Second-order NMR spectra at high field of common organic functional groups

The proton NMR spectra of aryl n-propyl sulfides gave rise to what may appear to be first-order proton NMR spectra. Upon oxidation to the corresponding sulfone, the spectra changed appearance dramatically and were clearly second-order. A detailed analysis of these second-order spectra, in the sulfone series, provided vicinal coupling constants which indicated that these compounds had a moderate preference for the anti-conformer, reflecting the much greater size of the sulfone over the sulfide. It also emerged, from this study, that the criterion for observing large second-order effects in the proton NMR spectra of 1,2-disubstituted ethanes was that the difference in vicinal coupling constants must be large and the difference in geminal coupling constants must be small. n-Propyl triphenylphosphonium bromide and 2-trimethylsilylethanesulfonyl chloride, and derivatives thereof, also exhibited second-order spectra, again due to the bulky substituents. Since these spectra are second-order due to magnetic nonequivalence of the nuclei in question, not chemical shifts, the proton spectra are perpetually second-order and can never be rendered first-order by using higher field NMR spectrometers.

Children’s Reasoning About the Temporal Order of Past and Future Events

Four- and five-year-olds completed two sets of tasks that involved reasoning about the temporal order in which events had occurred in the past or were to occur in the future. Four-year-olds succeeded on the tasks that involved reasoning about the order of past events but not those that involved reasoning about the order of future events, whereas 5-year-olds passed both types of tasks. Individual children who failed the past-event tasks were not particularly likely to fail the more difficult future-event tasks. However, children's performance on the reasoning tasks was predictive of their performance on a task assessing their comprehension of the terms “before” and “after.” Our results suggest that there may be a developmental change over this age range in the ability to flexibly represent and reason about the before-and-after relationships between events.

Order Flow and the Monetary Model of Exchange Rates: Evidence from a Novel Data Set

We propose an exchange rate model that is a hybrid of the conventional specification with monetary fundamentals and the Evans–Lyons microstructure approach. We estimate a model augmented with order flow variables, using a unique data set: almost 100 monthly observations on interdealer order flow on dollar/euro and dollar/yen. The augmented macroeconomic, or “hybrid,” model exhibits greater in-sample stability and out of sample forecasting improvement vis-à-vis the basic macroeconomic and random walk specifications.

Investigation on localisation accuracy for first and higher order ambisonics reproduced sound sources

Ambisonics and higher order ambisonics (HOA) technologies aim at reproducing sound field either synthesised or previously recorded with dedicated microphones. Based on a spherical harmonic decomposition, the sound field is more precisely described when higher-order components are used. The presented study evaluated the perceptual and objective localisation accuracy of the sound field encoded with four microphones of order one to four and decoded over a ring of loudspeakers. A perceptual test showed an improvement of the localisation with higher order ambisonic microphones. Reproduced localisation indices were estimated for the four microphones and the respective synthetic systems of order one to four. The perceptual and objective analysis revealed the same conclusions. The localisation accuracy depends on the ambisonic order as well as the source incidence. Furthermore, impairments linked to the microphones were highlighted.

Strategies for adding features to CAD models in order to optimize performance

This paper presents an approach which enables new parameters to be added to a CAD model for optimization purposes. It aims to remove a common roadblock to CAD based optimization, where the parameterization of the model does not offer the shape sufficient flexibility for a truly optimized shape to be created. A technique has been developed which uses adjoint based sensitivity maps to predict
the sensitivity of performance to the addition to a model of four different feature types, allowing the feature providing the greatest benefit to be selected. The optimum position to add the feature is also discussed. It is anticipated that the approach could be used to iteratively add features to a model, providing greater flexibility to the shape of the model, and allowing the newly-added parameters to be used as design variables in a subsequent shape optimization.

Decay of Cystalline Order and Equilibration during the Solid-to-Plasma Transition Induced by 20-fs Microfocused 92-eV Free-Electron-Laser Pulses

We have studied a solid-to-plasma transition by irradiating Al foils with the FLASH free electron laser at intensities up to 10(16) W/cm(2). Intense XUV self-emission shows spectral features that are consistent with emission from regions of high density, which go beyond single inner-shell photoionization of solids. Characteristic features of intrashell transitions allowed us to identify Auger heating of the electrons in the conduction band occurring immediately after the absorption of the XUV laser energy as the dominant mechanism. A simple model of a multicharge state inverse Auger effect is proposed to explain the target emission when the conduction band at solid density becomes more atomiclike as energy is transferred from the electrons to the ions. This allows one to determine, independent of plasma simulations, the electron temperature and density just after the decay of crystalline order and to characterize the early time evolution.

Instituting order: the limitations of Nasser’s post-colonial planning visions for Cairo in the case of the indigenous quarter of Bulaq (1952–1970)

This paper investigates the limitations of postcolonial planning practices that aimed to modernise Cairo’s urban spaces during Gamal Abdel Nasser rule (1952–70). Following the Free Officers revolution of 1952, ambition to display urban order through forceful change in the city’s built environment was in action. Nasser’s visions of modernity were explicit in a series of attempts to reshape several prime locations in central Cairo, which included the old traditional waterfront quarter, in Bulaq Abul Ela. An analysis of the Bulaq planning scheme drafted in 1966 reveals insights into how notions of order were spatialised to integrate with Cairo’s complex urban fabric. The official plans to regularise Bulaq also strongly demonstrates how this was a top-down, centralised process in terms of governance, with full utilisation of state resources, namely the military and the media. From a wider perspective, planning practices under Nasser demonstrated an evident break with the past to eliminate memories of colonisation and disorder. Drawing on original resources, archival material, meeting minutes and maps of this historical but dilapidated quarter of Cairo, this paper gives an insight into how Nasser’s government attempted to convey a sense of order in a revolutionary country without, however, having an understanding of order as a coherent, multilayered and sequential process of change.

Third harmonic order imaging as a focal spot diagnostic for high intensity laser-solid interactions

As the state of the art for high power laser systems increases from terawatt to petawatt level and beyond, a crucial parameter for routinely monitoring high intensity performance is laser spot size on a solid target during an intense interaction in the tight focus regime ( 10(19) Wcm(-2) is demonstrated experimentally and shown to provide the basis for an effective focus diagnostic. Importantly, this technique is also shown to allow in-situ diagnosis of focal spot quality achieved after reflection from a double plasma mirror setup for very intense high contrast interactions (> 10(20) Wcm(-2)) an important application for the field of high laser contrast interaction science.

High-order harmonics of 248.6-nm KrF laser from helium and neon ions

We report high harmonic generation from a 248.6-nm KrF laser giving harmonic orders up to the 37th (67 Angstrom) in a helium gas jet and the 35th (71 Angstrom) in neon, for laser intensities up to 4 x 10(17) W/cm(2) in 380-fs pulses. These observations are interpreted using theoretical modeling that identifies the ion species He+, Ne+, and Ne2+ as the sources of the highest harmonics.

The role of higher-order chromatin structure in the yield and distribution of DNA double-strand breaks in cells irradiated with X-rays or alpha-particles

Purpose: To determine whether the non-random distributions of DNA double-strand breaks in cells observed after alpha-particle irradiation are related to the higher-order structure of the chromatin within the nucleus.