Regio and diastereoselective multicomponent 1,3-dipolar cycloadditions between prolinate hydrochlorides, aldehydes and dipolarophiles for the direct synthesis of pyrrolizidines

A general synthesis of highly substituted pyrrolizidines can be performed by a multicomponent 1,3-dipolar cycloaddition using proline ester hydrochlorides, aldehydes and dipolarophiles, at room temperature without catalysts or in the presence of AgOAc (5 mol %). In the case of (2S,4R)-4-hydroxyproline derivatives it is possible to obtain enantioenriched pyrrolizidines with high control of the regio- and diastereoselectivity affording the adducts 2,4-trans-2,5-trans according to an endo-approach and a S-dipole geometry of the in situ generated azomethine ylide. For proline esters a similar regioselectivity and endo-diastereoselectivity are observed when the dipole promotes an α-attack. However, when ethyl glyoxylate is used as aldehyde component the γ-attack of the S-ylide takes place preferentially giving rise the opposite regioselectivity for acrylic dipolarophiles, being crucial the role of silver acetate. In this case, the exo-adducts with a 2,3-cis-2,5-trans relative configuration are diastereoselectively obtained. In addition, computational studies have also been carried out to shed light on the origins of the diastereo- and regioselectivity observed for the described 1,3-dipolar cycloadditions.

Nanoparticles of tungsten as low-cost monometallic catalyst for selective hydrogenation of 3-hexyne

Low-cost tungsten monometallic catalysts containing variable amounts of metal (4.5, 7.1 and 8.5%W) were prepared by impregnating alumina with ammonium metatungstate as an inexpensive precursor. The catalysts were characterized using ICP, XPS, XRD, TPR and hydrogen chemisorption. These techniques revealed mainly WO3-Al2O3 (W6+) species on the surface. The effects of the content of W nanoparticles and reaction temperature on activity and selectivity for the partial hydrogenation of 3-hexyne, a non-terminal alkyne, were assessed under moderate conditions of temperature and pressure. The monometallic catalysts prepared were found to be active and stereoselective for the production of (Z )-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z )-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Investigating the potential magnetic origin of wind variability in OB stars

In this thesis, the origin of large-scale structures in hot star winds, believed to be responsible for the presence of discrete absorption components (DACs) in the absorption troughs of ultraviolet resonance lines, is constrained using both observations and numerical simulations. These structures are understood as arising from bright regions on the stellar surface, although their physical cause remains unknown. First, we use high quality circular spectropolarimetric observations of 13 well-studied OB stars to evaluate the potential role of dipolar magnetic fields in producing DACs. We perform longitudinal field measurements and place limits on the field strength using Bayesian inference, assuming that it is dipolar. No magnetic field was detected within this sample. The derived constraints statistically refute any significant dynamical influence from a magnetic dipole on the wind for all of these stars, ruling out such fields as a cause for DACs. Second, we perform numerical simulations using bright spots constrained by broadband optical photometric observations. We calculate hydrodynamical wind models using three sets of spot sizes and strengths. Co-rotating interaction regions are yielded in each model, and radiative transfer shows that the properties of the variations in the UV resonance lines synthesized from these models are consistent with those found in observed UV spectra, establishing the first consistent link between UV spectroscopic line profile variability and photometric variations and thus supporting the bright spot paradigm (BSP). Finally, we develop and apply a phenomenological model to quantify the measurable effects co-rotating bright spots would have on broadband optical photometry and on the profiles of photopheric lines in optical spectra. This model can be used to evaluate the existence of these spots, and, in the event of their detection, characterize them. Furthermore, a tentative spot evolution model is presented. A preliminary analysis of its output, compared to the observed photometric variations of xi Persei, suggests the possible existence of “active longitudes” on the surface of this star. Future work will expand the range of observational diagnostics that can be interpreted within the BSP, and link phenomenology (bright spots) to physical processes (magnetic spots or non-radial pulsations).

Paleointensity of various DSDP sites (Table 3)

The existing database for paleointensity estimates of the ancient geomagnetic field contains more than 1500 data points collected through decades of effort. Despite the huge amount of work put into obtaining these data, there remains a strong bias in the age and global distribution of the data toward very young results from a few locations. Also, few of the data meet strict criteria for reliability and most are of unknown quality. In order to improve the age and spatial distribution of the paleointensity database, we have carried out paleointensity experiments on submarine basaltic glasses from a number of DSDP sites. Of particular interest are the sites that provide paleointensity data spanning the time period 0.3-5 Ma, a time of relatively few high quality published data points. Our new data are concordant with contemporaneous data from the published literature that meet minimum acceptance criteria, and the combined data set yields an average dipole moment of 5.49 +/- 2.36*10**22 Am**2. This average value is comparable to the average paleofield for the period 5-160 Ma (4.2 +/- 2.3*10**22 Am**2) (Juarez et al., 1998, doi:10.1038/29746) and is substantially less than the value of approximately 8*10**22 Am**2 often quoted for the last 5 Myr (e.g. McFadden and McElhinny (1982) J. Geomagn. Geoelectr. 34, 163-189; Goguitchaichvili et al., 1999, doi:10.1016/S0012-821X(99)00010-2).

