Self-assembled triple helicates with preferential helicity

The enantiomerically pure ligands LRR and LSS (N,N'-bis(-2,2'-bipyridyl-5-yl)carbonyl-(1S/R,2S/R)-(+/-)-1,2-diaminocyclohexane) have been synthesised by linking two 2,2'-bipyridine units by (R,R)- and (S,S)-1,2-diaminocyclohexane respectively. The crystal structure confirmed that the ligand had a twisted orientation between the two chelating units. The reaction of LRR and LSS with Fe(II), Co(III), Cd(II) and Zn(II) afforded dinuclear complexes confirmed by ES mass spectroscopy. CD spectroscopy indicated that the chiral diaminocyclohexane conferred helicity to the metal centre giving a dominant triple helicate diastereoisomer, with the LRR ligand giving a delta-configuration of each metal centre (P helicate) and the LSS ligand a lambda configuration (M helicate). 1H NMR spectroscopy confirmed a dominant major diastereoisomer with cadmium. The Zn(II) and Cd(II) complexes however were observed to undergo rapid ligand dissociation in solution.

Convergence of partial-wave expansions for energies, scattering amplitudes and positron annihilation rates

We use many-body theory to find the asymptotic behaviour of second-order correlation corrections to the energies and positron annihilation rates in many- electron systems with respect to the angular momenta l of the single-particle orbitals included. The energy corrections decrease as 1/(l+1/2)4, in agreement with the result of Schwartz, whereas the positron annihilation rate has a slower 1/(l+1/2)2 convergence rate. We illustrate these results by numerical calculations of the energies of Ne and Kr and by examining results from extensive con?guration-interaction calculations of PsH binding and annihilation.

Influence of alpha-helicity, amphipathicity and D-amino acid incorporation on the peptide-induced mast cell activation

Mast cell activation by polycationic substances is believed to result from a direct activation of G protein alpha subunits and it was suggested that the adaption of amphipathic, alpha-helical conformations would allow the peptide to reach the cytosolic compartment to interact with G proteins (Mousli et al., 1994, Immunopharmacology 27, 1, for review). We investigated the histamine-releasing activity of model peptides as well as analogues of magainin 2 amide and neuropeptide Y with different amphipathicities and alpha-helix content on rat peritoneal mast cells. Amphipathic helicity is not a prerequisite for mast cell activation. Moreover, non-helical magainin peptides with high histamine-releasing activity were less active in the liberation of carboxyfluoresceine from negatively charged liposomes, indicating that peptide-induced mast cell activation and peptide-induced membrane perturbation do not correlate. In contrast to the negligible influence of the secondary structure, amino acid configuration may exert a striking influence on peptide-induced mast cell activation. Thus histamine-release by substance P was markedly impaired when the L-amino acids in the positively charged N-terminal region were replaced by D-amino acids, with [D-Arg(1)]substance P being the most inactive substance P diastereoisomer.

Toward controlled growth of helicity-specific carbon nanotubes

The underlying mechanisms for the nucleation of carbon nanotubes as well as their helicity, remain elusive. Here, using van der Waals dispersion force calculations implemented within density functional theory, we study the cap formation, believed to be responsible for the chirality of surface-catalyzed carbon nanotubes. We find the energetics associated with growth along different facets to be independent of the surface orientation and that the growth across an edge along the axis of the metal particle leads to a perfect honeycomb lattice in a curved geometry. The formation of defects in the graphene matrix, which bend the carbon plane, requires that two or more graphene embryos with significantly different growth axis merge. Such scenario is only possible at the front- or back-end of the metal particle where growth symmetry is broken. The graphene embryos reconstruct their hexagonal structure into pentagons, heptagons, and octagons counterpart to accommodate the tube curvature.

Drivetrain Effects on Small Engine Performance

Presented is a study that expands the body of knowledge on the effect of in-cycle speed fluctuations on performance of small engines. It uses the methods developed previously by Callahan, et al. (1) to examine a variety of two-stroke engines and one four-stroke engine. The two-stroke engines were: a high performance single-cylinder, a low performance single-cylinder, a high performance multi-cylinder, and a medium performance multi-cylinder. The four-stroke engine was a high performance single-cylinder unit. Each engine was modeled in Virtual Engines, which is a fully detailed one-dimensional thermodynamic engine simulator. Measured or predicted in-cycle speed data were input into the engine models. Predicted performance changes due to drivetrain effects are shown in each case, and conclusions are drawn from those results. The simulations for the high performance single-cylinder two-stroke engine predicted significant in-cycle crankshaft speed fluctuation amplitudes and significant changes in performance when the fluctuations were input into the engine model. This was validated experimentally on a firing test engine based on a Yamaha YZ250. The four-stroke engine showed significant changes in predicted performance compared to the prediction with zero speed fluctuation assumed in the model. Measured speed fluctuations from a firing Yamaha YZ400F engine were applied to the simulation in addition to data from a simple free mass model. Both methods predicted similar fluctuation profiles and changes in performance. It is shown that the gear reduction between the crankshaft and clutch allowed for this similar behavior. The multi-cylinder, high performance two-stroke engine also showed significant changes in performance, in this case depending on the firing configuration. The low output two-stroke engine simulation showed only a negligible change in performance in spite of high amplitude speed fluctuations. This was due to its flat torque versus speed characteristic. The medium performance multi-cylinder two-stroke engine also showed only a negligible change in performance, in this case due to a relatively high inertia rotating assembly and multiple cylinder firing events within the revolution. These smoothed the net torque pulsations and reduced the amplitude of the speed fluctuation itself.

