,5R,6S)-4-cyano-2,2,6-trimethyl-3-azabicyclo[3.3.1]nonane-6-yl acetate. The structure of the compound was determined by high-resolution mass spectrometry, and IR and NMR spectroscopy and confirmed by single crystal X-ray crystallography. The compound crystallises in the monoclinic P21 space group, with unit cell parameters a 8.6120 (17), b 7.4570 (15), c 11.189 (2) Å, and β 110.16 (3)°

Regulation of Marginal Zone B-Cell Differentiation by MicroRNA-146a.

B-cell development in the bone marrow is followed by specification into functional subsets in the spleen, including marginal zone (MZ) B-cells. MZ B-cells are classically characterized by T-independent antigenic responses and require the elaboration of distinct gene expression programs for development. Given their role in gene regulation, it is not surprising that microRNAs are important factors in B-cell development. Recent work demonstrated that deficiency of the NFκB feedback regulator, miR-146a, led to a range of hematopoietic phenotypes, but B-cell phenotypes have not been extensively characterized. Here, we found that miR-146a-deficient mice demonstrate a reduction in MZ B-cells, likely from a developmental block. Utilizing high-throughput sequencing and comparative analysis of developmental stage-specific transcriptomes, we determined that MZ cell differentiation was impaired due to decreases in Notch2 signaling. Our studies reveal miR-146a-dependent B-cell phenotypes and highlight the complex role of miR-146a in the hematopoietic system

The shape of a moving fluxon in stacked Josephson junctions

We study numerically and analytically the shape of a single fluxon moving in a double stacked Josephson junctions (SJJ's) for various junction parameters. We show that the fluxon in a double SJJ's consists of two components, which are characterized by different Swihart velocities and Josephson penetration depths. The weight coefficients of the two components depend on the parameters of the junctions and the velocity of the fluxon. It is shown that the fluxon in SJJ's may have an unusual shape with an inverted magnetic field in the second junction when the velocity of the fluxon is approaching the lower Swihart velocity. Finally, we study the influence of fluxon shape on flux-flow current-voltage characteristics and analyze the spectrum of Cherenkov radiation for fluxon velocity above the lower Swihart velocity. Analytic expression for the wavelength of Cherenkov radiation is derived.Comment: 12 pages, 12 figure

Enhanced Transmission of Light and Particle Waves through Subwavelength Nanoapertures by Far-Field Interference

Subwavelength aperture arrays in thin metal films can enable enhanced transmission of light and matter (atom) waves. The phenomenon relies on resonant excitation and interference of the plasmon or matter waves on the metal surface. We show a new mechanism that could provide a great resonant and nonresonant transmission enhancement of the light or de Broglie particle waves passed through the apertures not by the surface waves, but by the constructive interference of diffracted waves (beams generated by the apertures) at the detector placed in the far-field zone. In contrast to other models, the mechanism depends neither on the nature (light or matter) of the beams (continuous waves or pulses) nor on material and shape of the multiple-beam source (arrays of 1-D and 2-D subwavelength apertures, fibers, dipoles or atoms). The Wood anomalies in transmission spectra of gratings, a long standing problem in optics, follow naturally from the interference properties of our model. The new point is the prediction of the Wood anomaly in a classical Young-type two-source system. The new mechanism could be interpreted as a non-quantum analog of the superradiance emission of a subwavelength ensemble of atoms (the light power and energy scales as the number of light-sources squared, regardless of periodicity) predicted by the well-known Dicke quantum model.Comment: Revised version of MS presented at the Nanoelectronic Devices for Defense and Security (NANO-DDS) Conference, 18-21 June, 2007, Washington, US

Preliminary Design of Reactive Distillation Columns

A procedure that combines feasibility analysis, synthesis and design of reactive distillation columns is introduced. The main interest of this methodology lies on a progressive introduction of the process complexity. From minimal information concerning the physicochemical properties of the system, three steps lead to the design of the unit and the specification of its operating conditions. Most of the methodology exploits and enriches approaches found in the literature. Each step is described and our contribution is underlined. Its application is currently limited to equilibrium reactive systems where degree of freedom is equal to 2 or less than 2. This methodology which provides a reliable initialization point for the optimization of the process has been applied with success to different synthesis. The production of methyl-tert-butyl-ether (MTBE) and methyl acetate are presented as examples

An alkaloid-like 3-azabicyclo[3.3.1]non-3-ene library obtained from the bridged Ritter reaction