(Table 2) Picked maximum velocities from 3 radars (RAY, SHK, and SUM), showing 10 explosions at Erebus volcano, Antarctica, and their respective directivity vectors

We used a novel system of three continuous wave Doppler radars to successfully record the directivity of i) Strombolian explosions from the active lava lake of Erebus volcano, Antarctica, ii) eruptions at Stromboli volcano, Italy, and iii) a man-made explosion in a quarry. Erebus volcano contains a convecting phonolite lava lake, presumably connected to a magma chamber at depth. It is one of the few open vent volcanoes that allow a direct observation of source processes during explosions. Its lava lake is the source of frequent violent Strombolian explosions, caused by large gas bubbles bursting at the lake surface. The exact mechanism of these bubble bursts is unclear, as is the mechanism of the creation of the infrasound signal accompanying the explosions. We use the Doppler radar data to calculate the directivity of Strombolian eruptions at Erebus. This allows us to derive information about the expected type of infrasound source pattern (i.e. the role of a dipole in addition to the monopole signature) and the physical structure of the volcano. We recorded 10 large explosions simultaneously with three radars, enabling us to calculate time series of 3D directivity vectors (i.e. effectively 4D), which describe the direction of preferred expansion of the gas bubble during an explosion. Such directivity information allows a comparison to dipole infrasound radiation patterns recorded during similar explosions only a few weeks later. Video observations of explosions support our interpretation of the measurements. We conclude that at Erebus, the directivity of explosions is mainly controlled by random processes. Since the geometry of the uppermost conduit is assumed to have a large effect on the directivity of explosions, the results suggest a largely symmetrical uppermost conduit with a vertical axis of symmetry. For infrasound recordings, a significant dipole signature can be expected in addition to the predominant monopole signature.

Entanglement induced by spontaneous emission in spatially extended two-atom systems

The role of the collective antisymmetric state in entanglement creation by spontaneous emission in a system of two non-overlapping two-level atoms has been investigated. Populations of the collective atomic states and the Wootters entanglement measure (concurrence) for two sets of initial atomic conditions are calculated and illustrated graphically. Calculations include the dipole-dipole interaction and a spatial separation between the atoms that the antisymmetric state of the system is included throughout even for small interatomic separations. It is shown that spontaneous emission can lead to a transient entanglement between the atoms even if the atoms were prepared initially in an unentangled state. It is found that the ability of spontaneous emission to create transient entanglement relies on the absence of population in the collective symmetric state of the system. For the initial state of only one atom excited, entanglement builds up rapidly in time and reaches a maximum for parameter values corresponding roughly to zero population in the symmetric state. On the other hand, for the initial condition of both atoms excited, the atoms remain unentangled until the symmetric state is depopulated. A simple physical interpretation of these results is given in terms of the diagonal states of the density matrix of the system. We also study entanglement creation in a system of two non-identical atoms of different transition frequencies. It is found that the entanglement between the atoms can be enhanced compared to that for identical atoms, and can decay with two different time scales resulting from the coherent transfer of the population from the symmetric to the antisymmetric state. In addition, it was found that a decaying initial entanglement between the atoms can display a revival behaviour.

Entanglement of two atoms

We discuss the problem of creation of entangled states in a system of two two-level atoms which are separated by an arbitrary distance r(12) and interact with each other via the dipole-dipole interaction and both are driven by a laser field. The entangled antisymmetric state of the system is included throughout, even for small inter-atomic separations. Different mechanisms leading to effective transfer of population to the antisymmetric state are identified. The steady-state values of concurrence which is a measure of entanglement are calculated showing that perfect entanglement can be reached in case of two non-identical atoms.