Calibration of the Radiocarbon Time Scale for the Southern Hemisphere: AD 1850-950

We have conducted a series of radiocarbon measurements on decadal samples of dendrochronologically dated wood from both hemispheres, spanning 1000 years (McCormac et al. 1998; Hogg et al. this issue). Using the data presented in Hogg et al., we show that during the period AD 950-1850 the 14C offset between the hemispheres is not constant, but varies periodically (~130 yr periodicity) with amplitudes varying between 1 and 10‰ (i.e. 8-80 yr), with a consequent effect on the 14C calibration of material from the Southern Hemisphere. A large increase in the offset occurs between AD 1245 and 1355. In this paper, we present a Southern Hemisphere high-precision calibration data set (SHCal02) that comprises measurements from New Zealand, Chile, and South Africa. This data, and a new value of 41 ± 14 yr for correction of the IntCal98 data for the period outside the range given here, is proposed for use in calibrating Southern Hemisphere 14C dates.

WASP-1b and WASP-2b: Two new transiting exoplanets detected with SuperWASP and SOPHIE

We have detected low-amplitude radial-velocity variations in two stars, USNO-B1.0 1219-0005465 (GSC 02265-00107 = WASP-1) and USNO-B1.0 0964-0543604 (GSC 00522-01199 = WASP-2). Both stars were identified as being likely host stars of transiting exoplanets in the 2004 SuperWASP wide-field transit survey. Using the newly commissioned radial-velocity spectrograph SOPHIE at the Observatoire de Haute-Provence, we found that both objects exhibit reflex orbital radial-velocity variations with amplitudes characteristic of planetary-mass companions and in-phase with the photometric orbits. Line-bisector studies rule out faint blended binaries as the cause of either the radial-velocity variations or the transits. We perform preliminary spectral analyses of the host stars, which together with their radial-velocity variations and fits to the transit light curves yield estimates of the planetary masses and radii. WASP-1b and WASP-2b have orbital periods of 2.52 and 2.15 d, respectively. Given mass estimates for their F7V and K1V primaries, we derive planet masses 0.80-0.98 and 0.81-0.95 times that of Jupiter, respectively. WASP-1b appears to have an inflated radius of at least 1.33 RJup, whereas WASP-2b has a radius in the range 0.65-1.26 RJup.

A developed stage of Alfven wave phase mixing

Alfven wave phase mixing is an extensively studied mechanism for dissipating wave energy in an inhomogeneous medium. It is common in the vast majority of phase mixing papers to assume that even though short scale lengths and steep gradients develop as a result of phase mixing, nonlinear wave coupling does not occur. However, weakly nonlinear studies have shown that phase mixing generates magnetoacoustic modes. Numerical results are presented which show the nonlinear generation of magnetosonic waves by Alfven wave phase mixing. The efficiency of the effect is determined by the wave amplitude, the frequency of the Alfven waves and the gradient in the background Alfven speed. Weakly nonlinear theory has shown that the amplitude of the fast magnetosonic wave grows linearly in time. The simulations presented in this paper extend this result to later times and show saturation of the fast magnetosonic component at amplitudes much lower than that of the Alfven wave. For the case when Alfven waves are driven at the boundary, simulating photospheric footpoint motion, a clear modulation of the saturated amplitude is observed. All the results in this paper are for a low amplitude (less than or equal to 0.1), single frequency Alfven wave and a uniform background magnetic field in a two dimensional domain. For this simplified geometry, and with a monochromatic driver, we concluded that the nonlinear generation of fast modes has little effect on classical phase mixing.

Observations of H alpha intensity oscillations in a flare ribbon

High-cadence Halpha blue wing observations of a C9.6 solar flare obtained at Big Bear Solar Observatory using the Rapid Dual Imager are presented. Wavelet and time-distance methods were used to study oscillatory power along the ribbon, finding periods of 40 - 80 s during the impulsive phase of the flare. A parametric study found statistically significant intensity oscillations with amplitudes of 3% of the peak flare amplitude, periods of 69 s (14.5 mHz) and oscillation decay times of 500 s. These measured properties are consistent with the existence of flare-induced acoustic waves within the overlying loops.

