Dissecting alkynes: full cleavage of polarized C≡C moiety via sequential bis-Michael addition/retro-Mannich cascade

The reaction of diaryl ketoalkynes with 1,2-diamino ethane leads to the full scission of the triple bond with the formation of acetophenone and imidazoline fragments. In this transformation, one of the alkyne carbons undergoes formal reduction with the formation of three C-H bonds, whereas the other carbon undergoes formal oxidation via the formation of three C-N bonds (one π and two σ). Computational analysis confirmed that the key fragmentation step proceeds via a six-membered TS in a concerted manner. Both amines are involved in the fragmentation: the N-H moiety of one amine transfers a proton to the developing negative charge at the enolate oxygen, while the other amine provides direct stereoelectronic assistance to the C-C bond cleavage via a hyperconjugative n(N) → σ*(C-C) interaction.     

Increasing risk aversion and life-cycle investing

Mathematics and Financial Economics - We derive the optimal portfolio for an investor with increasing relative risk aversion in a complete continuous-time securities market. The IRRA assumption...     

Unfolding the torus: Oscillator geometry from time delays

Summary We present a simple method of plotting the trajectories of systems of weakly coupled oscillators. Our algorithm uses the time delays between the “firings” of the oscillators. For any system ofn weakly coupled oscillators there is an attracting invariantn-dimensional torus, and the attractor is a subset of this invariant torus. The invariant torus intersects a suitable codimension-1 surface of section at an (n−1)-dimensional torus. The dynamics ofn coupled oscillators can thus be reduced,in principle, to the study of Poincaré maps of the (n−1)-dimensional torus. This paper gives apractical algorithm for measuring then−1 angles on the torus. Since visualization of 3 (or higher) dimensional data is difficult we concentrate onn=3 oscillators. For three oscillators, a standard projection of the Poincaré map onto the plane yields a projection of the 2-torus which is 4-to-1 over most of the torus, making it difficult to observe the structure of the attractor. Our algorithm allows a direct measurement of the 2 angles on the torus, so we can plot a 1-to-1 map from the invariant torus to the “unfolded torus” where opposite edges of a square are identified. In the cases where the attractor is a torus knot, the knot type of the attractor is obvious in our projection.     

Hydrodynamics of a particle impact on a wall

The problem of a particle impacting on a wall, a common phenomenon in particle-laden flows in the minerals and process industries, is investigated computationally using a spectral-element method with the grid adjusting to the movement of the particle towards the wall. Remeshing is required at regular intervals to avoid problems associated with mesh distortion and the constantly reducing maximum time-step associated with integration of the non-linear convective terms of the Navier–Stokes equations. Accurate interpolation between meshes is achieved using the same high-order interpolation employed by the spectral-element flow solver. This approach allows the full flow evolution to be followed from the initial approach, through impact and afterwards as the flow relaxes. The method is applied to the generic two-dimensional and three-dimensional bluff body geometries, the circular cylinder and the sphere. The principal case reported here is that of a particle colliding normally with a wall and sticking. For the circular cylinder, non-normal collisions are also considered. The impacts are studied for moderate Reynolds numbers up to approximately 1200. A cylindrical body impacting on a wall produces two vortices from its wake that convect away from the cylinder along the wall before stalling while lifting induced wall vorticity into the main flow. The situation for a sphere impact is similar, except in this case a vortex ring is formed from the wake vorticity. Again, secondary vorticity from the wall and particle plays a role. At higher Reynolds number, the secondary vorticity tends to form a semi-annular structure encircling the primary vortex core. At even higher Reynolds numbers, the secondary annular structure fragments into semi-discrete structures, which again encircle and orbit the primary core. Vorticity fields and passive tracer particles are used to characterize the interaction of the vortical structures. The evolution of the pressure and viscous drag coefficients during a collision are provided for a typical sphere impact. For a Reynolds number greater than approximately 1000 for a sphere and 400 for a cylinder, the primary vortex core produced by the impacting body undergoes a short-wavelength instability in the azimuthal/spanwise direction. Experimental visualisation using dye carried out in water is presented to validate the predictions.     

Helium cosmic ray flux measurements at Mars

The helium energy spectrum in Martian orbit has been observed by the MARIE charged particle spectrometer aboard the 2001 Mars Odyssey spacecraft. The orbital data were taken from March 13, 2002 to October 28, 2003, at which time a very intense Solar Particle Event caused a loss of communication between the instrument and the spacecraft. The silicon detector stack in MARIE is optimized for the detection of protons and helium in the energy range below , which typically includes almost all of the flux during SPEs. This also makes MARIE an efficient detector for GCR helium in the energy range of 50–. We will present the first fully normalized flux results from MARIE, using helium ions in this energy range.     

Detection of mycotic pseudoaneurysm of the ascending aorta using MRI

Mycotic pseudoaneurysms of the ascending aorta are rare cardiovascular lesions that carry the risk of potentially disastrous complications such as aortic rupture or widespread sepsis. Regardless of its location in the arterial system, this lesion carries a high mortality rate. Early diagnosis of mycotic pseudoaneurysm is paramount for optimizing the chances of surgical therapy. While imaging strategies of this lesion have included aortography, echocardiography, and computed tomography, the information gained from each of these individual studies may be acquired in a single MR imaging session. MRI offers the fundamental advantages of noninvasiveness, nonionization, and multiplanar imaging capabilities. Additionally, MRI provides excellent soft tissue contrast, a wide field of view, qualitative and quantitative flow analysis, and an independence of operator expertise or patient body habitus.     

Immobilization of a sulfide-oxidizing bacterium in a novel adsorbent biocatalyst support

Applied Biochemistry and Biotechnology - Preliminary experiments have shown thatT. denitrificans strain F can be immobilized in DuPont BIO-SEP beads and used to treat refinery spent sulfidic...     

Symmetries and pattern selection in Rayleigh-Bénard convection

This paper describes the process of pattern selection between rolls and hexagons in Rayleigh-Bénard convection with reflectional symmetry in the horizontal midplane. This symmetry is a consequence of the Boussinesq approximation, provided the boundary conditions are the same on the top and bottom plates. All possible local bifurcation diagrams (assuming certain non-degeneracy conditions) are found using only group theory. The results are therefore applicable to other systems with the same symmetries. Rolls, hexagons, or a new solution, regular triangles, can be stable depending on the physical system. Rolls are stable in ordinary Rayleigh-Bénard convection. The results are compared to those of Buzano and Golubitsky [1] without the midplane reflection symmetry. The bifurcation behavior of the two cases is quite different, and a connection between them is established by considering the effects of breaking the reflectional symmetry. Finally, the relevant experimental results are described.     

Radiative corrections to low-energy ππ scattering

Radiative corrections to low-energy ππ scattering are calculated. A chiral SU(2) × SU(2) Lagrangian is used to describe low-energy scattering. This strong interaction Lagrangian is modified in the presence of the electromagnetic field in a gauge invariant way. It is found that photons do not probe the strong vertex. Corrections to the cross sections are calculated to O(α). All the ultra-violet divergences cancel, and the results are independent of cut-off parameters. Corrections to the Weinberg scattering lengths of the order of 1% are defined by removal of the Coulomb pole terms. The field theoretic calculation is compared with a potential theory approach. It is argued that the potential theory calculation of radiative corrections is more reliable.