Entangling two atoms via spontaneous emission

We discuss the creation of entanglement between two two-level atoms in the dissipative process of spontaneous emission. It is shown that spontaneous emission can lead to a transient entanglement between the atoms even if the atoms were prepared initially in an unentangled state. The amount of entanglement created in the system is quantified by using two different measures: concurrence and negativity. We find analytical formulae for the evolution of concurrence and negativity in the system. We also find the analytical relation between the two measures of entanglement. The system consists of two two-level atoms which are separated by an arbitrary distance r(12) and interact with each other via the dipole-dipole interaction, and the antisymmetric state of the system is included throughout, even for small interatomic separations, in contrast to the small-sample model. It is shown that for sufficiently large values of the dipole-dipole interaction initially the entanglement exhibits oscillatory behaviour with considerable entanglement in the peaks. For longer times the amount of entanglement is directly related to the population of the slowly decaying antisymmetric state.

Effects of potential models in the vapor-liquid equilibria and adsorption of simple gases on graphitized thermal carbon black

In this paper, we investigate the effects of various potential models in the description of vapor–liquid equilibria (VLE) and adsorption of simple gases on highly graphitized thermal carbon black. It is found that some potential models proposed in the literature are not suitable for the description of VLE (saturated gas and liquid densities and the vapor pressure with temperature). Simple gases, such as neon, argon, krypton, xenon, nitrogen, and methane are studied in this paper. To describe the isotherms on graphitized thermal carbon black correctly, the surface mediation damping factor introduced in our recent publication should be used to calculate correctly the fluid–fluid interaction energy between particles close to the surface. It is found that the damping constant for the noble gases family is linearly dependent on the polarizability, suggesting that the electric field of the graphite surface has a direct induction effect on the induced dipole of these molecules. As a result of this polarization by the graphite surface, the fluid–fluid interaction energy is reduced whenever two particles are near the surface. In the case of methane, we found that the damping constant is less than that of a noble gas having the similar polarizability, while in the case of nitrogen the damping factor is much greater and this could most likely be due to the quadrupolar nature of nitrogen.

Multiquantum eigenstates of a linear chain of coupled qubits

We present a technique to identify exact analytic expressions for the multiquantum eigenstates of a linear chain of coupled qubits. A choice of Hilbert subspaces is described that allows an exact solution of the stationary Schrodinger equation without imposing periodic boundary conditions and without neglecting end effects, fully including the dipole-dipole nearest-neighbor interaction between the atoms. The treatment is valid for an arbitrary coherent excitation in the atomic system, any number of atoms, any size of the chain relative to the resonant wavelength and arbitrary initial conditions of the atomic system. The procedure we develop is general enough to be adopted for the study of excitation in an arbitrary array of atoms including spin chains and one-dimensional Bose-Einstein condensates.

Spin boson models for quantum decoherence of electronic excitations of biomolecules and quantum dots in a solvent

We give a theoretical treatment of the interaction of electronic excitations (excitions) in biomolecules and quantum dots with the surrounding polar solvent. Significant quantum decoherence occurs due to the interaction of the electric dipole moment of the solute with the fluctuating electric dipole moments of the individual molecules in the solvent. We introduce spin boson models which could be used to describe the effects. of decoherence on the quantum dynamics of biomolecules which undergo light-induced conformational change and on biomolecules or quantum dots which are coupled by Forster resonant energy transfer.

Atom counting in ultracold gases using photoionization and ion detection

We analyze photoionization and ion detection as a means of accurately counting ultracold atoms. We show that it is possible to count clouds containing many thousands of atoms with accuracies better than N-1/2 with current technology. This allows the direct probing of sub-Poissonian number statistics of atomic samples. The scheme can also be used for efficient single-atom detection with high spatiotemporal resolution. All aspects of a realistic detection scheme are considered, and we discuss experimental situations in which such a scheme could be implemented.

Performance comparison between uniformly and nonuniformly spaced adaptive antennas with respect to tolerance to pointing errors

The paper presents theoretical and experimental investigations into performances of narrowband uniformly and nonuniformly spaced adaptive linear dipole array antennas that are subjected to pointing errors. The analysis focuses on the array's output Signal to Interference plus Noise Ratio. The presence of mutual coupling between the array elements is taken into account. It is shown that the array's tolerance to pointing errors can be enhanced by controlling the interelement spacing. (c) 2006 Wiley Periodicals, Inc.

Receiving mutual impedance between two normal-mode helical antennas (NMHAs)

A new mutual impedance - the receiving mutual impedance - between two normal-mode helical antennas is defined, measured, and theoretically calculated. The variations of the receiving mutual impedance with antenna separation, with frequency, and with excitation source direction are critically investigated. An application of the receiving mutual impedance in direction finding demonstrates its more accurate description of the mutual coupling effect than that using the conventional mutual impedance.