Polarisation analysis of VUV synchrotron radiation emitted from a bending magnet source in the energy range 20-50 eV: A comparison between measurements and theoretical predictions

The results of a study to characterise the polarisation properties of the photon beam emerging from beamline 5D, mounted on a bending magnet source at the Synchrotron Radiation Source, Daresbury Laboratory, are presented. The expectation values for the Stokes parameters corresponding to the light transmitted by the beamline have been calculated by combining ray-tracing and optical methods. The polarisation of the light at the source is modified both by the beamline geometry and by the reflections at the optical components. Although it is often assumed that the polarising properties of grazing incidence optics are negligible, this assumption leads to rather inaccurate results in the VUV region. A study of the reflectivity shows that even at incidence angles (theta(i) = 80-85degrees) which are far from the Brewster angle (theta(B) similar to 45degrees for VUV and soft X-ray radiation) the residual changes in the amplitudes of the reflected light can result in non-negligible polarisation effects. Furthermore, reflection at grazing incidence gives rise to a substantial change in the phase, and this has the effect of rotating the elliptically polarised state. Theoretical Stokes parameters have been compared with full polarisation measurements obtained using a reflection polarimeter in the energy range 20-40 eV. (C) 2003 Elsevier B.V. All rights reserved.

A new look at the pulsating DB white dwarf GD 358: Line-of-sight velocity measurements and constraints on model atmospheres

We report on our findings of the bright, pulsating, helium atmosphere white dwarf GD 358, based on time-resolved optical spectrophotometry. We identify 5 real pulsation modes and at least 6 combination modes at frequencies consistent with those found in previous observations. The measured Doppler shifts from our spectra show variations with amplitudes of up to 5.5 km s-1 at the frequencies inferred from the flux variations. We conclude that these are variations in the line-of-sight velocities associated with the pulsational motion. We use the observed flux and velocity amplitudes and phases to test theoretical predictions within the convective driving framework, and compare these with similar observations of the hydrogen atmosphere white dwarf pulsators (DAVs). The wavelength dependence of the fractional pulsation amplitudes (chromatic amplitudes) allows us to conclude that all five real modes share the same spherical degree, most likely, l=1. This is consistent with previous identifications based solely on photometry. We find that a high signal-to-noise mean spectrum on its own is not enough to determine the atmospheric parameters and that there are small but significant discrepancies between the observations and model atmospheres. The source of these remains to be identified. While we infer Teff =24 kK and log g ~ 8.0 from the mean spectrum, the chromatic amplitudes, which are a measure of the derivative of the flux with respect to the temperature, unambiguously favour a higher effective temperature, 27 kK, which is more in line with independent determinations from ultra-violet spectra.

Parametric study of nonlinear electrostatic waves in two-dimensional quantum dusty plasmas

The nonlinear properties of two-dimensional cylindrical quantum dust-ion-acoustic (QDIA) and quantum dust-acoustic (QDA) waves are studied in a collisionless, unmagnetized and dense (quantum) dusty plasma. For this purpose, the reductive perturbation technique is employed to the quantum hydrodynamical equations and the Poisson equation, obtaining the cylindrical Kadomtsev–Petviashvili (CKP) equations. The effects of quantum diffraction, as well as quantum statistical and geometric effects on the profiles of QDIA and QDA solitary waves are examined. It is found that the amplitudes and widths of the nonplanar QDIA and QDA waves are significantly affected by the quantum electron tunneling effect. The addition of a dust component to a quantum plasma is seen to affect the propagation characteristics of localized QDIA excitations. In the case of low-frequency QDA waves, this effect is even stronger, since the actual form of the potential solitary waves, in fact, depends on the dust charge polarity (positive/negative) itself (allowing for positive/negative potential forms, respectively). The relevance of the present investigation to metallic nanostructures is highlighted.

Body temperature daily rhythm adaptations in African savanna elephants (Loxodonta africana)

The savanna elephant is the largest extant mammal and often inhabits hot and and environments. Due to their large size, it might be expected that elephants have particular physiological adaptations, such as adjustments to the rhythms of their core body temperature (T-b) to deal with environmental challenges. This study describes for the first time the T-b daily rhythms in savanna elephants. Our results showed that elephants had lower mean T-b values (36.2 +/- 0.49 degrees C) than smaller ungulates inhabiting similar environments but did not have larger or smaller amplitudes of T-b variation (0.40 +/- 0.12 degrees C), as would be predicted by their exposure to large fluctuations in ambient temperature or their large size. No difference was found between the daily T-b rhythms measured under different conditions of water stress. Peak T-b's occurred late in the evening (22: 10) which is generally later than in other large mammals ranging in similar environmental conditions. (C) 2007 Elsevier Inc. All rights reserved.