© 2016 Elsevier Ltd A small, diverse library of novel alkaloid-like compounds was synthesised using the bridged Ritter reaction with (−)-β-pinene and subsequent scaffold derivatisation. Structural diversity was achieved by varying the nitrile used in the reaction and thus provided an understanding of the influence nitriles have on the reaction outcome; it was determined that more nucleophilic nitriles, gave higher yields. Steric factors also determined the selectivity of scaffold types produced, with larger groups producing predominantly alkene products. X-ray crystallography and attempts to derivatise the imines obtained from the bridged Ritter reaction, highlighted the way the imino nitrogen reacted either not at all or in a stereospecific mannor, due to crowding by adjacent substituents. As the compounds contain either the 3-azabicyclo[3.3.1]nonane or 3-azabicyclo[3.3.1]non-3-ene core architecture, they will also be explored for their biological properties, due to the prevalence of bioactive alkaloids containing these core structures

Vapour reactive distillation process for hydrogen production by hi decomposition from hi-i2-h2o solutions

In this contribution, a sequential and hierarchical approach for the feasibility analysis and the preliminary design of reactive distillation columns is extended to systems involving vapour phase chemical reaction and is successfully applied to the HI vapour phase decomposition to produce H2. The complex phase and physico chemical behaviour of the quaternary HI-H2-I2-H2O system is represented by the Neumann’s thermodynamic model and instantaneous vapour phase chemical equilibrium is assumed. Then, from minimal information concerning the physicochemical properties of the system, three successive steps lead to the design of the unit and the specification of its operating conditions: the feasibility analysis, the synthesis and the design step. First, the analysis of reactive condensation curve map method (rCCM), assuming infinite internal liquid and vapour flow rate and infinite reflux ratio, is used to assess the feasibility of the process. It determines the column structure and estimates the attainable compositions. These results are used as inputs data for the synthesis step. Based on the boundary value design method (BVD), considering finite internal liquid and vapour flow rate and finite reflux ratio while neglecting all thermal effects and assuming a constant heat of vaporisation, the synthesis step provides more precise information about the process configuration (minimum reflux ratio, number of theoretical stages, localisation and number of reactive plates, position of the feed plate). Finally, the BVD method results are used to initialise rigorous simulations, based on an equilibrium stage model with energy balance, to estimate the reflux ratio taking into account thermal effect on the process. The resulting design configuration consists in a single feed and entirely reactive distillation column. The column operates under a pressure of 22 bars. The feed of the reactive distillation column, coming from the Bunsen reaction section [xHI=0.10; xI2=0.39 xH2O=0.51], is at its boiling temperature. The residue consists in pure iodine. Water and produced hydrogen are recovered at the distillate. The column operates at a reflux ratio of 5 and is composed of 11 theoretical plates including the reboiler and the partial condenser with the feed at the stage 10 (counted downwards). The obtained HI dissociation yield is 99.6%

Cognitive behaviour therapy versus counselling intervention for anxiety in young people with high-functioning autism spectrum disorders: a pilot randomised controlled trial

The use of cognitive-behavioural therapy (CBT) as a treatment for children and adolescents with autism spectrum disorder (ASD) has been explored in a number of trials. Whilst CBT appears superior to no treatment or treatment as usual, few studies have assessed CBT against a control group receiving an alternative therapy. Our randomised controlled trial compared use of CBT against person-centred counselling for anxiety in 36 young people with ASD, ages 12–18. Outcome measures included parent- teacher- and self-reports of anxiety and social disability. Whilst each therapy produced improvements inparticipants, neither therapy was superior to the other to a significant degree on any measure. This is consistent with findings for adults

Calibration and Stokes Imaging with Full Embedded Element Primary Beam Model for the Murchison Widefield Array

15 pages, 11 figures. Accepted for publication in PASA. © Astronomical Society of Australia 2017The Murchison Widefield Array (MWA), located in Western Australia, is one of the low-frequency precursors of the international Square Kilometre Array (SKA) project. In addition to pursuing its own ambitious science program, it is also a testbed for wide range of future SKA activities ranging from hardware, software to data analysis. The key science programs for the MWA and SKA require very high dynamic ranges, which challenges calibration and imaging systems. Correct calibration of the instrument and accurate measurements of source flux densities and polarisations require precise characterisation of the telescope's primary beam. Recent results from the MWA GaLactic Extragalactic All-sky MWA (GLEAM) survey show that the previously implemented Average Embedded Element (AEE) model still leaves residual polarisations errors of up to 10-20 % in Stokes Q. We present a new simulation-based Full Embedded Element (FEE) model which is the most rigorous realisation yet of the MWA's primary beam model. It enables efficient calculation of the MWA beam response in arbitrary directions without necessity of spatial interpolation. In the new model, every dipole in the MWA tile (4 x 4 bow-tie dipoles) is simulated separately, taking into account all mutual coupling, ground screen and soil effects, and therefore accounts for the different properties of the individual dipoles within a tile. We have applied the FEE beam model to GLEAM observations at 200 - 231 MHz and used false Stokes parameter leakage as a metric to compare the models. We have determined that the FEE model reduced the magnitude and declination-dependent behaviour of false polarisation in Stokes Q and V while retaining low levels of false polarisation in Stokes U.Peer reviewedFinal Accepted Versio